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AU715180B2 - Secondary battery - Google Patents
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AU715180B2 - Secondary battery - Google Patents

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Publication number
AU715180B2
AU715180B2 AU26133/97A AU2613397A AU715180B2 AU 715180 B2 AU715180 B2 AU 715180B2 AU 26133/97 A AU26133/97 A AU 26133/97A AU 2613397 A AU2613397 A AU 2613397A AU 715180 B2 AU715180 B2 AU 715180B2
Authority
AU
Australia
Prior art keywords
film
lithium
battery
negative electrode
manufactured
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
AU26133/97A
Other versions
AU2613397A (en
Inventor
Soichiro Kawakami
Naoya Kobayashi
Shinya Mishina
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Canon Inc
Original Assignee
Canon Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP4320559A external-priority patent/JP2771406B2/en
Priority claimed from JP32056092A external-priority patent/JP3487556B2/en
Priority claimed from JP4320558A external-priority patent/JP3067426B2/en
Priority claimed from JP4320557A external-priority patent/JP2943127B2/en
Priority claimed from JP34456392A external-priority patent/JP3423338B2/en
Priority claimed from JP07834293A external-priority patent/JP3530544B2/en
Priority claimed from AU52003/93A external-priority patent/AU5200393A/en
Application filed by Canon Inc filed Critical Canon Inc
Publication of AU2613397A publication Critical patent/AU2613397A/en
Publication of AU715180B2 publication Critical patent/AU715180B2/en
Application granted granted Critical
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H01M4/808—Foamed, spongy materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making

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Description

S F Ref: 257508D1
AUSTRALIA
PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT
ORIGINAL
_I_
Name and Address of Applicant: Actual Inventor(s): Canon Kabushiki Kaisha 30-2, Shimomaruko 3-chome Ohta-ku Tokyo 146
JAPAN
Soichiro Kawakami, Shlnya Mishina and Naoya Kobayashi Address for Service: Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Invention Title: Secondary Battery The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5845
AU]
CFO 9574 S -1- 1 Secondary Battery BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a secondary battery which can repeatedly be used, and more T particularly to a reliable secondary battery capable of preventing short circuit occurring due to dendrite even if the battery is repeatedly charged and discharged.
10 Related Background Art oe.eei Since global warming is expected to take place due to the greenhouse effect caused from an increase in CO2 and so forth, construction of thermal power plants encounters problems. Accordingly, it has been considered feasible to perform so-called load levelling for the pupose of effectively using generators by accumulating electric power at night in secondary batteries at homes to level the load.
There arises another desire for a development of secondary battery which exhibits a high energy density for use in an electric car that does not exhaust air contamination substances. Further, development of a high performance secondary battery has been needed for use as a power source for portable equipment, such as a book-type personal computer, a word processor, a video camera and a portable telephone.
A locking chair type lithium ion battery capable of serving as the foregoing high performance secondary battery and comprising a positive electrode active material comprising lithium ions introduced into an iihterl"aer compound thereof and a negative electrode active material comprising carbon has been developed and partially put into practical use.
However the lithium ion battery has not achieved the high energy density that is the original characteristics of the lithium battery which uses the metal lithium as the positive electrode active material. The reason why a large capacity lithium accumulator of the type that uses the lithium metal as the positive electrode has not been put into practical use is that generation of dendrite of the lithium (tree branch like crystal) which is the main cause of a short circuit cannot be prevented yet.
The lithium battery, nickel-zinc battery and the airzinc battery encounters that lithium or zinc is, as **described above, deposited on the surface of the negative electrode at the time of charge. At this time, the current S" 20 density is locally raised on the negative electrode surface 9 depending upon the surface condition, causing lithium or zinc to be selectively deposited in the foregoing place.
The deposited metal grows (dendrite) in the form of tree branch with the progress of the charge and discharge cycles 25 while penetrating a separator until it reaches the 9 9.
•coo ee e e IN:\LIBEO1316:MXL positive electrode, causing a short circuit to occur.
The dendrite reaction mechanism is considered as follows. Since lithium or zinc that depbsits'at the tirne of charge has a considerable reactivity, it reacts with electrolyte solution or water or the like in the electrolyte solution, causing an insulating film to be formed which has a large resistance. Therefore, the current density in the foregoing portion is raised at the time of the next charge, resulting in that the dendrite can further easily glow. It leads to a fact that a short circuit takes place between the negative electrode and the positive electrode, resulting in that the charge cannot be performed.
If the short circuit has taken place considerably, the energy of the battery will be consumed in a very short time, causing heat to be generated. As a result, the solvent of the electrolyte solution can be decomposed, resulting in generation of gas. Therefore, gas is generated, causing the internal pressure to be raised. In this case, an accident S" of an exposure or fire can be generated for the worst.
S 20 Therefore, there has been a desire for a long life of the S"deposit of lithium that does not easily cause the internal short circuit even if the charge and the discharge are a..
repeated.
Also nickel-zinc batteries and air-zinc batteries 25 generate dendrite of zinc due to repetition of charging and discharging, the dendrite penetrating o 9o*9o9 *o 9o 99 9 9.
t 9 (N:\LIBE]01316:MXL the separator. As a result the zinc negative electrode and the positive electrode encounter a short circuit.
Therefore, the foregoing conventional technology suffers from an excessively short cycle life.
SUMMARY OF THE INVENTION An object of the present invention is to provide a lithium, lithium alloy, zinc or zinc alloy secondary battery capable of overcoming the foregoing problems experienced with the conventional secondary batteries and exhibiting a long cycle life.
In order to overcome the foregoing problems experienced with the conventional technology, the inventors of the present invention have made energetic studies. As a result, a fact was found that generation of dendrite of lithium or zinc can be prevented by forming a film permitting ions relating to battery reactions to pass through on the surface of the negative electrode.
e a [N:\LIBE]O1316:JCA In accordance with one aspect of the present invention, there is provided secondary battery having a 0 0 0 0* 00 ~0 0 0 a a. a 0* a IN:\LIEI121 1:MXL -6negative electrode made of a negative electrode active material and a positive electrode made of a positive a a a .a
C
a a a a.
U
S.
a..
a a a a a. a a a a a.
[N:\LIBEJO1 21 1:MXL -7electrode active material and arranged in such a manner that said negative electrode active material and said positive a ee we r [N:\LIBE101211:MXL electrode active material are separated from each other by a separator, said secondary battery comprising: a. a a.
a a a a a a a.
a..
a.
a a a. a a.
[N:%LIBEJO1 21 1 MXL at least a multi-layered metal oxide film disposed between said positive electrode and said negative electrode, said multi-layered metal oxide film being prepared by using bimolecular film as a mold.
.0* a a a a a *aaa..
a a. a a a. a a.
a.
a a [R:\LIBE]0121 idoc Another fact was found that an arrangement that surface of the positive electrode is covered with a thin film
S
S S 5 S. S
SS
S.
555 S
S
55*555
S
S S *5 S S .5 S S [N:\LIBE]O1 21 1:VXF 11 made of an insulating material or a semiconductor which is free from electron conduction and which permits ions *e a a a a. a a a.
a a a..
a.
9 9* a a a. a a a *a [N:\LIBE1O121 1 :MXL 12relating to battery reactions will prevent short circuit in the battery between the negative electrode and the positive electrode even if dendrite is generated in the negative electrode.
S
ee [N:\LIBE]O1211:VXF -13- BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a basic structural view which illustrates a secondary battery according to an embodiment of the present invention; Fig. 2 is a schematic cross sectional view which illustrates a flat battery to which an embodiment of the present invention is applied; Fig. 3 is a schematic cross sectional view which illustrates an example of a cylindrical battery to which an embodiment of the present invention is applied; Fig. 4 is a schematic view which illustrates an example of a partial structure of a negative electrode covered with a film through which ions relating to battery reactions are able to pass; Fig. 5 is a basic structural view which illustrates another embodiment of the secondary battery according to the present invention; Fig. 6 is a schematic structural view which illustrates an apparatus for subjecting lithium for use in S 20 the secondary battery according to an embodiment of the present invention to surface treatment; Fig. 7 is a schematic structural view which S S illustrates an apparatus for subjecting lithium for use in the secondary battery according to an embodiment of the 25 present *5S*
SS:
S S .i o
*SS*S
So• IN:\LIBE]01316:MXL -14invention to surface treatment; Fig. 8 is a schematic view which illustrates an effect of the present invention; Figs. 9A to 9H are views which illustrate examples of layer stacking patterns according to the present invention including a conductor layer, a semiconductor layer and an insulating layer between the negative electrode and the separator thereof; Fig. 10 is another basic structural view which illustrates the secondary battery according to an embodiment of the present invention; Fig. 11 is a schematic cross sectional view which illustrates another cylindrical battery to which the present invention is applied; Fig. 12 is another basic structural view which illustrates the secondary battery according to an embodiment of the present invention; and ~Fig. 13 is another basic structural view which S" illustrates the secondary battery according to an embodiment S• 20 of the present invention.
S.
5 9 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Structure of Battery A secondary battery according to an embodiment of the 25 present invention comprises a negative electrode, a separator a positive electrode, an electrolyte and a collector. Fig. 1 is a basic structural view which illustrates the oooo•$
S
[N:\LIBE]01316:MXL secondary battery. Referring to Fig. 1, reference numeral 100 represents a negative collector, 101 represents a negative electrode substantially-made of negative electrode active material, 102 represents a shell, 103 represents a positive collector, 104 represents a positive electrode substantially made of positive electrode active material, 105 represents a electrolyte solution (electrolyte), 106 represents a negative terminal, 107 represents a positive terminal, 109 represents a case for the secondary battery, and 108 represents a separator. Figs. 5, 10 and 12 illustrate another basic structure in which a multi-layer oxide film 10102, an ion permeable film 12102 and a layer 5102 applied with lithium surface treatment in place of the film 102. If the lithium battery comprises the negative electrode 101 made of the negative active material which is lithium or lithium alloy, lithium ions in the electrolyte solution 105 are introduced into the space between the layers of the positive electrode active material of the positive electrode 104 through the permeable film due to the 20 discharge reaction in a case of the structure shown in Fig.
12. Simultaneously, lithium ions are dissolved and discharged from the negative electrode active material 101 into the electrolyte 105 through the film 102 and the multilayer metal oxide 10102. In the charging reaction, lithium 25 ions in the electrolyte solution 105 are, in the form of S.lithium metal, Ve [N:\LIBE]O1316:MXL 16precipitated into the negative electrode active material through the film 102 (dendrite can easily glow if the film 102 is not present). Simultaneously, lithium between the layers of the positive electrode active material 104 is dissolved and discharged into the electrolyte solution 105. Although lithium ions precipitated during the charging reaction are in a very active state to react with small-quantity water, oxygen, impurities or solvent in the electrolyte contained, the 10 structure in which the surface of the negative electrode 101 is covered with the film 102 prevents direct contact between the precipitated lithium and the electrolyte solution. Therefore, the generation of dendrite, which causes the battery short circuit to occur, can be prevented.
In a case of an alkali battery comprising the negative electrode active material 101 made of zinc or zinc alloy, the discharge reaction takes place in such a manner that hydroxyl ions in the electrolyte solution 105, similarly to the above, react with the negative electrode active material 101 of the negative electrode 101 through the film 102.
:Simultaneously hydroxyl ions are discharged into the electrolyte solution 105 from the positive electrode active material of the positive electrode 104. The charging reaction is performed in such a manner that hydroxyl ions
C.
25 are discharged from the negative electrode 101 into the electrolyte solution 105 r So eSOC
C
S .5C S C
C
IN:\LIBE]01 316:MXL -17through the film 102 (if the film 102 is not present at this time, zinc ions in the electrolyte solution 105 easily cause dendrite to glow on the negative electrode).
Simultaneously, hydroxyl ions in the electrolyte solution 105 react with the positive electrode 104. Similarly to the case where the negative electrode active material is lithium, the present of the film 102 prevents generation of zinc dendrite at the time of charging.
Therefore, the present invention is able to prevent short circuits in the battery, lengthen the life of the secondary battery and improve the safety.
If the foregoing negative electrode active material is lithium or lithium alloy, lithium ions are used in the reactions in the battery. In the case of the alkali battery containing zinc as the negative electrode active material, hydroxyl ions are used in the reactions. The batteries comprising zinc as the negative electrode active material is ~typified by nickel-zinc battery, air-zinc battery and I'g°°s bromine-zinc battery (however, the bromine-zinc battery
S
V.e: 20 comprises zinc ion as the negative side ion that are used in 0 •the inside reactions) Method of Forming Negative Electrode The negative electrode can be formed by any one of the
OS
25 following methods as well as the method for forming the same o by directly covering the surface of 0O 0 ego°
°OOO°
*0o° 0° @0 S 0 [N:\LIBE]01316:MXL -18the negative electrode active material with a coating material by a dipping method, a spraying method or a CVD method.
It is effective to employ a method in which a conductive and porous matrix (the base), for example, sponge-like or fiber metal or carbon, having communication holes is covered with a coating material through which ions for use in the reactions in the battery can be passed through, and then lithium or zinc, which is the negative electrode active material, is caused to electrochemical precipitate and adhere so that the negative electrode is formed. If a porous and conductive matrix has a wide specific area, the current density per unit area at the time of the charge and the discharge can be lowered. Therefore, the growth of the dendrite can be prevented and accordingly the charging/discharging efficienty can be improved.
It is preferable that the film made of a coating material, through which ions can be passed through, the small apertures serving as the space, in which the lithium can be precipitated, be formed into a 3D net shape.
Another effective method may be employed which has steps of directly immersing a porous and conductive matrix in the melted negative electrode active material, taking out the matrix, covering the surface of the conductive matrix 25 with the negative active material or 0 9 9 9 9* 99 9 0* 0 9* f [N:\LIBE]01316:MXL 19electrochemically covering the same with the negative electrode active material, and applying a coating material through which ions for use in the reactions in the battery can be passed to the surface.
Fig. 4 is a schematic view which illustrates a partial structure of a negative electrode formed by covering a conductive matrix 400 with a negative electrode active material 401 and a coating material 402 through which ions for use in the reactions in the battery can be passed.
Material for Covering the Surface of Negative Electrode The coating material for covering the surface of the negative electrode will now be described (1 to 7) i. Film Having an Inorganic Glass Structure By covering the surface of the negative electrode active material with the film having an inorganic glass structure, through which ions for use in the reactions in the battery can be passed, the reactions between lithium and water or oxygen can be prevented, causing easiness in handling if the negative electrode active material is lithium. Further, the direct contact between the lithium and the electrolyte solution does not take place.
Therefore, the growth of the polymer film formed from the solvent of the electrolyte solution on the surface of S: 25 lithium can be prevented. If the negative active material is zinc, the elution of zinc into the electrolyte solution can be oU o
U
S..
SO
S
S
C S [N:\LIBEO1 316:MXL prevented. As a result, formation of dendrite can be prevented and therefore the cycle life against charge and discharge can be lengthened. Since the film having the inorganic glass structure is flame retardant or incombustible, safety in an emergency breakage or the like can be improved. The foregoing inorganic glass may be made any one of a metal oxide selected from a group consisting of silica titanium oxide, alumina, zirconia oxide, magnesium oxide, tantalum oxide, molybdenum oxide, tungsten molybdenum, tin oxide, indium oxide, iron oxide, chrome oxide, aluminum phosphate, iron phosphate silicon phosphate and their mixtures. In particular, it is preferable to employ silica, titanium oxide, alumina, zirconia oxide or aluminum phosphate.
A sol-gel method is one of adequate methods for forming the inorganic glass. However the fact that lithium has a low melting point of 181 0 C causes a necessity to arise for the operation of directly applying the foregoing material to the surface of lithium to be performed at low temperature. Since lithium reacts with water and alcohol, the operation must be performed in a circumstance in which no water and alcohol is present (the case in which the inorganic glass is previously applied to the conductive matrix or the case where the negative electrode active 25 material is zinc are excluded) .Therefore, the sol-gel method, which is the typical C C .Co
C
C [N:\LIBE]01316:MXL -21 inorganic coating method at low temperature, must be performed with any particular means. The raw material for the material having the inorganic glass structure is obtained in such a manner that an acid or a base and water are added to a solution of alcohol of an organic metal compound such as a metal alkoxide to hydrolyze the raw material so as to form colloid particles having metal atomoxygen atom bonds, and then the solvent is substituted by a non-hydric solvent except alcohol.
The surface coating of the negative electrode active material is formed in a manner comprising steps of directly applying the foregoing colloid solution, or applying a solution, in which a monomer or an organic polymer or both organic polymer and a crosslinking material are dissolved in the colloid solution, and polymerizing it or drying and hardening it. By combining the organic polymers, strength against cracks and separations can be improved. If the electrolyte for forming the battery is dissolved in the colloid solution to form the film, wettability with the electrolyte solution can be improved, causing ions to be moved easily.
As an alternative to alkoxide, any one of the following organic metal compound may be employed: acetyl acetone salt, an alkyl metal compound, acetyl acetone metal 25 salt, napththene acid metal salt, and octyl acid metal salt.
9 a a.
a.
a a a.
[N:\LIBE]01316:MXL -22- The organic polymer for combining the organic polymers is exemplified by epoxy resin, polyester, polyimide, polyethylene, polypropylene, polyurethane, polystyrene, polyethylene glycol, nylon, fluorine resin and silicon resin.
The polymer crosslinking material is exemplified by diisocyanate, polyisocyanate prepolymer, block isocyanate, organic peroxide, polyamine, oxims, nitroso compound, sulfur or sulfur compound, selenium, magnesium oxide, lead oxide and zinc oxide. As an alternative to using the crosslinking material, a method may be employed in which radial rays or electron rays or ultraviolet rays are applied to polymerize or crosslink the polymer.
As an application method, a dipping method, screen printing, spraying or a roll coating method may be employed.
The viscosity of the liquid to be applied must adequately be adjusted to be adaptable to the application method.
In order to facilitate the movement of the charge at the time of the charging operation, powder or fiber or whisker of conductive material such as carbon or titanium may be mixed with the foregoing film forming solution.
It is preferable that the thickness of the film to be formed on the surface of the negative electrode active material ranges from 50 A to 100 t, further preferably a a a a.
s a [N:\LIBE]01316:MXL -23ranges from 100 A to 10 t. The optimum thickness of the film differs depending upon the density or the void ratio of the film and considerably differs depending upon the type of the electrolyte solution.
The thickness of the film can be adjusted by changing the concentration of the main material in the coating liquid for forming the film.
2. Polymer Film of Derivative of Aromatic Hydrocarbon Compound By covering the surface of the negative electrode active material with a polymer film of a derivative of an aromatic hydrocarbon compound, the reaction between lithium and water or oxygen can be prevented in the case where the negative electrode active material is lithium. It leads to a fact that handling can be facilitated. Further, the contact between lithium and electrolyte solution can be prevented.
Therefore, the growth of a polymer film, which is formed from the solvent of the electrolyte solution, on the surface of lithium can be prevented. If the negative electrode active material is zinc, elution of zinc into the electrolyte solution is prevented by the film.
As a result, formation of dendrite can be prevented and therefore the life against the charge and discharge cycle can be lengthened. The derivative of the aromatic S 25 hydrocarbon for forming the charge moving complex with h i.
lithium is one or more derivatives selected from a group *o.
*a oa ao *aa t r oee• a.
[N:\LIBE]01316:MXL 24 1 consisting of naphthalene, anthracene, phenanthlene, naphthacene, pyrene, triphenylene, perillene, picene, benzopyrene, coronene and ovalene. The polymer for use to form the coating material can be prepared by polymerization or copolymerization of vinyl monomer, monomer of acetylene derivative or dicarboxylic acid and a monomer such as glycol. The polymerization of the vinyl monomer can be performed by radical or ion polymerization. The monomer of the acetylene derivative 10 can be polymerized while using a chloride of tungsten as a catalyzer. The dicarboxylic acid and diamine can be polycondensed and the dicarboxylic acid and glycol can o* as well as be polycondensed. The monomer of the aromatic derivative for forming the polymer is 15 exemplified by 2 vinyl naphthalene, 2 vinyl pyridine, 9 vinyl anthracene, 9, 10 anthracene dipropionic acid, 9, 10 bis (phenyl ethyl) anthracene and 5, 12 bis (phenyl ethynyl) naphthalene. It is preferable to use 2 vinyl naphthalene or 9 vinyl anthracene.
A starting material for the radical polymerization is exemplified by azobisisobutylonitryl
(AIBN),
benzoylperoxide (BPO) and t-butylhydroperoxide.
A
starting material for the cation polymerization is exemplified by an acid such as H 2
SO
4
H
3
PO
4 HC10 4 CCl 3 or CO2H and Friedel-Craft catalyzer such as BF 3 AlCl 3 TiC14 or SnCl 4 A large ring compound having an aromatic ring can be polymerized by dehydrogenation in which the Friedel-Craft catalyzer and an oxidizer are combined to each other. A starting material for the anion polymerization may be an alkaline metal compound or an organic metal compound.
As an alternative to the foregoing method, a polymer into which an aromatic group can be obtained by subjecting the side chain of each polymer to a substitution reaction with a derivative of an aromatic compound. Another method may be employed in which an electrolytic polymerization reaction is caused to take place in an electrolyte solution containing a monomer mixed therein to form directly a polymer of an aromatic compound on the surface of lithium.
When the surface of lithium is applied with a coating by using the foregoing polymer solution, it is preferable to use a polymer solution dehydrated and deoxidized sufficiently in inactive gas dehydrated sufficiently. It is preferable to use a solvent in the foregoing solution which has been dehydrated with active alumina, molecular sheave, phosphorus pentaoxide or calcium chloride. As an alternative to this, it is preferable depending upon the type of the solvent that the solvent be distilled under presence of alkaline metal in inactive gas to remove impurities and to be dehydrated (however, the necessity of strictly controlling water can be eliminated when the pl er :polymer is r a a o oooo• IN:\LIBE]01316:MXL -26previously applied to the conductive matrix or when the negative electrode active material is zinc).
An electrolyte may previously be mixed when the foregoing film is formed. It leads to a fact that wettability between the electrolyte solution and the film can be improved, causing ions to easily pass through the film. In order to facilitate the movement of the charge at the time of charging, conductive powder, such as carbon or titanium, fiber or whisker may be mixed at the time of forming the film.
Since the performance of the battery deteriorates if the polymer coating film is dissolved in an organic solvent of the electrolyte, it is preferable to be crosslinked in such a manner, for example, ultraviolet rays, electron rays or radial rays are applied or a crosslinking material, such as a radical generating agent, is used.
It is preferable that the thickness of the film to be formed on the surface of the negative electrode active material ranges from 50 A to 100 t, more preferably ranges from 100 A to 10 p.
The optimum thickness of the film differs depending upon the density or the void ratio of the film and considerably differs depending upon the type of the electrolyte solution. The thickness of the film can be 25 adjusted by changing the concentration of the main material in the coating liquid for forming the film.
VS
V
S*
[N:\LIBE]01316:MXL 27 1 3. Organic Metal Compound When the surface of lithium and the organic metal compound react with each other, bonding with lithium atoms takes place so that a film having a surface which is organic-bonded is formed. As a result, the wettability (the lipophilic property) is improved, causing lithium ions to be easily introduced/discharged at the time of the charge and discharge. Further, the surface coating film prevents the direct contact between S. 10 lithium and the organic solvent, causing the formation, on the surface of lithium, of a polymerized film of the organic solvent, which increases the resistance in the battery, can be prevented. As a result, formation of dendrite can be prevented, and therefore life against 15 the charge and discharge cycle can be lengthened.
Further, reactions between lithium and water during the manufacturing process can be prevented and accordingly handling can be made easier. If the content of lithium in the film is high in the lithium battery according to the present invention, rapid reactions of lithium at an emergency breakage can be prevented.
The foregoing organic metal compound may be a material selected from a group consisting of: metal alkoxide, alkaline metal compound, acetyl acetone metal salt, naphthene acid metal salt, or oxtyl acid metal salt of metal, such as titanium, aluminum, silicon, zirconium, tantalum, magnesium, indium, tin, molybdenum, 28 1 tungsten or germanium. Among the foregoing organic metal compounds, it is preferable to use a metal compound of silicon or titanium or aluminum because of easy forming of the film and excellent stability of the formed film.
The organic silicon compound may be alkoxysilane, alkylsilane, halogenated silane, siloxane, silane containing vinyl group, amino group, epoxy group, methacrylic group or mercaptal group introduced thereto, 10 hydrogen denatured, vinyl denatured, hydroxyl group denatured, amino denatured, carboxylic group 0 denatured, chloro denatured, epoxy denatured, methachryloxy denatured, mercapto denatured, fluorine denatured, long chain alkyl denatured 15 or phenyl denatured polysiloxane, alkylene oxide denatured siloxane copolymer, silicon denatured copolymer, alkoxysilane denatured polymer, silicon denatured urethane or silicon denatured nylon.
The organic titanium compound may be alkoxytitanium, titanium chelate, titanium acylate or titanium polymer.
The organic aluminum compound may be alkoxyaluminum, alkylaluminum or a halogenated aluminum.
The organic silicon-titanium compound may be a tyranopolymer of a silicon polymer crosslinked to the main chain of a polycarbosilane skeleton with a titanium compound.
-29- Also a material prepared by introducing a derivative of an organic metal compound into a polymer by substitution may be used as the coating material.
The film may be formed by directly applying the organic compound or by applying it after diluted with a solvent if the organic compound is in the form of liquid.
If the organic compound is in the form of a solid, a solution dissolved in a solvent can be applied. The organic compound may be applied by dipping, screen printing, spraying or roll coating. The viscosity of the foregoing coating liquid must adequately be adjusted to be suitable for the employed coating method.
By mixing the organic metal compound at the time of forming the film, the wettability of the electrolyte solution can be improved and accordingly ions can easily be introduced/discharged at the time of the charge and the discharge. Further, the movement of the charge can be made easier at the time of the battery charge by mixing powder or fiber or whisker of conductive material such as carbon or titanium at the time of applying the organic metal compound.
It is preferable that the thickness of the film to be formed on lithium ranges from 50 A to 100 more preferably 100 A to 10 A. The optimum thickness of the film differs depending upon the density or the void ratio of the film and 25 considerably differs depending upon the type of the electrolyte solution. The a. a o• a a a.
a.
a.
as a a a a.
[N:\LIBEO01316:MXL 30 1 thickness of the film can be adjusted by changing the concentration of the main material in the coating liquid for forming the film.
4. Fluororesin Coating Material By using fluorine resin of a type having an ether bond to cover the surface of lithium, the surface coating process can be completed easily and the contact between lithium and the film can be improved.
The presence of oxygen atoms of the fluorine resin having the ether bond makes easier the coordination of lithium ions, enabling lithium ions to be moved easily in the fluorine resin.
Further, the surface coating film prevents the direct contact between the lithium metal and the organic 15 solvent, and therefore the formation of a polymerized film of the organic solvent, which increases the internal resistance of the battery, on the surface of *lithium can be prevented.
As a result, the formation of dendrite can be prevented and therefore the life against the charge and discharge cycle can be lengthened.
By covering the surface of lithium with the fluorine resin, reactions of lithium with water or oxygen can be prevented, causing handling to be facilitated.
Since the fluorine resin is a flame retardant resin, it exhibits safety at the time of an emergency 31 1 fire accident.
The fluorine resin for covering the surface of lithium is exemplified by: a copolymer with a vinyl monomer, such as vinyl ether, dioxysol, dioxyne or dioxycene having an ether bond with fluoroethylene or diene monomer derivative or a copolymer with a vinyl monomer, such as vinyl ether, dioxysol or dioxyne, dixycene having a fluorized ether bond with a diene 5 compound, such as ethylene. In particular, it is oft*: 10 preferable to use a copolymer with vinyl ether having an ether bond with fluoroethylene. The fluoroethylene may be a fluoroethylene derivative such as tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride or vinyl fluoride. The fluoroethylene 15 copolymer containing the ether bond can be polymerized by a solution, suspension, block or emulsion polymerization. As a starting material, a peroxide, alkyl boron, light or radial rays may be employed.
The fluororesin can be coated on lithium metal by any one of the following methods.
a. A solution of the fluororesin is applied by spraying, screen printing, by using a coater or by dipping.
b. The fluororesin is directly coated to the surface of lithium by a vacuum evaporation method such as sputtering.
c. A polymer film is directly formed by plasma 32polymerization under an atmosphere of monomer which is the raw material for the fluororesin.
If the lithium surface is coated by using the fluororesin solution, it is preferable to use, in an inactive gas dehydrated sufficiently, a fluororesin solution dehydrated and deoxidized sufficiently. It is preferable to use a solvent in the foregoing solution which has been dehydrated with active alumina, molecular sheave, phosphorus pentaoxide or calcium chloride. As an alternative to this, it is preferable depending upon the type of the solvent that the solvent be distilled under presence of alkaline metal in inactive gas to remove impurities and to be dehydrated.
However, the necessity of strictly controlling water can be eliminated when lithium is electrochemically inserted and allowed to adhere between the fluororesin and the conductive matrix.
An electrolyte may previously be mixed when the foregoing film is formed. It leads to a fact that wettability between the electrolyte solution and the film can be improved, causing ions to easily pass through the film. In order to facilitate the movement of the charge at the time of charging, conductive powder, such as carbon or titanium, fiber or whisker may be mixed at the time of forming the film.
25 Since the performance of the battery deteriorates if the fluororesin film is dissolved in o• r *c er e [N:\LIBE]01316:MXL -33an organic solvent of the electrolyte solution, it is preferable that the film is crosslinked.
As an alternative to the foregoing method of coating the lithium surface with the fluororesin solution, another method may be employed in which a fluorocompound, such as tetrafluoroethylene is polymerized with the main raw material with plasma to be applied to the surface. It is preferable to employ another method for improving the contact and strength of the film in which oxygen, hydrogen, helium, argon, nitrogen, silane, hydrocarbon or the like is mixed with the fluorocompound which is the main material.
The plasma can effectively be generated by a DC or RF glow discharge method, a microwave discharge method or a laser beam irradiation method.
It is preferable that the thickness of the film to be formed on the surface of lithium ranges from 50 A to 100 i, more preferably ranges from 100 A to 10 i. The optimum thickness of the film differs depending upon the density or the void ratio of the film and considerably differs depending upon the type of the electrolyte solution. The thickness of the film can be adjusted by changing the concentration of the main material in the coating liquid for forming the film.
Large Ring Compound By coating the surface of the negative electrode active material with a large ring compound through e• u [N:\LIBE]01316:MXL -34which ions for use in the reactions in the battery can be passed, the reactions between lithium and water or oxygen can be prevented if the negative active material is lithium.
As a result, handling can easily be performed. Further, the direct contact between lithium and the electrolyte solution can be prevented, and therefore the growth of a polymer film on the surface of lithium to be formed from the solvent of the electrolyte solution can be prevented. If the negative electrode active material is zinc, the dissolution of zinc into the electrolyte solution can be prevented. As a result, the formation of dendrite can be prevented, causing the life against the charge and discharge cycle can be lengthened.
The large ring compound is a large ring compound having heteroatoms composed of one or more types of atoms selected from a group consisting of oxygen, nitrogen and sulfur. In order to cause ions for use in the reactions in the battery to be passed satisfactorily, a compound having one or more structures selected from a group consisting of ring polyether, ring polyamide, ring polythioether, azacrown ether, ring thioether, thiocrown ether, cryptand, cycrum, nonactyne and bariomicine each having a hole having a radium lager than the radium of ions to be used in the reactions in the battery, thyracrown, cyclodextrin, cyclophane, 25 phtharocyanine and porphyrin each of which is crown a a.
a fo *r *r c [N:\LIBE]01316:MXL 35 ether having silicon atoms. It is preferable to use crown ether polymer, bariomicine, phthalocyanine or porphylin.
By covering the surface of the negative electrode active material with the large ring compound, the movement of ions for use in the battery reactions between the electrolyte solution and the negative electrode active material can be made easier. Therefore, local generation of zinc or lithium dendrite on the negative electrode can be prevented. Further, reactions between fresh lithium or zinc generated at the time of the charge with the solvent of the electrolyte solution can be prevented.
The surface coating of the large ring compound to be applied to the surface of the negative active agent can be performed in any of the following methods.
a. A polymer solution obtained, by polymerization, from the derivative of the large ring compound is applied by dipping, spraying, screen printing and coater coating.
b. A mixture of the binder polymer and the derivative of the large ring compound is applied, and then it is crosslinked so that the film is formed.
c. The derivative of the large ring compound is, as a monomer, dissolved in an electrolyte solution, an electric field is applied to the solution, and then the film is formed on the surface of the negative electrode a a.
a a.* ae ft [N:\LIBE101316:MXL 36 active material or the conductive matrix by electrolytic polymerization.
d. Lithium is immersed in a solution of the derivative of the large ring compound, which can be anionpolymerized by lithium, so that the polymer film is formed.
e. A polymer is applied, the polymer being obtained by heating and condensing a large ring compound having an aromatic ring and formaldehyde in a formic acid.
f. The film is formed by sputtering the large ring compound or the polymer of the same or by plasmapolymerizing the same.
An electrolyte may be mixed at the time of forming the foregoing film. As a result, the wettability between the electrolyte solution and the film can be improved, causing ions to be easily passed through the film. In order to facilitate the movement of the charge at the time of the charging operation, powder or fiber or whisker of conductive material such as carbon or titanium may be mixed at the time of forming the film.
As the polymer for use in the coating solution, poly [(dibenzo 18 crown 6) coformaldehyde] or the like can be used. A polymer for coating can newly be prepared by the following polymerization reactions. By condensation polymerization of a large ring compound 4e• a a ea [N:\LIBE]01316:MXL 37 1 having, at the terminative group thereof, carboxylic group or amino group or a hydroxyl group, polyamide can be obtained if the carboxylic group and the amino group react with each other. Polyester can be obtained if the carboxylic group and the hydroxyl group react with each other. The vinyl compound of the large ring compound or diene of the large ring compound enables an additive polymer to be obtained by radical polymerization, cation polymerization or anion polymerization. The 10 starting material of the radical polymerization may be azobisisobutylnitryl (AIBN), benzoylperoixde (BPO) or tbutylhydroperoxide. A starting material for the cation polymerization is exemplified by an acid such as H 2 SO4,
H
3
PO
4 HC10 4 CC1 3 or CO 2 H and Friedel-Craft catalyzer 15 such as BF 3 AC1 3 TiC1 4 or SnCl 4 A large ring compound having an aromatic ring can be polymerized by dehydrogenation in which the Friedel-Craft catalyzer and an oxidizer are combined to each other. A starting material for the anion polymerization may be an alkaline metal compound or an organic metal compound.
As the monomer of the large ring compound for use in the polymerization may be crown ether/(+) 18 crown 6 tetracarboxylic acid, 1, 5, 9, 13, 17, 21 hexathiacyclotetrakosan 3, 11 19 triol, 1, 5, 9, 13 tetrathiacyclohexadecan 3, 11 diol, 1 aza 12 crown 4, 1 aza 15 crown 5, 1 aza 18 crown 6, 1, 4, 10, 13 tetraxyso 7, 16 -38diazocyclooctadecan, 1, 4, 10 trioxa 7, 13 diazacyclopentadecan, or 6, 8 dioxabicyclo 2. 1] oxtane 7 on. As an alternative to this, dibenzocrown ether can be used.
In the foregoing polymerization, a copolymer of two more types of derivatives of the large ring compounds or a copolymer of the large ring compound and another monomer may be used as well as the polymer of the derivatives of the large ring compounds. A polymer obtainable by introducing the derivative of the large ring compound into a polymer by substitution may be employed.
When a battery is manufactured, a polymer must be selected so as not to be dissolved in the solvent of the electrolyte solution or the polymer crosslinking reactions are caused to proceed so as not be dissolved in the electrolyte solution.
The derivative of the large ring compound having, at the terminative group thereof, carboxylic group or amino group or a hydroxyl group or having a vinyl bond or a diene bond and a crosslinking material are mixed in the polymer serving as the binder, and then the mixed material is hardened. The crosslinking material is selected from a group consisting of disocyanate, a polyisocyanate prepolymer, block isocyanate, an organic peroxide, 25 polyamine, oxims, a nitroso compound, sulfur, a sulfur a compound, selene, a magnesium oxide, a lead 5* 9
*L
[N:\LIBE]01316:MXL 39oxide and a zinc oxide. The organic peroxide is exemplified by dicumyl peroxide, 2, 5 dimethyl 2, 5 di (t butyl peroxy) hexane, 1, 3 bis (t -butyl peroxy isopropyl) benzene, 1, 1 bis (t-butyl peroxy) 3, 3, 5 trimethyl cyclohexane, n-butyl 4 bis (tbutylperoxy) valelate, 2, 2 bis (t-butyl peroxide) butane, t-butyl peroxy benzene, and vinyl tris (tbutyl peroxy) silane. As an accelerating agent, a guanidine, aldehyde amine, aldhyde ammonia, thiazol, sulfonamide, thiourea, thiuram, dithiocarbamate, xanthate accelerating agent is used.
Another coating method using the binder polymer is exemplified by a method in which a mixture of the large ring compound and the binder polymer is applied, and then radial rays, electron rays or ultraviolet rays are applied to cause the applied material to be crosslinked.
As a method for covering the negative electrode active material pole by the electrolytic polymerization, a monomer, such as dibenzocrown ether, is mixed in the electrolyte solution, and then the electrolytic polymerization is performed while using the negative electrode active material or the conductive matrix as an anode. The solvent of the electrolyte solution is exemplified by acetonitryl (CH 3
CN),
benzonitryl (CgH 5 CN), propylene carbonate (PC), 25 dimethylformamide (DMF), tetrahydrofuran (THF),
S
*6 55 S S
S
f..t
*S.
fe C
*S
[N:\LIBE101316:JCA 40 1 nitrobenzene (C 6
H
5 NO2), dichloroethane, diethoxyethane, chlorobenzene, y butyrolactone and dioxolan and their mixture. It is preferable that the solvent be dehydrated with active alumina, molecular sheave, phosphorus pentaoxide or calcium chloride. As an alternative to this, it is preferable depending upon the type of the solvent that the solvent be distilled under presence of alkaline metal in inactive gas to remove impurities and to be dehydrated. The supporting electrolyte is an acid, such as H 2
SO
4 HC1 or HNO 3 or V 3 4. 4 salt composed of monovalent metal ion (Li K Na Rb or Ag or tetraammonia ion (tetrabutyl ammonia ion (TBA and tetraethyl ammonia ion (TEA and Lewis acid ion (BF 4
PF
6 AsF 6 or C10 4 It is preferable that 15 the foregoing salt is refined by re-crystallization or it is heated under lowered pressure to sufficiently dehydrate and deoxidize the salt.
SAs the monomer, crown ether/benzo 15 crown crown ether/benzo 18 crown 6, crown ether/N phenylaza 15 crown 5, crown ether/dibenzo 18 crown 6, crown ether/dibenzopyridino 18 crown 6, crown ether/dibenzo 24 crown 8, 1, 13 bis (8 quinolyl) 1, 4, 7, 10, 13 pentaoxatridecan, 5, 6 benzo 4, 7, 13, 16, 21, 24 hexaoxa 1, 10 diazabicyclo 8. 8] hexakosan, 5, 6 14, 15 dibenzo 4, 7, 13, 16, 21, 24 hexaoxa 1, 10 diazabicyclo 8. 8] hexakosan, bis [(benzo 15 -41 crown 5 15 ilmethyl] pimelate, crown ether/dibenzo 30 crown 10, N, N' dibenzyl 1, 4, 10, 13 tetraoxa 7, 16 diazacyclooxtadecan, dilithiumphthalocyanin, 4' nitrobenzo 15 crown 5, 3, 6, 9, 14 tetrathiabicyclo 2. 1] tetradeca 11, 13 diene and their mixture.
Since the performance of the battery deteriorates if the polymer film for covering the surface of the negative electrode active material is dissolved in the electrolyte solution, it is preferable to be crosslinked.
It is preferable that the thickness of the film to be formed on the surface of lithium ranges from 50 A to 100 further preferably ranges from 100 A to 10 p. The optimum thickness of the film differs depending upon the density or the void ratio of the film and considerably differs depending upon the type of the electrolyte solution. The thickness of the film can be adjusted by changing the concentration of the main material in the coating liquid for forming the film.
6. Polymer (polyphosphazene) Film in Which Phosphor Atoms and Nitrogen Atoms are Alternately Bonded in a Phosphor- Nitrogen Double Bond Manner.
The surface of the negative electrode active material is covered with a polymer (polyphosphazene) film through S, 25 which ions for use in the reactions in the battery can be passed and in which phosphor atoms and
S
S 4** S9 4 p
SS
9 S [N:\LIBE]01316:VXF -42nitrogen atoms are alternately phosphor-nitrogen double bond. As a result, lithium and the electrolyte solution do not come in contact with each other if the negative electrode active material is lithium. Therefore, formation of the polymer film from the solvent of the electrolyte solution on the surface of lithium can be prevented. If the negative electrode active material is zinc, elution of zinc into the electrolyte solution can be prevented. As a result, formation of dendrite can be prevented, and therefore the life against charge and discharge cycle can be lengthened.
Since the lithium battery according to an aspect of the present invention comprises the polyphosphazene film covering lithium is a flame retardant film, safety against emergency breakage can be improved.
The polymer for use as the covering material can be obtained by heating a dichloropolyphosphazene trimer to 200 to 300 0 C and by ring-opening polymerization. The dichloropolyphosphazene trimer can be synthesized from phosphorus pentachloride and ammonia chloride or ammonia.
Any one of the following catalyzer is used at the time of the polymerization: benzoic acid, sodium benzonate, 2, 6 di p cresol, water, methanol, ethanol, nitromethane, ether, heteropoly acid, sulfur, zinc, tin and sodium.
25 Further, various type of polyorganophosphazene can be obtained by substituting 0 [N:\LIBE]01316:MXL -43chloride atoms of polydichlorophosphazene by an organic reagent or an organic metal reagent.
If the surface of lithium is coated with the-foregoing polymer solution, it is preferable that the polymer solution dehydrated and deoxidized sufficiently be used in inactive gas dehydrated sufficiently (however, the necessity of strictly controlling water can be eliminated when the polymer is previously applied to the conductive matrix or when the negative electrode active material is zinc).
It is preferable to use a solvent in the foregoing solution which has been dehydrated with active alumina, molecular sheave, phosphorus pentaoxide calcium chloride.
As an alternative to this, it is preferable depending upon the type of the solvent that the solvent be distilled under presence of alkaline metal in inactive gas to remove impurities and to be dehydrated (however, the necessity of strictly controlling water can be eliminated when the polymer is previously applied to the conductive matrix or when the negative electrode active material is zinc).
An electrolyte may previously be mixed when the foregoing film is formed. It leads to a fact that wettability between the electrolyte solution and the film can be improved, causing ions to easily pass through the film. In order to facilitate the movement of the charge at 25 the time of charging, conductive 0 o 0 a a..
a a [N:\LIBE]01316:MXL -44powder, such as carbon or titanium, fiber or whisker may be mixed at the time of forming the film.
Since the performance of the battery deteriorates if the polymer coating film is dissolved in an organic solvent of the electrolyte, it is preferable to be crosslinked in such a manner, for example, utraviolet rays, electron rays or radial rays are applied or a crosslinking material, such as a radical generating agent, is used.
It is preferable that the thickness of the film to be formed on the surface of the negative electrode active material ranges from 50 A to 100 A, more preferably ranges from 100 A to 10 p.
The optimum thickness of the film differs depending upon the density or the void ratio of the film and considerably differs depending upon the type of the electrolyte solution. The thickness of the film can be adjusted by changing the concentration of the main material in the coating liquid for forming the film.
7. Other Organic Polymer Film The surface of the negative electrode is covered with an organic polymer containing one or more types of elements selected from a group consisting of oxygen, nitrogen and sulfur and permitting ions relating the battery reactions to pass through. The direct contact of fresh negative active 25 materials precipitated during g a e [N:\LIBE]01316:MXL the charging reactions can be prevented due to the foregoing cover film. Therefore, the negative electrode is not covered with a substance prepared due to-the reactions with the electrolyte solution and having low conductivity. As a result, the growth of dendrite can be prevented.
The organic polymer containing oxygen is exemplified by cellulose, alkyl cellulose, nitrocellulose, acetyl cellulose, chitin, chitosan, polyethylene glycol, polyethylene oxide, polypropylene oxide, polyvinyl alcohol, polyvinyl acetate, polylactide, polylactone, poly 3 hydroxyalcanoate, polyglycol acid, polyacetic acid, polydioxanon, glycol acid lactone copolymer, polyethylene terephthalate, polyphenylene oxide, polyether etherketone and the like. It is preferable to use acetyl cellulose, chitin or polyvinyl alcohol.
The organic polymer containing nitrogen is exemplified by collagen, chitin, chitosan, polyurethane, polyimide, polyether imide and the like.
The organic polymer containing sulfur is exemplified by polyphenylene sulfide, polysulfon and polyether sulfon.
The negative electrode is covered with the foregoing organic polymer film formed in such a manner that the solution of the organic polymer is applied and dried and S: then a crosslinking reactions are caused to occur.
*e
S
S
[N:\LIBE101316:MXL -46- Another method of forming the film may be employed in such a manner that the organic polymer is used as a target in a sputtering method. Another method may be employed in which a monomer serving as the organic polymer is plasmapolymerized to form the film.
The application may be completed by dipping, spraying or screen printing.
The crosslinking reactions can be performed by any one of the following methods: irradiation of ultraviolet rays, electron rays or radial rays; or decomposition of a radical generating material such as azobisbutylonitryl or peroxy benzoil. The reason why the organic polymer of the film is crosslinked is that elution of the film into the electrolyte solution must be prevented.
The thickness of the film must range so far as ions in the electrolyte solution relating to the battery reactions are able to pass through the same. It differs depending upon the material and the void ratio of the film and the type of the ion. It is preferable that the mean thickness ranges from 10 A to 100 p, more preferably 100 A to 10 A.
If the ion permeability through the film is unsatisfactory, an electrolyte may be mixed at the time of forming the film.
If the electrolyte solution of the battery is a water soluble solution and it is not hydrophilic, it a a *a a.
a a [N:\LIBE]01316:VXF -47is preferable to perform a treatment using a silane coupling material or a titanate coupling material to attain hydrophilic characteristics.
Although the various covering materials and coating methods have been described while employing the negative electrode active material is directly covered with the film, another method may be employed in which the conductive matrix is previously covered with the coating material and then the negative electrode active material is introduced.
Negative Electrode Active Material As the negative electrode active material 101, lithium, lithium alloy, zinc or zinc alloy is used. The lithium alloy may contain one or more types of elements selected from a group consisting of magnesium, aluminum, titanium, tin, indium, boron, gallium, potassium, sodium, calcium, zinc and lead and the like. The zinc alloy may containing one or more types of elements selected from a group consisting of aluminum, indium, magnesium, tin, titanium, copper, lead, tin, lithium and mercury and the like.
The negative electrode active material for the alkalizinc battery may be zinc, zinc alloy, zinc oxide or zinc hydroxide, the negative electrode active material being uniformly kneaded with a bonding material or a kneading 25 solution to obtain paste. The paste is applied to a collector followed by drying them so that a negative 0* a a a f [N:\LIBE]01316:MXL -48plate is obtained.
The bonding material is exemplified by polyvinyl alcohol, a cellulose material such as methyl cellulose or carboxymethyl cellulose, a polyolefin material such as polyethylene, a fluororesin such as polytetrafluoroethylene and a polyamide resin such as nylon.
The kneading solution may be an organic solvent such as ethylene glycol or water containing oxo acid salt such as sodium phosphate or the like.
The collector may be an iron plate applied with nickel plating and having apertures, a foam metal or nickel mesh or the like.
Positive Electrode The positive electrode is formed by mixing a positive electrode active material, conductive powder and a bonding material on the collector. In order to easily form the positive electrode active material, a solvent- resisting resin, such as polypropylene or polyethylene or fluororesin is used as the bonding material if necessary. In order to further easily collect electric currents, the conductive powder is mixed at the time of the formation. The material of the conductive powder is exemplified by various carbon, copper, nickel and titanium and the like.
Positive Electrode for Lithium Secondary Battery 25 The positive electrode active material 104 of the 96 t 6coo ef ftft** ft f ftr [N:\LIBE]01316:MXL -49lithium secondary battery is made of a compound having layers through which lithium ions can be passed, the compound being a transition metal such as a mrtal-oxide exemplified by manganese oxide, vanadium oxide, molybdenum oxide, chrome oxide, cobalt oxide, nickel oxide, titanium oxide, iron oxide, and tungsten oxide or a metal sulfide exemplified by titanium sulfide, molybdenum sulfide, iron sulfide and shebrell phase sulfide (MyMogS 8 -z metal such as copper, cobalt or nickel)). The transition metal element may be an element having partially shell d or shell f. The metal selenide is exemplified by niobium selenide. The metal hydroxide is exemplified by oxyhydroxide. The conductive polymer is exemplified by polyacetylene, polyparaphenyline, polyaniline, polythiophene, polypyrol and polytriphenylamine. The.composite oxide is exemplified by LiMn2_xMxO 4 and LiCoxNil-xO 2 The positive electrode is manufactured in such a manner that paste obtained by adding a bonding material, such as polyethylene, polypropylene or a fluororesin, to the positive electrode active material 104 is pressed against the positive electrode collector 103. In order to improve the collecting performance of the positive electrode, it is preferable to add conductive powder to the paste.
The conductive powder may be a carbon material such as 25 acetylene black or metal such as copper, nickel or titanium.
The collector 103 may be fiber-like, porous **9 5 ft .i 9 9 [N:\LIBE]01316:MXL or mesh-shape carbon material, stainless steel, titanium, nickel, copper, platinum or gold Positive Electrode for Nickel-Zinc Battery The positive electrode of the nickel-zinc battery is categorized to a paste type pole formed by directly charging nickel hydroxide powder into the collector and a sintering type formed by immersing nickel hydroxide into a small apertures of the nickel sintered plate.
The paste type positive electrode is formed in such a manner that paste obtained by uniformly kneading an additive, such as nickel or cobalt, with a bonding material or a kneading solution is applied to the collector followed by drying them.
The bonding material and the collector are made of materials of the same type as those of the zinc negative electrode.
The sintered type positive electrode is manufactured in such a manner that a sintered plate obtained by sintering nickel powder on the nickel-plated iron plate having apertures is immersed in a mixed solution of nickel salt serving as a main active material and cobalt salt serving as an additive and then caused to react with an alkali solution of, for example, sodium hydride so that nickel.hydroxide is impregnated into the sintered plate.
25 Positive Electrode for Air-Zinc Secondary Battery The positive electrode of the air-zinc secondary a.
eg io [N:\LIBE]01316:MXL 51 battery is made of a material composed of an air pole, a water-repellent film and a diffuser paper sheet.
The catalyzer of the air pole is prepared insuch'a manner that silver, manganese dioxide, nickel-cobalt composite oxide or platinum is added to a carbon material, such as porous carbon (active carbon) or carbon black, porous nickel, copper oxide or the like having a specific area of 200 to 1000 m 2 /g.
The water-repellent film is provided to prevent leakage of the electrolyte solution passed through the air pole to the outside of the battery. The water-repellent film is made of a fluororesin such as polytetrafluoroethylene. The diffuser paper sheet is provided for the purpose of uniformly supplying oxygen to the overall surface of the air pole, the diffuser paper sheet being made of cellophane or the like.
A zinc-bromine battery comprising the negative electrode active material which is zinc includes bromine to serve as the positive electrode active material.
Coating of Positive Electrode In order to prevent generation of dendrite causing the short circuit at the time of the charge, the surface of the positive electrode is covered with a film through which ions for use in the reactions in the battery can be passed so 25 that the life of the battery against the cyclic usage can be lengthened.
The coating material may be a polymer of the ea a..
a a coo* *oo or t [N:\LIBE]01316:JCA 52 derivative of a large ring compound, a polymer of the derivative of an aromatic hydrocarbon, fluororesin, silicon resin, titanium resin, polyolefin, inorganic oxide,- nitride, carbide or halide. It is effective to improve the safety of the lithium secondary battery to cover the positive electrode with a flame retardant or non-combustible material, such as fluororesin, polyphosphazene, an inorganic oxide, nitride, carbide or halide.
If the film through which ions for use in the reactions in the battery can be passed is a multi-layer metal oxide film formed by using a bimolecular film as a mold, an effect of a separator can be obtained and an effect of preventing the short circuit between the negative electrode and the positive electrode can further be improved.
Electrolyte The electrolyte is used as it is or in the form of a solution in which it is dissolved in a solvent or after it has been solidified by adding a gelatinizing material, such as a polymer, to the solution. Generally an electrolyte solution, in which the electrolyte is dissolved in a solvent, is held in a porous separator.
The conductance of the electrolyte must be raised as much as possible because it relates to the internal 25 resistance of the battery and considerably affects the current density at the time of the charge and the S S 4**S*S
S
[N:\LIBE01 316:JCA -53discharge. It is preferable that the conductance at 25 0 C be 1 x 10 3 S/cm or higher, more preferably 5 x 10 3 S/cm or higher.
[In a Case Where Negative Electrode Active Material is Lithium or Lithium Alloy] The electrolyte is made of an acid, such as H 2 S0 4 HCe or HNO 3 a salt composed of Lewis acid ion (BF 4
PF
6 g, AsF 6 or C04 or their mixture. Further, positive ions, such as sodium ions, potassium ions, tetraalkylammonium ions, and the Lewis acid ions may be used together. It is preferable that the foregoing salt is heated under lowered pressure to sufficiently dehydrate and deoxidize the salt.
The solvent of the electrolyte is exemplified by acetonitryl (CH 3 CN), benzonitryl (CgH 5 CN), propylene carbonate ethylene carbonate dimethyl formamide (DMF), tetrahydrofuran (THF), nitrobenzene (CgH 5
NO
2 dichloroethane, diethoxyethane, chlorobenzene, y butylolactone, dioxolan, sulforan, nitromethane, dimethylsulfide, dimethylsuloxide, dimethoxyethane, methyl formate, 3 methyl 2 oxydazolidinone, 2 methyltetrahydrofuran, sulfur dioxide, phosphoryl chloride, thionyl chloride, sulfulyl chloride, dimethyl formardehyde, y buthlolactone and tetrahydrofuran and their mixture.
It is preferable that the foregoing solvent be 25 dehydrated with active alumina, molecular sheave, S S
S
[N:\LIBE0O1316:VXF -54phosphorus pentaoxide or calcium chloride. As an alternative to this, it is preferable depending upon the type of the solvent that the solvent be distil-led-underpresence of alkaline metal in inactive gas to remove impurities and to be dehydrated.
It is preferable to gel the electrolyte solution to prevent leakage of the electrolyte solution. As the gelling material, it is preferable to use a polymer of a type which swells when it absorbs the solvent of the electrolyte solution, the gelling material being a polymer exemplified by a polyethylene oxide, polyvinyl alcohol and an polyacryl amide.
[In a Case Where the Negative Electrode Active Material is Zinc or Zinc Alloy] As the electrolyte solution, salt of alkali or zinc borate is used which is a sole or a mixed solution of potassium hydroxide, sodium hydroxide, lithium hydroxide or ammonium hydroxide.
It is preferable to gel the electrolyte solution to prevent leakage of the electrolyte solution. As the gelling material, it is preferable to use a polymer of a type which swells when it absorbs the solvent of the electrolyte solution, the gelling material being a polymer exemplified by a polyethylene oxide, polyvinyl alcohol and an polyacryl 25 amide.
S. In a case of a battery such as a bromine zinc battery except for the alkali battery, a salt such as
C*
CC
oo ~e o• °•eg ooe oeooe oo o• o o [N:\LIBE]01316:JCA 55 zinc borate is used.
The solid electrolyte is manufactured in such a manner that a polymer compound of a polyethylene oxide (PEO) type and salt of the electrolyte are dissolved in the foregoing non-aqueous-soluble solvent to be gelled and then they are developed on, for example, a flat board to evaporate the non-aqueous-soluble solvent. The PEO polymer compound is exemplified by polyethylene oxide or a poly (methoxyethoxyphosphazene) crosslinked by polyethylene oxide or isocyanate.
The electrolyte solution for the alkali-zinc secondary battery may be a solution of sodium hydroxide, potassium hydroxide or lithium hydroxide or their mixture.
Separator The separators (108, 208 and 308) are provided to prevent short circuits between the positive electrode and the negative electrode. They also act to hold the electrolyte solution.
The separator must meet the following conditions.
The separator cannot be dissolved in the electrolyte solution and must be stable with respect to the same.
The separator is able to absorb a large quantity of the electrolyte solution and must exhibit satisfactory 25 holding force.
The separator must have small apertures f o e•* o* [N:\LIBE]01316:VXF -56through which lithium ions and hydroxide ions can be passed.
4) The separator must have small apertures each having a size which is able to prevent the penetration of dendrite.
5) The separator must be mechanically strong so as not to be broken or deformed excessively when it is wound.
The material that is able to meet the foregoing conditions is exemplified by a unwoven fabric or a micropore structure of glass, polypropylene, polyethylene, or fluororesin.
Also a metal oxide film having small apertures or a resin film formed by combining metal oxides may be used. If a metal oxide film in the form of a multi-layer structure is used, dendrite cannot easily pass through it and therefore an effect of preventing the short circuits can be obtained.
If a fluororesin film which is a flame retardant or a glass or a metal oxide film which is a noncombustible material is used, the safety can further be improved.
Since the electrolyte solution of the alkali-zinc secondary battery is a water-type solvent, a hydrophilic separator must be used which is exemplified by a non-woven fabric or a micropore structure of nylon, polypropylene or hydrophilic polypropylene.
a a [N:\LIBE101316:VXF 57- Collector Collectors 100, 103, 200 and 300 are made of fiber, porous or mesh-like carbon, stainless steel, titanium, nickel, copper, platinum or gold.
Shape and Structure of Battery The battery is formed into a flat, cylindrical, square (rectangular) or a sheet shape battery. The spiral and cylindrical structure is enabled to have a large electrode area by winding while interposing the separator between the negative electrode and the positive electrode so that a large electric current can be caused to flow at the time of the charge and the discharge. The rectangular type battery enables an accommodation space for accommodating the secondary battery to be used effectively. The structure may be a single-layer structure and a multi-layer structure.
Figs. 2 and 3 illustrate the schematic cross sectional views which respectively illustrate an example of a singlelayer flat battery and a spiral and cylindrical battery.
Referring to Figs. 2 and 3, reference numeral 201 and 301 represent negative electrodes covered with films, and 200 and 300 represent collectors for the negative electrodes 201 and 301. Reference numeral 203 and 303 represent positive electrode made of the positive electrode active material.
Reference numeral 304 represents a collector for the 25 positive electrode, and 206 and 306 represent negative t :terminals (caps for the
C
ee U e e eeoc 0* 4
C
444* 4 4444 [N:\LIBE]O1316:VXF 58negative electrodes 201 and 301). Reference numeral 207 and 307 represent outer cases (cases serving as positive electrode cases and battery cases), 208 and 308 represent separators which hold the electrolyte solution, 210 and 310 represent insulating packings, and 311 represents an insulating plate.
Referring to Fig. 5, reference numeral 5201 and 5301 represent lithium members subjected to surface treatment. In the structure shown in Fig. 5, reference numeral 201 and 310 represent lithium members subjected to surface treatment.
The batteries shown in Figs. 2 and 3 are manufactured in such a manner that the separators 208 and 308 are held between the negative electrodes 201, 201 subjected to the surface treatment and the positive electrodes 203 and 303 to be placed in the positive electrode cases 207 and 307 followed by injecting the electrolyte solution. Then, the negative electrode caps 206, 306, the insulating packing 210 and 310 are assembled so that the batteries are manufactured.
In the case of the lithium battery, it is preferable that the preparation of the material and assembling of the battery are performed in dry air from which water has sufficiently be removed or in a dry inactive gas.
Battery Case (Outer Case) 25 The battery case may be a metal outer case also 6 6e6 6 r 6 o** [N:\LIBE]01316:VXF 59serving as an output terminal or a plastic resin case.
The positive electrode cases 207, 307, the negative electrode caps 206 and 306 are made of stainless steel, and in particular, titanium clad stainless steel or copper clad stainless steel or a steel plate applied with nickelplating.
Although the structures shown in Figs. 2 and 3 comprises the positive electrode cases 207 and 307 also serving as the battery cases and the output terminals. The battery case may be made of metal such as aluminum or zinc, plastic such as polypropylene or a composite material of metal, glass fiber and plastic as well as the stainless steel.
Insulating Packing The insulating packings 210 and 310 may be made of fluororesin, polyamide resin, polysulfon resin or rubber.
Cap The capping method may be a bonding method, welding method, soldering method or a glass sealing method as well as a caulking method using a gasket such as an insulating packing.
Insulating Plate The insulting plate 311 for insulating the inside of the battery may be made of an organic resin or ceramics.
S
S P..
1 o• [N:\LIBE]01316:MXL Safety Valve A safety valve (not shown in Figs. 2 and 3) using rubber, a spring or a metal ball may be used to serve as a safety means to act if the internal pressure in the battery has been raised.
The basic structure of another embodiment of the lithium secondary battery according to the present invention comprises a side opposing at least the positive electrode, the side being composed of a lithium negative electrode subjected to treatment using a reactive gas containing nitrogen or halogen, a separator, a positive electrode active material, electrolyte and a collector. Fig. 5 is a basic structural view which illustrates the lithium secondary battery according to an aspect of the present invention. Referring to Fig. 5, reference numeral 100 represents a collector for a negative electrode, 101 represents a negative electrode active material (lithium or lithium alloy), 102 represents a surface treatment layer for the lithium portion, 103 represents a collector for the positive electrode, 104 represents a positive electrode active material, 105 represents an electrolyte solution, 106 represents a negative terminal, 107 represents a positive terminal, 108 represents a separator, and 109 represents a battery case. In the discharge reactions, lithium ions in the electrolyte solution 105 are introduced into the Sinterlayer of the positive electrode active material 104.
S
0 0 o• @0.
g•oo *0:00 0ooo Bo
S
@555
S
0000.6 0 0 500.
[N:\LIBE]01316:VXF -61- Simultaneously, lithium ions are eluted from the lithium negative electrode 101 into the electrolyte solution 105 by way of a treatment-applied surface 5102.- In the chargihg reactions, lithium ions in the electrolyte solution 105 are, lithium metal ions are precipitated to the lithium negative electrode 101 by way of the treatment-applied surface 5102.
Simultaneously, lithium in the interlayer of the positive electrode active material 104 is eluted into the electrolyte solution 105.
Surface Treatment for Lithium Negative Electrode The nitrogen compound for treating the surface of lithium or the lithium alloy is exemplified by nitrogen, ammonia and nitrogen trifluoride. If nitrogen is used as the nitride, it must be activated as to be formed into a plasma form by DC or high frequency discharge or by laser beam application. Also other nitrides are enabled to have improved reactivity when formed into plasma.
The halogen compound is exemplified by fluorine, chlorine, bromine, iodine, hydrogen fluoride, hydrogen chloride, hydrogen bromide, chlorine trifluoride, methane tetrafluoride, methane tetrachloride, methane trifluoride, methane fluoride trichloride, sulfur hexafluoride and boron trichloride. The inactive gas such as carbon halide must be formed into plasma as to have improved reactivity. It is 25 preferable that the very active gas such as fluorine, 99.
9 [N:\LIBE]01316:MXL -62chlorine, hydrogen fluoride, hydrogen chloride or chloride trifluoride be diluted with inactive gas such as argon gas or helium gas.
The nitrogen compound and the halogen compound may be mixed with each other or contain oxygen gas, hydrogen gas, argon gas, helium gas, xenon gas or the like added thereto to improve the activity of the reactive gas or to control the activity. The negative electrode may be treated with plasma of hydrogen gas or argon gas prior to treating the surface of the negative electrode so that a fresh negative electrode surface is caused to appear.
More specifically, according to an aspect of the present invention, there is provided a secondary battery manufactured in such a manner that active nitrogen plasma or fluorine plasma or hydrogen fluoride is brought into contact with the surface of lithium to cause reactions to take place, an inactive thin film made of lithium nitride or lithium fluoride and allowing lithium ions to pass through is formed on the surface of lithium, and the lithium portion is used as the negative electrode. As a result, the direct contact of lithium precipitated at the time of the charge with the electrolyte solution is prevented so that the 0.
*generation of dendrite at the time of the charge is prevented. Therefore, a lithium battery exhibiting a long life against the charge and discharge cycle can be obtained.
Further, the application of the foregoing ee e e• 9e e• 9 *e 9*9 9 9* 9 r 9 99e9 [N:\LIBEO1316:MXL -63treatment to the surface of lithium prevents the reactions between lithium and water. Further, handling can be made easier.
It is preferable that the thickness of the treatment layer to be formed on the surface of lithium ranges from A to 1 AL, more preferably 50 A to 1000 A. The thickness is adjusted by the reaction time or the concentration of the reaction gas.
It is preferable that the concentration of nitrogen atoms or halogen atoms in the treatment layer formed on the surface of lithium be gradually lowered from the surface to the inside portion of lithium.
Positive Electrode Active Material The positive electrode active material 5104 may be a material into which lithium can be introduced into the interlayer thereof, the material being exemplified by a metal oxide such as a nickel oxide, cobalt oxide, titanium oxide, iron oxide, vanadium oxide, manganese oxide, molybdenum oxide, chrome oxide or tungsten oxide, or a metal sulfide such as molybdenum sulfide, iron sulfide or titanium sulfide, a hydroxide such as oxy iron hydroxide, or a conductive polymer such as polyacetylene, polyaniline, S.polypyrol or polythiophene.
2 pyy In order to make easier the formation of the positive 25 electrode active material, solvent-resisting resin, such as polypropylene, polyethylene or fluororesin is used as a bonding material if necessary.
a [N:\LIBE]01316:MXL -64 In order to further facilitate collection of electric current, it is preferable to mix conductive powder at the time of molding the positive active material. The conductive powder may be carbon black, copper, nickel or titanium.
Fig. 8 illustrates an example of a pattern of stacked layers according to an aspect of the present invention in which a conductive layer, a semiconductor layer and an insulating layer are formed between the negative electrode and the separator. Referring to Fig. 8, reference numeral 001 represents a negative electrode, 002 represents a dendrite, 003 represents the conductive layer or the semiconductor layer, 004 represents a separator, 005 represents an insulating layer, 006 represents an electrolyte solution, and 007 represents a positive electrode.
Fig. 8 is a schematic view which illustrates an effect of the present invention in an example in which the insulating layer through which lithium ions can be passed and a conductive layer are stacked on the surface of the lithium negative electrode.
When the charging mode, lithium (or zinc) is S precipitated on to the negative electrode 001. At this time, a portion in which the current density is high is 25 locally generated on the negative electrode 001 depending upon the projections and pits of the surface and upon the :thickness of the insulating film. Lithium (or zinc) ae a a. a a [N:\LIBEJO1316:MXL 65 is selectively precipitated, causing the dendrite 002 to grow. With proceeding of the charging or discharging cycle, the dendrite 002 reach the conductive layer 003. When a short circuit state between the dendrite 002 and the conductive layer 003 is realized, the current density at the negative electrode is lowered at the time of the charge.
Therefore, the further growth of the dendrite 002 is prevented, and therefore penetration of the dendrite 002 through the separator 004 to reach the positive electrode 007 can be prevented.
By covering the negative electrode with the ion permeable insulating layer 005, active lithium (or zinc) precipitated at the time of the charge cannot easily react with the electrolyte solution. Therefore, the generation of the growth of the insulating film can be prevented.
Figs. 9A to 9H illustrate various examples in which one or more types of layers selected from the ion permeable conductor, semiconductor and insulating material are formed between the negative electrode and the separator. Reference numerals shown in Figs. 9A to 9H are the same as those shown in Fig. 8. The present invention is not limited to the structure shown in Figs. 9A to 9H.
It is preferable that the conductive layer to be 'formed between the negative electrode and the separator be 25 made of carbon, Ni, Ti, Pt, Al, Pb, Cr, Cu, V, Mo, W, Fe, Co, Zn or Mg, more preferably made of carbon, Ni o *i [N:\LIBE101316:MXL 66or Ti.
If the semiconductor layer is formed in place of the conductive layer, a similar effect obtainable from the conductive layer can be obtained. If the semiconductor layer is employed, the current density at the time of the growth of dendrite is higher than that in the case where the conductive layer is formed. However, the conductivity is lowered as compared with the case where the conductive layer is formed.
Therefore, an advantage can be realized that the easy conduction with the positive electrode is prevented.
The semiconductor layer may be made of diamond, Si, nickel oxide, copper oxide, manganese oxide, titanium oxide, zinc oxide, zirconium oxide, tungsten oxide, molybdenum oxide or vanadium oxide.
The insulating layer may be made of a halide such as lithium fluoride or magnesium fluoride, a nitride such as silicon nitride, a carbon such as silicon carbide, or a polymer such as polyethylene, polypropylene or fluororesin.
The forming method and materials of the conductive layer, the semiconductor layer, the insulating layer and the composite layer will now be described. When lithium is used, the following two desires must be met.
If water is left in the raw material, water and 25 lithium react with each other. Therefore, water must be previously removed by a method by dehydration using a o a.
*@a a.t [N:\LIBE]01316:MXL -67active alumina, molecular sheave, phosphorus pentaoxide or calcium chloride. If a solvent is used, it is sometimes preferable that the solvent be distilled under presence of alkaline metal in inactive gas to remove impurities and to be dehydrated.
The temperature at which the foregoing layer is applied to the surface of the negative electrode must be lower than a level at which the negative electrode active material is melted.
Conductive Layer As a typical example of the conductive layer, manufacturing method of carbon conductive layer or a metal conductive layer made of, for example, Ni or Ti, will now be described.
Carbon The form of the carbon crystal is categorized to crystal, amorphous, and a mixture of them. The carbon to be applied may be carbon powder or carbon fiber or a carbon paper sheet or the like obtainable by paper machining.
The surface of the negative electrode can be covered with carbon by any one of the following methods.
A solution obtained by uniformly dispersing .carbon powder or carbon fiber in an organic solvent such as toluene or xylene is, under inactive atmosphere of Ar, is 25 applied to the surface of the negative electrode by a spraying method, screen printing method, a coater method a a o 4 IN:\LIBE]01316:MXL -68or a dipping method followed by drying the solution, and then carbon are pressed against the surface.
The carbon paper is stacked on the surface of the negative electrode, and then the carbon is pressed against the surface.
A vacuum evaporation method such as sputtering using carbon as the target is performed so that the surface of the negative electrode is covered with carbon.
A CVD (Chemical Vapor Deposition) method is performed under the presence of an organic compound which is the raw material of carbon so that the negative electrode is covered with carbon.
In the foregoing coating method, the carbon powder or the carbon fiber must be pressed against the surface so that the contact is improved. The pressing work is performed by using a pressing machine or a roller press. The temperature at the time of the pressing work must be lower than a level at which the negative electrode active material is melted.
It is preferable that the thickness of the coating range from 10 to 100 pim, more preferably from 50 mm or thinner in order to prevent reduction of the quantity of the contained negative electrode active material.
The pressing method to be performed after the carbon paper has been stacked may be a method using a pressing 25 machine or a roller press, a method in which the positive electrode plate and the negative electrode plate are
*OW
S.
oo o e [N:\LIBE101316:MXL -69wound while interposing the separator, and a method in which winding pressure or stacking pressure is applied while interposing the carbon paper at the time of stacking the carbon paper. The latter method is able to eliminate a process of previously pressing the carbon paper against the negative electrode and the carbon paper can be pressed in the winding or the stacking process. It is preferable that the carbon paper having a thickness ranging from 150 to 300 jim be pressed to have a thickness ranging from 75 to 150 jim.
The sputtering coating method is performed in such a manner that carbon is used as the target in an inactive atmosphere of argon and DC or RF discharge is performed so that the surface of the negative electrode is covered with carbon.
The raw material of the CVD carbon coating method may be saturated hydrocarbon such as methane, unsaturated hydrocarbon such as acetylene, ethylene, propylene or benzene, carbon monoxide, alcohol or acetone. The exciting method is exemplified by a method using plasma, laser or heating filament. It is preferable that the thickness of the carbon applied be 1 gm or thinner, more preferably 1000
A.
r In the case of the plasma CVD method, the power source for the glow discharge may be a high frequency or a DC power 25 source. The high frequency source may be a usual band source such as radio frequency VHF or go* o [N:\LIBE]01316:MXL microwave source. The wavelength of the radio waves is typified by 13.56 MHz, while that of the microwave is typified by 2.45 GHz.
If the laser CVD is employed, an ultraviolet ArF eximer laser or infrared ray CO 2 is used as the laser beam source.
Metal Such as Ni or Ti The metal such as Ni or Ti is applied to the surface of the negative electrode by a sputtering method as is employed to apply carbon, a CVD method, an electron beam evaporation method or a cluster ion beam evaporation method.
The target for use in the sputtering method may be Ni or Ti or the like. When a composite film is formed, two or more kinds of targets are used to perform either or both of the targets are subjected to the sputtering process. The sputtering method must be performed under an inactive atmosphere of argon similarly to carbon.
The CVD coating method employs the following materials as the raw materials.
As the raw material for Ni and Ti, a solution in which organic metal such as acetylacetone complex of nickel (or titanium) is dissolved in non-aqueous-soluble solvent such as hexane, acetone or toluene or a solution in.which a halide such as nickel chloride (or titanium) is dissolved in 25 a non-aqueous-soluble solvent such as ethanol is subjected to bubbling in a carrier gas 9*
S
oe [N:\LIBE]01316:MXL 71 1 (hydrogen or the like) and then the solution is introduced into the CVD reaction chamber to cause the CVD reactions to take place so that coating is performed.
When a composite film of Ni and carbon is formed, a hydrocarbon such as methane is used together with a metal compound.
Semiconductor Layer The semiconductor layer is exemplified by diamond, 10 Si, nickel oxide, copper oxide, cobalt oxide, manganese S" oxide, titanium oxide, zinc oxide, zirconium oxide, tungsten oxide, molybdenum oxide or vanadium oxide. The coating method may be a sputtering method, an electron beam evaporation method, a plasma CVD method, a light 15 CVD method, a laser CVD method or a heat CVD method.
Si .As the target for use in the sputtering method, Si or the like is used.
In the CVD method, the raw material for Si may be hydroxide gas such as SiH 4 or Si2H, fluorine gas such as SiHF 3 SiH 2
F
2 or SiH 3 F, or a chlorine gas such as SiHCl,3 SiH 2 Cl 2 or SiHCl 3 If the foregoing raw material is in the form of liquid, it is heated as to be in the form of vapor or subjected to bubbling by a carrier gas before it is introduced. If a composite film of Si and carbon material is formed, hydrocarbon such as methane is used together with the foregoing gas. A compound comprising -72carbon, P or B may be adequately mixed.
Oxide such as Nickel Oxide and Titanium Oxide The nickel oxide and titanium oxide can be prepared by a sol-gel method in which alkoxide such as nickel or titanium or organic metal is dissolved in alcohol and then it is hydrolyzed, an anodic oxidation method in which a solution in which nickel salt or titanium salt is dissolved is electrolyzed, or a CVD method or an electron beam evaporation method to introduce oxygen gas into the reaction chamber.
Insulating Layer As the insulating layer, a halide, a nitride, a carbide or resin such as polyethylene polypropylene (PP) or fluororesin is used. As the coating method, a sputtering method, a plasma CVD method or a coating method is used.
Other resins may be used such that a resin obtained by gasifying a monomer of an organic polymer and by plasma polymerizing it or a resin obtained by sputtering an organic polymer or a film of an organic polymer may be used. In this case, the resin member must have small aperture through which ions can be passed and must not react with the electrolyte solution.
Nitride 25 In the sputtering method, a target comprising nitride exemplified by silicon nitride or lithium nitride is used.
As an alternative to this, Si or Li is a ag* e *55* r.
[N:\LIBE]01316:MXL 73 1 used as the target, nitrogen gas or ammonia is used as the reaction gas and sputtering is performed in the foregoing state.
PE and PP In the plasma CVD method, SiH 4 or Si 2
H
6 and ammonia, nitrogen gas or NF 3 are used together as the raw materials.
In the sputtering method, a PE or PP target is used to perform sputtering to cover the insulating 10 layer,.
In the plasma polymerization method, ethylene is used as the raw material in the case of PE, while propylene is used in the case of PP.
Fluororesin 15 In the sputtering method, the target comprises a polymer or a copolymer such as polytetrafluoroethylene, polytrifluoroethylene, vinyl fluoride, vinylidene fluoride or dichlorodifluoroethylene.
As the raw material gas for use in the plasma polymerization method, tetrafluoroethylene, trifluoroethylene, vinyl fluoride, vinylidene fluoride or dichlorofluoroethylene is used.
A fluororesin film having micropores can be used.
Composite Layer The composite layer is selected from a group consisting of the foregoing conductor, semiconductor and insulating material. By using two or more types or raw -74materials, the composite layer is formed by a sputtering method of a CVD method. As an alternative to this, two or more types of powder selected from a group consisting of conductor powder, semiconductor powder and insulating material powder are melted in a melted or dissolved resin so that the film for use as the composite film is manufactured.
Another structure may be employed as a preferred structure in which the concentrations (content) of the conductor, semiconductor and the insulating material in the composite layer are change continuously or discontinuously in the direction of the thickness of the layer.
The apertures in the layer can be formed in such a manner that: an electrolyte is mixed with the raw material at the time of applying the conductor, semiconductor and the insulating material by the sputtering method or the CVD method to add the electrolyte into the conductor, semiconductor and the insulating material. The foregoing electrolyte is eluted into the electrolyte solution of the battery so that a micropore structures are formed in the conductor, semiconductor and the insulating material. Since lithium ions and hydroxide ions can easily be introduced and discharged in the micropores, the charging and discharging efficiencies can be improved. Since the pore has a small size, the growth of the dendrite can be *a
S
e* e e, [N:\LIBE]01316:MXL prevented, and therefore the life against the charging and discharging cycle can be lengthened.
Stacked Structure The conductor, semiconductor and the insulating material layers may be formed into a single layer or a multi-layer composed of two or more layers.
The stacking method comprises a step of stacking a film selected from the group consisting of the conductor, semiconductor and the insulating material between the negative electrode and the separator. The film is stacked on the surface of the negative electrode, or stacked between the negative electrode and the separator in a non-contact manner or stacked on the surface of the separator. As an alternative to this, the negative electrode or the separator or a substance through which ions can be passed may be used as the base on which the conductor, semiconductor and the insulating material are stacked by a sputtering method or a CVD method.
Thickness The optimum thickness of the single, multi-layer or the composite layer composed of the one or more types of layers selected from the group consisting of the conductor, semiconductor and the insulating material differs depending upon the void ratio, the aperture distribution, the material 25 of the layers and the number of layers. If the material "includes a large volume gaps as the polymer material, it is preferable the thickness e.
eC Cgo *otSC eec.
.e C Ce [N:\LIBE]O1316:MXL 76 1 be 10 pm or thinner, more preferably 1 pm or thinner.
If a precise material such as the inorganic compound is used, it is preferable to make the thickness to be 1 pm or thinner, more preferably 1000 A or thinner.
Multi-Layer Metal Oxide The multi-layer metal oxide 10102 must contain one or more types of materials selected from a group consisting of alumina, titanium oxide, silica, selium oxide, zirconia oxide, magnesium oxide, chrome oxide, calcium oxide, tin oxide, indium oxide and germanium 0* .00 oxide.
The multi-layer metal oxide film is formed by molding a bimolecular film in a mold. By forming the metal oxide film by using the bimolecular film, a metal 15 oxide film having small apertures and a large specific area and formed into a multi-layer film structure can be obtained.
Method of Preparing Multi-Layer Metal Oxide The preparation is usually in such a manner that: a sol in which very fine particles of the metal oxide is, in a collide manner, dispersed in a solvent, such as water, is added to a supersonic dispersion solution of water or buffer solution of a film forming compound for forming a bimolecular film selected depending upon the type of the sol and upon the surface charge so that a uniformly-dispersed solution is prepared; then it is developed on a fluororesin film or a glass plate 77 1 followed by developing the solution; and a cast film is manufactured. If the uniformly-dispersed film cannot be obtained, the any one of the following methods is employed: A cast film is formed by adding a low-melting point organic solvent, such as alcohol, chloroform, acetone or tetrahydrofuran, is added to the film forming compound and dispersing the materials, and then water or a buffer solution is added to the solution from which the solvent 1 0 has been gradually evaporated, and then the mixture is 0.dispersed with ultrasonic waves.
Water or a buffer solution is added to the cast film described in and the material is heated to a level higher than the phase transition temperature of 15 the film.
The film forming compound is dissolved in an organic solvent, such as diethylether or ethylalcohol, and the solution is injected into water and a buffer solution.
As a method of obtaining the bimolecular film which serves as the mold of the film shape of the metal oxide, the mechanical strength can be improved by any one of the following methods: The film forming compound is impregnated into a porous polymer film to form the bimolecular solid film.
A hydrophobic polymer or a hydrophilic polymer and the film forming compound are dissolved in a solvent, 78 1 and the solution is developed so that a cast film is obtained.
A solution of a polymer electrolyte having a charge opposing that of the ionic film forming compound is mixed with a solution in which the ionic film forming compound is dispersed so that sedimentation of polyion complex is obtained, and then the polyion complex is dissolved in an organic solvent followed by developing it so that the cast film is obtained.
1 0 Alternatively, any one of the following methods may be employed: a chloric acid (surface active agent.) method which is used at the time of preparing ribosome; a freezing-melting method; an inverse-phase evaporation method; and a macro-ribosome preparation method.
15 The film forming compound may be a compound having hydrophobic group and a hydrophilic group (substance having amphipathic property) is used. The film forming compound may be an ammonia compound, an anion compound, a nonion compound and a polymerable compound depending upon the molecular structure. The hydrophobic group of the film forming compound is categorized to a hydrocarbon, fluorine carbide, unsaturated hydrocarbon, and unsaturated fluorine carbide. A material containing a chromophore structure introduced thereto in order to improve the molecular orientation in the film forming compound may be used.
The film forming compound is exemplified by -79p octyloxyaniline hydrochloride, p (octyloxy) p' hydroxyazobenzene, p (10 octyloxy) p' octyloxyazobenzene, dodecyl N [p {p (10 bromodecyloxy)phenylazo}benzoil]L -alaninate, L glutamic acid didodecylester hydrochloride, N [11 bromoundecanoyl] L glutamic acid didodecylester, dimethyldihexadecylammonium bromide, N [P (trimethylammonio)etyloxybenzoil]didodecyl L glutamic acid bromide, dioctadecylmethyldimethylammomonium bromide, N [11 hydroxyundecanoyl] L glutamic acid ditetradecylester, N [11 phospholoundecanoyl] L acid ditetradecylester, 1, 2 bis (hexadecyloxycarbonyl) ethane 1 sulfonic acid sodium, N oxo 1, 3, 2 oxazaphosphoryl) 11 oxadodecanoyl] L glutamic acid didoecylester, N trimethylammonio ethylphosphonate)undecanoyl] L glutamic acid didodecylester, N ammomonio ethylphosphonate)undecanoyl] L glutamic acid didodecyl ester and 1, 3 hexadecyl 2 polyethylene glycolylglyceline.
It is preferable that the surface of the multi-layer metal oxide film of a non-aqueous-soluble battery of a type S 25 comprising the negative electrode active material which is lithium is subjected to lipophillic treatment using an organic metal compound such as a silane 0 0 e ft f"'.t r f f ft ftf ftft tf ft [N:\LIBE]01316:VXF coupling material or titanate coupling agent.
In order to lower the current density at the leading portion of the dendrite at the time of the charge and to prevent the growth of dendrite, the surface of the multilayer metal oxide film on the negative electrode side may be applied with a conductive material by evaporation or plating.
Very Fine Particle Sol of Metal Oxide The dispersed sol of very fine particles of the metal oxide is usually obtained by an acid, a base and water are added to an alcohol solution of an organic metal compound such as metal alkoxide as to be hydrolyzed to form colloid of the very fine particles of the metal oxide. The dispersion medium of the very fine particle sol is obtained by substituting to an organic solvent if necessary.
The alkoxide is typified by tetramethoxysilane, tetraethoxysilane, aluminum isopropoxide, and titanium isopropoxide. Another metal organic compound such as acetyl acetone complex salt, alkyl metal compound, acetylacetone metal salt, naphthenate metal salt or octylate metal salt may be used.
The very fine particles of the metal oxide can be obtained by another method for obtaining the same from the gas phase reaction of the vapor of the organic metal 25 compound or the metal. The obtained very fine particles of the oxide are dispersed in a solvent so that a a *4 *g a a 9 4 a.
[N:\LIBE]01316:MXL -81 dispersed sol is prepared.
If the negative electrode active material is lithium or lithium alloy, lithium ions relate to-the battery reactions. In the case of an alkali battery comprising the negative electrode active material which is zinc, hydroxyl ions relate to the same. The typical battery of a type comprising the negative electrode active material which is zinc is exemplified by a nickel-zinc battery and an air-zinc battery.
By covering the surface of the positive electrode 104 of the battery with a film 12102 which is made of an insulating material or a semiconductor through which ions relating to the battery reactions can be passed, dendrite of lithium or zinc grown from the negative electrode 101 through the separator 108 during the repetition of the charge and the discharge are not substantially brought into contact with the conductor or a collector in the positive electrode 104. As a result, short circuits in the battery can be prevented, and therefore the life of the secondary battery can be lengthened. Further, the safety can be improved.
Covering of Positive Electrode of Secondary Battery ~As the insulating material of the coating material of
S
the positive electrode of the secondary battery, any one of 25 the following materials may be used which is selected from a too**: 0 :group consisting of a polymer of the derivative of a large ring compound, a polymer of the derivative of too o 0 0 to so41 ,••go So
S
*SSS
[N:\LIBE01316:MXL -82 an aromatic hydrocarbon, fluororesin, silicon resin, titanium resin, polyorefin, inorganic oxide, nitride, carbide and halide. It is effective for the positive electrode of the lithium secondary battery to be covered with the polymer of the derivative of the large ring compound of the polymer of the derivative of the aromatic hydrocarbon or the fluororesin.
Polymer of Derivative of Large Ring Compound The large ring compound is a ring compound of a type comprising hetero-atoms of one or more types selected from a group consisting of oxygen, nitrodgen, sulfur and phosphorus. The large ring compound is a ring polyether having hole each having a radius larger than the radius of the lithium ion. The large ring compound has one or more structures selected from a group consisting of ring polyamine, ring polythioether, azacrown ether, ring thioether, thiocrown ether, cryptand, cyclam, nonactine, variomicine, thyracrown which is a crown ether containing silicon atoms, cyclodextrin, cyclofan, phthalocyanin and porphyrin compound.
The surface of the positive electrode is covered with the large ring compound by any one of the following methods.
a. A polymer solution obtainable from polymerization of the derivative of the foregoing large ring 25 compound is applied by a coating method such as 0 0 o 000 *0 0 *0 0 fte* ee [N:\LIBE]01316:MXL -83dipping, spraying, screen-printing or coating application method.
b. A mixture in which the derivative of the large ring compound is mixed with the polymer serving as the binder is applied and then crosslinked to form the film.
c. The derivative of the large ring compound is used as a monomer to be dissolved in an electrolyte solution, and then an electric field is applied to electrolyze and polymerize the material so that the film is formed on the surface of the positive electrode.
d. The molded positive electrode is immersed in a solution of the derivative of the large ring compound, which anion-polymerizes, so that the polymer film is formed.
e. A polymer obtainable by heating and condensing the large ring compound having an aromatic ring and formaldehyde in a formic acid is applied.
f. The film is formed by sputtering of a polymer of the large ring compound or the derivative of the large ring compound or by plasma-polymerizing the large ring compound.
An electrolyte may be mixed at the time of forming the film. As a result, the wettability between the electrolyte solution and the film can be improved, causing ions to easily pass through the film.
The polymer for uses as the coating solution may be poly [(dibenzo 18 crown 6) co formaldehyde] 0 *e gr o ee 055*05 {N:\LIBE]01316:MXL 84 1 or the like. The coating polymer can be newly formed by the following polymerizing reactions: a large ring compound having a carboxylic group or an amino group or a hydroxyl group at the terminal group thereof is condensed and polymerized so that polyamide is obtained if the carboxylic group and the amino group react with each other. If the carboxylic group and the hydroxyl group react with each other, polyester can be obtained.
e The vinyl compound of the large ring compound or diene 1 0 of the large ring compound can be obtained in the form of an addition polymer by radical polymerization, cation polymerization or anion polymerization. The starting material in the radical polymerization may be azobisisobutylonitryl (AIBN), benzoylperoxide (BPO) or t 15 butylhydroperoxide. A starting material for the cation polymerization is exemplified by an acid such as
H
2
SO
4
H
3
PO
4 HCIO41 CCl3CO2H and Friedel-Craft catalyzer such as BF 3 A1C1 3 TiCl 4 or SnCl 4 A large ring compound having an aromatic ring can be polymerized by dehydrogenation in which the Friedel- Craft catalyzer and an oxidizer are combined to each other. A starting material for the anion polymerization may be an alkaline metal compound or an organic metal compound.
As the monomer of the large ring compound for use in the polymerization may be crown ether/(+) 18 crown 6 tetracarboxylic acid, 1, 5, 9, 13, 17, 21 hexathiacyclotetrakosan 3, 11 19 triol, 1, 5, 9, 13 tetrathiacyclohexadecan 3, 11 diol, 1 aza 12 crown 4, 1 aza 15 crown 5, 1 aza 18 crown 6, 1, 4, 10, 13 tetraxyso 7, 16 diazocyclooctadecan, 1, 4, 10 trioxa 7, 13 diazacyclopentadecan, or 6, 8 dioxabicyclo 2. 1] oxtane 7 on. As an alternative to this, dibenzocrown ether can be used.
In the foregoing polymerization, a copolymer of two more types of derivatives of the large ring compounds or a copolymer of the large ring compound and another monomer may be used as well as the polymer of the derivatives of the large ring compounds. A polymer obtainable by introducing the derivative of the large ring compound into a polymer by substitution may be employed.
When a battery is manufactured, a polymer must be selected so as not to be dissolved in the solvent of the electrolyte solution or the polymer crosslinking reactions are caused to proceed so as not be dissolved in the electrolyte solution.
The derivative of the large ring compound having, at the terminative group thereof, carboxylic group or amino group or a hydroxyl group or having a vinyl bond or a diene bond and a crosslinking material are mixed in the polymer serving as the binder, and then the mixed material is hardened. An accelerating 0 .00 V.000: .00.
IN:\LIBEI01316:MXL -86material may be mixed at this time. The crosslinking material is selected from a group consisting of disocyanate, a polyisocyanate prepolymer, block isocyanate, an organic peroxide, polyamine, oxims, a nitroso compound, sulfur, a sulfur compound, selene, a magnesium oxide, a lead oxide and a zinc oxide. The organic peroxide is exemplified by di cumyl peroxide, 2, 5 dimethyl 2, 5 di (t butyl peroxy) hexane, 1, 3 bis (t-butyl peroxy isopropyl) benzene, 1, 1 bis (t-butyl peroxy) 3, 3, 5 trimethyl cyclohexane, n buty 4, 4 bis (t butylperoxy) valelate, 2, 2 bis (t butyl peroxide) butane, t butyl peroxy benzene, and vinyl tris (t butyl peroxy) silane. As an accelerating agent, a guanidine, aldehyde amine, aldhyde-ammonia, thiazol, sulfonamide, thiourea, thiuram, dithiocarbamate, xanthate accelerating agent is used.
Another coating method using the binder polymer is exemplified by a method in which a mixture of the large ring compound and the binder polymer is applied, and then radial rays, electron rays or ultraviolet rays are applied to cause the applied material to be crosslinked.
As a method for covering the positive electrode by the electrolytic polymerization, a monomer, such as dibenzocrown ether, is mixed in the electrolyte a a a 4 *aa a. a a.
[N:\LIBE]01316:MXL -87solution, and then the electrolytic polymerization is performed while using the negative electrode active material or the conductive matrix as an anode. The solvent of the electrolyte solution is exemplified by acetonitryl (CH 3
CN),
benzonitryl (C 6 HsCN), propylene carbonate (PC), dimethylformamide (DMF), tetrahydrofuran (THF), nitrobenzene
(C
6 H5NO 2 dichloroethane, diethoxyethane, chlorobenzene, y butyrolactone and dioxolan and their mixture.
It is preferable that the solvent be dehydrated with active alumina, molecular sheave, phosphorus pentaoxide or calcium chloride.
The supporting electroyte is an acid, such as H 2 SO4,
HC
1 or HNO 3 or salt composed of monovalent metal ion (Li+, Na+, Rb+ or Ag+) or tetraammonia ion (tetrabutyl ammonia ion (TBA and tetraethyl ammonia ion and Lewis acid ion (BF4-, PF6-, AsF 6 or C10 4 It is preferable that the foregoing salt is refined by re-crystallization or it is heated under lowered pressure to sufficiently dehydrate and deoxidize the salt.
As the monomer, crown ether/benzo 15 crown crown ether/benzo 18 crown 6, crown ether/N -phenylaza 15 crown 5, crown ether/dibenzo 18 25 crown 6, crown ether/dibenzopyridino 18 crown 6, crown ether/dibenzo 24 crown 8, 1, 13 bis (8 -quinolyl) 1, 4, 7, 10, 13 pentaoxatridecan, ta ft: *tee *eo 9e ft• ea oooo *t f f f ftoo oetoo [N:\LIBE]01316:MXL -88- 6 benzo 4, 7, 13, 16, 21, 24 hexaoxa 1, 10 diazabicyclo 8. 8] hexakosan, 5, 6 14, 15 dibenzo 4, 7, 13, 16, 21, 24 hexaoxa 1, 10 diazabicyclo [8.
8. 8] hexakosan, bis [(benzo 15 5 crown 5 15 ilmethyl] pimelate, crown ether/dibenzo 30 crown N, N' dibenzyl 1, 4, 10, 13 teraoxa 7, 16 diazacyclooxtadecan, dilithiumphthalocyanin, 4' nitrobenzo 15 crown 5, 3, 6, 9, 14 tetrathiabicyclo 2. 1] tetradeca -11, 13 diene and their mixture.
Since the performance of the battery deteriorates if the polymer film for covering the surface of the negative electrode active material is dissolved in the electrolyte solution, it is preferable to be crosslinked.
It is preferable that the thickness of the film to be formed on the surface of lithium ranges from 10 A to 100 V, further preferably ranges from 50 A to 10 p. The optimum thickness of the film differs depending zo upon the density or the void ratio of the film and considerably differs depending upon the type of the electrolyte solution. The thickness of the film can be adjusted by changing the concentration of the main material in the coating liquid for forming the film.
Polymer of Derivative of Aromatic Hydrocarbon As the derivative of the aromatic hydrocarbon for forming the charge moving complex is one or more 4 9 e o et ^e ro oo r e• [N:\LIBE]01316:MXL 89 1 types of derivatives selected from a group consisting of naphthalene, anthracene, phenanthlene, naphthacene, pyrene, triphenylene, perillene, picene, benzopyrene, coronene and ovalene.
The polymer for use to form the coating material can be prepared by polymerization or copolymerization of vinyl monomer, monomer of acetylene derivative or dicarboxylic acid and diamine, and dicarboxylic acid and glycol. The polymerization 10 of the vinyl monomer can be performed by radical or ion polymerization. The monomer of the acetylene derivative can be polymerized while using a chloride of tungsten as a catalyzer. The dicarboxylic acid and 9 diamine can be polycondensed and the dicarboxylic acid 15 and glycol can as well as be polycondensed.
The monomer of the aromatic derivative for forming the polymer is exemplified by 2 vinyl naphthalene, 2 vinyl pyridine, 9 vinyl anthracene, 9, 10 anthracene dipropionic acid, 9, 10 bis (phenyl ethyl) anthracene and 5, 12 bis (phenyl ethynyl) naphthalene.
A starting material for the radical polymerization is exemplified by azobisisobutylonitryl (AIBN), benzoylperoxide (BPO) and t butylhydroperoxide.
A starting material for the cation polymerization is exemplified by an acid such as H 2
SO
4
H
3 P0 4 HC10 4 CCl 3 or CO 2 H and Friedel-Craft catalyzer such as BF 3 A1C1 3 TiC1 4 or SnCl 4 A large ring compound having an aromatic ring can be polymerized by dehydrogenation in which the Friedel-Craft catalyzer and an oxidizer are combined to each other. A starting material for the anion polymerization may be an alkaline metal compound or an organic metal compound.
As an alternative to the foregoing method, a polymer into which an aromatic group can be obtained by subjecting the side chain of each polymer to a substitution reaction with a derivative of an aromatic compound. Another method may be employed in which an electrolyte polymerization reaction is caused to take place in an electroytic solution containing a monomer mixed therein to form directly a polymer of an aromatic compound on the surface of positive electrode.
When the surface of the positive electrode is applied with a coating by using the foregoing polymer solution, it is preferable to use a polymer solution dehydrated and deoxidized sufficiently in inactive gas dehydrated sufficiently. It is preferable to use a solvent in the foregoing solution which has been dehydrated with active alumina, molecular sheave, phosphorus pentaoxide or calcium chloride. As an alternative to this, it is preferable depending upon the type of the solvent that the solvent be distilled under presence of alkaline metal in inactive gas to remove impurities and to be dehydrated.
4 4 *c [N:\LIBE]01316:MXL -91 An electrolyte may previously be mixed when the foregoing film is formed. It leads to a fact that wettability between the electrolyte solution and the film can be improved, causing ions to easily pass through the film.
Since the performance of the battery deteriorates if the polymer coating film is dissolved in an organic solvent of the electrolyte, it is preferable to be crosslinked in such a manner, for example, ultraviolet rays, electron rays or radial rays are applied or a crosslinking material, such as a radical generating agent, is used.
Fluororesin The fluororesin for covering the surface of the positive electrode is exemplified by ethylene tetrafluorideethylene copolymer, ethylene tetrafluoride chloride, ethylene tetrafluoride per fluoroalkylvinyl ether copolymer, ethylene tetrafluoride propylene hexafluoride copolymer, vinylidene fluoride resin, vinyl fluoride resin, and ethylene tetrafluoride resin. Since the foregoing materials are not dissolved in a solvent, it is preferable to employ sputtering or plasma polymerization to cover the surface of the positive electrode with the fluororesin.
Among the fluororesins, those having an ether bond is able to facilitate the surface covering because they can easily be dissolved in a solvent and to improve t
S
4 S. S Si [N:\LIBE101316:MXL l ,J 92 1 the affinity with lithium ions. The fluororesin having the ether bond is exemplified by: a copolymer of ethylene fluoride and vinyl monomer such as vinyl ether, dioxysol, dioxyne or dioxycene having an ether bond or dienemonomer derivative or a copolymer with a vinyl monomer, such as vinyl ether, dioxysol or dioxyne, dixycene having a fluorized ether bond with a diene compound, such as ethylene. The fluoroethylene may be a fluoroethylene derivative such as tetrafluoroethylene, 10 chlorotrifluoroethylene, vinylidenefluoride or vinyl fluoride. The fluoroethylene copolymer containing the 00 ether bond can be polymerized by a solution, suspension, block or emulsion polymerization. As a starting 4 0 0 material, a peroxide, alkyl boron, light or radial rays 15 may be employed.
6* The fluororesin can be coated on lithium metal by any one of the following methods.
a. A solution of the fluororesin is applied by spraying, screen printing, by using a coater or by dipping.
b. The fluororesin is directly coated to the surface of lithium by a vacuum evaporation method such as sputtering.
c. A polymer film is directly formed by plasma polymerization under an atmosphere of monomer which is the raw material for the fluororesin.
If the lithium surface is coated by using the 93 fluororesin solution, it is preferable to use, in an inactive gas dehydrated sufficiently, a fluororesin solution dehydrated and deoxidized sufficiently. It is preferable to use a solvent in the foregoing solution which has been dehydrated with active alumina, molecular sheave, phosphorus pentaoxide or calcium chloride. As an alternative to this, it is preferable depending upon the type of the solvent that the solvent be distilled under presence of alkaline metal in inactive gas to remove impurities and to be dehydrated.
An electrolyte may previously be mixed when the foregoing film is formed. It leads to a fact that wettability between the electrolyte solution and the film can be improved, causing ions to easily pass through the film.
Since the performance of the battery deteriorates if the fluororesin film is dissolved in an organic solvent of the electrolyte solution, it is preferable that the film is crosslinked.
As an alternative to the foregoing method of coating the surface with the fluororesin solution having the ether bond, another method may be employed in which ethylene fluoride and vinyl monomer are used as the main raw material as to be plasma-polymerized so that the surface is covered.
In order to easily cause the plasma polymerization to take place easily or to improve the contact of the film and the strength of the same, it is o *e *ooe r [N:\LIBE]01316:MXL -94preferable to add, to the fluorine compound serving as the raw material, oxygen, hydrogen, helium, argon, nitrogen, silane, hydrocarbon or the like. The plasma can effectively be generated by a DC or RF glow discharge method, a microwave discharge method or a laser beam irradiation method. The fluororesin having the ether bond may be sputtered to cover the surface of the positive electrode.
It is preferable that the thickness of the film to be formed on the surface of lithium ranges from 10 A to 100 lI, more preferably ranges from 50 A to 10 p. The optimum thickness of the film differs depending upon the density or the void ratio of the film and considerably differs depending upon the type of the electrolyte solution. The thickness of the film can be adjusted by changing the concentration of the main material in the coating liquid for forming the film. If the plasma polymerization or sputtering is performed, the thickness can be adjusted by controlling the deposition time period.
Silicon Resin The organic silicon compound may be any one of a material selected from a group consisting of alkoxysilane, alkylsilane, halogenated silane, siloxane, silane containing vinyl group, amino group, epoxy group, methacrylic group or mercaptal group introduced thereto, hydrogen denatured, vinyl denatured, hydroxyl group
*LI
X..
S
[N:\LIBEI01316:MXL 95 1 denatured, amino denatured, carboxylic group denatured, chloro denatured, epoxy denatured, methachryloxy denatured, mercapto denatured, fluorine denatured, long-chain-alkyl denatured or phenyl denatured polysiloxane, alkylene oxide denatured siloxane copolymer, silicon denatured copolymer, alkoxysilane denatured polymer, silicon denatured urethane or silicon denatured nylon.
9 If the organic compound is liquid, the film can 10 be formed by a direct coating method or the organic compound is diluted in a solvent and then applied. If the organic compound is solid, a solution dissolved in a solvent may be applied. The application method may be a dipping method, a screen printing method, a spraying 15 method, a roll coating method or the like. The 9* viscosity of the coating solution must adequately be adjusted to be adaptable to the coating method.
Titanium Polymer A titanium polymer obtained by causing an organic titanium compound to act on an organic polymer may be used. For example, a thiranopolymer of silicon polymer formed by cross linking the main chain of a polycarbosilane skeleton with the titanium organic compound may be used.
As an alternative to the titanium polymer, a material obtained by introducing the derivative of an organic metal compound, such as an organic aluminum -96compound, into a polymer by substitution reactions may be used as the coating material.
Polyphosphazene Polyphosphazene which is a polymer in which phosphor atoms and nitrogen atoms alternately form phosphor-nitrogen double bonds can be obtained by heating a dichloropolyphosphazene trimer to 200 to 300 0 C and by ringopening polymerization. The dichloropolyphosphazene trimer can be synthesized from phosphorus pentachloride and ammonia chloride or ammonia. Any one of the following catalyzer is used at the time of the polymerization: benzoic acid, sodium benzonate, 2, 6 di p cresol, water, methanol, ethanol, nitromethane, ether, heteropoly acid, sulfur, zinc, tin and sodium.
Further, various type of polyorganophosphazene can be obtained by substituting chloride atoms of polydichlorophosphazene by an organic reagent or an organic metal reagent.
If the surface of positive electrode is coated with the foregoing polyphosphazene, it is preferable that the polymer solution dehydrated and deoxidized sufficiently be used in inactive gas dehydrated sufficiently. It is preferable to use a solvent in the foregoing solution which has been dehydrated with active alumina, molecular sheave, phosphorus pentaoxide or calcium chloride. As an alternative to this, it is preferable depending upon
*OO
*e.
C
CC C
C
IN:\LIBE101316:MXL -97the type of the solvent that the solvent be distilled under presence of alkaline metal in inactive gas to remove impurities and to be dehydrated.
An electrolyte may previously be mixed when the foregoing film is formed. It leads to a fact that wettability between the electrolyte solution and the film can be improved, causing ions to easily pass through the film.
Since the performance of the battery deteriorates if the polymer coating film is dissolved in an organic solvent of the electrolyte, it is preferable to be crosslinked in such a manner, for example, ultraviolet rays, electron rays or radial rays are applied or a crosslinking material, such as a radical generating agent, is used.
It is preferable that the thickness of the film to be formed on the surface of lithium ranges from 10 A to 100 p, more preferably ranges from 50 A to 10 p.
The optimum thickness of the film differs depending upon the density or the void ratio of the film and considerably differs depending upon the type of the electrolyte solution. The thickness of the film can be adjusted by changing the concentration of the main material in the coating liquid for forming the film.
Polyolefin As polyorefin, polyethylene or polypropylene may be used. Polyorefin is used in such a manner that the
C
e IN:\LIBE]01316:MXL -98positive electrode is dipped in a solution dissolved in a solvent such as tetrahydrofuran or o-dichlorobenzene, the positive electrode is then dried and crosslinked by ultraviolet, electrons, radial rays or the like so that the film is formed on the surface of the positive electrode.
The film can be formed by sputtering or plasma CVD method. In the material in the plasma CVD method, ethylene gas or propylene gas may be used.
Inorganic Oxide The inorganic glass is made of a material, such as silica, titanium oxide, alumina, zirconia oxide, magnesium oxide, tantalum oxide, molybdenum oxide, tungsten molybdenum, tin oxide, indium oxide, iron oxide, chrome oxide, aluminum phosphate, iron phosphate, silicon phosphate and their mixtures. A sol-gel method is one of adequate methods for forming the inorganic glass. The raw material for the material having the inorganic glass structure is obtained in such a manner that an acid or a base and water are added to a solution of alcohol of an organic metal compound such as a metal alkoxide to hydrolyze the raw material so as to form colloid particles having metal atomoxygen atom bonds, and then the collide solution is directly applied to the surface of the positive electrode. As an alternative to this, a solution in which a monomer or an organic polymer or the organic polymer and a crosslinking material are dissolved in the collide solution is a** ta f ft ft ft fft f ft *fftt [N:\LIBE]01316:MXL -99applied, and then the solution is polymerized or dried and polymerized so that the film is formed. By forming the composite organic polymer, strength against cracks-and separation can be improved. If the electrolyte forming the lithium battery is dissolved in the collide solution to form the film, the wettability with the electrolyte solution can be improved and ions are enabled to move easily.
As an alternative to alkoxide, any one of the following organic metal compound may be employed: acetyl acetone complex salt, an alkyl metal compound, acetyl acetone metal salt, naphthene acid metal salt, and octyl acid metal salt.
The organic polymer for combining the organic polymers is exemplified by epoxy resin, polyester, polyimide, polyethylene, polypropylene, polyurethane, polystyrene, polyethylene glycol, nylon, fluorine resin and silicon resin.
The polymer crosslinking material is exemplified by diisocyanate, polyisocyanate prepolymer, block isocyanate, organic peroxide, polyamine, oxims, nitroso compound, sulfur or sulfur compound, selenium, magnesium oxidet lead oxide and zinc oxide.
As an alternative to using the crosslinking material, a method may be employed in which radial rays or electron rays or ultraviolet rays are applied to polymerize or crosslink the polymer.
C
C
C C CC 1- [N:\LIBE101316:MXL 100 1 As an application me'hod, a dipping method, screen printing, spraying or a roll coating method may be employed. The viscosity of the liquid to be applied must adequately be adjusted to be adaptable to the application method.
Another method of forming the film by the glass inorganic oxide may be employed, for example, any one of the following evaporation method or a CVD method may be employed: a sputtering method, an electron beam evaporation method, a plasma CVD (Chemical Vapor Deposition) method, and a laser CVD method.
The sputtering process and the electron beam evaporation can be performed by a method in which the oxide material is directly evaporated or by a method in 15 which silicon or metal vapor and oxygen gas are caused to react with each other to form the film.
*The plasma CVD method and the laser CVD method is performed in such a manner that oxygen gas and any one of a hydroxide or halide of silicon or metal and an organic metal compound are used as the raw materials to be decomposed by discharge or laser so that the film is formed.
The inorganic oxide can be used to form the film by another method, that is, an electrochemical method comprising the steps of forming a metal film made of aluminum, titanium, tantalum, niobium by sputtering or electron beam, anode-oxidizing the film by using an 101 oxalic acid, a phosphoric acid or ammonia borate as an electrolyte solution to form the oxide film.
A film forming method may be employed which utilizes the equilibrium reaction in the water solution to precipitate and cause the oxide film to grow on the surface of the dipped substrate. In this case, silica (a silicon oxide), titanium oxide or vanadium oxide film can be formed.
A specific method of forming the silica film comprises the step of dipping the positive electrode in a solution in which silica is saturated in a water solution of hydrofluosilisic acid to form the film.
Nitride The nitride can be obtained from silicon nitride, titanium nitride, aluminum nitride or boron nitride or the like. The nitride film can be formed on the positive electrode by sputtering, an electron beam evaporation method, a plasma CVD method or a laser CVD method.
The sputtering and the electron beam evaporation methods are categorized to a method in which the nitride material is directly evaporated and a method in which vapor of silicon, titanium or aluminum and nitrogen plasma generated from nitrogen gas or ammonia gas are caused to react with each other to form the film.
The plasma CVD method and the laser CVD method respectively comprise the step of decomposing the raw material Qas. such as nitrogrn gas aoE-L U gas or "3 Y.I tIIi tu tiL a gas or 99 9 9o 9 rr-* [N:\LIBE]O1316:MXL 102 1 nitrogen trifluoride and a hydroxide such as silicon, titanium or aluminum, halide or an organic metal compound by discharge or laser to form the film.
Carbide The carbide can be obtained from a material exemplified by amorphous carbon, silicon carbide, titanium carbide, vanadium carbide and tungsten carbide.
The carbide film can be formed by a similar method employed to form the nitride.
The sputtering and the electron beam evaporation methods are categorized to a method in which the material from which the carbide is obtained is directly ~evaporated and a method in which silicon, titanium, vanadium or tungsten and carbon are used as the raw 15 materials to form the film.
The plasma CVD method and the laser CVD method ::-respectively comprise the step of, by laser, decomposing the material, such as hydrocarbon, from which carbon is obtained and a hydroxide such as silicon, titanium, vanadium or tungsten or a halide or an organic metal compound to form the film.
Halide The halide can be obtained from a material selected from a group consisting of lithium fluoride, magnesium fluoride, sodium fluoride, potassium fluoride, barium fluoride or lithium chloride.
The halide film can be formed by a sputtering 103method or an electron beam evaporation method. A CVD method such as the plasma CVD method or the laser CVD method may be employed. Semiconductor The semiconductor for covering the positive electrode is made of a material exemplified by diamond (carbon), silicon, nickel oxide, copper oxide, vanadium oxide, tin oxide and zinc oxide.
Alkali metal, phosphorus or boron may be added as impurities.
The semiconductor film may be formed by sputtering, electron beam evaporation, plasma CVD or laser CVD as well as the foregoing method of forming the inorganic acid film.
Covering of Positive Electrode of Nickel-Zinc Secondary Battery or Air-Zinc Secondary Battery The material and the method of covering the positive electrode of a nickel-zinc secondary battery or air-zinc secondary battery may be the same as those employed to cover the positive electrode of the lithium secondary battery.
Also a polymer of a type which is dissolved in an organic solvent but which is not dissolved in water may be used. If the covering material has water repellant characteristics, a hydrophilic group must be introduced or must be subjected to hydrophilic treatment using a silane coupling material.
9 a 9 9 -Vf *r *r n [N:\LIBE]01316:MXL -104- Thickness of Film Covering the Surface of Positive Electrode The thickness of the film for covering the surface of the positive electrode can be controlled-by adjusting the concentration of the solution if the surface is covered by utilizing the liquid layer reactions performed by the polymer solution or the sol-gel method. The same can be controlled by adjusting the deposition time if sputtering, the electron beam evaporation, the CVD method or the plasma polymerization is employed.
Aperture in Coating Film on Positive Electrode Surface The apertures and the void ratio of the coating film for covering the surface of the positive electrode can be controlled by adjusting the concentration of the solution or the drying condition if covering is performed by using the polymer solution or by utilizing the sol-gel method.
Further, any one of the following methods may be employed: a method for forming the film while causing foam to be generated by adjusting the concentration of the foaming material; a method having the steps of forming a film in which the content of the electrolyte is adjusted, and dissolving the electrolyte; a method for controlling the evaporation rate; and a method for adjusting the mixture ratio of the reactive materials.
If the negative electrode is covered with the coating material of a type employed to cover the positive electrode, growth .of dendrite from the negative electrode can be a a a° a a
C
(N:\LIBE]01316:MXL 105prevented. Therefore, short circuits in the battery can be prevented in effect obtainable from covering the positive electrode. As a result, the battery cycle can further be lengthened.
Then, a positive electrode according to an aspect of the present invention composed of transition metal and group 6A element will now be described.
Transition Metal Element The transition metal element in the positive electrode active material according to an aspect of the present invention may be an element having partially shell d or shell f and selected from a group consisting of T, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Wn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag and Au. Any one of the first transition system metal is mainly used which is exemplified by Ti, V, Cr, Mn, Fe, Co, Ni or Cu. A compound of the transition metal and the group 6A element is manufactured by a material exemplified by the transition metal, the salt of the transition metal, an oxide of the transition metal and a hydroxide of the transition metal.
Group Element The positive electrode active material according to an aspect of the present invention comprises the group 6A element exemplified by O, S, Se, Te and Po. Among the foregoing elements, 0 or S is mainly employed. A compound of the transition metal and the group 6A element can be 50
S
ee 0
S
0
S
555055
S
0. 5*r S 00 [N:\LIBE]01316:MXL 106manufactured by a material exemplified by a compound of a hydroxide, halide, halide oxide or oxide of sulfur, selene, tellurium, polonium.
Additive Element By adding elements except the transition metal, the distortion of the positive electrode active material occurring due to the introduction/discharge of lithium ions can be relaxed. The element can be effectively added by a method comprising the step of adding the salt, the halide or an organic metal compound of one or more types of elements selected from a group consisting of lithium, magnesium, sodium, potassium, aluminum, zinc, calcium, barium, lead, indium, boron, silicon, tin, phosphor, arsenic, antimony, bismuth, chlorine and fluorine. It is preferable that the atom ratio of the additive element with respect to the transition metal element be 1 or less.
Method of Manufacturing Compound of Transition Metal and Group 6A Element The compound of the transition metal and the group 6A element according to an aspect of the present invention is manufactured by any one of methods categorized to a method in which the compound is prepared from the solution of the salt of the transition metal or the organic transition metal compound by way of a hydroxide, a method comprising the steps of melting the transition metal or the transition V6060 metal compound and rapidly S.*00 .0 0
S
S.
ooo 00 00
OOS
0 0050 550005 o OO oo 0
S
5 0 o 0OO [N:\LIBE]O1316:MXL 107 1 cooling it, and a method in which the transition metal compound is caused to react in a gas phase.
The method of preparing the transition metal oxide from the hydroxide is exemplified by a method comprising the step of baking or drying hydroxide in air or in an oxygen atmosphere to prepare powder. A specific example of preparing the transition sulfide from the hydroxide is exemplified by a method comprising the step of baking a hydroxide in a hydrogen reduction 1 0 atmosphere in which a hydrogen sulfide is mixed to prepare powder.
The rapid cooling method for preparing the e.o. transition metal oxide comprises the steps of melting the transition metal compound, such as the transition 15 metal or the transition metal oxide, and spraying oxygen gas containing inactive gas mixed thereto to a rotating disc to prepare the powder.
The method of preparing the transition metal oxide by the gas phase reactions comprises the step of oxidizing or hydrolyzing the salt of the transition metal or causing vapor of the transition metal to react with the group 6A element or a compound of the group 6A element or decomposing the organic transition metal compound to prepare the powder.
It is preferable that each process be performed at 400 0 C or lower, more preferable 3001c or lower.
The liquid phase reaction method, the gas phase 108 I reaction method and the melting and rapid cooling method will now be described.
Liquid Phase Reaction A method of preparing the hydroxide for use in the main reaction in the method of manufacturing the material from the solution by way of the hydroxide is exemplified by: Method of Preparing Hydroxide It is preferable that the transition metal ':10 hydroxide be prepared by reactions between the salt of S S the transition metal and alkali or by hydrolysis of the organic transition metal compound or by reactions •:'""between the transition metal and alkali. It is preferable that the preparation temperature be 150'C 15 or lower, more preferably 100 0 C or lower.
S
Reactions between Salt of Transition Metal and Alkali By causing alkali to react with the salt of the transition metal, a hydroxide of the transition metal is sedimentated to be prepared. By mixing salts of two or more types of the transition metals, a hydroxide of a composite transition metal can be obtained.
The salt of the transition metal is typified by a carbonate, a nitrate, a halide, a sulfate, a sulfamate, acetate, oxalate, critate, tertrate, formate or ammonate.
The alkali may be lithium hydroxide, sodium hydroxide, potassium hydroxide or ammonia hydroxide. As 109 1 an alternative to this,-urea or thiourea may be used which raises the pH by generating hydroxide ions when heated.
It is preferable that an organic acid or inorganic acid or an amine is, in a small quantity, added or an organic solvent such as alcohol is added at the time of causing alkali to react with the water solution of the transition metal salt in order to fine the sediment particles of the hydroxide.
i0 By vibrating the sediment with ultrasonic waves, the sediment particles can be fined. Therefore, the specific area can be enlarged.
Hydrolysis Reaction of Organic Transition Metal Compound The hydroxide of the transition metal can be 15 prepared by hydrolyzing an organic metal compound of the transition metal, such as alkoxide, acetyl acetenate, octylate or naphthalate.
The hydrolysis of alkoxide is specifically performed in such a manner that alkoxide of the transition metal is dissolved by water, alcohol or ethanol amine or the like, and an inorganic acid such as hydrochloric acid or an organic acid such as acetic acid or ammonia hydroxide or amine is added.
The alkoxide of the transition metal may be a material selected from a group consisting of Mn(OC 2
H
5 2 Mn(OC 3
H
7 2 Mn(OC 4
H
9 2 Ni(OC 2
H
5 Ni(OC 3
H
7 2 Ni(OC 4
H
9 2 Co(OC 2
H
5 2 Co(OC 3
H
7 2 Co(OC 4
H
9 2 110 1 Ti(C 2 H 5 2 1 Ti(OC 3 H 7 2 1 Ti(C 4 H 9 2 Fe(0C 2 H 5 2 1 Fe(0C 3 H 7 2 1 Fe(0C 4
H
9 2 1 Cu(0C 2 H 5 2 1 Cu(0C 3 H 7 2 1 Cu(0C 4 H 9 2 1 VO(OCH 3 3 1 VO(0C 2 H 5 3 VO(0C 3 H 7 3 1 VO(0C 4 H 9 3 and Y(0C 4 H 9 3 The acetylacetonate of the transition metal is exemplified by Cu(C 5 H 7 0 2 2 Co(C 5 H 7 0 2 2 (H 2 0) 2 Co(C 5 H 7 0 2 3 1 Ni(C 5 H 7 0 2 2 (H 2 0) 2 f Mn(C 5 H 7 0 2 2 (H 2 0) 2 Cr(C 5 H 7 0 2
VO(C
5 H 7 0 2 2'2 Fe(C 5 H 7 0 2 )31 Ti(OC 4 H 9 2 (C 5
H
7 o0) 2 La(C H 0 3 Y(C H 09 3 and Zr(C H 0 The octylate of the transition metal is exemplified by Cu(C H 15 COO), Ni(C H 15 COO), Fe(C H 15
COO),
Mn(C 7 H 15 COO) 2 CO(C 7 H 15 COO) 2 Zr(C 7 H 15 COO) 2 P Y(C 7 H 15 COO) 2 f and La(C H 15
COO).
The naphtate of the transition metal is **15 exemplified by the salt of naphthate expressed by a general formula C nH 2 n- 2 O0 2 that is, cobalt naphthenate, copper naphthenate, manganese naphthenate, iron naphthenate, nickel naphthenate, vanadium naphthenate, yttrim naphthenate and lanthanum naphthenate.
The alcohol is exemplified by methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol and propylene glycol.
Dehydrating Reaction In order to obtain the oxide of the transition metal by dehydration from the transition metal hydroxide prepared by the foregoing solution reactions, it is preferable that the transition metal hydroxide is 111 1 immersed in an organic solvent such as alcohol or acetone which is mixed with eater to sufficiently substitute water, and then it is dried in a vacuum state at 100'C or higher. As an alternative to this, heating and dehydration is performed by using microwaves. If the drying temperature is too high, crystallization is enhanced and therefore the hydroxide groups are decreased. Therefore, it is preferable that the temperature be 400C or lower. It is preferable that the frequency of the microwaves be a frequency which can easily be absorbed by water.
In order to enlarge the specific area, another *.method may be employed in which the dehydration is performed by freezing and drying.
15 Hydrogen Treatment "'"Hydrogen is mixed into the dried atmosphere at the time of drying the transition metal oxide followed by performing heat treatment. As an alternative to this, a method is employed in which the transition metal hydroxide or the transition metal oxide is subjected to hydrogen plasma treatment. The hydrogen plasma can be generated by a hydrogen gas discharge method or by a method of exciting and decomposing the hydrogen gas by laser beams.
Introduction of Group 6A Element Except Oxygen A method is employed in which the transition metal hydroxide or the transition metal oxide is treated 112 1 with hydrogen sulfide or hydrogen selenide or the group 6A element is mixed at the time of preparing the transition metal hydroxide.
Gas Phase Reaction Method As a method of preparing a compound of the transition metal and the group 6A element, a gasified transition metal salt or an organic transition metal compound or vapor of the transition metal and the group o 6A element or the group 6A element compound are caused 10 to react with each other in the gas phase to prepare powder. Another method may be employed in which the gasified transition metal salt or the organic transition metal compound containing the group 6A element is decomposed in the gas phase to prepare the compound of 15 the transition metal and the group 6A element.
If the transition metal salt or the organic transition metal compound is in the form of solid, it is heated as to be formed into vapor or it is heated as to be formed into liquid. Then, carrier gas is bubbled as to be introduced into the reaction chamber. If the transition metal salt or the organic transition metal compound is in the form of liquid, it may be heated as to be formed into vapor or carrier gas is bubbled as to be introduced into the reaction chamber.
The salt of the transition metal may mainly be a halide such as a chloride. As an alternative to this, a carbonate, a nitrate, a sulfate, sulfominate, acetate, 113 1 citrate, tertrate, formate or ammonate. The chloride is exemplified by VOCl 3 MnCl 2 MoCI5, TiC14, NiCI2, CoCI 2 FeCl 3 WC1 6 YC13 and ZrCl 4 The raw material from which the group 6A element can be obtained is exemplified by the group 6A element, the hydroxide of the group 6A element and the halide of the group 6A element.
By mixing hydrogen gas in the foregoing gas phase reaction, a compound of the transition metal and the 10 group 6A element containing hydrogen can be prepared.
S: In the foregoing gas phase reaction, it is preferable to employ any one of the following methods: a heat CVD (Chemical Vapor Deposition) method, a plasma CVD method, a laser CVD method, a filament method, a S15 reactive sputtering method and the electron beam method.
Sputtering is performed by heat in the heat CVD method, by charge in the plasma CVD method, by heat 555 energy or light energy of laser beams in the laser CVD method, by heat of a filament made of tungsten or the like in the filament method, and in the reactive sputtering method in the reactive gas atmosphere, and by electron beam heating in the electron beam method. As a result, gas phase reactions are respectively performed so that the material is prepared. It is preferable that the raw material be in the form of solid in the reactive sputtering method or the electron beam method.
114 1 Rapid Cooling Method In this case, any one of the following methods may be employed: a gun method comprising the steps of generating, while breaking a Mylar film, shock waves by helium gas, in which oxygen or hydrogen sulfide is mixed, as to be sprayed to the transition metal or the transition metal compound melted with high frequency waves, and causing blown compound powder to impact C 0 against a cooling steel plate in the form of a slide 10 disposed below so that the temperature is rapidly to too cooled; a method in which a molten bath is dispersed by spraying with inactive gas jet in which oxygen or hydrogen sulfide is mixed; and an atomization method in which molten bath of the transition metal or the 015 transition metal compound is sprayed in an atmosphere 0040 to. containing the group 6A element such as oxygen or group 6A element compound such as hydrogen sulfide as to be formed into powder. By mixing hydrogen gas into the inactive gas, hydrogen can be introduced into the product.
It is preferable that the rapid cooling rate be 1 8 2 to 10 K, more preferable 10 to 108 K.
The melting and heating furnace may be a crucible furnace, an induction furnace, an arc furnace or an electron beam furnace.
The method of causing the alkali to directly react with the transition metal is exemplified by a 115 1 method in which metal such as vanadium is caused to react with molten alkali to prepare an oxide.
Conductor Core When conductor powder is mixed at the time of preparing the compound of the transition metal and the group 6A element to cause the compound of the transition metal and the group 6A element to grow while using the conductor powder as the core, the collecting efficiency can be raised. Therefore, the introduction and .1 0 discharge of lithium ions can be made easier, and therefore the battery capacity can be enlarged.
The conductor powder may be made of one or more types of materials selected from a group consisting of carbon, titanium, nickel, cobalt, iron, chrome, 15 manganese, vanadium, platinum, paradium, copper, silver, gold, zinc, tin, indium, lead, tungsten and molybdenum.
.It is preferable to use one or more types of elements selected from a group consisting of carbon, titanium, nickel, cobalt, iron, chrome, manganese, vanadium and platinum.
The shape of the conductor powder is formed into one or more types of shapes selected from a group consisting of a spherical shape, a flake shape, a needle shape and a fiber shape. As a result, also the compound powder of the transition metal and the group 6A element can be formed into the spherical, flake, needle or fiber shape. Therefore, the efficiency of the electron 116movement between the positive electrode active material can be raised, and therefore the charging and discharging efficiency can be improved.
It is preferable that the diameter of the conductor powder be 10 A to 100 g when measured by an electron microscope, more preferably 10 A to 10 g.
Crushing of Positive Electrode Active Material The prepared positive electrode active material must be crushed as to have an adequate grain size if obtained positive electrode active material is in the form of a block.
It is preferable to crush the positive electrode active material by using, while combining, means selected from a group consisting of a compression crushing machine, a shearing crushing machine, an impact crushing machine, a roll mill, a roller mill, a high-speed rotational mill, a ball mill, a medium stirring mill, a jet mill, a mortar and a stamping mill.
Coating Film Made of Conductor The prepared compound of the transition metal and the group 6A element is covered with a conductor thin film by chemical plating (non-electrolytic plating) or by evaporation. As a result of the foregoing process, the current collecting efficiency can be raised, the introduction/discharge of lithium ion can be facilitated and the battery capacity can be enlarged.
The conductor thin film may be made of one or *f 4 4 4* [N:\LIBE]01316:MXL -117more types of materials selected from a group consisting of carbon, titanium, nickel, cobalt, iron, chrome, manganese, vanadium, platinum, paradium, copper, silver, 7old-, zinc, tin, indium, lead, tungsten and molybdenum. It is preferable to use one or more types of elements selected from a group consisting of carbon, titanium, nickel, cobalt, iron, chrome, manganese, vanadium and platinum.
The chemical plating method is a method in which metal ions are deoxidized by a deoxidizer such as formaldehyde to precipitate the metal film.
The evaporation is performed by any one of the following methods: a method in which vapor of metal is generated by electron beams or laser beams as to be applied to the subject; a method in which a carbon or metal target is sputtered as to be applied to the subject; a method in which hydrocarbon or organic solvent or an organic metal compound is decomposed by discharge or laser or heat as to be applied to the subject. The decomposition of the hydrocarbon and the organic solvent enables a carbon film to be formed, while the decomposition of the organic metal compound enables a metal film to be formed.
It is preferable that the thickness of the conductor film ranges from 50 A to 1 x.
Lipophilic Treatment 25 The positive electrode active material is [N:\LIBE]01316:MXL 118 1 subjected to the lipophilic treatment in such a manner that the organic metal compound is immersed in a solution, in which an organic solvent is dissolved, and then it is dried.
It is preferable that the organic metal compound for use in the lipophilic treatment be an organic metal compound such as silane coupling material or organic titanate. If dilution is performed, the dilution concentration with respect to the solvent ranges from 10 0.05 to 2 wt%.
The silane coupling material is exemplified by vinyltrimethoxysilane, vinylethoxysilane, N (2 aminoethyl) 3 aminopropylmethyl dimethoxysilane, N (2 aminoethyl) 3 aminopropyltrimethoxysilane, 15 3 aminopropyltriethoxysilane, 3 glycidexypropyltrimethoxysilane, 3 glycidexypropylmethyldimethoxysilane, 2 (3,4 epoxycychlohexyl) ethyltrimethoxysilane, 3 chloropropylmethyldimethoxysilane, 3 chloropropyltrimethoxysilane, 3 methacryloxytrimethoxysilane, 3 mercaptotrimethoxysilane, and N [2 (vinylpenzilamino)ethyl] 3 aminopropyltrimethoxysilane.
The organic titanate is exemplified by tetra i propoxytitanium, tetra n butoxytitanium, tetrakis (2 ethylhexyloxy)titanium, tetrastearyloxytitanium, -119di i proxy.bis (acetylacetate)titanium, dihydroxy.bis (lactato)titanium, titanium i propoxyoctylene glycol, titanium stearate, propane dioxytitanbis (ethylacetoacetate), propanedioxytitanium (acetylacetonate) (ethylacetoacetate), oxotitanbis (monoammonaium oxalate), tri n butoxytitanmonostearate, and titan polymer.
Analysis of Transition Metal and Group 6A Element Measurement of Size of Crystal Grain The size of crystal grains was evaluated from the peak half width and the angle of diffraction of x-ray diffraction curve in accedence with the following Scherrer's Formula: t 0.9X/BcosOB (Scherrer's Formula) where t: size of crystal grain X: wave length of x-ray beam B: peak half width OB: angle of diffraction It is preferable that the average size of the crystal grain of the positive electrode active material which is the compound of the transition metal and the group 6A element for use in the secondary battery according to the present invention by 500 A or less when calculated by using the foregoing Scherrer's Formula, more preferably 200 A or less.
Observation of Crystal Structure The crystal structure of the positive electrode o** o*
*S
[N:\LIBE]01316:VXF 120active material and the group 6A element prepared by the method according to an aspect of the present invention can be observed in such a manner that the waveform of the radial distribution function can be observed by x-ray diffraction, the diffraction pattern can be observed by reflecting high speed electron beam diffraction (RHEED) and the waveform of the x-ray diffraction curve can be observed.
The radial distribution function can be obtained by Fourier transforming the dispersion intensity of measured xray or neutron beam. The radial distribution function is expressed by the presence possibility of atoms with respect to an arbitrary atom or a function of the deviation distance from an average numerical density. If the specimen is made of amorphous material, a moderate peak curve can be obtained. If the specimen is crystal material, a discontinuous sharp peak can be obtained.
The RHEED enables a halo pattern to be observed if the specimen is made of amorphous material, enables a ring pattern to be observed if the specimen is made of microcrystal material and enables a spot pattern to be observed if the specimen is made of a multi-crystal material.
The dispersion angle and the dispersion intensity obtainable in the x-ray small angle dispersion method also 25 enables of fluctuation of ununiform density 0*
S
S
S
S S [N:\LIBE]01316:MXL 121 peculiar to the amorphous material.
Further, the differential thermal analysis enables heat absorption or heat generation due to the _tructural relaxation or the crystallization structural change occurring to the temperature rise to be observed if the specimen is amorphous material. If a hydroxide group is present, heat absorption due to dehydration can be observed.
By using the foregoing means, the structure of the compound of the transition metal and the group 6A element prepared by the manufacturing method according to an aspect of the present invention can be analyzed so that the amorphous structure, the microcrystal structure and the multi-crystal structure are confirmed.
Analysis of Hydrogen The compound of the transition metal containing hydrogen and the group 6A element is subjected to qualitatively analyzed by SIMS (Secondary Ion Mass Spectrometry) analysis.
Manufacturing of Positive Electrode The positive electrode is manufactured in such a manner that the bonding material, and conductive powder if necessary, is mixed with the powder of the compound of the transition metal and the group 6A element manufactured by the foregoing method, and then formed into the positive 25 electrode together with the collector. It is preferable that the forgoing forming process be 9* oo .9 9o 9 9 9 *oo oo oo [N:\LIBE01316:MXL -122performed in dry air from which water has sufficiently be removed, more particularly under inactive gas atmosphere.
The conductive powder acts to enhance thE electron conduction and facilitate the current collection because the active material, which is the compound of the transition metal and the group 6A element, does not substantially have the electron conductivity.
The conductive powder may be carbon material, such as acetylene black, ketchen black or graphite powder, or metal, such as nickel, titanium, copper or stainless steel. It is preferable that the mixture ratio of the conductive powder with respect to the positive electrode active material be 1 or less.
The bonding material bonds the positive electrode active material powder to one another and prevents generation of cracks in the charge and discharge cycle to prevent the separation from the collector. The bonding material may be one or more types of resin which are stable against the organic solvent and which are selected from a group consisting of fluororesin, polyethylene, polypropylene and silicon resin. It is preferable that the foregoing resin be in the form of liquid or solution or having a low melting point. Further, it is preferable that the solvent be removed and the resin is crosslinked during the process of
C
C Co oe C eeoo
C
C
CC
C.
C c [N:\LIBE]O1316:MXL -123manufacturing the positive electrode. As a result, the content of the bonding material in the positive electrode can be lowered and the capacity of the batterycan be improved. The liquid resin or the resin which can be dissolved in the solvent is exemplified by fluororesin having an ether bond and silicon resin. If the fluororesin having the ether bond is used, the concentration can be lowered when it is dissolved in a solvent. Therefore, the content in the positive electrode can be lowered as much as possible and the void ratio can be raised. Further, the state is very stable after crosslinking has been performed so that a satisfactory effect can be obtained upon the charge and discharge cycle.
It is also preferable that dehydration is performed with heat generated by microwaves and a vacuum drier is used to dehydrate the positive electrode after the positive electrode has been formed.
It is preferable that the mixture ratio of the bonding material with respect to the positive active material be 0.1 or less.
Examples Examples of the. present invention will now be described. It should be noted that the present invention is 25 not limited to the examples below.
Example 1-1 A flat type battery having a simple structure,
S
go oo oo [N:\LIBE]01316:MXL 124exhibiting assembling easiness and having a cross sectional structure schematically shown in Fig. 2 was assembled to evaluate the characteristics of the secohdary Battery while mainly evaluating the life against cycle operation.
First, a solution in which colloidal silica manufactured by Shokubai Kasei and subjected to hydrophobic treatment in an atmosphere of dry argon gas was dispersed in N, N dimethylformamide was dehydrated by active alumina.
Then, lithium metal foil to which titanium mesh collector 200 was pressed against the reverses side was immersed in the colloidal silica solution prepared by the foregoing method, and then dried at 120 0 C so that a lithium negative electrode 201 covered with silica was manufactured.
A positive electrode active material 203 was manufactured in such a manner that a mixture of dehydrated and electrolyzed manganese dioxide and lithium carbonate was heated so that a lithium-manganese composite oxide was prepared. Then, tetrafluoroethylene polymer powder was mixed, and then pressed against the titanium mesh as to be formed into a designed shape.
The electrolyte solution was obtained by dissolving, by 1 M (mol/l), lithium arsenate hexafluoride salt in an equally mixed solvent of propylene carbonate (PC) and dimethoxyethane (DME).
A separator 208 was formed in such a manner that
S
S
S. S S
S
[N:\LIBE]01316:MXL -125a separator made of polypropylene and having small apertures was sandwiched by unwoven polypropylene sheets.
The assembling process was performed in-Uch a manner that the separator 208 was place between the negative electrode 201 and the positive electrode 203 followed by inserting them into a positive electrode case 207 made of titanium clad stainless steel. Then, an electrolyte solution was injected followed by sealing the positive electrode case 207 with a negative cap 206 made of titanium clad stainless steel and an insulating packing 210 made of fluororubber so that a secondary battery was manufactured.
Comparative Example 1-1 A lithium secondary battery was manufactured by a method similar to Example 1-1 except for excluding the surface covering treatment using the metal lithium foil performed in Example 1-1.
Example 1-2 A battery similar to that according to Example 1-1 was manufactured.
The preparation of the materials and assembly were performed in an atmosphere of dry argon similarly to Example 1-1.
First, aluminum trichloride and phosphoric acid were allowed to reach with each other in ethyl alcohol, and S 25 gradually heated to 100 0 C so that glass form a go *o o a.
a a a a a a* a a a oeoo o o o ft [N:\LIBE]O1316:MXL 126 1 -aluminum phosphate was obtained. Then, it was dispersed in n-hexane so that a film forming solution was prepared. The film forming solution was applied to a lithium metal foil to which the titanium mesh collector was pressed. Then, a film was formed at 1200C. Then, similar processes to those according to Example 1-1 were performed so that a lithium battery was manufactured.
Example 1-3 A battery similar to that according to Example 0 1-1 was manufactured.
The preparation of the materials and assembly were performed in an atmosphere of dry argon similarly to Example 1-1.
First, acetic acid and water were added to an 15 ethyl alcohol solution of tetrabutoxytitanium to be S' hydrolyzed. Then, diethylamine was added so that colloidal titanium oxide was formed. Then, colloidal titanium oxide was dissolved in a xylene solution of polyethylene so that a film forming solution was prepared. The film forming solution was applied to the lithium metal foil to which the stainless mesh collector was pressed followed by drying it at 1000C.
Then, electron beams were applied to crosslink the polyethylene so that a film was formed. Then, similar processes to those according to Example 1-1 were performed so that a lithium battery was manufactured.
127 1 Example 1-4 A battery similar to that according to Example 1-1 was manufactured.
The preparation of the materials and assembly were performed in an atmosphere of dry argon similarly to Example 1-1.
A toluene solution of triethylaluminum was mixed with an isopropyl alcohol solution of tetrabutoxytitanium, followed by adding acetic acid 0 and water as to be hydrolyzed. Then, diethylamine was added so that colloidal titanium oxide-alumina was formed. Then, the colloidal titanium oxide-alumina was dispersed in a toluene solution which acrylic resin and epoxy resin were dissolved so that the film forming solution was prepared. The film forming solution was applied to a lithium metal foil to which the stainless mesh collector was pressed, and then a film was formed *o e at 80 0 C. Then, similar processes to those according to Example 1-1 were performed so that a lithium battery was manufactured.
Example A battery similar to that according to Example 1-1 was manufactured.
The preparation of the materials and assembly were performed in an atmosphere of dry argon similarly to Example 1-1.
First, acetic acid and water were added to an -128ethyl alcohol solution of tetraethoxysilane as to be hydrolyzed. Then, diethyl amine was added so that colloidal silica oxide was formed. Then, the colloidaliTrica was dispersed in an acetonitryl solution of polyethylene glycol, followed by adding azobisisobutylonitryl and arsenic hexafluoride lithium salt so that a film forming solution was prepared. The film forming solution was applied to the lithium metal foil to which the stainless mesh collector was pressed, followed by drying it at 100 0 C as to crosslink polyethylene glycol so that a film was formed. Then, similar processes to those according to Example 1-1 were performed so that a lithium battery was manufactured.
Example 1-6 A battery similar to that according to Example 1-1 was manufactured.
Firstt felt-shape carbon was immersed in silica coating solution NT-G326, which was manufactured by Nissan Kagaku and to which boron tetrafluoride lithium salt was added, and taken out from it. Then it was hardened at 1100C for 20 minutes and 3000C for 30 minutes so that silica coating was performed. The obtained felt-shape carbon covered with the silica was used as the cathode and the lithium metal was used as the anode in an electrolyte solution in which arsenic hexafluoride lithium salt was, by 25 1 M (mol/l), dissolved in an equal-quantity mixture solvent of propylene
S
ft f* ft** *t [N:\LIBE]01316:MXL -129carbonate and dimethoxyethane dehydrated sufficiently. As a result, lithium was introduced and allowed to adhere to the felt-shape carbon covered with silica so-that he negative electrode 201 was manufactured.
Then, similar processes to those according to Example 1-1 were performed so that a battery was manufactured.
Example 1-7 A battery similar to that according to Example 1-1 was manufactured.
First, paste obtained by mixing zinc oxide powder, metal zinc powder and water glass was injected into foamed nickel (Celmet) manufactured by Sumitomo Denko. Then, the material was hardened at 80 0 C for 20 minutes and 200 0 C for minutes so that the negative electrode 201 was formed.
Then, paste obtained by mixing, with nickel hydroxide, nickel powder, cobalt powder, carboxylic methyl cellulose serving as the bonding material, ethylene glycol and water was injected into the Celmet manufactured by Sumitomo Denko.
Then, it was dried and pressed so that the positive electrode 203 was formed.
The separator was formed in such a manner that polypropylene film subjected to hydrophilic treatment and having small apertures was sandwiched by unwoven polyamide sheets. The electrolyte solution was a 30 wt% potassium hydroxide solution. The assembly was ee r• o
S
r
S
[N:\LIBE]01316:MXL -130performed similarly to Example 1-1 so that a nickel-zinc secondary battery was manufactured.
Comparative Example 1-2 A nickel-zinc secondary battery was manufactured by a method similar to Example 1-7 except that the negative electrode was manufactured by mixing polyethylene serving as the bonding material and ethylene glycol in place of the water glass.
Example 1-8 A battery having a structure similar to that according to Example 1-1 was manufactured. However, a positive electrode case having small apertures for receiving oxygen in air was employed.
The negative electrode 201 was formed similarly to that according to Example 1-7.
The positive electrode 203 was formed in such a manner that the positive catalyzer layer was formed by adding manganese dioxide to active carbon, and a water repellant film made of polytetrafluoroethylene and cellulose-type diffusion paper were stacked on the positive catalyzer layer.
The separator 208 comprises a cellophane film, while the electrolyte solution comprises a 30 wt% potassium hydroxide solution.
25 The battery was assembled in such a manner that the separator 208 was held between the negative electrode 201 and the positive electrode 203, followed by inserting them 0 o a 0* 3S 0 0 [N:\LIBE]01316:MXL 131 into the positive electrode case 207 having small apertures for receiving oxygen in air and made of titanium clad stainless steel. Then, the electrolyte soluti-wn--was injected, and sealing was performed by the negative cap 206 made of the titanium clad stainless steel and the insulating packing 210 made of fluorine rubber so that the air-zinc secondary battery was manufactured.
Comparative Example 1-3 An air-zinc secondary battery was manufactured by a method similar to that according to Example 1-8 except that the negative electrode according to Comparative Example 1-2 was used.
Evaluation of Performance of Secondary Battery The performance of lithium secondary batteries according to Examples 1-1 to 1-6 and Comparative Example 1- 1, the nickel-zinc secondary battery according to Example 1- 7 and Comparative Example 1-2, and the air-zinc secondary battery according to Example 1-8 and Comparative Example 1-3 was evaluated. The evaluation was performed by a charge and discharge cycle test under the following conditions with respect to the cycle life of the batteries according to Comparative Examples 1-1, 1-2 and 1-3. The conditions for the cycle test were made as follows: the charge and discharge was performed by 0.2C (electric current which was 25 0.2 times capacity/time), pause for 30 minutes and a cut-off voltage of 1.0V was applied. A charging/discharging
C
0 0, 0 og e oo [N:\LIBE]01316:MXL 132apparatus HJ-101M6 manufactured by Hokuto Electric was used.
The charge/discharge test was commenced at discharge, the battery capacity was evaluate the quantity of-_the third.
discharge and the cycle life was evaluate by the number of cycles when the battery capacity had deteriorated to 60% or less.
The cycle life of each battery with respect to the cycle life of the battery according to Comparative Example 1-1 which was made to be 1 was as shown in Table 1.
As can be understood from the results of comparisons made between Examples 1-1 to 1-6 and Comparative Example 1- 1, between Example 1-7 and Comparative Example 1-2 and between Example 1-8 and Comparative Example 1-3, the cycle life can considerably be lengthened due to use of the foil made of the negative electrode active material according to an aspect of the present invention and arranged in such a manner that the surface is covered with the film having an inorganic glass structure through which lithium ions can be passed.
*E
[N:\LIBE]O1316:MXL 133 Table 1
S
Cycle Life according to the present Secondary Battery Manufactured invention Cycle Life.
Example Comparative according to Example Comparative Example Example 1-1 Comparative Example 1-1 Example 1-2 Comparative Example 1-1 Example 1-3 Comparative Example 1-1 Example 1-4 Comparative Example 1-1 Example 1-5 Comparative Example 1-1 Example 1-6 Comparative Example 1-1 3.4 Example 1-7 Comparative Example 1-2 Example 1-8 Comparative Example 1-3 -134- Example 2-1 A flat battery which had a simple structure, which could be assembled simply and which had a cros- sectional shape schematically shown in Fig. 2 was assembled to evaluate the characteristics of the secondary battery while evaluating the cycle life.
First, a peroxide benzoyl was, in an atmosphere of dry argon gas, dissolved in a toluene solution of poly (2-vinyl napthalene) manufactured by Aldrich Chemical Company, Inc.
Then, a lithium metal foil to which the stainless mesh collector 200 was pressed from the reverse side was immersed in it. Then, heat treatment at 100 0 C was performed so that a lithium pole 201 covered with the poly (2-vinyl napthalene) was manufactured.
The positive electrode active material 203 comprised a lithium-manganese composite oxide prepared by heat treatment subjected to a mixture of dehydrated electrolytic manganese dioxide and lithium carbonate and a graphite mixture. Then, tetrafluoroethylene polymer powder was mixed and then pressed against a titanium mesh as to be formed.
The electrolyte solution was prepared by dissolving, by 1 M (mol/l), arsenate hexafluoride lithium salt in an equal-quantity mixture solvent of propylene carbonate (PC) and dimethoxyethane (DME).
25 The separator 208 was formed by sandwiching go go e• [N:\LIBE]01316:MXL 135 1 a separator made of propylene and having small apertures by unwoven polypropylene sheets.
Comparative Example 2-1 A lithium secondary battery was manufactured by a method similar to Example 2-1 except for that the metal lithium foil surface covering treatment according to Example 2-1 was omitted.
Example 2-2 A battery similar to that according to Example o 10 2-1 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 2-1.
First, 0.03 M azobisisobutylnitryl was added to 15 a 5M tetrahydrofuran solution of 9-vinyl antracene, following by performing polymerization at 45 0 C so that a polymer solution was obtained. Then, the polymer S solution was applied to lithium metal foil to which a titanium mesh collector was pressed followed by drying the polymer solution. Then, ultraviolet rays were applied so that a lithium pole covered with the polyvinyl antracene film was manufactured. Then, similar processes to those according to Example 2-1 were performed so that the lithium secondary battery was manufactured.
Example 2-3 A battery similar to that according to Example 136 1 2-1 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 2-1.
First, 9, 10-antracene dipropionic acid and ethylene glycol of the same mol and a small quantity of zinc acetate were injected into a reaction chamber followed by dehydrating and condensing them at 2000C in an argon gas flow. Then, azobisisobutlonitryl was added, and the lithium metal foil to which a stainless steel mesh collector was pressed was immersed followed by taking out it. Then, it was heated to 1000C so that a film was formed on the surface of lithium. Then, similar processes to those according to Example 2-1 were performed so that the lithium secondary battery was manufactured.
Example 2-4 A battery similar to that according to Example 2-1 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 2-1.
Tantalum pentachloride was dissolved in toluene at 80°C, and a toluene solution of 5, 12-bits (phenylethynyl) naphthalene was added followed by polymerizing them at 80 0 C. An obtained polymer was cleaned with methyl alcohol, dried and again dissolved
I
137 1 in toluene so that a film forming solution was prepared. Then, a lithium metal foil to which a stainless steel mesh collector was pressed was immersed, followed by raising it and drying the same.
Then, electron beams were applied to crosslink the material so that a film was formed on the surface of lithium. Then, similar processes to those according to Example 2-1 were performed so that the lithium secondary battery was manufactured.
S 10 Example 9 A lithium secondary battery similar to that according to Example 2-1 was manufactured except that peroxide benzoyl was dissolved in a toluene solution of poly 2 -vinyl naphthalene), and then arsenate hexafluoride lithium salt was added so that the film 9 forming solution was prepared.
S020 *0 138- Example 2-6 A battery similar to that according to Example 2-1 was manufactured. The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 2-1.
Felt-form carbon, which had been dehydrated and dried, was immersed in lithium dissolved in a stainless container, followed by cooling the same so that felt-form carbon was manufactured. Then, it was immersed in a toluene solution of poly (2-vinyl naphthalene) to which azobisisobutylonitryl was added, followed by raising the felt carbon. It was then dried at 80 0 C, irradiated with ultraviolet rays to be crosslinked so that the negative electrode 201 was manufactured. Then, similar processes to those according to Example 2-1 were performed so that the lithium secondary battery was manufactured.
Evaluation of Performance of Lithium Secondary Battery The performance of lithium secondary batteries according to Examples 2-1 to 2-5 and Comparative Example 2-1 was evaluated. The evaluation was performed by a charge and discharge cycle test under the following conditions with respect to the cycle life of the batteries according to Comparative Example 2-1. The conditions for the cycle test 25 were made as follows: the charge and discharge was performed by 0.2C (electric
S..
SS
S
r [N:\LIBE01316:MXL -139current which was 0.2 times capacity/time), pause for minutes and a cut-off voltage of 1.0V was applied. A charging/discharging apparatus HJ-101M6 manufaif~ured by Hokuto Electric was used. The charge/discharge test was commenced at discharge, the battery capacity was evaluate the quantity of the third discharge and the cycle life was evaluate by the number of cycles when the battery capacity had deteriorated to 60% or less.
The cycle life of each battery with respect to the cycle life of the battery according to Comparative Example 1-1 which was made to be 1 was as shown in Table 2.
As can be understood from the results of comparisons made between Examples 2-1 to 2-5 and Comparative Example 2- 1, the cycle life can considerably be lengthened due to use of the negative electrode comprising the lithium foil covered with the polymer of the derivative of the aromatic hydrocarbon compound according to an aspect of the present invention.
ft *S*
*S
e f [N:\LIBE]01316:MXL 140- Table 2 Manufactured Lithium Cycle Life of Example Battery Cycle Life of Comparative Example Comparative Example 2-1 Example 2-1 Example 2-2 Example 2-3 Example 2-4 Example 2-5 Example 2-6 3.7 Example 3-1 A flat battery which had a simple structure, which could be assembled simply and which had a cross sectional shape schematically shown in Fig. 2 was assembled to evaluate the characteristics of the secondary battery while evaluating the cycle life.
First, a titanium mesh collector 200 was pressed from the reverse side of the lithium metal foil in an atmosphere of dry argon gas. Then, the lithium metal foil was immersed in a dioxane solution of tetrabutoxytitanium, followed by drying it so that the lithium pole 201 having a film formed 15 as described above was manufactured.
The positive electrode active material 203 was prepared in such a manner that a mixture of a
C
CC
C.
C
C
CC
C
C
C
C. C C CC [N:\LIBE]01316:MXL -141 dehydrated and electrolyzed manganese deoxide and a lithium carbonate were heated so that a lithium-manganese composite oxide was prepared. Then, tetrafluoroethylene polymer powder was mixed, and then it was pressed against a titanium mesh as to be formed as designed.
The electrolyte solution was prepared in such a manner that arsenate hexafluoride lithium salt was, by 1 M (mol/l) was dissolved in an equal quantity mixture solvent of propylene carbonate (PC) and dimethoxyethane (DME).
The separator 208 was manufactured in such a manner that a propylene separator having small apertures was sandwiched by unwoven polypropylene sheets.
Comparative Example 3-1 A battery similar to that according to Example 3-1 was manufactured except that the metal lithium foil surface treatment was omitted.
Example 3-2 A battery similar to that according to Example 3-1 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 3-1. A solution in which peroxide benzoyl was added to a hexane solution of Tirano Coat (polytitanocarbosilane) manufactured a *a a a.
a..
a a a a.o. a U a a p a.
o [N:LIBE]01316:MXL 142 1 by Ube Kosan was applied to a lithium metal foil to which a titan mesh collector was pressed, followed by drying it. Then, it was heated to 800C, and then heated to 1500C so that a lithium pole having a Tirano Coat film formed thereon was manufactured.
Then, similar processes to those according to Example 3-1 were performed so that the lithium secondary battery was manufactured.
Example 3-3 10 A battery similar to that according to Example 3-1 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of S* dry argon similarly to Example 3-1.
First, 2, 4, 6 -trimethyl-tris 3, 3trifluoropropyl)cyclotrisiloxane was heated to 76 0
C
in an argon gas. Then, calcium silate catalyzer was added and polymerization was performed so that a polymer was obtained. Then, peroxide benzoyl was added to the polymer, and then a lithium metal foil to which the stainless steel mesh collector was pressed was immersed in the solution, and rayed from the solution.
Then, heat treatment at 100°C was performed so that a lithium pole having a polysiloxane film formed thereon was manufactured.
Then, similar processes to those according to Example 3-1 were performed so that the lithium 143 1 secondary battery was manufactured.
Example 3-4 A battery similar to that according to Example 3-1 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 3-1.
First, azobisiosbutylonitryl was added to tetramethyldivinyldisiloxane, and then a lithium metal 1 0 foil to which a stainless steel mesh collector was pressed was immersed, followed by raising it. Then, ultraviolet rays were applied so that a lithium pole covered with the polysiloxane film was manufactured.
Then, similar processes to those according 15 to Example 3-1 were performed so that the lithium secondary battery was manufactured.
Example A battery similar to that according to Example 3-1 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 3-1.
A lithium secondary battery was manufactured similarly to Example 3-2 except that lithium was immersed in a solution in which arsenate hexafluoride lithium salt was added to a solution in which peroxide benzoyl was added to a hexane solution of Tirano Coat -144- (polytitanocarbosilane) manufactured by Ube Kosan.
Evaluation of Performance of Lithium Secondary Battery The performance of lithium secondary batteries according to Examples 3-1 to 3-5 and Comparative Example 3-1 was evaluated. The evaluation was performed by a charge and discharge cycle test under the following conditions with respect to the cycle life of the batteries according to Comparative Example 2-1. The conditions for the cycle test were made as follows: the charge and discharge was performed by 0.2C (electric current which was 0.2 times capacity/time), pause for 30 minutes and a cut-off voltage of 1.0V was applied. A charging/discharging apparatus HJ- 101M6 manufactured by Hokuto Electric was used. The charge/discharge test was commenced at discharge, the battery capacity was evaluate the quantity of the third discharge and the cycle life was evaluate by the number of cycles when the battery capacity had deteriorated to or less.
The cycle life of each battery with respect to the cycle life of the battery according to Comparative Example 1-1 which was made to be 1 was as shown in Table 3.
As can be understood from the results of comparisons made between Examples 3-1 to 3-5 and Comparative Example 3- 25 1, the cycle life can considerably be lengthened due to use of the negative electrode comprising S. S of o *e ft ftf f [N:\LIBE]01316:MXL 145the lithium foil covered with the organic metal compound according to an aspect of the present invention.
Table 3 Manufactured Lithium Cycle Life of Example Cycle Battery Life of Comparative Example Comparative Example 3-1 Example 3-1 Example 3-2 Example 3-3 Example 3-4 Example 3-5 Example 4-1 A flat battery which had a simple structure, which could be assembled simply and which had a cross sectional shape schematically shown in Fig. 2 was assembled to evaluate the characteristics of the secondary battery while evaluating the cycle life.
a tanium mesh collector 200 was pressed against lithium metal foil from the reverse sidein an atmosphere 15 of dry argon. Then, the lithium metal foil was immersed in "a teflon AF solution which was a copolymer of o•:...:tetrafluoroethylene and 2, 2- bistrifluoromethyl 4, ":".difluoro-l, 3 dioxysol and which was manufactured by Dupont, followed by bring the lithium metal foil. As a 20 result, the lithium [N:\LIBE]01316:MXL 146negative electrode 201 covered with amorphous fluororesin was manufactured. The positive electrode active material 203 comprised a lithium-manganese composite oxide prepared by heating a mixture of dehydrated and electrolyzed manganese dioxide and lithium carbonate and a mixture of graphite. Then, tetrafluoroethylene polymer powder was mixed, and pressed against the titanium mesh as to be formed as designed. The electrolyte solution was prepared by dissolving, by 1 M (mol/l), arsenate hexafluoride lithium salt in an equal quantity mixture solvent of propylene carbonate (PC) and dimethoxyethane (DME). The separator 208 was manufactured in such a manner that a propylene separator having small apertures was sandwiched by unwoven polypropylene sheets. The battery was assembled in such a manner that the separator 208 was held between the negative electrode 201 and the positive electrode 203, followed by inserting them into a positive electrode case 207 made of titanium clad stainless steel, followed by injecting the electrolyte solution. Then, the negative electrode cap 206 made of the titanium clad stainless steel and the insulating packing 210 made of fluorine rubber were used for sealing so that the lithium secondary battery was manufactured.
Comparative Example 4-1 A lithium secondary battery was manufactured under the 25 same conditions as those according to Example a a [N:\LIBE]01316:MXL 147 1 4-1 except that the metal lithium foil surface covering was omitted.
Example 4-2 A battery similar to that according to Example 4-1 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 4-1. The lithium metal foil to which a titanium mesh collector was pressed 1 0 was inserted into a chamber of a sputtering apparatus, ,woe and then retained gas was exhausted to a vacuum level of 5 x 10- 6 Torr. Then, argon gas was allowed to flow to control the internal pressure to 3 x 10- 3 Torr, followed by performing RF discharge to generate 15 plasma for use in sputtering using Neoflon PFA which was a copolymer of tetrafluoroethylene and perfluoroalkylvinyl ether and manufactured by Daikin as a target.
I As a result, a lithium pole having a film formed thereon was manufactured. Then, similar processes to those according to Example 4-1 were performed so that the lithium secondary battery was manufactured.
Example 4-3 A battery similar to that according to Example 2-1 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 4-1. The lithium metal 148 1 foil to which a stainless steel mesh collector was pressed was inserted into a chamber of an RF (Radio Frequency) plasma CVD apparatus, and then the retained gas was exhausted to realize a vacuum level of 2 x 10 6 Torr. Then, vinylidene fluoride was introduced into the chamber, and isobutyl vinyl ether was introduced into the chamber while using hydrogen gas as the carrier gas. While controlling the internal S* pressure to 1 Torr, RF discharge was caused to take 10 placeso that a plasma polymer film was formed on the surface of lithium. Then, similar processes to those according to Example 4-1 were performed so that the lithium secondary battery was manufactured.
Example 4-4 15 A battery similar to that according to Example 4-1 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 4-1. A lithium secondary battery was manufactured similarly to Example 4-1 except that the titanium mesh collector was pressed from the reverse side, and then it was immersed in a xylene solution of Lumiflon which was a copolymer of tetrafluoroethylene and non-fluorine-type vinyl ether, which was manufactured by Asahi Glass and to which isocyanate and graphite powder were added. Then, it was dried at 140 0 C for 10 minutes so that the lithium -149pole covered with the amorphous fluororesin was manufactured.
Example A battery similar to that according to Example 4-1 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 4-1. First, coating fluororesin was prepared. An autoclave having a stirring machine received 200 parts of pure water, 40 parts of vinyl fluoride, parts of ethylvinyl ether, 0.6 parts of perofluorocarboxylic acid, 0.2 parts of persulfuric ammonium and 3 parts of water. Then, the solution was heated to 46 0 C while maintaining the pressure at 42.5 atmosphere to perform polymerization for 8 hours. An obtained polymer was cleaned with hot methanol, followed by drying it. Then, it was dissolved in tetrahydrofuran dehydrated sufficiently, followed by adding peroxide benzoyl. Then, the lithium metal foil to which a stainless steel mesh collector was pressed was immersed followed by raising it. Then, it was heated to 100 0 C so that a lithium pole covered with fluororesin was manufactured.
Then, similar processes to those according to Example *4-1 were performed so that the lithium secondary battery was 25 manufactured.
o p o p [N:\LIBE101316:MXL 150 1 Example 4-6 A battery similar to that according to Example 2-1 was manufactured.
First, a lithium pole was manufactured. The lithium metal foil to which a stainless steel mesh collector was pressed was injected into a vacuum chamber of a parallel and flat type plasma CVD apparatus to which a 13.56 MHz high frequency power source was connected in such a manner that it was placed perpen- 1 0 dicular to the parallel and flat electrode. Then, retained gas was exhausted to realize a vacuum level of 1 0 5 Torr. Then, 10 seem of tetrafluoroethylene, 2 sccm of ethylene, 2 seem of hydrogen, 1 seem of helium and 1 seem of oxygen were introduced into the 15 vacuum chamber, which was a reaction chamber, and then the internal pressure was maintained at 0.8 Torr.
Then, 200 watts of high frequency power was supplied to the parallel and flat electrode so that a plasma polymer film of the fluororesin was formed on the surface of lithium. By using the lithium pole covered with the fluororesin prepared by the foregoing method so that a lithium secondary battery was manufactured by the similar processes to those according to Example 4-1.
Evaluation of Performance of Lithium Secondary Battery The performance of lithium secondary batteries according to Examples 4-1 to 4-6 and Comparative Example -151 4-1 was evaluated. The evaluation was performed by a charge and discharge cycle test under the following conditions with respect to the cycle life of the batteries according to Comparative Example 4-1. The conditions for the cycle test were made as follows: the charge and discharge was performed by 0.2C (electric current which was 0.2 times capacity/time), pause for 30 minutes and a cut-off voltage of 1.0V was applied. A charging/discharging apparatus HJ- 101M6 manufactured by Hokuto Electric was used. The charge/discharge test was commenced at discharge, the battery capacity was evaluate the quantity of the third discharge and the cycle life was evaluate by the number of cycles when the battery capacity had deteriorated to 60% or less.
The cycle life of each battery with respect to the cycle life of the battery according to Comparative Example 4-1 which was made to be 1 was as shown in Table 4.
As can be understood from the results of comparisons made between Examples 4-1 to 4-6 and Comparative Example 4- 1, the cycle life can considerably be lengthened due to use of the negative electrode comprising the lithium foil covered with the fluororesin having the ether bond according to an aspect of the present invention.
e
S
S.
S
[N:\LIBE]01316:MXL 152 Table 4 Manufactured Lithium Battery Comparative Example 4-1 Example 4-1 Example 4-2 Example 4-3 Example 4-4 Example 4-5 Example 4-6 Cycle Life Cycle Life of of Comparative Example Example 4-1 S.
S
S.r S
S
Example 5-1 A flat battery which had a simple structure, which could be assembled simply and which had a cross sectional shape schematically shown in Fig. 2 was assembled to evaluate the characteristics of the secondary battery while evaluating the cycle life.
In an atmosphere of dried argon gas, the titanium mesh collecting pole 200 was pressed to the reverse side of the lithium metal foil. Then, the lithium metal foil was immersed in a tetrahydrofuran solution of Cryptofix 222 B Polymer which was a large ring compound polymer and which was manufactured by E. Merch. Then, it was dried, and then heated to 150 0 C so that a lithium pole 201 covered with the large ring compound polymer was manufactured.
-153- The positive electrode active material comprised a lithium-manganese composite oxide prepared by heat treatment applied to a mixture of dehydrated and electrolyzed manganese dioxide and lithium carbonate and a mixture of graphite. Then, tetrafluoroethylene polymer was mixed, and then pressed against the stainless steel mesh as to be formed as designed.
The separator 208 was manufactured in such a manner that a propylene separator having small apertures was sandwiched by unwoven polypropylene sheets.
The electrolyte solution was prepared by dissolving, by 1 M (mol/l), arsenate hexafluoride lithium salt in an equal quantity mixture solvent of propylene carbonate (PC) and dimethoxyethane (DME).
Assembling of the battery were performed similarly to Example 1-1.
Comparative Example 5-1 A lithium secondary battery was manufactured similarly to Example 5-1 except that the metal lithium foil surface covering was omitted.
Example 5-2 A battery similar to that according to Example 5-1 was manufactured.
The preparation of materials and assembling of the 25 battery were performed in an atmosphere of dry argon similarly to Example 2-1. A lithium metal e* S o *o* IN:\LIBE]O1316:MXL 154 1 foil, to which a titanium mesh collector was pressed, was placed in acetonyl solution in which 0.1 M of a monomer of benzo-15-crown-5 and 0.2 M of boron tetrafluoride tetrabutylammonium salt as to be electrolyzed and polymerized with a voltage level of 3 V while using a platinum electrode as the cathode electrode. As a result, a lithium pole having a large ring compound polymer film formed thereon was manufactured.
10 Then, similar processes to those according to Example 5-1 were performed so that the lithium secondary battery was manufactured.
Example 5-3 A battery similar to that according to Example 15 5-1 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 5-1. First, 18 crown 6 tetracarboxylic acid (0.4 mol), 1, 4 butanediol (0.8 mol), tetratitanate n butylester (0.08 g) and butylhydroxytinoxide (0.03 g) were mixed.
Then, the temperature was maintained at 220°C, and distillation was performed for 60 minutes to remove products such as water. Then, the product and titanate tetra-n-butylester (0.02 g) were injected into an automatic crepe, and the pressure was lowered and heating to 2500C was performed for 22 hours so that 155 1 a polymer was obtained.
Trylenediisocyanate was added to the thusobtained polymer, and then the lithium metal foil, to which a titanium mesh collector was pressed, was immersed. Then, the lithium metal foil was raised, and then it was heated, and dried at 80 0 C so that the surface of the lithium foil was covered with a large ring compound polymer.
Then, similar processes to those according to Example 5-1 were performed so that the lithium secondary battery was manufactured.
Example 5-4 i.
A battery similar to that according to Example 2-1 was manufactured.
15 The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 5-1. A lithium metal foil, to which a titanium steel mesh collector was pressed, was immersed in a toluene solution of 3, 3'dibenzyl 1, 4, 8, 11 tetraoxacyclotetradecan to which azobisisobutylnitryl and arsenate hexafluoride lithium salt were added. Then, the lithium metal was raised from the solution, and then ultraviolet rays were applied to crosslinking so that the surface of the lithium metal foil was covered.
Then, similar processes to those according to Example 5-1 were performed so that the lithium 156 1 secondary battery was manufactured.
Example A battery similar to that according to Example 2-1 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 5-1. Styrene and 4, 7, 13, 16, 21, 24 hexaoxa 1, 10-diazobicyclo [8.8.8] hexakosan were dissolved in a tetrahydrofuran solution 10 of naphthalene degasified and dehydrated sufficiently.
Then, graphite powder was mixed. The lithium metal foil, to which a titanium mesh collector was pressed, *.99 was immersed to perform polymerization reaction, followed by drying as to be hardened. As a result, 15 the surface of lithium was covered with a large ring compound polymer.
Then, similar processes to those according to Example 5-1 were performed so that the lithium secondary battery was manufactured.
Example 5-6 A battery similar to that according to Example 5-1 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry air.
A porous nickel sheet manufactured by Osaka Gas was dehydrated and dried as to be used as an anode, -157while a platinum electrode was used as a cathode so that electrolytic polymerization was performed in an acetonitryl solution in which 0.1 M of banzo-18-crown-6 and 0.2 M or boron tetrafluoride tetrabutylammonia salt were dissolved.
As a result, a porous nickel sheet covered with a crown ether polymer was manufactured. Then, an electrolyte solution was prepared in such a manner that 1M of boron tetrafluoride lithium salt was dissolved in an equalquantity mixture solvent of propylene carbonate and dimethoxyethane. An obtained porous nickel sheet thus covered was used as a cathode and lithium metal was used as an anode. Then, lithium was inserted between the porous nickel sheet cover and the nickel as to be allowed to adhere so that the negative electrode 203 was formed.
Then, similar processes to those according to Example 5-1 were performed so that the lithium secondary battery was manufactured.
Example 5-7 A nickel-zinc battery having a similar structure as that of the battery according to Example 5-1 was manufactured.
First, paste was prepared by mixing polyvinyl alcohol, phthalocyanine zinc, zinc oxide powder, zinc powder, formaldehyde, formic acid and water. The paste was applied 25 to a nickel mesh and heated so that the negative electrode 201 was manufactured.
t..
e *9 9.* t tftftf
I
ft f ft« ft [N:\LIBE]01316:MXL 158- Then, paste obtained by mixing nickel powder, cobalt powder, carboxylic cellulose serving as a bonding material, ethylene glycol and water with nickel hydroxide was injected into foamed nickel (Celmet) manufactured by Sumitomo Denko.
Then, it was dried and pressed 80 that a positive electrode 203 was formed.
The separator 208 was formed in such a manner that a polyamide film subjected to hydrophilic treatment and having small apertures was sandwiched by unwoven polyamide sheets.
The electrolyte solution was a 30 wt% potassium hydroxide solution. The assembly was performed similarly to Example 5-1 so that a nickel-zinc secondary battery was manufactured.
Comparative Example 5-2 A nickel-zinc secondary battery was manufactured except that the negative electrode 201 was formed by applying paste obtained by mixing zinc oxide powder, zinc powder, polyvinyl alcohol and ethylene glycol to the nickel mesh followed by drying.
Example 5-8 A battery having a structure similar to that according to Example 5-1 was manufactured. However, a positive electrode case having small apertures for receiving oxygen I in air was used.
25 The negative electrode 201 was manufactured in such a manner that paste was applied to a nickel mesh followed by heating to dry the negative electrode 201, *0* 9, 9 [N:\LIBE101316:MXL -159the paste being obtained by mixing zinc oxide powder, zinc powder, polyacrylamide, water, formaldehyde, lithium hydroxide and phthalocyanine zinc.
The positive electrode 203 was formed in such a manner that a positive catalyzer layer was formed by adding manganese dioxide to active carbon, and a water repellent film made of polytetrafluoroethylene and cellulose dispersed paper were stacked on the positive catalyzer layer.
The separator 209 comprised a cellophane film and the electrolyte solution comprised 30 wt% solution of potassium hydroxide.
Assembling was performed in such a manner that the separator 208 was held between the negative electrode 201 and the positive electrode 203, and they were inserted into the positive electrode case 207 having small apertures for receiving oxygen in air and made of titanium clad stainless steel. Then, the electrolyte solution was injected and sealing was performed by using the negative electrode cap 206 made of titanium clad stainless steel and the insulating packing made of fluorine rubber. As a result, an air-zinc secondary battery was manufactured.
Comparative Example 5-3 An air-zinc secondary battery was manufactured similarly to Example 5-8 except that the negative electrode 25 according to Comparative Example 5-2 was used.
*0@Se 0 S0 [N:\LIBE]01316:MXL 160- 1 Evaluation of Performance of Lithium Secondary Battery The performance of lithium secondary batteries according to Examples 5-1 to 5-5 and Comparative Example 5-1 was evaluated. The evaluation was performed by a charge and discharge cycle test under the following conditions with respect to the cycle life of the batteries according to Comparative Example 1. The conditions for the cycle test were made as follows: the charge and discharge was performed by 0.2C (electric 10 current which was 0.2 times capacity/time), pause for 30 minutes and a cut-off voltage of 1.OV was applied.
A charging/discharging apparatus HJ-101M6 manufactured by Hokuto Electric was used. The charge/discharge test was commenced at discharge, the battery capacity 15 was evaluate the quantity of the third discharge and the cycle life was evaluate by the number of cycles when the battery capacity had deteriorated to or less.
The cycle life of each battery with respect to the cycle life of the battery according to Comparative Example 5-1 which was made to be 1 was as shown in Table 2.
As can be understood from the results of comparisons made between Examples 5-1 to 5-6 and Comparative Example 2-1 and those between Example 5-7 and Comparative Example 5-3, the cycle life can considerably be lengthened due to use of the negative -161 electrode comprising the lithium or zinc covered with the large ring compound polymer according to an aspect of the present invention.
Table Manufactured Lithium Battery Cycle Life of Example Cycle Life of Comparative Example Example Comparative Example Example 5-1 Comparative Example 5-1 Example 5-2 Comparative Example 5-1 Example 5-3 Comparative Example 5-1 Example 5-4 Comparative Example 5-1 Example 5-5 Comparative Example 5-1 Example 5-6 Comparative 4.2 Example 5-1 Example 5-7 Comparative 2.8 Example 5-2 Example 5-8 Comparative 2.7 Example 5-2
S
S
S SS S
S
S
S
S
SS
Example 6-1 A flat battery which had a simple structure, which 10 could be assembled simply and which had a cross sectional shape schematically shown in Fig. 2 was assembled to evaluate the characteristics of the secondary battery while evaluating the cycle life.
[N:\LIBE]01316:MXL -162- First, the titanium collector 200 was pressed against the reverse side of the lithium metal foil in an atmosphere of dry argon gas, and then the lithium metal foil was immersed in a toluene solution PPZ-U1001 manufactured by Idemitsu.
Then, it was previously dried, and ultraviolet rays were applied so that the lithium pole 201 covered with phosphazene was manufactured.
The positive electrode active material 204 was prepared in such a manner that a lithium-manganese composite oxide was prepared by heating a mixture of dehydrated and electrolyzed manganese dioxide and lithium carbonate. Then, tetrafluoroethylene polymer powder was mixed followed by pressing to a titanium mesh as to be formed as designed.
The electrolyte solution was prepared by dissolving, by 1 M (mol/l), arsenate hexafluoride lithium salt in an equal quantity mixture solvent of propylene carbonate (PC) and dimethoxyethane (DME). The separator 208 was manufactured in such a manner that a propylene separator having small apertures was sandwiched by unwoven polypropylene sheets.
Comparative Example 6-1 A lithium secondary battery was manufactured similarly to Example 6-1 except that the surface covering of the metal foil was omitted.
S* lithium foil was omitted.
a [N:\LIBE]01316:MXL 163 1 Comparative Example 6-2 A battery similar to that according to Example 6-1 was manufactured. The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 6-1.
First, hexachlorotriphosphazene was repeatedly degasified, melted and solidified, and then it was heated to 250 0 C as to be polymerized so that olydichlorophosphazene was obtained. Then, a 1 0 tetrahydrofuran solution of aniline was added to a benzene solution of polychlorophosphazene, followed by heating and refluxed. Then, the solution was allowed to stand to remove aniline hydrochloride by filtering followed by again sedimented it and drying it. Then, 15 it was again dissolved in tetrahydrofuran so that a solution of poly [bis (phenylamino)phosphazene] was prepared. Then, the foregoing solution was applied to the lithium metal foil, to which a titanium mesh collector was pressed, followed by drying the solution.
Then, ultraviolet rays were applied so that a lithium pole covered with polyphosphazene was manufactured.
Then, similar processes to those according to Example 6-1 were performed so that the lithium secondary battery was manufactured.
Example 6-3 A battery similar to that according to Example 5-1 was manufactured. The preparation of materials 164 1 and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 6-1.
First, a benzene solution of polydichlorophosphazene was, while being stirred, slowly dropped in a tetrahydrofuran solution of sodium alkoxide of trifluoroethanol, followed by heating and refluxing it. Then, it was neutralized, filtered, cleaned with water and ethyl alcohol, and again sedimented with acetone and water, followed by drying. As a result, 10 polybis (trifluoroethoxy) phosphazene was obtained.
The acetone solution of the polyfluorokoxyphosphazene was applied to the lithium metal foil, to which a °S stainless steel mesh collector was pressed. Then,
S
it was dried, and then irradiated with electron beams 15 so that a lithium pole covered with polyphosphazene was manufactured. Then, similar processes to those according to Example 6-1 were performed so that the lithium secondary battery was manufactured.
Example 6-4 A battery similar to that according to Example 5-1 was manufactured. The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 6-1.
First, sodium alkoxide of naphthalene ethanol was, in dioxane, prepared from naphthalene ethanol and sodium hydroxide. Then, tetra-n-butyl ammonia bromide was added to the sodium alkoxide, and then a dioxane 165 1 solution of polydichlorophosphazene was added while being dripped. The thus-obtained mixed was subjected to a heating reactions at 80 0 C, and the solvent was somewhat removed. Then, it was again sedimented with tetrahydrofuran and water, and then it was refined, followed by Soxhlet-extracting it. As a result, polydiphenoxyphosphazene was obtained. Then, azoisobutylnitryl was added to a tetrahydrofuran solution of the obtained polymer. Then, the lithium 10 metal foil, to which a stainless steel mesh collector was pressed, was immersed and raised from it followed by drying it and subjecting to a heat treatment set to 80 0 C. As a result, a lithium pole covered with polyphosphazene was manufactured. Then, similar 15 processes to those according to Example 6-1 were performed so that the lithium secondary battery was manufactured.
Example A battery similar to that according to Example 5-1 was manufactured. The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 6-1.
A lithium secondary battery was manufactured similarly to Example 6-1 except that arsenate hexafluoride lithium salt was added to a toluene solution of PPZ-Ul001 manufactured by Idemitsu, and then lithium was immersed in the thus-prepared solution.
166- Evaluation of Performance of Lithium Secondary Battery The performance of lithium secondary batteries according to Examples 6-1 to 6-5 and Comparative Example 6-1 was evaluated. The evaluation was performed by a charge and discharge cycle test under the following conditions with respect to the cycle life of the batteries according to Comparative Example 6-1. The conditions for the cycle test were made as follows: the charge and discharge was performed by 0.2C (electric current which was 0.2 times capacity/time), pause for 30 minutes and a cut-off voltage of 1.0V was applied. A charging/discharging apparatus HJ- 101M6 manufactured by Hokuto Electric was used. The charge/discharge test was commenced at discharge, the battery capacity was evaluate the quantity of the third discharge and the cycle life was evaluate by the number of cycles when the battery capacity had deteriorated to 60% or less. The cycle life of each battery with respect to the cycle life of the battery according to Comparative Example 6-1 which-was made to be 1 was as shown in Table 6. As can be understood from the results of comparisons made between Examples 6-1 to 6-5 and Comparative Example 6-1, the cycle life can considerably be lengthened due to use of the negative electrode comprising the lithium or zinc covered with the large ring compound polymer according to an aspect of the present invention.
*.9C 9 o *ooo [N:\LIBE]01316:MXL 167- Table 6 Manufactured Lithium Cycle Life of Example Cycle Battery Life of Comparative Example Comparative Example 6-1 Example 6-1 Example 6-2 Example 6-3 Example 6-4 Example 6-5 Example 7-1 A flat battery which had a simple structure, which could be assembled simply and which had a cross sectional shape schematically shown in Fig. 2 was assembled. The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon.
First, the titanium mesh collector 200 having a lead was pressed against the reverse side of the lithium metal foil in an atmosphere of dry argon. Then, it was immersed in a nitromethane solution of acetyl cellulose to which azobisisobutylotryl and boron tetrafluoride lithium salt.
S* 15 Then, it was dried, and irradiated with ultraviolet rays so that a film was formed. As a result, the lithium negative electrode 201 was manufactured.
a* o [N:\LIBE]01316:MXL -168- The positive electrode active material was prepared in such a manner that a lithium-manganese oxide was prepared by mixing electrolyzed manganese dioxide and lithium carbonate at a ratio of 1:0.4 and by heating the mixture at 800 0
C.
Then, ketchen black and Super Konak, which is a fluororesin paint manufactured by Nihon Yushi were mixed to the prepared lithium-manganese oxide. Then, it was pressed against a nickel mesh as to be formed as designed followed by performing heat treatment set to 170 0 C. As a result, the positive electrode 203 was manufactured.
The separator 208 was manufactured in such a manner that a porous layer-shape alumina film, an unwoven polypropylene sheet and polypropylene separator having small apertures were sandwiched.
The electrolyte solution was prepared by dissolving, by 1 M (mol/l), tetrafluoride borate lithium salt in an equal quantity mixture solvent of propylene carbonate (PC) and dimethoxyethane (DME).
The assembly was performed in such a manner that the negative electrode 201, the positive electrode 203 and the separator 208 were sandwiched as to be inserted into the positive electrode case 207 made of titanium clad stainless steel, and then the electrolyte solution was injected.
Then, sealing was performed by the negative cap 206 made of 25 the titanium clad stainless steel and the insulating packing 210 made of fluorine [N:\LIBE]01316:MXL 169rubber so that a lithium secondary battery was manufactured.
Example 7-2 A battery similar to that according to Example 7-1 and shown in Fig. 2 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 7-1.
A lithium secondary battery was manufactured by a method similar to that according to Example 7-1.
First, the titanium mesh collector 200 having a lead was pressed against the reverse side of the lithium metal foil in an atmosphere of dry argon gas. Then, it was immersed in a tetrahydrofuran solution of a polyethylene oxide to which peroxide benzoyl was added, and then it was dried at 110 0 C, and ultra- violet rays were applied so that a film was formed. As a result, the lithium negative electrode 201 was manufactured.
The positive electrode active material was prepared in such a manner that a lithium-manganese oxide was prepared by mixing electrolyzed manganese dioxide and lithium carbonate at a ratio of 1:0.4 and by heating the mixture at 800 0
C.
Then, ketchen black and tetrafluoroethylene polymer powder were mixed with the prepared lithium-manganese oxide. Then, it was pressed against a nickel mesh as to be formed *e
DU.
a o o** o *oo o [N:\LIBEO01316:MXL -170as designed followed by performing heat treatment set to 250 0 C. As a result, the positive electrode 203 was manufactured.
The separator 208 was manufactured by sandwiching a unwoven polypropylene sheet and a polypropylene separator having small apertures.
The electrolyte solution was prepared by dissolving, by 1 M (mol/l), tetrafloride borate lithium salt in a solvent of propylene carbonate (PC).
Then, similar processes to those according to Example 7-1 were performed so that the lithium secondary battery was manufactured.
Example 7-3 A battery similar to that according to Example 15 7-1 and shown in Fig. 2 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 7-1.
First, the lithium surface film was manufactured in such a manner that lithium foil to which the nickel mesh collector 200 was pressed was placed in a sputtering apparatus. Then, a degree of vacuum of 1.5 x 10- 4 pascal by lowering the pressure and by degasifying the inside of the S. sputtering apparatus. Then, argon gas was introduced by 25 sccm, and the internal pressure in the film forming chamber was maintained at 6 x 10 1 pascal to perform sputtering while using polyether o• [N:\LIBE]01316:MXL 171 sulfon as a target so that the lithium negative electrode 201 covered with chitosan having a thickness of 500 A was obtained.
Then, similar processes to those according to Example 7-2 were performed so that the lithium secondary battery was manufactured.
Example 7-4 Under the same conditions as those according to Example 7-3 except that lithium foil to which the nickel mesh collector 200 was pressed was placed in a sputtering apparatus. Then, a degree of vacuum of 1.5 x 10 4 pascal by lowering the pressure and by degasifying the inside of the sputtering apparatus. Then, argon gas was introduced by seem, and the internal pressure in the film forming chamber was maintained at 6 x 10- 1 pascal to perform sputtering while using chitosan as a target so that the lithium negative electrode 201 covered with chitosan having a thickness of 1000 A was obtained.
Then, similar processes to those according to Example 7-2 were performed so that the lithium secondary battery was manufactured.
o. Example S• A flat nickel-zinc secondary battery which had a
C
simple structure, which could be assembled simply and which 25 had a cross sectional shape schematically shown in Fig. 2 was manufactured.
V C.
ft
C
[N:\LIBE101316:MXL -172- The negative electrode was manufactured in such a manner that ethylene tetrafluoride polymer powder serving as a bonding material was added to a mixture of zinc powder and zinc oxide powder as to be pressed against the two sides of a copper punching metal plate so that the negative electrode was formed. The negative electrode was immersed in an acetone-ethylalcohol solution of acetyl cellulose to which azobisisobutylonitryl was added, and then it was dried and heated to 110 0 C. Then, ultraviolet rays were applied so that a film was formed. As a result, the zinc negative electrode 201 was manufactured.
The positive electrode 203 was manufactured in such a manner that nickel hydroxide was impregnated in a sintered nickel pole plate and it was covered with an acetylcellulose film similarly to the negative electrode.
The separator 208 was manufactured in such a manner that a hydrophilic unwoven nylon sheet and a nylon film having small apertures were sandwiched.
The electrolyte solution comprised 30 wt% potassium hydroxide water solution to which lithium hydroxide was added.
The battery was assembled similarly to Example 7-1.
Example 7-6 A flat nickel-zinc secondary battery which
C
CVo e
C
o ooo ooeoI oeoeo go e9 [N:\LIBE]01316:MXL 173had a simple structure, which could be assembled simply and which had a cross sectional shape schematically shown in Fig. 2 was manufactured.
Under the same conditions as those according to Example 7-5 except that the formed zinc negative electrode was placed in a sputtering apparatus, and the inside pressure was lowered to a degree of vacuum of 1.5 x 10 4 pascal by lowering and degasifying the inside. Then, argon gas was introduced by 5 sccm, and the internal pressure in the film forming chamber was maintained at 6 x 10-1 pascal.
Then, sputtering was performed while using collagen as a target so that a zinc negative electrode covered with collagen having a thickness of 1000 A was obtained.
The positive electrode 203 was manufactured by impregnating nickel hydroxide into a sintered nickel pole plate.
Then, similar processes to those according to Example 2-1 were performed so that the nickel- zinc secondary battery was manufactured.
In order to evaluate the performance of the batteries according to the foregoing Examples, batteries according to Comparative Examples were manufactured.
Comparative Example 7-1 .A lithium secondary battery was manufactured by a 25 method similar to Example 7-2 except that the surface of the S: metal lithium foil was not covered.
0: f 9 *0O [N:\LIBE]01316:MXL -174- Comparative Example 7-2 A nickel-zinc secondary battery was manufactured by a method similar to Example 7-6 except that the surface of the zinc negative electrode was not covered.
Evaluation of Performance of Lithium Secondary Battery The performance of lithium secondary batteries and nickel-zinc secondary batteries according to Examples and Comparative Examples was evaluated. The evaluation was performed by a charge and discharge cycle test under the following conditions with respect to the cycle life of the batteries according to Comparative Examples.
The conditions for the cycle test were made as follows: the charge and discharge was performed by 0.2C (electric current which was 0.2 times capacity/ time), pause for 30 minutes and a cut-off voltage of 1.0V was applied. A charging/discharging apparatus HJ-101M6 manufactured by Hokuto Electric was used. The charge/discharge test was commenced at discharge, the battery capacity was evaluate the quantity of the third discharge and the cycle life was evaluated by the number of cycles when the battery capacity had deteriorated to 60% or less.
The cycle life of batteries according to Examples of *o* S* the present invention with respect to the cycle life of the 00 batteries according to Comparative Examples which was made 25 to be 1.0 was as shown in Table 7.
00 00 S 0 4 00 [N:\LIBEO131 6:MXL -175- Table 7 Manufactured Lithium Battery Cycle Life of Example Cycle Life of Comparative Example Example Comparative Example Example 7-1 Comparative 3.6 Example 7-1 Example 7-2 Comparative 1.7 Example 7-1 Example 7-3 Comparative 1.3 Example 7-1 Example 7-4 Comparative 1.6 Example 7-1 Example 7-5 Comparative 1.8 Example 7-2 Example 7-6 Comparative 1.4 Example 7-2 Example 7-2 As can made between be understood from the results of comparisons Examples 7-1 to 7-4 and Comparative Example 7-1 .0 and those between Example 7-5 and Comparative Example 7-2, the cycle life can considerably be lengthened due to use of the secondary battery according to an aspect of the present invention.
Example 8 A battery which had a simple structure, which could be assembled simply and which had a cross sectional shape 15 schematically shown in Fig. 2 was manufactured.
First, an RF (Radio Wave Frequency) discharge plasma processing apparatus having a structure [N:\LIBE]01316:MXL -176schematically shown in Fig. 6 was used to apply surface treatment to a lithium negative electrode. In an atmosphere of dry argon gas, a nickel mesh collector was pressed against the reverse side of the lithium metal foil. In order to protect the surface of lithium, a polyester film was interposed at the time of coiling them. The coil-shape lithium foil 400 was mounted on a conveyance roll 407 of the plasma processing apparatus, and then the retained gas was exhausted to realize a degree of vacuum of 2 x 10 6 Torr.
Then, 20 sccm of nitrogen gas and 10 sccm of argon gas were introduced to a plasma processing chamber 405 through a gas introduction pipe 406. While controlling the internal pressure in the plasma processing chamber to 0.5 Torr, waves having a high frequency of 13.56 MHz were supplied by 200 watts to cause discharge to take place. Then, a winding roll 408 was used to hold and take up the protection film comprising the polyester film so that the surface of lithium was plasma-treated. Then, the lithium foil subjected to the plasma treatment was cut so that a negative electrode was manufactured.
The protection film to be interposed at the time of the winding operation in the plasma process, a separator for a battery may be used.
The positive electrode active material 203 was 25 prepared in such a manner that a lithium-manganese oxide was prepared by mixing electrolyzed manganese o o• o• [N:\LIBE]01316:MXL -177dioxide and lithium carbonate at a ratio of 1:0.4 and by heating the mixture at 850 0 C. Then, graphite and tetrafluoroethylene polymer powder were mixed to the prepared lithium-manganese oxide. Then, it was pressed against a nickel mesh as to be formed into a desired positive electrode.
The electrolyte solution was prepared by dissolving, by 1 M (mol/l), tetrafloride borate lithium salt in an equal quantity mixture solvent of propylene carbonate (PC) and dimethoxyethane (DME).
The separator 208 was manufactured in such a manner that a polypropylene separator having small apertures was sandwiched by unwoven polypropylene sheets.
Example 9 A battery similar to that according to Example 8 and shown in Fig. 2 was manufactured.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon similarly to Example 8.
A lithium secondary battery was manufactured by a method similar to that according to Example 8.
First, a microwave discharge plasma processing apparatus having a structure schematically shown in Fig. 7 was.used to apply surface treatment to a lithium negative 25 electrode. In an atmosphere of dry argon gas, a nickel mesh collector was pressed against the reverse o [N:\LIBE]01316:MXL 178side of the lithium metal foil, and then disposed on a sheet processing substrate holder 501 followed by injecting them in a load chamber 508 of the microwave discharge plasma processing apparatus. Then, the retained gas in the load chamber 508 was exhausted to realize a degree of vacuum of 1 x 10 6 Torr. Then, a gate valve 509 was opened, and the substrate holder was conveyed to the plasma processing chamber 502 and the gate valve 509 was closed. Then, sccm of carbon tetrafluoride gas and 5 sscm of hydrogen gas were introduced into the plasma processing chamber 502 through the gas introduction pipe 504. While controlling the internal pressure in the plasma processing chamber to 0.01 Torr, microwaves having a frequency of 2.45 GHz were supplied by 100 watts through a wave guide pipe 506 and a microwave introduction window 505 to cause discharge to take place. As a result, the surface of lithium was plasmaprocessed. The lithium foil plasma-processed was used as the negative electrode.
Then, similar processes to those according to Example 8 were performed so that the lithium secondary battery was manufactured.
Example Under the same conditions as those according to Example 9 except that 10 sccm of gas of nitrogen trifluoride 25 was, as the lithium surface treatment a o
A
[N:\LIBE]01316:MXL -179gas, introduced through the gas introduction pipe 504 in place of the 10 sccm of the carbon tetrafluoride gas and the seem of the hydrogen gas. As a result, the surface of lithium was processed similarly to Example 9. Then, similar processes to those according to Example 8 were performed so that the lithium secondary battery was manufactured.
Example 11 Under the same conditions as those according to Example 8 except that 5 seem of chlorine trifluoride gas, 2 sccm of oxygen gas and 100 seem of helium gas were, as the lithium surface treatment gas, introduced through the gas introduction pipe 504 in place of the 5 sccm of chlorine trifluoride gas and 2 seem of oxygen gas. Then, the surface of lithium was processed while omitting discharge.
Then, similar processes to those according to Example 8 were performed so that the lithium secondary battery was manufactured.
In order to compare and evaluate the performance of the batteries according to the foregoing Examples, the following comparative battery was manufactured.
Comparative Example 8 A lithium secondary battery was manufactured similarly to Example 8 except that the metal lithium foil, to which the.nickel mesh was pressed, was, as it is, used as the 25 negative electrode.
*a a a [N:\LIBE]01316:MXL -180- Evaluation of Performance of Secondary Battery The performance of lithium secondary batteries according to Examples and Comparative Example was evaluated.
The evaluation was performed bya charge and discharge cycle test under the following conditions with respect to the cycle life of the batteries according to Comparative Example.
The conditions for the cycle test were made as follows: the charge and discharge was performed by 0.2C (electric current which was 0.2 times capacity/ time), pause for 30 minutes and a cut-off voltage of 1.OV was applied. A charging/discharging apparatus HJ-101M6 manufactured by Hokuto Electric was used. The charge/discharge test was commenced at discharge, the battery capacity was evaluated the quantity of the third discharge and the cycle life was evaluated by the number of cycles when the battery capacity had deteriorated to 60% or less.
The cycle life of batteries according to Examples of the present invention with respect to the cycle life of the battery according to Comparative Example which was made to be 1.0 was as shown in Table 8.
As can be understood from the results of comparisons Smade between Examples 8 to 11 and Comparative Example 8, the cycle life can considerably be lengthened due to use of the secondary battery according to an aspect of the present invention.
S e• So So [N:\LIBE]O1316:MXL 181 Table 8 Lithium Battery Manufactured Cycle Life of Example Cycle Life of Comparative Example 8 Comparative Example 8 Example 8 Example 9 Example 10 Example 11 1.7 Example 12 A liquid-rich test cell similar to the apparatus shown in Fig. 1 was used to conduct tests.
The preparation of materials and assembly of the battery were performed in an atmosphere of dry Ar. Lithium metal foil, to which a titanium collector was pressed, was inserted into the chamber of an RF plasma CVD apparatus.
Then, the retained gas was exhausted to realize a degree of vacuum of 2 x 10-6 Torr. Then, tetrafluoroethylene, ethylene, hydrogen, helium and oxygen were introduced into 15 the chamber, and the internal pressure was maintained at 0.8 Torr. Then, high frequency power of 200 watts was supplied to a parallel and flat electrode so that a plasma polymer film of fluororesin was formed on the foregoing sample to have a thickness of 100 A.
C
C C IN:\LIBE]01316:MXL -182- Then, acetylene gas was, as raw material gas, introduced into the chamber, and the pressure in the chamber was controlled to 0.1 Torr, and then RF discharge was performed so that a carbon film was formed on the surface of lithium to have a thickness of 200 A so that a sample negative electrode was manufactured (see Fig. 9A).
The positive electrode active material was prepared by heating a mixture of dehydrated and electrolyzed manganese deoxide, lithium carbonate and black lead. The lithiummanganese composite oxide was mixed with tetrafluoroethylene polymer powder, and then it was pressed against titanium mesh to be formed into a desired positive electrode.
The separator was manufactured by sandwiching a polypropylene separator having small apertures and unwoven polypropylene sheets.
The electrolyte solution was prepared by dissolving 1 M of arsenate hexafluoride lithium salt in an equal-quantity mixture solvent of propylene carbonate and dimethoxyethane.
A lithium secondary battery was manufactured as shown in Fig. 1.
Example 13 Under the same conditions as those according to Example 12 except that lithium metal foil covered with a plasma polymer film of fluorine resin was inserted 9 [N:\LIBE]01316:MXL 183into the chamber of the RF plasma CVD apparatus. Then, the retained gas was exhausted to realize a degree of vacuum of 2 x 10-6 Torr. Monosilane gas was, as the raw material gas, introduced into the chamber, and then the pressure in the chamber was controlled to 0.1 Torr. Then, RF discharge was performed so that an amorphous silicon film was formed on the surface of the lithium metal foil to have a thickness of 100 A as to be used as a sample pole. A battery similar to that according to Example 12 was manufactured except that the foregoing sample pole was used as the negative electrode.
Example 14 Petroleum type pitch was spun by a flow method, and subjected to heat treatment in an atmosphere of inactive gas so that black lead fiber having a specific area of 10 m 2 /g was obtained. By heating the fiber to completely remove water, and dispersed in toluene dehydrated by a molecular sheave as to be applied to the lithium metal foil. Then, the material was dried and pressed by a pressing machine so that a sample was obtained (comprised a fiber layer having a thickness of 50 VLm). Then, a titanium mesh collector was pressed against the reverse side of the sample so that a .negative electrode was obtained. A battery similar to that according to Example 12 was manufactured except that the 25 foregoing negative electrode was used as the
U..
*U. U U
O
e oeee [N:\LIBE]01316:MXL 184negative electrode.
Example A solution in which Lumifron, which was fluororesin paint manufactured by Asahi Glass, and lithium hexafluoride salt were dissolved was applied to the surface of the separator, and then it was pressed. A battery similar to that according to Example 12 was manufactured except that the separator was disposed as shown in Fig. 9F.
Example 16 A battery was manufactured under the same conditions as those according to example 12 except that black lead fiber having a specific area of 10 m 2 /g or more was-papermade and thus-obtained black lead paper (having a thickness of 200 jm) was disposed between the negative electrode and the separator as shown in Fig. 9B.
Example 17 The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon.
Lithium metal foil, to which a titanium mesh collector was pressed, was inserted into the chamber of an RF plasma CVD apparatus. Then, the retained gas was exhausted to realize a degree of vacuum of 2 x 10-6 Torr. A hexane solution of acetylacetone complex of nickel was used as the material, and it was bubbled with hydrogen gas as to be introduced *o «i [N:\LIBEO01316:MXL 185into the chamber. The pressure in the chamber was controlled to 1 Torr, and RF discharge was performed so that a nickel film was formed on the surface of the metal foil to have a thickness of 200 A as to be served as a sample pole.
A battery was manufactured under the same conditions as those according to example 12 except that the foregoing sample pole was used as the negative electrode.
Example 18 RF discharge was performed under the same conditions as those according to Example 17 except that oxygen gas was used as the material together with the hexane solution of acetylacetone complex of nickel. As a result, a nickel oxide film was formed on the surface of the lithium metal foil to have a thickness of 50 A to serve as a sample pole.
A battery was manufactured under the same conditions as those according to example 12 except that the foregoing sample pole was used as the negative electrode.
09* a ea *e *eoe [N:\LIBE01316:MXL -186- Example 19 The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon.
Lithium metal foil, to which a titanium mesh collector was pressed, was inserted into the chamber of the RF plasma CVD apparatus. Then, the retained gas was exhausted to realize a degree of vacuum of 2 x 10- 6 Torr. Monosilane gas and ammonia gas were, as raw material gas, introduced into the chamber, and then the pressure in the chamber was controlled to 0.1 Torr to perform RF discharge. As a result, a silicon nitride film was formed on the lithium metal foil to have a thickness of 200 A as to be serve as a sample pole. A battery was manufactured under the same conditions as those according to example 12 except that the foregoing sample pole was used as a negative electrode.
Example The RF discharge was performed under the same conditions as those according to Example 17 except that methane gas was used as the raw material together with the hexane solution of acetylacetone complex of titanium. As a result, a composite film of titanium and carbon was formed on the surface of the lithium metal foil to have a thickness of 250 A to serve as a sample pole. A battery was manufactured under the same conditions as those according to 25 example 12
S
S
[N:\LIBE]01316:MXL 187except that the foregoing sample pole was used as the negative electrode.
Example 21 A polypropylene separator was inserted into the chamber of the RF plasma CVD apparatus. Then, the retained gas was exhausted to realize a degree of vacuum of 2 x 10- 6 Torr. Acetylene gas was introduced into the chamber, and then the pressure in the chamber was controlled to 0.1 Torr and RF discharge was performed. As a result, a carbon film was formed on the surface of the separator to have a thickness of 200 A. A battery was manufactured under the same conditions as those according to example 12 except that the foregoing separator was used and disposed as shown in Fig. 9F.
Example 22 Under the same conditions as those according to Example 21 except that monosilane gas was used as the raw material gas to cover the separator with an amorphous silicon film. A battery was manufactured under the same conditions as those .according to example 12 except that the separator was used and disposed as shown in Fig. 9F.
Example 23 .The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon. A 25 polypropylene separator was inserted into p ft*ftpf [N:\LIBE]01316:MXL 188 1 the chamber of the RF plasma CVD apparatus. Then, the retained gas was exhausted to realize a degree of vacuum of i0- 5 Torr. Then, tetrafluoroethylene, ethylene,
H
2 helium and oxygen were introduced into the chamber, and the internal pressure was maintained at 0.8 Torr. High frequency power was, by 200 watts, supplied to a parallel and flat electrode so that a plasma polymer film of fluororesin was formed on the separator. Then, acetylene gas was, as the raw S. 1 0 material gas, introduced into the chamber, and the internal pressure in the chamber was controlled to 0.1 Torr to perform RF discharge. As a result, a carbon film was formed to have a thickness of 200 A.
A battery was manufactured under the same conditions 15 as those according to example 12 except that the foregoing separator was used and disposed as shown in Fig. 9G.
Example 24 The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon. A fluororesin film having micropores was inserted into the chamber of the RF plasma CVD apparatus. Then, the retained gas was exhausted to realize a degree of vacuum of 2 x 10- 6 Torr. A hexane solution of acetylacetone complex of nickel was, as the raw material, used as to be bubbled with hydrogen gas as to be introduced into the chamber. The pressure 189 1 in the chamber was controlled to 1 Torr to perform
RF
discharge so that a nickel film was formed on the surface of the separator to have a thickness of 300 A.
A battery was manufactured under the same conditions as those according to example 12 except that the foregoing film was used and disposed as shown in Fig. 19C.
Example Under the same conditions as those according to Example 24 except that monosilane gas was used as the raw material gas to form an amorphous silicon film on the fluororesin film having micropores. A battery was manufactured under the same conditions as those according to example 12 except that the foregoing film was used and disposed as shown in Fig. 9C.
15 Example 26 0.
The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon. Lithium metal foil, to which a titanium mesh collector was pressed, was inserted into the chamber of the RF plasma CVD apparatus. Then, the retained gas was exhausted to realize a degree of vacuum of 2 x 10- 6 Torr. Monosilane gas and acetylene gas were, as the raw material gas, introduced into the chamber, and then the pressure in the chamber was controlled to 0.1 Torr to perform RF discharge. As a result, the surface of the lithium metal foil was covered with silicon carbide film having a thickness of 300 A to serve as a sample 190pole. A battery was manufactured under the same conditions as those according to example 12 except that the foregoing sample pole was used as the negative electrode- Example 27 The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon.
Lithium metal foil, to which a titanium mesh collector was pressed, was inserted into the chamber of the RF plasma CVD apparatus. Then, the retained gas was exhausted to realize a degree of vacuum of 5 x 10-6 Torr. Then, Ar gas was allowed to flow to make the inside of the chamber to be an inactive atmosphere. Then, the pressure in the chamber was lowered to 3 x 10-3 Torr, and black lead and Si were used as the target for use in the RF discharge. Sputtering of Si was commenced at the initial stage of the discharge and the proportion of black lead sputtering was gradually raised so that a composite layer of carbon and Si was formed on the surface of the lithium metal foil to have a thickness of 300 A to serve as a sample pole. A battery was manufactured under the same conditions as those according to example 12 except that the foregoing sample pole was used as the negative electrode.
Example 28 A battery was manufactured under the same
S
**l [N:\LIBE]01316:MXL 191 conditions as those according to example 27 except that black lead, Si and polytetrafluoroethylene were used as target and the thus-formed composite film was=stacked on the surface of the lithium metal foil.
Example 29 The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon. The sample according to Example 12 was inserted into the chamber of the RF plasma CVD apparatus. Then, the retained gas was exhausted to realize a degree of vacuum of 10 5 Torr. Then, tetrafluoroethylene, ethylene, hydrogen, helium and oxygen were introduced into the chamber, and the internal pressure was maintained at 0.8 Torr. Then, high frequency power was, by 200 watts, supplied to a parallel and flat electrode to form a plasma polymer film of fluororesin on the foregoing sample so that a sample pole was obtained. A battery was manufactured under the same conditions as those according to example 12 except that the foregoing sample pole was used as the negative electrode.
Example The preparation of materials and assembling of the battery were performed in an atmosphere of dry argon.
Lithium metal foil, to which a titanium mesh collector was pressed, was inserted into the chamber of sputtering 25 apparatus. Then, the retained gas was 0 4 [N:\LIBE]01316:MXL 192exhausted to realize a degree of vacuum of 5 x 10- 6 Torr. Ar gas was allowed to flow to make the inside of the chamber to be an inactive atmosphere. Then, pressure in=--he chamber was lowered to 3 x 10-3 Torr, and black lead and LiAsF 6 were used as the targets to perform RF discharge. As a result, carbon and LiAsF 6 were formed on the surface of the lithium metal foil to have a thickness of 300 A so that a sample pole was obtained. A battery was manufactured under the same conditions as those according to example 12 except that the foregoing sample pole was used as the negative electrode.
Example 31 The separator according to Example 21 and covered with carbon was used, and a fluororesin film having micropores was stacked on the coated carbon as shown in Fig. 9H. A battery was manufactured under the same conditions as those according to example 12 except that the foregoing film was used.
Example 32 The spiral and cylindrical battery shown in Fig. 3 was used in the test, the battery being KR-A type battery having a contour of 17.0 mm and 50.5 mm high.
Paste obtained by, together with ethylene glycol, kneading zinc oxide and metal zinc serving as the main 25 active material and polyvinyl alcohol
S
S
o o o [N:\LIBE]01316:MXL 193serving as the bonding material was applied to an iron plate applied with nickel plating having apertures.
Then, drying and pressing were performeadso that a zinc pole plate was obtained.
The zinc pole plate was inserted into the chamber of the RF plasma CVD apparatus to perform RF discharge in such a manner that the proportion of tetrafluoroethylene was high in the initial stage of the discharge process and the proportions of acetylene and oxygen were raised in the following stage of the discharge process. As a result, a fluororesin film having a thickness of 200 A was formed on the surface of the zinc pole plate so that a sample pole was obtained.
The positive electrode plate was manufactured in such a manner that paste was obtained by kneading a solution in which nickel and cobalt were added to nickel hydroxide and carboxydimethyl cellulose serving as a bonding material, and water was added to the kneaded solution. The paste was injected into foamed metal (Celmet manufactured by Sumitomo Denko), and it was dried and pressed.
A separator (Cell Guard manufactured by Cellanese) was used which was manufactured by integrating a film having small apertures and unwoven polypropylene sheet.
The electrolyte solution comprised 30 wt% t, a.
a a a. a a [N:\LIBE]01316:MXL -194potassium solution.
Assembly was performed in such a manner that a wound group in which a separator was interposed bet wen the negative electrode and the positive electrode was inserted into a battery case made of titanium clad stainless steel.
Then, the electrolyte solution was injected, and the negative electrode cap made of titanium stainless steel and an insulating packing made of fluorine rubber were inserted and they were caulked so that a nickel-zinc secondary battery was manufactured.
Example 33 The flat type battery shown in Fig. 2 was used to conduct the test.
Tetrafluoroethylene polymer powder was mixed to zinc oxide and metal zinc, and then was pressed against a nickel mesh as to be formed into a zinc pole plate. The zinc negative electrode was inserted into chamber of the RF plasma CVD apparatus, and then fluororesin having a thickness of 50 A and carbon having a thickness of 200 A were formed on the surface of the zinc pole plate so that a negative electrode was formed.
A positive electrode catalyzer layer was formed by adding manganese dioxide to active carbon. Then, a water repellent film made of polytetrafluoroethylene and dispersed 25 paper made of cellulose were stacked on the positive electrode catalyzer layer so that a positive t o.
a.
a• [N:\LIBE101316:MXL -195electrode was formed. A separator made of cellophane and wt% potassium hydroxide serving as the electrolyte solution were employed.
Assembly was performed in such a manner that a separator was interposed between the negative electrode and the positive electrode and they were inserted into a battery case made of stainless steel and having small apertures.
Then, the electrolyte solution was injected, and then a negative electrode cap made of titanium clad stainless steel and an insulating packing made of fluorine rubber were used to perform sealing. As a result, an air-zinc secondary battery was manufactured.
Comparative Example 12 A battery was manufactured under the same conditions as those according to example 12 except that a negative electrode, which comprised lithium metal foil having no carbon film, was used.
Comparative Example 13 A battery was manufactured under the same conditions as those according to example 31 except that a negative electrode, which comprised a zinc pole plate which was not covered with the composite film of the fluororesin and carbon, was used.
Comparative Example 14 25 A battery was manufactured under the same conditions as those according to example 33 except that a negative electrode, which comprised a zinc pole plate a a• a.
a.
a a a [N:\LIBEIO1316:MXL -196which was not covered with the composite film of the fluororesin and carbon, was used.
The batteries respectively according to -Fxamples 12 to 31 and Comparative Example 12 were charged with a current of 0.2 C to a level of 4.0 V, then paused for 30 minutes, and then discharged with a current of 0.2 C to a level of 2.8 V.
The foregoing test was repeated, resulting in as shown in Table 9.
The batteries respectively according to Examples 32 and 33 and Comparative Examples 13 and 14 were charged with a current of 0.2 C to 150 then paused for 30 minutes, and then discharged with a current of 0.2 C to 1.0 V.
The results of the cycle life tests of the respective Examples with respect to Comparative Examples are shown in Table 9 while making the cycle life of the batteries according to Comparative Examples 12 to 14 to be i. As can be understood from the results shown in Table 9, the charge/discharge cycle life can significantly be lengthened as compared with Comparative Examples when a single layer, a multi-layer or a composite layer is disposed between the negative electrode and the separator, the single layer, the multi-layer or the composite layer being the conductor layer made of carbon or nickel or titanium, the semiconductor layer made of silicon or the metal oxide, and the insulating 25 layer made of the halide, nitride, carbide *e 9 9 9 9 9* 9 9 a [N:\LIBE]01316:MXL 197 1 or the organic polyer (according to respective Examples).
Table 9 Manufactured Secondary Battery Cycle Life of Example Cycle Life of Examples Comparative Examples Comparative Example Example 12 Comparative Example 12 S; Example 13 Comparative Example 12 2.1 Example 14 Comparative Example 12 Example 15Comparative Example 12 1.3 Example 16 Comparative Example 12 1.3 Example 17 Comparative Example 12 2.2 Example 18 Comparative Example 12 2.3 Example 19 Comparative Example 12 Example 20 Comparative Example 12 2.1 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Comparative Example 12 1.6 Comparative Example 12 Comparative Example 12 1.7 Comparative Example 12 Comparative Example 12 Comparative Example 12 2.2 Comparative Example 12 2.1 Comparative Example 12 2.2 Comparative Example 12 Comparative Example 12 2.6 Comparative Example 12 1.6 Comparative Example 13 2.2 Comparative Example 14 2.2
I
Example 34 A polysiloxane film was formed by the following method.
-198- As the film forming compound, 0.05 M (mol/1) an amphipathic compound N-[b-(trimethylammonio) ethyloxybenzoyl]-didodecyl-L-glutamic acid broide-and 0.15 M of trimethoxymethyl silane were processed with supersonic waves for 3 minutes as to be dispersed in water. The dispersion solution was developed on a tetrafluoroethylene polymer sheet (Goatex manufactured by Japan Goa Tex) and allowed to stand at 25 0 C and 60% relative humidity for 3 days so that a multi-layer bimolecular film was obtained.
The film was treated with ammonia gas in a sealed glass container to hydrolyze and condense the methoxysilane group.
Ethyl alcohol was used to extract and remove the amphipathic compound so that a polysiloxane film was obtained on the Goa Tex sheet.
Manufacturing of Secondary Battery A lithium secondary battery which had a simple structure, which could be assembled simply and which had a cross sectional shape schematically shown in Fig. 2 was manufactured.
The positive electrode active material 203 was prepared in such a manner that electrolyzed manganese dioxide and lithium carbonate were mixed at a ratio of 1:0.4, and then heated at 800 0 C so that a lithium-manganese oxide was prepared. Then, graphite and tetrafluoroethylene 25 polymer powder were mixed to the prepared lithium-manganese oxide, and then pressed a a *r [N:\LIBEI01316:MXL 199against a nickel mesh as to be formed into the positive electrode.
Then, silica sol dispersion ethyl alcohol (manufactured by Shokubai Kasei) was mixed in water in which N-[b-(trimethylammonio)ethyloxybenzoyl]-didodecyl-L-glutamic acid bromide, which was the film forming compound, was dispersed. The positive electrode was dipped in the foregoing dispersion solution, dried at room temperature, further dried at 80 0 C, and cleaned with hexane to remove the film forming compound. Then, it was dried at 250 0 C in a vacuum atmosphere so that the positive electrode 203 covered with the multi-layer silica film was manufactured.
In an atmosphere of dry argon gas, titanium mesh collector 200 was pressed against the reverse side of the lithium metal foil, and then the lithium metal foil was immersed in a solution of Lumiflon, which was a copolymer of ethylene tetrafluoride and vinyl ether and which was manufactured by Asahi Glass, and then dried as to be hardened. As a result, the lithium negative electrode 201 covered with fluororesin was manufactured.
The electrolyte solution was prepared by dissolving, by 1 M (mol/1), boron tetrafluoride lithium salt in an equal quantity mixture solvent of propylene carbonate (PC) and dimethoxyethane
(DME).
25 The separator 208 comprised a composite member C C
C
C C o
*C.
C
IN:\LIBE]01316:MXL -200of the polysiloxane film prepared as described above and the Goa Tex sheet.
Assembly was performed in such a manner'that-the separator 208 was interposed between the negative electrode 201 and the positive electrode 203 as to be inserted into the positive electrode case 207 made of titanium clad stainless steel. Then, the electrolyte solution was injected, and then the negative electrode cap 206 made of titanium clad stainless steel and the insulating packing 210 made of fluorine rubber were used to seal so that a lithium secondary battery was manufactured.
Example Preparation of Multi-Layer Metal Oxide A titanium oxide was prepared by the following method.
A film forming compound, that is, dihexadecylphosphate was mixed to a sol dispersed solution of very small particles of titanium oxide (manufactured by Idemitsu), and dispersed with ultrasonic waves similarly to Example 34.
Then, it was developed on a tetrafluoroethylene polymer membrane filter. Then, it was dried at room temperature, resulting in a cast film to be obtained which was then cleaned with ethyl alcohol. Then, it was baked at 300 0 C so that a titanium oxide film was formed.
25 The separator 208 was manufactured in such a manner that the thus-formed titanium oxide, unwoven
S
*o [N:\LIBEI01316:MXL 201 1 pQlypropylene sheets and a polypropylene separator having small apertures were sandwiched.
A battery was manufactured under the same conditions as those according to example 34 except the foregoing arrangements.
Example 36 A lithium secondar battery was manufactured under the same conditions as those according to example 35 except that the titanium oxide film was 10 immersed in 0.1 ethylalcohol solution of silane o. coupling SH6020 (manufactured by Toray Dowconing).
Example 37 Preparation of Multi-Layer Metal Oxide A cast film obtained similarly to Example was based at 800°C so that an alumina film was manufactured, the cast film being obtained from a film forming compound brought into class four from N-(l1bromoundecanoyl)-L-glutamic acid didodecylester with o* triethyl amine and amorphous alumina super fine particle sol.
The N-(ll-bromoundecanoyl)-L-glutamic acid didodecylester was prepared in such a manner that Lglutamic acid didodecylester hydrochloride salt was synthesized from L-glutamic acid and dodecylalcohol, and then the L-glutamic acid didodecylester hydrochloride salt, triethylamine, cyanophsophoric acid diethyl and ll-bromoundecan acid were used.
-202- Assembly of Secondary Battery A nickel-zinc secondary battery which had a simple structure, which could be assembled simply and-which had a cross sectional shape schematically shown 5 in Fig. 2 was manufactured.
The positive electrode was manufactured by impregnating nickel hydroxide into a sintered nickel pole plate.
The negative electrode was formed in such a manner that tetrafluoride ethylene polymer powder serving as the bonding material was added to a mixture of zinc powder and zinc oxide powder and they were pressed against the two sides of a copper punching metal to be formed into the desired shape. Then, alumina trichloride and phosphoric acid were, in ethyl alcohol, caused to react with each other at 0°C as to dip the negative electrode. Then, it was gradually heated up to 100 0 C so that glass-type aluminum phosphate film was formed on the negative electrode.
The electrolyte solution comprised 30 wt% potassium hydroxide containing lithium hydroxide added thereto.
The battery was assembled similarly to Example 34.
Example 38 A nickel-zinc secondary battery was manufactured under the same conditions as those according f 0 e 000, 0t f ft *ft 4 0 0 *f [N:\LIBE]01316:MXL -203to Example 37 except that the surface of the negative surface was not covered with the aluminum phosphate.
Example 39 A nickel-zinc secondary battery was manufactured under the same conditions as those according to Example 37 except that a positive electrode manufactured as follows was used.
A dispersion solution in which was mixed a film forming compound obtained by bringing N-(llbromoundecanoyl)-L-glutamic acid didodecylester into class four with triethylamine, amorphous alumina very small particles sol and polyvinyl alcohol water solution containing crosslinking material added thereto was developed on the surface of the positive electrode formed by causing a sintered nickel plate to impregnate nickel hydroxide, followed by drying the developed solution. Then, crosslinking reactions were caused to take place at 120 0
C,
and cleared with ethyl alcohol. Then, the material was dried in a vacuum atmosphere so that a positive electrode covered with a composite film of alumina and polyvinyl alcohol was manufactured.
In order to compare and evaluate the foregoing batteries, the following comparative batteries were manufactured.
Comparative Example 34 25 A lithium secondary battery was manufactured under the same conditions as those according to *i 4 [N:\LIBE]01316:MXL 204example 35 except that no titanium oxide was used and the lithium of the negative electrode was not covered.
Comparative Example 35 A nickel-zinc secondary battery was manufactured under the same conditions as those according to example 37 except that no alumina was used and zinc of the negative electrode was not covered.
Evaluation of Performance of Secondary Battery The performance of lithium secondary batteries according to Examples and Comparative Examples was evaluated. The evaluation was performed by a charge and discharge cycle test under the following conditions with respect to the cycle life of the batteries according to Comparative Examples.
The conditions for the cycle test were made as follows: the charge and discharge was performed by 0.2C (electric current which was 0.2 times capacity/ time), pause for 30 minutes and a cut-off voltage of l.0V was applied.
A
charging/discharging apparatus HJ-101M6 manufactured by Hokuto Electric was used. The charge/discharge test was commenced at discharge, the battery capacity was evaluate the quantity of the third discharge and the cycle life was evaluate by the number of cycles when the battery capacity had deteriorated to 60% or less.
25 The cycle life of each battery with respect to the cycle life of the battery according to Comparative a a o [N:\LIBE01316:MXL -205- Examples which was made to be 1 was as shown in Table 2.
As can be understood from the results of comparisons made between Examples 34 to 36 and Comparative Example 34 and those between Examples 37 to 39 and Comparative Example 35, the cycle life can be lengthened due to use of the secondary battery having the structure according to an aspect of the present invention.
Table
I
Manufactured Lithium Battery Example Example 34 Example 35 Example 36 Example 37 Example 38 Example 39 Comparative Example Comparative Example 34 Comparative Example 34 Comparative Example 34 Comparative Example Comparative Example Comparative Example Cycle Life of Example Cycle Life of Comparative Example 5.4 2.1 2.3 2.6 1.9 2.2 .9 9.
S
9 9 9 99*9 9 9 9.
9** 9 9 9 9 9* 9 Example A lithium secondary battery which had a simple structure, which could be assembled simply and which 25 had 15 a cross sectional shape schematically shown in Fig. 2 was manufactured.
The positive electrode active material 203 was [N:\LIBE]01316:MXL -206manufactured in such a manner that electrolyzed manganese dioxide and lithium carbonate were mixed at a ratio of 1:0.4. Then, the mixture was heated to 800 0 C so that a lithium-manganese oxide was prepared. Graphite and tetrafluoroethylene polymer powder were added to the prepared lithium-manganese oxide, and pressed against a nickel mesh as to be formed into the positive electrode.
Then, the positive electrode was immersed in a solution of Teflon AF which was a copolymer of tetrafluoroethylene and 2 2 1, 3-dioxol and which was manufactured by Dupont, and then it was dried. As a result, the positive electrode 203 covered with the fluororesin was manufactured.
In an atmosphere of dry argon gas, the titanium mesh collector 200 was pressed against the reverse side of the lithium metal foil, and then the lithium metal foil was immersed in a solution which was a copolymer of ethylene tetrafluoride and vinyl ether and which was manufactured by Asahi Glass. Then, it was dried as to be hardened so that the lithium negative electrode 201 covered with the fluororesin was manufactured.
The electrolyte solution was prepared by dissolving, by 1 M (mol/l), boric acid tetrafluoride lithium salt in an equal quantity mixture solvent of propylene carbonate
(PC)
S* 25 and dimethoxyethane
(DME).
4 4 4 *44* [N:\LIBE101316:MXL -207- The separator 208 was manufactured in such a manner that a polypropylene separator having small apertures was sandwiched by unwoven polypropylene sheets.
The assembly was performed in such a manner that the separator 208 was held between the negative electrode 201 and the positive electrode 203 as to be inserted into the positive case 207 made of titanium clad stainless steel.
Then, the electrolyte solution was injected, and then the negative electrode cap made of titanium clad stainless steel and the insulating packing 210 made of fluorine rubber were used for sealing so that a lithium secondary battery was manufactured.
Example 41 A lithium battery was manufactured under the same conditions as those according to example 40 except the process for covering the positive electrode.
The positive electrode was manufactured similarly to Example 40. Then, the positive electrode was immersed in an acetonitryl solution, in which were dissolved 0.1 M of monomer of benzo-15-crown-5 and 2.0 M of electrolytic boronic acid tetrafluoride tetrabutyl ammonium salt. Then, the platinum electrode was used as the cathode pole, and voltage of 3 V was applied to perform electrolysis and polymerization so that a large ring compound polymer 25 covering film was formed e a g 55..
0
S
S. Si O 55 S S [N:\LIBE1O1316:MXL -208on the surface of the positive electrode.
In an atmosphere of dry argon gas, the titanium mesh collector 200 was pressed against the lithium-_metal foil so that the negative electrode was manufactured.
Then, similar processes to those according to Example were performed so that the lithium secondary battery was manufactured.
Example 42 A lithium secondary battery which had a simple structure, which could be assembled simply and which had a cross sectional shape schematically shown in Fig. 2 was manufactured.
The positive electrode was manufactured by a similar process according to Example 40. Then, peroxide benzoyl and boronic acid tetrafluoride lithium were dissolved in a tetrahydrofuran solution of poly (2-vinyl naphthalene) manufactured by Aldrich Chemical Company, Inc. Then, the positive electrode was immersed in it, and then heated to 100 0 C so that the positive electrode 203 covered with poly (2-vinyl naphthalene) was manufactured.
Then, similar processes to those according to Example 41 were performed so that the lithium secondary battery was manufactured.
Example 43 25 The positive electrode was manufactured by a process e t (N:\LIBE]01316:MXL -209similar to that according to Example 40. Then, boronic acid tetrafluoride lithium salt was added and dissolved in a toluene solution PPZ-U1001 manufactured by Idemitsu. Then, the positive electrode was immersed, and previously dried, and then ultraviolet rays were applied so that the positive electrode 203 covered with polyphosphazene was manufactured.
Then, similar processes to those according to Example 41 were performed so that the lithium secondary battery was manufactured.
Example 44 The positive electrode was manufactured by a process similar to that according to Example 40. The thusmanufactured positive electrode was injected into a sputtering apparatus. Then, the retained gas was exhausted to realize a degree of vacuum of 2 x 10-6 Torr. Then, argon gas, which was a mixture of 10% nitrogen gas and acetylene gas, was allowed to flow. The internal pressure was controlled to 3 x 10-3 Torr, and lithium fluride was made to be a target of sputtering. As a result, the positive electrode covered with carbon and a film made of lithium nitride containing fluorine were formed.
Then, similar processes to those according to Example 41 were performed so that the lithium secondary battery was S: manufactured.
25 Example S ••go *o **r [N:\LIBE]01316:MXL -210- A nickel-zinc secondary battery which had a simple structure, which could be assembled simply and which had a cross sectional shape schematically shown in-FTgT 2 was manufactured.
The positive electrode was manufactured in such a manner that nickel hydroxide was impregnated in a sintered nickel pole plate. Then, acetic acid and water were added to an ethyl alcohol solution of tetraethoxy silane to be dehydrated. Then, diethylamine was added so that colloidal silica was formed. Then, the positive electrode was immersed in the colloidal solution of the silica, and dried at 100 0 C. As a result, a silica film was formed on the surface of the positive electrode.
The negative electrode was manufactured in such a manner that ethylene tetrafluoride polymer powder serving as a bonding material was added to a mixture of zinc powder and zinc oxide powder, then they were pressed to the two sides of a copper punching metal as to be formed into the negative electrode.
The electrolyte solution comprised 30 wt% potassium hydroxide water solution to which lithium hydroxide was added.
The battery was assembled similarly to Example In order to compare and evaluate the performance of 25 the batteries according to Examples, the [N:\LIBE]O1316:MXL -211 following comparative batteries were manufactured.
Comparative Example A lithium secondary battery was manufactured under the same conditions as those according to example 40 except that the positive electrode and the negative electrode were not covered.
Comparative Example 41 A nickel-zinc secondary battery was manufactured under the same conditions as those according to example 45 except that the surface coating was omitted.
Evaluation of Performance of Secondary Battery The performance of the secondary batteries according to Examples and Comparative Examples was evaluated. The evaluation was performed by a charge and discharge cycle test under the following conditions with respect to the cycle life of the batteries according to Comparative Examples. The conditions for the cycle test were made as follows: the charge and discharge was performed by 0.2C (electric current which was 0.2 times capacity/time), pause for 30 minutes and a cut-off voltage of 1.0V was applied.
A
charging/discharging apparatus HJ-101M6 manufactured by Hokuto Electric was used.
The charge/discharge test was commenced at discharge, the battery capacity was evaluate the quantity of the third 25 discharge and the cycle life was evaluate by the number of cycles when the battery
S
S a o [N:\LIBE]01316:MXL -212capacity had deteriorated to 60% or less.
The cycle life of each battery with respect to the cycle life of the battery according to Comparative Examples which was made to be 1 was as shown in Table 11.
As can be understood from the results of comparisons made between Examples 40 to 44 and Comparative Example 11 and those between Example 45 and Comparative Example 41, the cycle life can be lengthened due to use of the secondary battery having the structure according to an aspect of the present invention.
Table 11 Manufactured Lithium Battery Cycle Life of Example Cycle Life of Comparative Example Example Comparative Example Example 40 Comparative 5.1 Example Example 41 Comparative Example Example 42 Comparative 1.4 Example Example 43 Comparative 1.6 Example Example 44 Comparative 1.8 Example Example 45 Comparative 1.7 Example 41 15 Preparation of Positive Electrode Active Material Methods of preparing the positive electrode active material according to an aspect of the present invention are
S
S
S
S
S
S.
S S [N:\LIBEO01316:MXL 213 1_ exemplified in Preparation Methods 46 to 55 and the conventional preparation methods are exemplified by Comparative Preparation Methods.
Preparation Method 46 A lithium-manganese oxide was prepared as follows.
Manganese acetate was dissolved in water, and then super fine nickel powder ENP-005 manufactured by Sumitomo Denko was suspended in a water solution of manganese nitrate. Then, a water solution of lithium hydroxide was dripped until the pH was 8 or higher while vibrating the suspension solution with supersonic vibrations of 20 kHz so that sedimentation was generated. Then, ethyl alcohol was added, and supernatant 15 liquid of the solution including the sediment was removed by decantation. The ethylalcohol cleaning and the decantation were repeated. Then, it was *dissolved in 0.1% methyl alcohol solution of Sila Ace S210 (vinylmethoxysilane) which was a silane coupling material manufactured by Chisso. Then, the solvent was removed by a centrifugal separator. The obtained sedimentation was dried at 120°C, and dried at 200°C in a vacuum drier so that grains of manganese oxide were prepared.
The size of crystal grains was measured from the half value width of the X-ray analysis curve with respect to a manganese oxide and the angle of 214 1 diffraction in accordance with the Scherrer's Equation. The size of the crystal grain was 60 A or larger.
The RHEED pattern resulted in a ring pattern like a halo pattern.
The X-ray radial distribution function resulted in a continuous and moderate peak curve.
The scattering angle and the scattering intensity obtainable from the X-ray small angle too*: scattering method resulted in non-uniform density fluctuation to be observed.
The specific area was measured by the BET method, resulting in that the specific area was 123 m /g.
15 Preparation Method 47 Vanadium oxide was prepared as follows.
Vanadium pentaoxide was gradually added to a water solution of lithium hydroxide as to be dissolved.
While applying supersonic vibrations, the water solution was sprayed into liquid nitrogen as to be frozen. Then, the temperature was raised to -20 0
C,
and the pressure was lowered so that freezing and drying were performed to dehydrate and dry the material.
Obtained grains were dried at 150°C, and further dried in a vacuum drier at 250°C so that grains of vanadium oxide were obtained. Then, the sample was immersed in 0.1 isopropylalcohol solution of 215 1 tetra-iso-propoxytitanium, and then the solvent was remove by a centrifugal separator. The obtained sedimentation was dried at 120°C, and then dried at 200°C in a vacuum state so that grains of manganese oxide were prepared.
Although the size of crystal grains was intended to measure from the half value width of the X-ray analysis curve and the angle of diffraction in accordance with the Scherrer's Equation, it could not 10 be measured because the diffraction curve resulted in a broad form.
The RHEED pattern resulted in a halo pattern.
The X-ray radial distribution function resulted in a continuous and moderate peak curve.
15 The scattering angle and the scattering intensity obtainable from the X-ray small angle scattering method resulted in non-uniform density o* fluctuation to be observed.
The specific area was measured by the BET method, resulting in that the specific area was 105 m 2 /g.
Preparation Method 48 A lithium-nickel oxide was prepared as follows.
Nickel acetate was dissolved in a mixture solvent of acetic acid, ethyl alcohol and water.
While vibrating the solution with supersonic vibrations of 20 kHz, an ethyl alcohol solution of 216 -1 ethoxylithium, which was alkoxide, was dripped as to be mixed. Then, the solution was heated to to enhance the hydrolysis decomposition reactions so that sol was generated. The supernatant liquid of the solution including the sol-shape sedimentation was removed by decantation, cleaned with ethyl alcohol, the decantation was repeated and the solvent was removed by a centrifugal separator. The obtained sedimentation was dried at 150 0 C, and then suspended in a non-electrolyzed nickel plating solution Ni-701 *a manufactured by Kojundo Kagaku. Then, it was heated to 70 0 C, nickel coating was performed, and water cleaning and decantation were repeated. Then, ethyl alcohol cleaning was performed, and decantation was 15 repeated, and then the solvent was removed by a centrifugal separator. The sample was dried at 230°C in a vacuum state so that grains of nickel oxide were obtained.
Although the size of crystal grains was intended to measure from the half value width of the X-ray analysis curve and the angle of diffraction in accordance with the Scherrer's Equation, it could not be measured because the diffraction curve with respect to an oxide resulted in a broad form.
The RHEED pattern resulted in a ring pattern considered due to nickel plating. The pattern before the nickel plating process resulted in a halo 217 I pattern.
The X-ray radial distribution function resulted in a continuous and moderate peak curve. The scattering angle and the scattering intensity obtainnable from the X-ray small angle scattering method resulted in non-uniform density fluctuation to be observed.
The specific area was measured by the BET method, resulting in that the specific area was 210 m /g.
Preparation Method 49 A lithium-nickel-cobalt oxide was prepared by the following method.
Nickel nitrate and cobalt nitrate were 15 dissolved in water, and then a water solution of lithium hydroxide was dripped to a solution of the nickel nitrate and cobalt nitrate while vibrating with e00. supersonic vibrations of 20 kHz until the pH was 8 or higher so that sedimentation was generated. Then, ethyl alcohol was added so that the supernatant liquid of the solution including the sedimentation was removed by decantation. the ethyl alcohol cleaning and the decantation were repeated and the solvent was removed by a centrifugal separator. The obtained sedimentation was dryed at 120'C, dried at 2000C in a vacuum state so that grains of a nickel cobalt oxide were prepared.
218 1 The size of crystal grains was measured from the half value width of the X-ray analysis curve and the angle of diffraction in accordance with the Scherrer's Equation. The size of the crystal grain was 140A.
The RHEED pattern resulted in a ring pattern like a halo pattern.
The X-ray radial distribution function resulted in a continuous and moderate peak curve.
The scattering angle and the scattering intensity obtainable from the X-ray small angle scattering method resulted in non-uniform density fluctuation to be observed.
The specific area was measured by the BET 15 method, resulting in that the specific area was 160 2 ••om /g.
Preparation Method .*o e* e Vanadium-molybdenum oxide was prepared as follows.
Vandyl sulfate and molybdenum sulfate were added to water as to be suspended, and acetic acid was gradually added as to be dissolved. Then, a water solution of lithium hydroxide was dripped to a solution of the vanadium oxide and acetic acid while vibrating with supersonic vibrations of 20 kHz until the pH was 8 or higher so that sedimentation was generated.
Then, ethyl alcohol was added so that the supernatant 219 1 liquid of the solution including the sedimentation was removed by decantation. The ethyl alcohol cleaning and the decantation were repeated and the solvent was removed by a centrifugal separator. The obtained sedimentation was dryed at 120°C, dried at 200 0 C in a vacuum state so that grains of a vanadium oxide were prepared.
The size of crystal grains was measured from the half value width of the X-ray analysis curve and the angle of diffraction in accordance with the .Scherrer's Equation. The size of the crystal grain was 80 A.
The RHEED pattern resulted in a ring pattern like a halo pattern.
15 The X-ray radial distribution function resulted in a continuous and moderate peak curve.
The scattering angle and the scattering intensity obtainable from the X-ray small angle scattering method resulted in non-uniform density fluctuation to be observed.
The specific area was measured by the BET method, resulting in that the specific area was 100 2 m /g.
Preparation Method 51 Vanadium-molybdenum oxide was prepared by the following method.
The vanadium oxide and the molybdenum oxide 220 1 were mixed at a ratio of 7:3, and heated up to 8000c as to be melted and mixed so that a molten bath was made. Then, the molten bath was dispersed by jet gas which was a mixture of 20% oxygen and 2% hydrogen with argon gas. It was sprayed at high speed to a cooled and retaining metal disc so that grains of vanadium oxide and molybdenum oxide were prepared.
The size of crystal grains was measured from the half value width of the X-ray analysis curve and e 10 the angle of diffraction in accordance with the Scherrer's Equation. The size of the crystal grain was 110 A.
The RHEED pattern resulted in a ring pattern having weak intensity.
15 The X-ray radial distribution function resulted in a continuous and moderate peak curve.
The scattering angle and the scattering :intensity obtainable from the X-ray small angle scattering method resulted in non-uniform density fluctuation to be observed.
The specific area was measured by the BET method, resulting in that the specific area was m2/ g.
Preparation Method 52 Titanium sulfide was prepared by the following method.
Hydrogen gas was allowed to flow by 500 sccm 221 1 into a reaction chamber of a plasma CVD apparatus degasified as to be vacuum state. The pressure was maintained at 10 Torr and discharge was caused to take place at a high frequency wave of 13.56 MHz. Then, 200 sccm of helium gas was, as a carrier gas, bubbled in a hexane solution of tetrabutoxytitanium, and injected by 200 sccm through a nozzle into the reaction chamber of the plasma CVD apparatus.
Simultaneously, 250 sccm of hydrogen sulfide was introduced as to be reacted in a gas phase to capture grains of titanium sulfide by a capturing machine.
The size of crystal grains was measured from the half value width of the X-ray analysis curve and the angle of diffraction in accordance with the 15 Scherrer's Equation. The size of the crystal grain was 200 A.
The RHEED pattern resulted in a ring pattern having weak intensity.
The X-ray radial distribution function resulted in a continuous and moderate peak curve.
The scattering angle and the scattering intensity obtainable from the X-ray small angle scattering method resulted in non-uniform density fluctuation to be observed.
The specific area was measured by the BET method, resulting in that the specific area was 175 2 m /g.
222 1 -Preparation- Method 53 Lithium-iron-cobalt oxide was prepared by the following method.
A mixture solution of 0.5 mol/l cobalt chloride and 1 mol ferric chloride mixed at a ratio of 1:1 was gradually added to a 5 mol/1 water solution of lithium hydroxide while stirring and bubbling argon gas.
Then, reaction chamber was set to 1000C to be matured.
After the maturation, it was injected into cooled water, and cleaning was performed with water cooled by water by means of decantation until the pH of the solution was 8. It was dried at 200'C in a vacuum state, and crushed by a ball mill in an atmosphere of argon gas.
The size of crystal grains was measured from the half value width of the X-ray analysis curve and the angle of diffraction in accordance with the Scherrer's Equation. The size of the crystal grain was 150 A.
The RHEED pattern resulted in a ring pattern having weak intensity to be observed.
The X-ray radial distribution function resulted in a continuous and moderate peak curve.
The scattering angle and the scattering intensity obtainable from the X-ray small angle scattering method resulted in non-uniform density fluctuation to be observed.
-223- The specific area was measured by the BET method, resulting in that the specific area was 2100 m 2 /g.
Preparation Method 54 Manganese Acetate, magnesium chloride and urea were added to a solution in which 300 g of vanadium pentoxide was dissolved in 2 litters of hydrochloric acid, followed by heating the solution to 95 to 95 0 C for 10 minutes to generate ammonia. Lithium hydride solution was dripped to make the pH to generate sediment. Then, decantation and water cleaning were repeated, and then cleaning with ethyl alcohol was performed, and the material was dried by a spray drier. Then, the sample was dried at 200 0 C in a vacuum state.
The size of crystal grains was measured from the half value width of the X-ray analysis curve and the angle of diffraction in accordance with the Scherrer's Equation.
The size of the crystal grain was 90 A.
The RHEED pattern resulted in a ring pattern like a halo pattern.
The X-ray radial distribution function resulted in a continuous and moderate peak curve.
The scattering angle and the scattering intensity obtainable from the X-ray small angle scattering method resulted in non-uniform density
V..
[N:\LIBE101316:MXL 224 1 fluctuation to be observed.
The specific area was measured by the BET method, resulting in that the specific area was m2/ g.
Preparation Method A lithium-copper-cobalt oxide was prepared by the following method.
An oxalic acid was added to a water solution in .which a copper sulfate and a cobalt nitrate were eeoee .1 0 dissolved. Then, supersonic vibrations were applied, and lithium hydroxide was dripped until the pH was 7 so that sedimentation was generated. Water cleaning and decantation were repeated, and then, a water solution of lithium hydroxide was added, supersonic vibrations were applied, and an ethyl alcohol was added. Decantation and cleaning with ethyl alcohol were repeated, and the material was dried by using a spray drier. Further, the material was dried at 200 0
C
in a vacuum state.
The size of crystal grains was measured from the half value width of the X-ray analysis curve and the angle of diffraction in accordance with the Scherrer's Equation. The size of the crystal grain was 160 A.
The RHEED pattern resulted in a ring pattern having weak intensity.
The X-ray radial distribution function resulted 225 a continuous and moderate peak curve.
The scattering angle and the scattering intensity obtainable from the X-ray small angle scattering method resulted in non-uniform density fluctuation to be observed.
The specific area was measured by the BET method, resulting in that the specific area was 50 m 2 /g.
Other Analyses The SIMS analysis resulted that the positive electrode active materials according to Preparation Methods 46 to contained hydrogen and lithium. Also the dehydration peak of each TG (Thermogravimetric analysis), DTA (Differential Thermal Analysis) and DSC (Differential Scan Thermal Heating Value Measurement) and the absorption spectrum of FTIR (Fourier Transform Infrared) resulted that a hydroxyl group was present.
Comparative Preparation Method 46 A lithium-manganese oxide was prepared by the following method.
Powder of electrolyzed manganese dioxide manufactured by Mitsui Kinzoku and lithium carbonate were mixed with each other at a ratio of 1:0.4 and they were heated at 800 0 C so that lithium manganese oxide was prepared.
The size of crystal grains was measured from ,The size of crystal grains was measured from
C
m [N:\LIBE]01316:MXL 226 I the half value width of the X-ray analysis curve and the angle of diffraction in accordance with the Scherrer's Equation. The size of the crystal grain was 600 A or larger.
The RHEED pattern resulted in a ring pattern in which a spot pattern could be confirmed.
The X-ray radial distribution function resulted in discontinuous peak curve.
'The specific area was measured by the BET method, resulting in that the specific area was 40 m 2/g.
Comparative Preparation Method 47 A reagent manufactured by Wako was dried at 400°C in a vacuum state.
The size of crystal grains was measured from the 15 half value width of the X-ray analysis curve and the angle of diffraction in accordance with the Scherrer's Equation. The size of the crystal grain was 800 A.
The RHEED pattern resulted in a ring pattern in which a spot pattern could be confirmed.
The X-ray radial distribution function resulted in discontinuous peak curve.
The specific area was measured by the BET method, resulting in that the specific area was 4 m2/g.
Comaprative Preparation Method 48 A lithium-nickel oxide was prepared by the following method.
227 1 A lithium carbonate and nickel nitrate were mixed at an equal mol ratio of 1:1 and the mixture was heated to 800°C so that a lithium-nickel oxide was prepared.
The size of crystal grains was measured from the half value width of the X-ray analysis curve and the angle of diffraction in accordance with the Scherrer's Equation. The size of the crystal grain was 2000 A or larger.
The RHEED pattern resulted in a ring pattern in which a spot pattern could be confirmed.
The X-ray radial distribution function resulted S..o.
in discontinuous peak curve.
The specific area was measured by the BET 15 method, resulting in that the specific area was 50 m2/g.
Comparative Preparation Method 49 A lithium-nickel-cobalt oxide was prepared by *o the following method.
A lithium carbonate, nickel carbonate and cobalt carbonate were mixed at a mol ratio of 10:3:7 and the mixture was heated to 900 0 C for 20 hours as to be decomposed so that a nickel-cobalt oxide was prepared.
The size of crystal grains was measured from the half value width of the X-ray analysis curve and the angle of diffraction in accordance with the Scherrer's Equation. The size of the crystal grain was 228 1 1100 A or larger.
The RHEED pattern resulted in a ring pattern in which a spot pattern could be confirmed.
The X-ray radial distribution function resulted in discontinuous peak curve.
The specific area was measured by the BET method, resulting in that the specific area was 40 m 2 /g.
Comparative Preparation Method A vanadium-molybdenum oxide was prepared by rooo the following method.
S. A vanadium oxide and a molybdenum oxide were mixed at a ratio of 7:3, and the mixture was heated to 800°C in a platinum crucible as to be melted and mixed. Then, the mixture was cooled gradually so that 15 the block-shape vanadium oxide and molybdenum oxide were prepared. They were crushed by a roller mill so that grains of vanadium oxide-molybdenum oxide were ooo S" prepared.
The size of crystal grains was measured from the half value width of the X-ray analysis curve and the angle of diffraction in accordance with the scherrer's Equation. The size of the crystal grain was 700 A or larger.
The RHEED pattern resulted in a ring pattern in which a spot pattern could be confirmed.
The X-ray radial distribution function resulted in discontinuous peak curve.
229 1 The specific area was measured by the BET method, resulting in that the specific area was m2/g.
Comparative Preparaton method 51 A titanium sulfide was prepared by the following method.
A titanium disulfide powder manufactured by Kojundo Kagaku was dried at 400°C in a vacuum state.
The size of crystal grains was measured from the half value width of the X-ray analysis curve and the angle of diffraction in accordance with the Scherrer's Equation. The size of the crystal grain was 900 A or larger.
The RHEED pattern resulted in a ring pattern 15 in which a spot pattern could be confirmed.
The X-ray radial distribution function resulted in discontinuous peak curve.
*o The specific area was measured by the BET method, resulting in that the specific area was 50 m2/g.
Comparative Preparation method 52 A lithium-iron-cobalt oxide was prepared by the following method.
Lithium carbonate, iron acetate and cobalt carbonate were mixed at the same mole ratio, and decomposed at 600°C in air so that an iron cobalt oxide was prepared. Then, it was crushed by a ball mill so that grains were obtained.
230 1 The size of crystal grains was measured from the half value width of the X-ray analysis curve and the angle of diffraction in accordance with the Scherrer's Equation. The size of the crystal grain was 1000 A or larger.
The RHEED pattern resulted in a ring pattern in which a spot pattern could be confirmed.
~The X-ray radial distribution function .resulted in discontinuous peak curve.
The specific area was measured by the BET method, resulting in that the specific area was 40 m 2 /g.
Comparative Preparation Method 53 A manganese containing magnesium added theretovanadium oxide was prepared by the following method.
"15 A manganese dioxide, vanadium pentaoxide and magnesium hydroxide were mixed at a mol ratio of 10:10: 1, and then they were decomposed at 700'C in air. As a result, the manganese containing magnesium added thereto-vanadium oxide was prepared. Then, they were crushed by a ball mill so that grains were obtained.
The size of crystal grains was measured from the half value width of the X-ray analysis curve and the angle of diffraction in accordance with the Scherrer's Equation. The size of the crystal grain was 1300 A or larger.
The RHEED pattern resulted in a ring pattern in which a spot pattern could be confirmed.
231 1 The X-ray radial distribution function resulted in discontinuous peak curve.
The specific area was measured by the BET method, resulting in that the specific area was 27 m2/g.
Comparative Preparation Method 54 A lithium-copper-cobalt oxide was prepared by the following method.
A lithium carbonate, cobalt carbonate and 99e** 10 copper carbonate were mixed at the same mol ratio, and then they were decomposed at 600°C in air. As a result, the manganese containing magnesium added thereto-vanadium oxide was prepared. Then, they were crushed by a ball mill so that grains were obtained.
15 The size of crystal grains was measured from the half value width of the X-ray analysis curve and the angle of diffraction in accordance with the Scherrer's Equation. The size of the crystal grain was 1100 A or larger.
The RHEED pattern resulted in a ring pattern in which a pot pattern could be confirmed.
The X-ray radial distribution function resulted in discontinuous peak curve.
The specific area was measured by the BET method, resulting in that the specific area was m 2/g.
Analyzing Apparatus 232- The positive electrode active material prepared by Preparation Methods 46 to 55 and Comparative Preparation Methods 46 to 54 were analyzed by using the following apparatuses. The X-ray diffraction measurement was performed by using MXP3VA manufactured by MacScience.
The RHEED measurement was performed by using JEM-100SX manufactured by Nihon Denshi.
The specific area measurement by the BET method was performed by using GEMIN12300 manufactured by Micromeritex.
As a result of the comparisons between the transition metal and the group 6A element according to Preparation Methods according to the present invention and those according to Comparative Preparation Methods, the compounds according to an aspect of the present invention exhibited smaller particle grain size as compared with the results of Comparative Preparation Method while having an amorphous or microcrystal structure.
Manufacturing of Lithium Secondary Battery Lithium secondary batteries were manufactured by using the positive electrode active materials prepared by the foregoing preparation methods.
C
C
[N:\LIBE101316:MXL -233- Example 46 The positive electrode active material prepared by the foregoing Preparation Method 46 was used to manufacture a battery which had a simple structure, which could be assembled simply and which had a cross sectional shape schematically shown in Fig. 2.
In an atmosphere of dry argon gas, the negative electrode active material 201 was used in such a manner that the titanium mesh collector 200 was pressed against the reverse side of the lithium metal foil. Then, the surface of lithium was covered with a fluororesin thin film by using thin solution of Lumiflon, which was a fluororesin paint manufactured by Asahi Glass, so that the negative electrode was manufactured.
Acetylene black powder and xylene solution of the Lumiflon, which was a fluororesin paint manufactured by Asahi Glass, were mixed with the positive electrode active material which was prepared by Preparation Method 46 and which was lithium-manganese oxide. The mixture was applied to the titanium mesh, and it was hardened at 80 0 C, and then heated with microwaves. As a result, the positive electrode 203 was formed.
9* The electrolyte solution was prepared by dissolving, by 1 M (mol/l), boronic acid tetrafluoride lithium salt in 25 an equal quantity mixture solvent of propylene carbonate (PC) and dimethoxyethane (DME).
The separator 208 was manufactured in such a a a.. a a.* *aa.
a a [N:\LIBE01316:MXL 234manner that a polypropylene separator having small apertures was sandwiched by unwoven polypropylene sheets.
The assembly was performed in such a manner that the separator 208 was sandwiched between the negative electrode 201 and the positive electrode 203, followed by inserting them into a positive electrode case 207 made of titanium clad stainless steel. Then, the electrolyte solution was injected. Then, the negative electrode cap 206 made of the titanium clad stainless steel and the insulating packing 210 made of fluorine rubber were used for sealing so that the lithium secondary battery was manufactured.
Example 47 The vanadium oxide prepared by Preparation Method 47 was used as the positive electrode active material, a battery having a cross sectional shape schematically shown in Fig. 2 was manufactured.
First, the nickel mesh collector was pressed against the reverse side of the lithium metal foil in an atmosphere of dry argon gas so that the negative electrode was manufactured.
Acetylene black powder and Super Konak F which was a fluororesin paint manufactured by Nihon Yushi were mixed with the vanadium oxide serving as the positive electrode active material and prepared by Preparation Method 2, 25 followed by adding xylene by a small quantity.
S* a [N:\LIBE01316:MXL -235- The mixture was applied to the nickel mesh, and it was hardened at 150 0 C. As a result, the positiveelectrode was manufactured.
Then, similar processes to those according to Example 46 were performed so that the lithium secondary battery shown in Fig. 2 was assembled.
Example 48 By using the positive electrode active material prepared by Preparation Method 48, a battery which had a simple structure, which could be assembled simply and which had a cross sectional shape schematically shown in Fig. 2 was assembled.
First, the nickel mesh collector was pressed against the reverse side of the lithium metal foil in an atmosphere of dry argon gas so that the negative electrode was manufactured.
Acethylene black powder and tetrafluoroethylene polymer powder were mixed with the lithium-nickel oxide prepared by Preparation Method 48 and serving as the positive electrode active material. The mixture was pressed against the nickel mesh with heat as to be formed into the positive electrode 203.
Then, similar processes to those according to Example S: 46 were performed so that the lithium secondary battery 25 shown in Fig. 2 was assembled.
Example 49 The lithium-nickel-cobalt oxide prepared by 9e** a [N:\LIBE]O1316:MXL 236 Preparation Method 49 was used as the positive electrode active material so that the battery shown in Fig. 2 was manufactured by the process similar to that according to Example 48.
Example The vanadium-molybdenum oxide prepared by Preparation Method 50 was used as the positive electrode active material so that the battery shown in Fig. 2 was manufactured by the process similar to that according to Example 48.
Example 51 The vanadium-molybdenum oxide prepared by Preparation Method 51 was used as the positive electrode active material so that the battery shown in Fig. 2 was manufactured by the process similar to that according to Example 48.
Example 52 The titanium sulfide prepared by Preparation Method 52 was used as the positive electrode active material so that the battery shown in Fig. 2 was manufactured by the process similar to that according to Example 48.
Example 53 The lithium-iron-cobalt oxide prepared by Preparation Method 53 was used as the positive electrode active material so that the battery shown in Fig. 2 was manufactured by the process similar to that [N:\LIBE]01316:MXL -237according to Example 48.
Example 54 The manganese containing magnesium added thereto vanadium oxide prepared by Preparation Method 54 was used as the positive electrode active material so that the battery shown in Fig. 2 was manufactured by the process similar to that according to Example 48.
Example The lithium-copper-cobalt oxide prepared by Preparation Method 55 was used as the positive electrode active material so that the battery shown in Fig. 2 was manufactured by the process similar to that according to Example 48.
Comparative Example 46 By using the positive electrode active material prepared by Comparative Preparation method 46, the battery having a cross sectional shape schematically shown in Fig. 2 was manufactured.
First, the titanium mesh collector 200 was pressed against the reverse side of the lithium metal foil in an atmosphere of dry argon so that the negative electrode was manufactured.
Acetylene black powder and tetrafluoroethylene polymer S: powder were mixed to the lithium-manganese oxide prepared by 25 Comparative Preparation Method 46 and serving as the positive electrode active material as to be, with heat, pressed and formed into the positive electrode to oo ft ft t f ft f r ftft ft [N:\LIBE]01316:MXL -238- 203.
Then, similar processes to those accordingto Example 46 were performed so that the lithium secondary battery was assembled.
Comparative Example 47 The vanadium oxide prepared by Comparative Preparation Method 47 was used as the positive electrode active material so that the battery shown in Fig. 2 was manufactured by the process similar to that according to Example 48.
Comparative Example 48 The lithium-nickel oxide prepared by Comparative Preparation Method 48 was used as the positive electrode active material so that the battery shown in Fig. 2 was manufactured by the process similar to that according to Example 48.
Comparative Example 49 The lithium-nickel-cobalt oxide prepared by Comparative Preparation Method 49 was used as the positive electrode active material so that the battery shown in Fig.
2 was manufactured by the process similar to that according to Example 48.
Comparative Example The vanadium-molybdenum oxide prepared by Comparative Preparation Method 50 was used as the positive electrode 25 active material so that the battery shown in Fig. 2 was manufactured by the process similar a a a.* a.
[N:\LIBE]O1316:MXL -239to that according to Example 48.
Comparative Example 51 The titanium sulfide prepared by Comparative Preparation Method 51 was used as the positive electrode active material so that the battery shown in Fig. 2 was manufactured by the process similar to that according to Example 48.
Comparative Example 52 The lithium-iron-cobalt oxide prepared by Comparative Preparation Method 52 was used as the positive electrode active material so that the battery shown in Fig. 2 was manufactured by the process similar to that according to Example 48.
Comparative Example 53 The manganese containing magnesium added thereto vanadium oxide prepared by Comparative Preparation Method 53 was used as the positive electrode active material so that the battery shown in Fig. 2 was manufactured by the process similar to that according to Example 48.
Comparative Example 54 The lithium-copper-cobalt oxide prepared by Comparative Preparation Method 54 was used as the positive electrode active material so that the battery shown in Fig.
S 2 was manufactured by the process similar to that according 25 to Example 48.
Evaluation of Performance of Lithium Secondary Battery *a *9 [N:\LIBE]01316:MXL 240- The performance of lithium secondary batteries according to Examples and Comparative Examples,wasevaluated. The evaluation was performed by a charge and discharge cycle test under the following conditions with respect to the cycle life of the batteries according to Comparative Examples.
The conditions for the cycle test were made as follows: the charge and discharge was performed by 0.2C (electric current which was 0.2 times capacity/time), pause for 30 minutes and a cut-off voltage of 1.0V was applied. A charging/discharging apparatus HJ-101M6 manufactured by Hokuto Electric was used. The charge/discharge test was commenced at discharge, the battery capacity was evaluate the quantity of the third discharge and the cycle life was evaluate by the number of cycles when the battery capacity had deteriorated to 60% or less.
The lithium batteries using the positive electrode active materials respectively according to an aspect of the present invention and the comparative examples, that is, the battery capacities and cycle life of the examples of the present invention and the comparative examples were evaluated as shown in Table 12 while making the performance S of the battery according to the comparative example to be a reference value of 1.
25 As can be understood from Table 12, the comparisons :made between Examples 46 to 55 and e• 05* *0 o .3 0*0eS 0 0S S 00 [N:\LIBE]01316:MXL -241 Comparative Examples 46 to 54 resulted that the use of the batteries according to an aspect of the present invention enabled the capacity of the battery to be enlarged and the cycle life to be lengthened.
Table 12 Capacity of Manufactured Lithium Battery Cycle Life Battery (Present (Present Invention Invention) Example Comparative Comparative Comparative Example Example) Example Example 46 Comparative 2.3 4.8 Example 46 Example 47 Comparative 3.1 3.2 Example 47 Example 48 Comparative 2.1 1.7 Example 48 Example 49 Comparative 2.0 1.4 Example 49 Example 50 Comparative 4.1 2.9 Example Example 51 Comparative 3.2 2.1 Example Example 52 Comparative 2.4 1.4 Example 51 Example 53 Comparative 2.3 Example 52 Example 54 Comparative 1.7 Example 53 Example 55 Comparative 2.2 1.8 Example 54 Further, combinations of the embodiments of the present invention will enable further improved secondary [N:\LIBE101316:MXL 242 battery to be obtained.
According to an aspect of the present inlvention, if dendrite of lithium or zinc grows at the time of charge, short circuits between the negative electrode and the positive electrode can be prevented. Therefore, a lithium secondary battery, a nickel zinc secondary battery and an air zinc secondary battery exhibiting a long charge/discharge cycle life can be manufactured. Further, the metal lithium can be used as the negative electrode active material. Therefore, a secondary battery exhibiting a high energy density can be manufactured while improving safety.
Although the invention has been described in its preferred form with a certain degree of particularly, it is understood that the present disclosure of the preferred form can be changed in the details of construction and the combination and arrangement of parts may be resorted to without departing from the spirit and the scope of the invention as hereinafter claimed.
V. [N:\LIBE]01316:MXL

Claims (5)

  1. 2. A secondary battery according to claim 1, wherein said multi-layered metal oxide film contains one or more types of materials selected from a group consisting of alumina, titanium oxide, silica, selenium oxide, zirconia oxide, magnesium oxide, chrome oxide, calcium oxide, tin oxide, indium oxide and germanium oxide.
  2. 3. A secondary battery according to claim i, wherein said bimolecular film is compound of an amphipathic *material having both hydrophobic group and a hydrophilic 25 group.
  3. 4. A secondary battery according to claim 1, wherein said bimolecular film is formed in a film shape combining an amphipathic material and a polymer compound. 9* A secondary battery according to claim i, 9wherein said bimolecular film is a polyion complex reactant o of an ionic amphipathic material and a polymer electrolyte. 35
  4. 6. A secondary battery according to claim 1, wherein said multi-layered metal oxide film is a composite with an organic polymer. [R:\LIBE]0121 .doc
  5. 244- 7. A secondary battery according to claim i, wherein said multi-layered metal oxide film is a portion of said separator. 8. A secondary battery according to claim 1i, wherein the surface of said positive electrode made of said positive electrode active material and opposing said negative electrode is covered with at least a film through which ions relating to battery reactions are able to pass. 9. A secondary battery according to claim 1, wherein the surface of said negative electrode made of said negative electrode active material and opposing said positive electrode is covered with at least a film through which ions relating to battery reactions are able to pass. A secondary battery according to claim 8, wherein said film through which the ions relating to the battery reactions are able to pass is made of a multi- layered metal oxide film prepared in a mold made of a bimolecular film. 11. A secondary battery according to claim 1, wherein said negative electrode active material is lithium 25 or lithium alloy. 12. A secondary battery according to claim 1, wherein said negative electrode active material is zinc or zinc alloy. 13. A secondary battery according to claim 1, wherein said multi-layered metal oxide film is subjected to lipophilic treatment. S g. 35 14. A secondary battery according to claim 1, wherein said multi-layered metal oxide film has a conductor member on the surface thereof which opposes said negative electrode. [R:\LIBE]01211 .doc -245 A secondary battery according to claim 1, wherein said bimolecular film is selected from a group consisting of p octyloxyaniline hydrochloride, P (octyloxy) p' hydroxyazobenzene, p (10 octyloxy) p' octyloxyazobenzene, dodecyl N [p {p (10 bromodecyloxy)phenylazo}benzoil]L -alaninate, L glutamic acid didodecylester hydrochloride, N [11 bromoundecanoyl] L glutamic acid didodecylester, dimethyldihexadecylammonium bromide, N [P (trimethylammonio)etyloxybenzoil]didodecyl L glutamic acid bromide, dioctadecylmethyldimethylammomonium bromide, N [11 hydroxyundecanoyl] L glutamic acid ditetradecylester, N [11 phospholoundecanoyl] L acid ditetradecylester, 1, 2 bis (hexadecyloxycarbonyl) ethane 1 sulfonic acid sodium, N oxo 1, 3, 2 oxazaphosphoryl) 11 oxadodecanoyl] L glutamic acid didoecylester, N trimethylammonio ethylphosphonate)undecanoyl] L glutamic acid didodecylester, N ammomonio ethylphosphonate)undecanoyl] L glutamic acid didodecyl ester and 1, 3 hexadecyl 2 polyethylene S 5 glycolylglyceline. 16. A secondary battery, substantially as herein described herein with reference to any one of the embodiments as illustrated in the drawings. 0e90 DATED this eighteenth Day of November, 1999 Canon Kabushiki Kaisha Patent Attorneys for the Applicant SPRUSON FERGUSON 0@ [R:\LIBE]01211.doc
AU26133/97A 1992-11-30 1997-06-19 Secondary battery Ceased AU715180B2 (en)

Applications Claiming Priority (13)

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JP4320557A JP2943127B2 (en) 1992-11-30 1992-11-30 Rechargeable battery
JP4-320559 1992-11-30
JP4320559A JP2771406B2 (en) 1992-11-30 1992-11-30 Rechargeable battery
JP4-320557 1992-11-30
JP4320558A JP3067426B2 (en) 1992-11-30 1992-11-30 Lithium secondary battery and method for producing positive electrode active material
JP4-320560 1992-11-30
JP4-320558 1992-11-30
JP32056092A JP3487556B2 (en) 1992-11-30 1992-11-30 Lithium secondary battery
JP34456392A JP3423338B2 (en) 1992-12-24 1992-12-24 Rechargeable battery
JP4-344563 1992-12-24
JP5-78342 1993-04-05
JP07834293A JP3530544B2 (en) 1992-09-14 1993-04-05 Rechargeable battery
AU52003/93A AU5200393A (en) 1992-11-30 1993-11-29 Secondary battery

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WO2008004168A3 (en) * 2006-07-01 2008-02-28 Gillette Co Lithium cell

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US5147739A (en) * 1990-08-01 1992-09-15 Honeywell Inc. High energy electrochemical cell having composite solid-state anode

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US3953241A (en) * 1970-03-12 1976-04-27 Westinghouse Electric Corporation Heat resistant substrates and battery separators made therefrom
US5147739A (en) * 1990-08-01 1992-09-15 Honeywell Inc. High energy electrochemical cell having composite solid-state anode

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008004168A3 (en) * 2006-07-01 2008-02-28 Gillette Co Lithium cell
EP2146388A1 (en) * 2006-07-01 2010-01-20 The Gilette Company Lithium cell

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