JPH11233116A - Electrode structure for lithium secondary battery, method for manufacturing the same, and lithium secondary battery - Google Patents

Abstract

(57) [Problem] To provide a long-life lithium secondary battery that suppresses capacity reduction. SOLUTION: A metal 103 which is not alloyed with lithium is used as a current collector, and a metal 104 which is alloyed with lithium is provided on the surface of the current collector.
In the negative electrode 102 made of the electrode structure for a lithium secondary battery in which is disposed, the metal 103 used as the current collector is deformed according to the volume change of the metal 104 alloyed with lithium caused by charging and discharging. . A lithium secondary battery using the electrode structure for a lithium secondary battery as a negative electrode.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrode structure for a lithium secondary battery, a method for producing the same, and a secondary battery using the structure as a negative electrode. In particular, the present invention relates to a lithium secondary battery capable of preventing a current collector from being broken due to repetition of charge and discharge and suppressing a decrease in capacity.

[0002]

2. Description of the Related Art In recent years, due to the problem of environmental protection and the spread of portable devices, various studies have been made on secondary batteries more than ever. Regarding the problem of environmental protection, research is being conducted to eliminate carbon dioxide emitted from vehicles running on current fossil fuels by replacing them with electric vehicles. Also,
From the viewpoint of effectively utilizing power, secondary batteries for load leveling have also been studied. The performance required for these secondary batteries includes high capacity, light weight, long life, and low cost. On the other hand, portable devices are required to be particularly high-capacity, small, and lightweight.

To satisfy these characteristics, nickel-hydrogen secondary batteries and lithium secondary batteries have been put into practical use.
Furthermore, research and development are being vigorously pursued for higher performance. Nickel-metal hydride rechargeable batteries are inferior to lithium rechargeable batteries in that they are lightweight, but because of their low cost and ease of manufacture, they can be used as power sources for portable devices.
In addition, it has begun to be practically used as a power source for electric vehicles, though partly.

On the other hand, lithium secondary batteries initially used metallic lithium. However, there were problems such as that lithium dendrite was easily generated at the negative electrode, the life was short, and short-circuit was easy. As a means for solving this problem, a lithium ion secondary battery using carbon for the negative electrode and lithium cobaltate or lithium nickelate for the positive electrode has been developed,
Commercialized. In this battery, lithium ions are taken in and out between carbon crystal layers by charge / discharge, so that dendrites are extremely unlikely to be generated, and the above-described problems are unlikely to occur. For this reason, it is currently widely used as a power source for portable devices.

[0005]

The above-mentioned lithium ion secondary battery has a sufficiently high energy density, which is a feature of the lithium secondary battery, as compared with a lithium secondary battery using metallic lithium as a negative electrode active material. Not achieved. This is because the capacity density of metallic lithium is 3850 mAh / g, while the capacity density of carbon is 372 mAh / g. For this reason, it cannot be said that the original lithium secondary battery has been put to practical use.

A method using a lithium alloy such as lithium-aluminum is disclosed as a method for approaching the intrinsic capacity density of lithium metal and suppressing the generation of dendrite. For example, JP-A-63-13264, JP-A-5-47381, JP-A-5-1901
No. 71 publication. However, even when a lithium alloy is used for the negative electrode, the negative electrode repeatedly expands and contracts during repeated discharges, and cracks and the like may occur in the negative electrode, making it impossible to maintain a sufficient current collecting property.

Japanese Patent Application Laid-Open No. 63-114057 discloses a negative electrode having a base made of a mixture of fibrous aluminum and metal fibers which do not alloy with lithium. However, in this case, due to expansion and contraction of the fibrous aluminum due to charge and discharge, a decrease in the bonding force between lithium and a metal fiber that does not alloy with lithium and generation of cracks at the interface therewith occur.
In some cases, sufficient current collecting properties could not be maintained.

Further, Japanese Patent Application Laid-Open No. Hei 5-234585 discloses a method of uniformly depositing a metal powder which hardly forms an intermetallic compound with lithium metal on the surface of a substrate made of lithium metal to reduce precipitation of dendrite. A battery is disclosed that increases charging efficiency and improves cycle life. However, lithium metal, which is the base material, expands due to charge and discharge,
As a result of repeated shrinkage, the attached powder may fall off or the substrate may crack, as described above, sufficient current collection of the negative electrode may not be maintained and dendrite deposition may not be sufficiently controlled.

Also, JOURNAL OF APPLI
ED ELECTROCEHMISTRY 22,62
0-627, (1992), report of a lithium secondary battery using an aluminum foil whose surface has been subjected to an etching treatment as a negative electrode. However, when the charge / discharge cycle is repeated up to the practical range, the aluminum foil is cracked by the repetition of charge / discharge, and the current collecting property is reduced and dendrite growth occurs. Therefore, even in this case, a secondary battery having a long life at a practical level has not been obtained.

An invention which solves many of these disadvantages is disclosed in Japanese Patent Application Laid-Open No. Hei 8-50922. This is because the negative electrode is composed of a metal element that forms an alloy with lithium and a metal element that does not form an alloy with lithium, and the output terminal on the negative electrode side is pulled out from the current collector where the metal that does not form an alloy with lithium is arranged. And a battery having a long life and a high energy density has been achieved. However, in order to further increase the energy density, when a positive electrode, a negative electrode, and a separator are efficiently wound or laminated, and a case is densely filled to produce a battery, a metal that forms an alloy with lithium by charging is used. In this case, the volume expands, and as a result, a crack is generated in a current collecting portion provided with a metal that does not form an alloy with lithium, so that the negative electrode is cut off and the current collecting ability of the negative electrode may be reduced. For this reason, although high energy density can be obtained, cycle life characteristics have not been satisfactory.

An object of the present invention is to solve the above problems and to provide a long-life, high-capacity lithium secondary battery, an electrode structure for the lithium secondary battery, and a method of manufacturing the same.

[0012]

That is, a first aspect of the present invention is an electrode for a lithium secondary battery in which a metal that does not alloy with lithium is used as a current collector, and a metal that alloys with lithium is disposed on the surface of the current collector. An electrode structure for a lithium secondary battery, wherein a metal that does not alloy with lithium used as a current collector is deformed in accordance with a change in volume of a metal that alloys with lithium due to charge and discharge. .

It is preferable that the material of the metal not alloyed with lithium is nickel, copper, titanium, iron, cobalt, chromium, tungsten, silver or a combination thereof. It is preferable that the metal that does not alloy with lithium has pores two-dimensionally or three-dimensionally. It is preferable that the porosity of the metal not alloyed with lithium is 5 to 50%.

It is preferable that the metal not alloyed with lithium is a punched metal, felt, expanded, or foam. It is preferable that a cut is provided in the metal that is not alloyed with lithium. It is preferable that the thickness of the metal that does not alloy with lithium is 8 to 15 μm.

It is preferable that the metal to be alloyed with lithium is aluminum, tin, indium, zinc, lead, magnesium, potassium, sodium, calcium, strontium, silicon or a combination thereof. The porosity of the metal alloyed with lithium is 20 to 8
It is preferably 0%. It is preferable that the thickness of the metal alloyed with lithium is 10 to 50 μm.

According to a second aspect of the present invention, there is provided an electrode structure for a lithium secondary battery in which a metal which is not alloyed with lithium used as a current collector is deformed in accordance with a change in volume of a metal which is alloyed with lithium by charge / discharge. A method for producing an electrode structure for a lithium secondary battery, comprising: using a metal that does not alloy with lithium as a current collector; and disposing a metal that alloys with lithium on the surface of the current collector. .

The method of arranging the metal that is to be alloyed with lithium with respect to the metal that is not to be alloyed with lithium is as follows. Is preferred.

When arranging a metal which is to be alloyed with lithium on the metal which is not to be alloyed with lithium, at least one of polyvinyl alcohol, cellulose, polytetrafluoroethylene and polyvinylidene fluoride is used as a binder and alloyed with lithium. After the metal powder is formed into a slurry, it is preferable to apply the metal to a metal that does not alloy with lithium.

When a metal which is alloyed with the binder and lithium is used as a slurry, a conductive agent is preferably added.
Preferably, the conductive agent is carbon.

With respect to the metal not alloying with lithium, the method of arranging the metal alloying with lithium is as follows: the metal alloying with lithium is formed by electrolytic plating, electroless plating, laser plating, sputtering, or resistance heating. It is preferable to use a combination of at least one selected from an evaporation method, an electron beam evaporation method, a thermal CVD method, a reduced pressure CVD method, a plasma CVD method, and a laser CVD method.

It is preferable that the sheet-shaped metal not being alloyed with lithium is disposed on the surface of the metal to be alloyed with lithium and then punched or expanded. The metal not alloyed with lithium is punched,
It is preferable to arrange a metal which is in an expanded state and alloys with helium.

According to a third aspect of the present invention, there is provided a negative electrode for a lithium secondary battery, comprising the above electrode structure for a lithium secondary battery.

According to a fourth aspect of the present invention, there is provided a positive electrode for a lithium secondary battery, and a metal which is not alloyed with lithium as a current collector,
A metal alloying with lithium is placed on the surface,
Along with the volume change of the metal alloyed with lithium due to charge / discharge, the negative electrode consisting of the electrode structure for a lithium secondary battery in which the metal that does not alloy with lithium used as the current collector is deformed is wound through a separator. A lithium secondary battery characterized in that:

It is preferable that the material of the metal not alloyed with lithium is nickel, copper, titanium, iron, cobalt, chromium, tungsten, silver or a combination thereof.

It is preferable that the metal not alloyed with lithium has two-dimensional or three-dimensional vacancies. It is preferable that the porosity of the metal not alloyed with lithium is 5 to 50%. Preferably, the metal that does not alloy with lithium is a punched metal, felt, expanded or foamed material.

It is preferable that the metal not being alloyed with lithium has a cut. It is preferable that the thickness of the metal that does not alloy with lithium is 8 to 15 μm. The metal alloyed with lithium is aluminum,
Tin, indium, zinc, lead, magnesium, potassium,
Preferably it is sodium, calcium, strontium, silicon or a combination thereof.

The porosity of the metal alloyed with lithium is preferably 20 to 80%. It is preferable that the thickness of the metal alloyed with lithium is 10 to 50 μm. It is preferable to use aluminum as the current collector of the positive electrode.

Preferably, the current collector of the positive electrode is a sheet, punched metal, felt, expanded or foamed material. A sheet used as a current collector for the positive electrode,
Expanded or punched metal thickness 15-3
It is preferably 0 μm. It is preferable to use lithium nickelate or a material in which part of nickel is replaced with manganese, cobalt, or magnesium as the active material of the positive electrode. The ratio of the thickness of the negative electrode to the positive electrode is preferably 20 to 50%.

Further, the present invention provides a positive electrode for a lithium secondary battery as described above and a metal which is not alloyed with lithium as a current collector,
A metal alloying with lithium is placed on the surface,
With the change in volume of the metal that is alloyed with lithium by charging and discharging, the metal that is not alloyed with lithium used as the current collector is deformed. In the secondary battery, the cross-sectional area obtained by subtracting the total cross-sectional area of the positive electrode, the negative electrode, and the separator from the cross-sectional area of the inner diameter of the battery case is 0.3 to 1.0 times the cross-sectional area of the metal alloyed with lithium of the negative electrode. It is a lithium secondary battery characterized by the following. Preferably, the separator is made of a film-like polypropylene or polyethylene, and has a thickness of 15 to 40 μm.

The present invention also provides a positive electrode for a lithium secondary battery as described above, and a metal which is not alloyed with lithium as a current collector.
A metal alloying with lithium is placed on the surface,
With the change in volume of the metal that is alloyed with lithium by charging and discharging, the metal that is not alloyed with lithium used as the current collector is deformed. The separator is a lithium secondary battery, wherein the separator comprises a film and a nonwoven fabric. The separator is made of polypropylene or polyethylene and has a thickness of 15
It is preferably from 50 μm to 50 μm.

Further, the present invention provides a positive electrode for a lithium secondary battery as described above, and a metal which is not alloyed with lithium as a current collector,
A metal alloying with lithium is placed on the surface,
With the change in volume of the metal that is alloyed with lithium by charging and discharging, the metal that is not alloyed with lithium used as the current collector is deformed. A lithium secondary battery comprising: a non-woven fabric as at least a separator; and an electrolyte in a gel state.

Preferably, the separator is made of polypropylene or polyethylene and has a thickness of 15 to 40 μm. It is preferable to use polyethylene oxide, polyvinyl alcohol or polyacrylamide as the gelling agent.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of study to solve the above problems, the present inventor has confirmed that a metal alloyed with lithium becomes an intermetallic compound of lithium and metal upon charging, and that the volume expands. did. The degree of expansion depends on the type of metal used and the level of charge. If the degree of the expansion is large, a stress is applied to the current collector, which is a metal not alloyed with lithium, and a crack is generated, which may cause the current collector to break. In some cases, it may be broken into multiple pieces. The present invention is based on the finding of these results.

In order to solve the above problems and achieve the object, at least a metal which is not alloyed with lithium is used as a current collector for an electrode structure for a lithium secondary battery, and the surface thereof is alloyed with lithium. In the electrode structure for a lithium secondary battery in which a metal is disposed, it is necessary that the metal that is not alloyed with lithium used as the current collector is deformed due to a change in volume of the metal that is alloyed with lithium by charging and discharging. There is.

The electrode structure for a lithium secondary battery of the present invention can be used as a negative electrode and a positive electrode of a secondary battery and a negative electrode and a positive electrode of a lithium primary battery. preferable.

Further, the lithium secondary battery of the present invention is a lithium secondary battery having a positive electrode for a lithium secondary battery, a current collector made of a metal that does not alloy with lithium, and a metal that is alloyed with lithium disposed on the surface thereof. In a battery (discharged state) in which a negative electrode composed of an electrode structure is wound via a separator, the cross-sectional area of the positive electrode, the cross-sectional area of the negative electrode, and the cross-sectional area of the separator are calculated from the cross-sectional area of the battery can (cross-sectional area of the inner circumference of the battery can). Is 0.3 to 1.0 times, preferably 0.4 to 0.8 times the cross sectional area of the metal alloyed with lithium of the negative electrode. . The cross-sectional area of the gap in this case includes the cross-sectional area of the winding axis at the time of winding.

Further, the lithium secondary battery of the present invention is a lithium secondary battery having a positive electrode for a lithium secondary battery, a current collector made of a metal not alloyed with lithium, and a metal alloyed with lithium disposed on the surface thereof. In a battery in which a negative electrode composed of an electrode structure is wound via a separator, the separator is made of a film and a nonwoven fabric.

The function of the present invention is as follows. When a metal that is alloyed with lithium expands due to charge and discharge, when a metal that is not alloyed with lithium is used as the current collector, the current collector is deformed. By doing so, cracking or breaking of the negative electrode comprising the electrode structure for a lithium secondary battery is to be prevented beforehand. The deformation of the current collector depends on the material of the current collector,
It can be appropriately generated by a method by selecting a shape, a method of optimizing a battery design in a wound type battery, and a method of using a shrinkable separator. By performing these, a lithium secondary battery having high capacity and long life can be obtained.

As a method of selecting the shape and material of the current collector, it is important to provide a two-dimensional or three-dimensional space. Specifically, the current collector is a punched metal, felt, expanded, or foamed material, and it is desirable to provide an appropriate gap. With these shapes, the current collector, which is a metal that does not alloy with lithium, easily expands as the volume of the metal that alloys with lithium expands upon charging. The expansion of the negative electrode comprising the electrode structure for a lithium secondary battery expands and deforms mainly in the two-dimensional or three-dimensional void direction of the current collector. Therefore, the stress can be relieved in a relatively narrow range, and there is no crack or breakage.

The porosity of the current collector (volume ratio of vacancies existing in the current collector) indicates the ratio of space per unit volume.
Approximately 5 to 50%, preferably 20 to 40% is desirable. The reason for this is that if it is less than 5%, depending on the type of metal alloyed with lithium, the type of metal not alloyed with lithium, and the type of current collector, the expansion caused by the alloying of lithium and metal during charging is completely absorbed. I can't do things. If it exceeds 50%, problems such as a decrease in current collecting properties and difficulty in production will occur. It is also effective to make a cut in the current collector, and the stress due to the volume expansion of the metal alloyed with lithium can be reduced.

The porosity is defined as the weight of the current collector / the apparent volume of the current collector (the external shape of the current collector, for example, the volume of a sheet if it is a sheet) = the apparent density and the apparent density. The density / true density of the current collector (actual density of the current collector material obtained from the composition of the current collector material) = porosity.

On the other hand, when the current collector is in the form of a general sheet, both sides are pressed by the positive electrode via the separator, and the stress cannot be relaxed in a relatively narrow range. Cracks and fractures may occur. When the current collector that is a metal that does not alloy with lithium and the metal that forms an alloy with lithium have low adhesion, the metal that forms an alloy with lithium may peel off from the current collector. Therefore, the material and shape of the current collector are selected as described above,
Prevents current collector peeling and cracking.

Nickel, copper, titanium, nickel, copper, titanium, and the like, which are not alloyed with lithium used as the material of the current collector.
Aluminum, tin, indium, zinc, lead, magnesium, potassium, sodium, calcium, strontium, silicon or a combination of these as iron, cobalt, chromium, tungsten, silver or a combination thereof and a metal alloying with lithium There is a match.

On the other hand, as described above, the current collector comprises a positive electrode for a lithium secondary battery and a metal which does not alloy with lithium, and has an electrode structure for a lithium secondary battery in which a metal which alloys with lithium is disposed on the surface thereof. In a battery in which the negative electrode is wound through a separator, the cross-sectional area obtained by subtracting the cross-sectional area of the positive electrode, the cross-sectional area of the negative electrode, and the cross-sectional area of the separator from the cross-sectional area of the battery can is the cross-sectional area of the metal that is alloyed with lithium of the negative electrode. 0.3 ~
The function of the lithium secondary battery, characterized by being 1.0 times, is that when the volume of the metal alloyed with lithium expands due to charging, a gap is provided in the battery case to allow the metal not alloyed with lithium to be formed. It is to relieve stress by deforming.

In a wound battery, a gap is generally formed at the center of the wound group due to restrictions from the viewpoint of manufacturing. This gap is centered on two shafts made of steel, stainless steel, etc.
When the positive electrode and the negative electrode are wound through a separator and filled in a battery case, the shaft is removed to remove the shaft. To increase the capacity, it is important to reduce the gap. In fact, this is an important issue for lithium ion batteries that have relatively small volume changes. However, in a battery using a metal that alloys with lithium for the negative electrode, the volume change of the negative electrode is large, so if the gap at the center of the wound group or the gap between the outer periphery of the wound group and the case is not optimized, current collection will occur. In some cases, a metal that is not alloyed with lithium, which is a body, cannot be deformed, and the stress is partially concentrated, resulting in cracking or fracture.

The volume expansion of the metal alloying with lithium is
Depending on the charge, it depends on the type of metal that is alloyed with lithium and the amount of charge, but is approximately 2 to 4 times in a normal charge state. Since the metal alloyed with lithium usually has a porosity of several tens to 80%, some of the pores can absorb the expansion, but there is a limit. Therefore, as the size of the gap with respect to the winding group (at the time of discharge),
Although it depends on the type of metal that is alloyed with lithium,
As described above, 0.3 to 1.0 times the metal alloyed with lithium is required in comparison with the cross-sectional area of the battery. In order to alleviate this expansion, it is most desirable that the area of the gap at the center of the winding group and the area of the gap between the outer periphery of the winding group and the case be substantially the same. However, the effect can be obtained even if one of the gaps is increased. In this case, the deformation of the negative electrode for alleviating the expansion partially increases.

When tin is used as the metal to be alloyed with lithium, it is particularly greatly alloyed with lithium to form Li ₂₂ S
When n ₅ is formed, the volume becomes 3.8 times. However, in the alloying reaction by actual charging, the alloying of lithium does not proceed up to this region, and the alloying probably ends at Li ₇ Sn ₂ or Li ₁₃ Sn ₅ , and is 2.5 to 2.9 times. Inflates to The layer actually obtained by plating is about 50
% Porosity, but the expansion that can be absorbed by these pores is approximately 70% of the expansion, and absorption for other expansions must be determined for other layers than the tin layer. For that purpose, the above gap is required.

The porosity of the layer made of a metal alloyable with lithium provided on the current collector is formed by the top surface of the layer provided on the current collector and the current collector surface. The ratio of the space (vacancies) not actually occupied by the metal material in the apparent space of the metal layer to be alloyed with lithium. Specifically, the volume (thickness × area) of the layer is expressed by V ′
When the weight and specific gravity (true density) of the constituent materials of the layer (metal material alloying with lithium) are wi and di, respectively, the true volume V (V = Σ (wi / d
i)), where the porosity is (V'-V) / V '. (Weight of the layer of metal alloyed with lithium W = Ｗw
i (W = w in the case of one kind of metal material), and the bulk density of the layer is d ′ = w / V). Although the porosity is substantially the same as the porosity of the above-described current collector, a plurality of types of metal elements are often used for the metal layer that is alloyed with lithium. Since it is necessary to strictly determine the true density of the material forming the layer in consideration of the composition of the material of the layer, the true density is specified as described above.

Actually, a wound group was prepared using a negative electrode comprising an electrode structure for a lithium secondary battery prepared by the above-described tin plating method. At this time, a gap at the center of the wound group was formed by the winding shaft. It was changed by changing the diameter. When this gap was 0.2 times the cross-sectional area of the tin plating layer, the copper sheet used as the current collector during charging was broken. However, when 0.3 times, the negative electrode slightly deformed, but did not break. The larger the gap, the easier it is to absorb the expansion of tin, but the capacity is reduced, so there is naturally a limit, and the effective upper limit is naturally determined.

The lithium secondary battery of the present invention has an electrode structure for a lithium secondary battery in which a positive electrode for a lithium secondary battery and a metal that does not alloy with lithium are used as a current collector, and a metal that alloys with lithium is disposed on the surface of the current collector. In a battery in which a negative electrode made of a body is wound with a separator interposed therebetween, the separator is characterized by being made of a film and a nonwoven fabric.
The nonwoven fabric can relieve the stress of the metal that does not alloy with lithium, which is caused by the expansion of the metal alloyed with lithium that occurs during charging.

In lithium secondary batteries, including lithium ion secondary batteries, a film-like separator having micropores with a thickness of several tens of μm is generally used. This is used to prevent a short circuit due to dendrite of lithium metal, which is easily generated at the negative electrode of a lithium secondary battery. In addition, this film also prevents short-circuiting due to minute foreign matters and the like mixed during the production. However, this film-shaped separator does not have enough flexibility to relieve the stress of the metal that does not alloy with lithium due to the expansion of the metal that alloys with lithium when charged.

On the other hand, the non-woven fabric is made by collecting short fibers to a certain thickness and has a higher flexibility in the thickness direction than a film-like separator. Very suitable. However, this nonwoven fabric has large gaps between short fibers, and cannot prevent short-circuiting due to dendrite or short-circuiting due to contaminating foreign substances as in the above-described film-like separator. For this reason, it is desirable to use together with a film-like separator.

On the other hand, in a battery using a gel as an electrolyte, which is called a polymer battery, the gel electrolyte acts like a film separator and prevents short-circuiting due to dendrites and short-circuiting due to contaminants. For this reason, in a battery using a gel electrolyte, there is no problem even if only a nonwoven fabric is used. As described above, by using a nonwoven fabric as the separator, the metal that is alloyed with lithium expands during charging, and the stress applied to the metal that is not alloyed with lithium can be reduced.

As described above, by forming a negative electrode by combining a metal alloying with lithium and a metal not alloying with lithium, a high capacity can be achieved, and the metal alloying with lithium at the time of charging expands. In this case, a metal that is not alloyed with lithium, that is, a current collector, is appropriately deformed to reduce stress of the current collector, thereby achieving a long life.

An embodiment of the present invention will be described below with reference to FIG. FIG. 1 is a schematic view showing a cross section of a negative electrode comprising an electrode structure for a lithium secondary battery used in a secondary battery of the present invention. As an example, a negative electrode using a punching metal is shown. FIG. 1A is a plan view, and FIG. 1B is a sectional view taken along line AA. Reference numeral 101 denotes a void portion (opening portion), and reference numeral 102 denotes a negative electrode in which a metal 103 (anode active material) that is alloyed with lithium is disposed on a metal 103 (a negative electrode current collector) that is not alloyed with lithium. . In this figure, a broken line 10 shows a state after assembling and before charging, and a solid line 20 shows a state after the negative electrode after charging is deformed. The current collector expands and deforms so that the hole becomes smaller. The same applies when an expanded foam is used. When a sheet-shaped current collector is used,
It extends mainly in the longitudinal direction of the winding. In an actual battery, because it is tightly wound or laminated, it is almost impossible to stretch, it cannot relax the stress, and cracks, breaks, or peeling of the metal alloying with lithium from the current collector occurs .

A specific example of a method for manufacturing a negative electrode will be described. (1) When the ionization tendency of the metal element that forms an alloy with lithium has a higher ionization tendency than the metal element that does not form an alloy with lithium, a member made of the metal element that forms an alloy with lithium is replaced with a metal element that does not form an alloy with lithium. By dipping in a salt solution, a part of the metal element that forms an alloy with lithium can be replaced with a metal element that does not form an alloy with lithium. The replacement amount can be controlled by the time of immersion in the solution, the concentration of the salt in the solution, and the temperature of the solution. That is, the longer the time of immersion in the solution, the greater the amount of substitution, and the higher the concentration of the salt in the solution or the higher the temperature of the solution, the faster the speed of the substitution reaction.

(2) Other methods include electrolytic plating, electroless plating, laser plating, sputtering, resistance heating vapor deposition, electron beam vapor deposition, cluster ion beam vapor deposition, and thermal plating of a layer containing a metal element forming an alloy with lithium. CVD
(Chemical Vapor Deposition
n), a method of coating on a current collector by low pressure CVD, plasma CVD, laser CVD, or the like can be used. In addition, a method of coating an ink or paste containing a metal element that forms an alloy with lithium by a method such as screen printing can also be used.

(3) In addition, a base made of a metal element that does not form an alloy with lithium is used as a current collector as it is, and a layer made of a metal element that forms an alloy with lithium is formed thereon by sputtering, resistance heating evaporation, Electron beam evaporation, cluster ion beam evaporation, thermal CVD (Chemicalapo)
r Deposition), low pressure CVD, plasma C
A method of coating on a current collector by VD, laser CVD, or the like can be used. Further, an ink or paste coating method containing a metal element that does not form an alloy with lithium by a method such as screen printing can also be used.

In common with the above (1), (2) and (3), as a metal (a material of the current collector) which does not alloy with lithium, a punching metal or a. In the case of using an expand, a metal that does not alloy with lithium (a material of the current collector) is punched or expanded from the beginning, and even if a metal that forms an alloy with lithium is disposed in the above-described manner. Well, conversely, after arranging a metal that forms an alloy with lithium on the sheet-shaped current collector in the above manner, punching out or punching, slitting and pulling,
It may be expanded.

The metal which is not alloyed with lithium, which is the current collector of the negative electrode comprising the electrode structure for a lithium secondary battery in the present invention, efficiently supplies or consumes the current consumed in the electrode reaction during charging and discharging. Is responsible for collecting power. Therefore, as a material for forming the current collector of the negative electrode, a material having high conductivity and inert to a battery reaction is desirable. Preferred materials include nickel, titanium, copper, aluminum, stainless steel, platinum, palladium, gold, zinc, various alloys, and two or more composite metals of the above materials.

The metal elements forming an alloy with lithium of the negative electrode comprising the electrode structure for a lithium secondary battery according to the present invention include aluminum, magnesium, potassium, sodium, calcium, strontium, barium, silicon, germanium, tin, lead, and the like. Indium, zinc and the like can be used, and aluminum, germanium, magnesium, calcium, lead and tin are particularly preferable.

FIG. 2 is a schematic view showing a cross section of a secondary battery according to the present invention.
03, an electrolyte, a battery case 204, and a gap 205. (A) shows before charging, and (b) shows after charging. When the negative electrode 201 forms the deformed portion 206, the positive electrode 202 and the separator 203 are also deformed, but no cracks or cuts occur in the negative electrode 201. Of course, positive electrode 2
No cracking or breakage occurs in the separator 02 and the separator 203 as well.
This is an effect of appropriately providing the gap 205 as shown in FIG. 2 in the battery case. Further, in the structure shown in the figure, a gap (for example, about 0.1 mm) may be provided between the battery 204 and a wound structure composed of an electrode and a separator.

FIG. 3 shows an example of a conventional secondary battery. This is a cross-sectional view of the battery after using a sheet-shaped current collector, filling the case with the winding group tightly with a small gap 306 at the winding shaft portion, and repeating charging and discharging. The breakage portion 305 occurs because the negative electrode 301 cannot relieve the stress. At the same time, the separator 303 and the positive electrode 302 are also broken. As a result of the charge / discharge life test, a remarkable capacity reduction occurred, but it was clear that the cause was this breakage. Although the wound type battery is described in FIG. 2, this method can be applied to a square battery or a sheet battery.

Next, the structure of the lithium secondary battery of the present invention
The manufacturing method will be described. The positive electrode in the present invention is composed of a current collector, a positive electrode active material, a conductive auxiliary material, a binder, and the like. This positive electrode has a positive electrode active material, a conductive auxiliary material,
And a mixture of a binder and a binder formed on the surface of the current collector.

Examples of the conductive auxiliary agent used for the positive electrode include graphite, carbon black such as Ketjen black and acetylene black, and fine metal powder such as nickel. As the binder used for the positive electrode, for example, when the electrolytic solution is a non-aqueous solvent system, a polyolefin such as polyethylene or polypropylene, or a fluororesin such as polyvinylidene fluoride or tetrafluoroethylene polymer, or an electrolytic solution in an aqueous solution In the case of a system, polyvinyl alcohol, cellulose, or polyamide is used.

As the current collector used for the positive electrode, the same material and shape as the current collector used for the negative electrode can be used.

In a lithium battery in which the negative electrode active material is lithium, the positive electrode active material may be a transition metal oxide, a transition metal sulfide, a lithium-transition metal oxide, or a lithium-transition metal oxide.
Transition metal sulfides are commonly used. Examples of the transition metal element of the transition metal oxide or the transition metal sulfide include, for example, S
c, Y, lanthanoid, actinoid, Ti, Zr, H
f, V, Nb, Ta, Cr, Mo, W, Mn, Tc, R
e, Fe, Ru, Os, Co, Rh, Ir, Ni, P
d, Pt, Cu, Ag, and Au. In particular, the first transition series metals Ti, V, Cr, Mn, Fe, C
o, Ni, and Cu are preferably used.

The current collector of the positive electrode in the present invention has a role of efficiently supplying a current consumed in an electrode reaction at the time of charging / discharging or collecting current generated. Therefore, as a material for forming the current collector of the positive electrode, a material having high conductivity and inert to a battery reaction is desirable. Preferred materials include nickel, titanium, aluminum, stainless steel, platinum, palladium, gold, zinc, various alloys, and two or more composite metals of the above materials. As the shape of the current collector, for example, a plate shape, a foil shape, a mesh shape, a sponge shape, a fiber shape, a punching metal, an expanded metal, and the like can be adopted.

The separator in the present invention has a role of preventing a short circuit between the negative electrode and the positive electrode. In some cases, it has a role of holding an electrolytic solution.

The separator must have pores through which lithium ions can move, and must be insoluble and stable in the electrolytic solution. Therefore, as the separator, for example, a nonwoven fabric such as glass, polyolefin such as polypropylene or polyethylene, or a fluororesin or a material having a micropore structure is preferably used. Further, a metal oxide film having fine pores or a resin film in which a metal oxide is compounded can be used. In particular, when a metal oxide film having a multilayered structure is used, the dendrite hardly penetrates, which is effective in preventing a short circuit. When a fluororesin film which is a flame retardant material, or a glass or metal oxide film which is a nonflammable material is used, safety can be further improved. The nonwoven fabric is the same material as the film and has no problem.

The use of the electrolyte in the present invention is as follows.
There are the following three cases. (1) A method used as it is. (2) A method of using as a solution dissolved in a solvent. (3) A method in which a gelling agent such as a polymer is added to a solution so that the solution is immobilized.

Generally, an electrolytic solution obtained by dissolving an electrolyte in a solvent is used. The liquid is retained on a porous separator before use. The conductivity of the electrolyte is preferably 1 at 25 ° C.
× 10 ^-3 S / cm or more, more preferably 5 × 10 ^-3 S /
cm or more. In a lithium battery in which the negative electrode active material is lithium, the following electrolyte and its solvent are suitably used.

As the electrolyte, for example, H ₂ SO ₄ , H
Acids such as Cl and HNO ₃ , lithium ions (Li ⁺ ) and Lewis acid ions (BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , Cl)
Salts composed of O ₄ ⁻ , CF ₃ SO ₃ ⁻ , BPh ₄ ⁻ (Ph: phenyl group), and mixed salts thereof are exemplified. Also,
Salts composed of cations such as sodium ion, potassium ion, tetraalkylammonium ion and Lewis acid ions can also be used. It is desirable that the salt is sufficiently dehydrated and deoxygenated by heating under reduced pressure.

Examples of the solvent for the electrolyte include acetonitrile, benzonitrile, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, dimethylformamide, tetrahydrofuran, nitrobenzene, dichloroethane, diethoxyethane, 1,2-dimethoxyethane, chlorobenzene, and the like. γ
-Butyrolactone, dioxolane, sulfolane, nitromethane, dimethylsulfide, dimethylsulfoxide, dimethoxyethane, methyl formate, 3-methyl-2-
Oxidazolidinone, 2-methyltetrahydrofuran, 3
-Propylsydnone, sulfur dioxide, phosphoryl chloride,
Thionyl chloride, sulfuryl chloride, or a mixture thereof can be used.

The solvent may be dehydrated with, for example, activated alumina, molecular sieve, phosphorus pentoxide, calcium chloride, or the like, or may be distilled in an inert gas in the presence of an alkali metal to remove impurities and dehydrate. Good to do.

In order to use only the nonwoven fabric as the separator, it is preferable to gel. As the gelling agent, it is desirable to use a polymer that absorbs the solvent of the electrolytic solution and swells. As such a polymer, polyethylene oxide, polyvinyl alcohol, polyacrylamide and the like are used. The gelation can also prevent liquid leakage.

[Battery Shape and Structure] Specific shapes of the secondary battery of the present invention include, for example, a flat shape, a cylindrical shape, a rectangular parallelepiped shape, and a sheet shape. The structure of the battery is as follows:
For example, there are a single layer type, a multilayer type, a spiral type, and the like. Among them, the spiral cylindrical battery has a feature that the electrode area can be increased by winding the separator between the negative electrode and the positive electrode with the separator interposed therebetween, and a large current can flow during charging and discharging. In addition, the rectangular or sheet-shaped battery has a feature that the storage space of a device configured to store a plurality of batteries can be effectively used.

Hereinafter, the shape and structure of the battery will be described in more detail with reference to FIGS. FIG. 5 is a sectional view of a single-layer flat (coin-shaped) battery, and FIG. 4 is a sectional view of a spiral cylindrical battery. The basic configuration of these lithium batteries includes a negative electrode, a positive electrode, an electrolyte / separator, a battery housing, and an output terminal.

In FIGS. 4 and 5, 403 and 501
Are negative electrodes, 406 and 502 are positive electrodes, 408 and 505 are negative electrode terminals (negative electrode cap or negative electrode can), 409 and 506 are positive electrode terminals (positive electrode can or positive electrode cap), 407 and 50
3 is a separator / electrolyte solution, 410 and 504 are gaskets, 401 is a negative electrode current collector, 404 is a positive electrode current collector, 411
Is an insulating plate, 412 is a negative electrode lead, 413 is a positive electrode lead,
414 is a safety valve.

In the flat (coin-shaped) secondary battery shown in FIG. 5, a positive electrode 502 including a positive electrode material layer and a negative electrode 501 including a negative electrode material layer are laminated via a separator 503 holding at least an electrolytic solution. The laminate is accommodated from the positive electrode side in a positive electrode can 506 as a positive electrode terminal, and the negative electrode side is covered with a negative electrode cap 505 as a negative electrode terminal. A gasket 50 is placed on the other part of the positive electrode can.
4 are arranged.

In the spiral cylindrical secondary battery shown in FIG. 4, the positive electrode active material layer 4 formed on the positive electrode current collector 404
A positive electrode 406 having a negative electrode 05 and a negative electrode 403 having a negative electrode active material layer 402 formed on a negative electrode current collector 401 are opposed to each other via a separator 407 holding at least an electrolytic solution, and are wrapped in multiple layers. To form a layered structure. The laminate having the cylindrical structure is accommodated in a negative electrode can 408 serving as a negative electrode terminal. Also, the negative electrode can 408
Is provided with a positive electrode cap 409 as a positive electrode terminal, and a gasket 410 is disposed at another portion in the negative electrode can. The stacked body of the electrodes having the cylindrical structure is separated from the positive electrode cap side via the insulating plate 411. The positive electrode 406 is connected to a positive electrode cap 409 via a positive electrode lead 413. The negative electrode 403 is connected to a negative electrode can 408 via a negative electrode lead 412. A safety valve 414 for adjusting the internal pressure inside the battery is provided on the positive electrode cap side.

Hereinafter, an example of a method of assembling the battery shown in FIGS. 4 and 5 will be described. (1) Negative electrode (403, 501) and positive electrode (406, 50)
Between 2), sandwich the separators (407, 503),
It is incorporated in the negative electrode can (408) or the positive electrode can (506). (2) After injecting the electrolyte, the positive electrode cap (409) or the negative electrode cap (505) and the gasket (410, 5
04) is assembled. (3) The battery is completed by caulking the above (2).

It should be noted that the above-described lithium battery material preparation,
It is desirable that the battery be assembled in dry air from which moisture has been sufficiently removed or in a dry inert gas.

The gasket (410, 50) of the present invention
As the material of 4), for example, various resins such as a fluorine resin, a polyamide resin, a polysulfone resin, and polypropylene can be used. As a method for sealing the battery, a method such as a glass tube, an adhesive, welding, soldering, or the like is used in addition to “caulking” using a gasket as shown in FIGS. Various organic resin materials and ceramics are used as the material of the green plate of FIG.

The negative electrode can (408) of the battery according to the present invention,
As a material of the negative electrode cap (505), stainless steel is preferably used. In particular, a titanium clad stainless steel plate, a copper clad stainless steel plate, a nickel plated steel plate and the like are frequently used. Conversely, the battery can is
6) and when the cap becomes the positive electrode (409),
Examples of the material of the battery case (housing) include metals such as zinc and aluminum, plastics such as polypropylene, and composite materials of metal or glass fiber and plastic, in addition to stainless steel.

The battery of the present invention is provided with a safety valve 414 as a safety measure when the internal pressure of the battery increases.
As the safety valve, for example, rubber, spring, metal ball, rupture foil and the like can be used.

[0087]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on embodiments. Note that the present invention is not limited to these examples.

Example 1 AA size (14Φ × 50) lithium secondary battery having the sectional structure shown in FIG. 4 was manufactured. First. A description will be made from the preparation of the negative electrode. A current collector made of a metal that does not alloy with lithium of the negative electrode has a hole of 1.2 mm in diameter in a copper sheet having a thickness of 14 μm, and its porosity (porosity) is 5%, 10%, 30%
%, 50%, and 60%.

On the other hand, tin was used as a metal to be alloyed with lithium. The current collector prepared as described above was plated with tin. An aqueous solution of tin sulfate 1N at 20 ° C. was used as a plating bath, and tin was used as a counter electrode. Electric current was applied at a current density of 10 mA / cm ² for 30 minutes to precipitate tin. The deposition amount was 25 mg / cm ² . The thickness was 30 +/− 3 μm on both sides. The density of this deposited layer is 4. lg / cm ³ and a porosity of about 50%. The current density is the apparent current density,
Holes of punched metal and expanded are also included as areas. Therefore, the weight of plated tin was the same for all current collectors, and the greater the porosity, the thicker the plated thickness.

As the positive electrode active material, electrolytic manganese dioxide and lithium carbonate were mixed at a ratio of 1: 0.4.
Heating at 0 ° C. prepared the lithium-manganese oxide.
3% by weight (3% by weight) of acetylene black carbon powder and 5% by weight of polyvinylidene fluoride powder are mixed with the adjusted lithium-manganese oxide, and N-methyl-2-pyrrolidone is added to adjust the mixture into a paste. The positive electrode was formed by dry coating on a foil.

As the separator, a polypropylene microporous film having a thickness of 25 μm was used. As the electrolytic solution, a solution obtained by dissolving 1 M (mol / 1) of lithium tetrafluoroborate in a mixed solvent of equivalent amounts of ethylene carbonate (EC) and dimethyl carbonate (DMC) from which water had been sufficiently removed was used.

The assembly was performed in a dry nitrogen atmosphere, and wound between a positive electrode and a negative electrode with a separator interposed therebetween. The diameter of the wound shaft was 2.5 mm. Since the thickness of the negative electrode is different, the diameter of the winding group is 13.7 mm, and the lengths in the winding direction are different. The battery case used was nickel-plated iron. The lid used was nickel-plated iron with a safety valve. The packing used was a fluororesin.

Example 2 A current collector was prepared by cutting a copper sheet into slits and having a long diameter of 1.5 m.
m, a diamond-shaped expanded shape having a short diameter of 1.0 mm. The porosity is also 5%, 10%, 30%, 50%
% And 60%. In addition, the negative electrode, the positive electrode, the assembling method, and the like are the same as those in the first embodiment.

Example 3 A three-dimensional current collector (nonwoven fabric) had an average thickness of copper of 10 μm.
It was obtained by sintering short fibers having an average length of 0.5 mm in a hydrogen atmosphere at 800 ° C. The porosity of the sintered body is 50%
Met. In addition, the negative electrode, the positive electrode, the assembling method, and the like are the same as those in the first embodiment.

Example 4 Using a 14 μm thick copper sheet as a current collector, tin was plated in the same manner as in Example 1 to obtain a negative electrode. Combined with the positive electrode of Example 1, the thickness of the wound shaft was 3.0 mm, 4.0 mm, and 5.0.
0 mm, and the battery was wound. The cross-sectional area of the winding shaft is about 30% of the cross-sectional area of the tin plating layer,
%, 100%. Since changing the diameter of the winding shaft changes the diameter of the winding group, the negative electrode, the positive electrode, and the separator were appropriately cut, and the diameter of the winding group was set to 13.7 mm. In addition, the electrolyte, the battery case, and the upper lid were the same as in Example 1.

Example 5 A 14 μm thick copper sheet was used as a current collector, and tin was plated in the same manner as in Example 1 to obtain a negative electrode. This negative electrode was wound in combination with the positive electrode of Example 1. The diameter of the winding shaft is 2.5mm
And In order to make the wound group diameter 13.8 mm, the positive electrode, the negative electrode, and the separator of this example were appropriately cut. As the separator, a polypropylene nonwoven fabric and a microporous film were sandwiched and adjusted to a thickness of 50 μm.

Comparative Example 1 A current collector not alloyed with lithium of the negative electrode was 14 μm thick.
Using a copper sheet, tin-plated as in Example 1,
A negative electrode was used. In addition, the positive electrode, the separator, the electrolyte, the battery case, and the upper lid are the same as those in the first embodiment.

The lithium secondary batteries thus manufactured were evaluated under the following conditions. In the cycle test, charge and discharge were performed at 0.5 CmA (0.5 times the capacity / time) based on the electric capacity calculated from the weight of the positive electrode active material. Charge 2
Time, cut-off voltage is 4.5V, and charging pause time is 3
0 minutes. The discharge cutoff voltage was 2.5V.
The charge cutoff voltage was determined so that the decomposition of the solvent in the electrolyte did not proceed. For charging and discharging of the battery, HJ-106M manufactured by Hokuto Denko was used. The battery capacity was defined as the third discharge capacity of charge and discharge, and the cycle life (charge and discharge life) was defined as the number of cycles at which the charge potential reached 4.5 V.

The results of the battery capacity and the cycle life of the lithium secondary battery of the example and the comparative example 1 which were produced using the negative electrode comprising the electrode structure for a lithium secondary battery of the present invention were compared with 100% of the comparative example. As shown in Table 1.

[0100]

[Table 1]

From Table 1, it can be seen that the negative electrodes of all the examples using the current collector having pores have a large thickness, and since the negative electrodes are placed in a battery can having a predetermined size, the length of the positive electrodes is short. Positive electrode capacity has decreased and battery capacity has decreased. In the case of the first embodiment, if the current collector has 5% of holes, the plating thickness is about 5%.
The thickness increases. However, the thickness of the negative electrode is about 3 times the thickness of the positive electrode.
Since it is 0%, the effect on capacity is -1.
At 2%, it was 98.8%. On the other hand, the life is 1100
%. Hereinafter, the same tendency was also observed in Examples other than Example 1. When the comparative example 1 was disassembled at the end of its life, it was cracked at five places, and two of them were completely broken. In all of the batteries of Examples, although the capacity was slightly lower than that of Comparative Example 1, the cycle life was able to be significantly improved.

Table 2 shows the test results of the batteries in which the diameter of the winding shaft was changed and the cross-sectional area of the tin plating layer with respect to the winding shaft diameter was changed. In Comparative Example 1, the ratio of the cross-sectional area of the tin plating layer to the diameter of the wound shaft was 20%.

[0103]

[Table 2]

In Example 4A, the capacity was reduced by 2% to 98% of Comparative Example 1, but the life was 850%, which was a long life. The same was true for Examples 4B and 4C. However, even if the diameter of the wound shaft is larger than necessary, the disadvantage that the life is not extended and the capacity is reduced is conspicuous. After dismantling the battery after the end of its life,
In Comparative Example 1, cracks and breaks were found, but no cracks were seen in Example 4A and the like. A deformation as shown in FIG. 2B was observed in a part of the wound group. Even if such deformation occurs,
It does not seem to affect battery characteristics.

Table 3 shows the results of the battery using the film and the nonwoven fabric as the separator. The capacity of the battery of Example 5 was reduced by 10% because the separator was thickened.
90% of Comparative Example 1. The charge / discharge life was greatly increased to 950%. When the battery of Example 5 was disassembled, slight deformation was observed in the negative electrode, the positive electrode, and the separator, but the deformation was smaller than that of the battery of Example 4A.

[0106]

[Table 3]

[0107]

As described above, according to the present invention, in a negative electrode comprising a lithium secondary battery electrode structure in which a metal not alloying with lithium and a metal alloying with lithium are arranged, a negative electrode is formed. Therefore, the metal that does not alloy with lithium in the negative electrode elongates or deforms, thereby relaxing the strain caused by the expansion of the metal that forms alloy with lithium, preventing the metal that does not alloy with lithium in the negative electrode from cracking or breaking, and providing a long life. At the same time, a high capacity lithium secondary battery can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a negative electrode comprising an electrode structure for a lithium secondary battery used in a secondary battery of the present invention.

FIG. 2 is a schematic view showing a cross section of one embodiment of the secondary battery of the present invention.

FIG. 3 is a schematic view showing a cross section of a conventional secondary battery.

FIG. 4 is a schematic view of a vertical section of a cylindrical battery.

FIG. 5 is a schematic view of a longitudinal section of a flat battery.

[Explanation of symbols]

 10 After assembly, before charging (broken line) 20 After charging (solid line) 101 Void (opening) 102, 201, 301, 403, 501 Negative electrode 103 Metal not alloyed with lithium 104 Alloyed with lithium Metal 202, 302, 406, 502 Positive electrode 203, 303 Separator 204, 304 Battery case 205 Gap 401 Negative current collector 402 Negative active material layer 404 Positive current collector 405 Positive active material layer 407, 503 Separator / electrolyte 408 Negative electrode Can (negative electrode terminal) 409 Positive electrode cap (positive electrode terminal) 410, 504 Gasket 411 Green plate 412 negative electrode lead 413 positive electrode lead 414 Safety valve 505 Negative cap (negative electrode terminal) 506 Positive electrode can (positive terminal)

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01M 4/66 H01M 4/66 A 4/80 4/80 C 10/40 10/40 B

Claims (41)

[Claims] An electrode structure for a lithium secondary battery in which a metal that does not alloy with lithium is used as a current collector and a metal that forms an alloy with lithium is disposed on the surface of the current collector. An electrode structure for a lithium secondary battery, wherein a metal that does not alloy with lithium used as a current collector is deformed with a change in volume. 2. The lithium secondary battery according to claim 1, wherein the material of the metal that does not alloy with lithium is nickel, copper, titanium, iron, cobalt, chromium, tungsten, silver, or a combination thereof. Electrode structure. 3. The electrode structure for a lithium secondary battery according to claim 1, wherein the metal that is not alloyed with lithium has holes two-dimensionally or three-dimensionally. 4. The electrode structure for a lithium secondary battery according to claim 3, wherein the porosity of the metal not alloyed with lithium is 5 to 50%. 5. The electrode structure for a lithium secondary battery according to claim 3, wherein the metal that does not alloy with lithium is a punched metal, felt, expanded or foamed material. 6. The electrode structure for a lithium secondary battery according to claim 1, wherein a cut is provided in the metal that is not alloyed with lithium. 7. The method according to claim 1, wherein the thickness of the metal that is not alloyed with lithium is 8 to 15 μm.
The electrode structure for a lithium secondary battery according to any one of the above items. 8. The method according to claim 1, wherein the metal to be alloyed with lithium is aluminum, tin, indium, zinc, lead, magnesium, potassium, sodium, calcium, strontium, silicon or a combination thereof. An electrode structure for a lithium secondary battery. 9. The electrode structure for a lithium secondary battery according to claim 1, wherein the porosity of the metal alloyed with lithium is 20 to 80%. 10. The electrode structure for a lithium secondary battery according to claim 8, wherein the thickness of the metal alloyed with lithium is 10 to 50 μm. 11. A method for manufacturing an electrode structure for a lithium secondary battery in which a metal that does not alloy with lithium used as a current collector is deformed according to a change in volume of a metal that alloys with lithium due to charge and discharge. A method for producing an electrode structure for a lithium secondary battery, comprising: using a metal that does not alloy with lithium as a current collector; and arranging a metal that alloys with lithium on the surface of the current collector. 12. The method of arranging a metal that is to be alloyed with lithium with respect to a metal that is not to be alloyed with lithium includes mixing a powder of a metal that is alloyed with lithium with a binder solution,
The method for producing an electrode structure for a lithium secondary battery according to claim 11, wherein the slurry is applied and filled as a slurry. 13. When arranging a metal that forms an alloy with lithium on a metal that does not form an alloy with lithium, at least one of polyvinyl alcohol, cellulose, polytetrafluoroethylene, and polyvinylidene fluoride is used as a binder. The method for producing an electrode structure for a lithium secondary battery according to claim 12, wherein the powder of the metal to be converted is formed into a slurry, and then applied to a metal that is not alloyed with lithium. 14. The method for producing an electrode structure for a lithium secondary battery according to claim 12, wherein a conductive agent is added when the metal which is alloyed with the binder and lithium is used as a slurry. 15. The method for producing an electrode structure for a lithium secondary battery according to claim 14, wherein the conductive agent is carbon. 16. A method for arranging a metal which is alloyed with lithium with respect to a metal which is not alloyed with lithium, comprising:
Laser plating, sputtering, resistance heating evaporation,
12. A combination of at least one selected from an electron beam evaporation method, a thermal CVD method, a low pressure CVD method, a plasma CVD method, and a laser CVD method.
The manufacturing method of the electrode structure for lithium secondary batteries as described in the above. 17. The lithium secondary battery according to claim 11, wherein the sheet-shaped metal that is not alloyed with lithium is disposed on the surface of the metal that is alloyed with lithium and then punched or expanded. Of manufacturing an electrode structure for use. 18. The method according to claim 1, wherein the metal not alloying with lithium is in a punching shape or an expanding shape, and a metal alloying with lithium is arranged there.
18. The method for producing an electrode structure for a lithium secondary battery according to any one of items 1 to 17. 19. A negative electrode for a lithium secondary battery, comprising the electrode structure for a lithium secondary battery according to any one of claims 1 to 10. 20. A positive electrode for a lithium secondary battery, a current collector made of a metal that does not alloy with lithium, and a metal that is alloyed with lithium is disposed on the surface of the current collector. A lithium secondary battery comprising a negative electrode comprising an electrode structure for a lithium secondary battery in which a metal that does not alloy with lithium used as a current collector is deformed in accordance with a change in volume of the lithium secondary battery with a separator interposed therebetween. . 21. The lithium secondary battery according to claim 20, wherein the material of the metal not alloyed with lithium is nickel, copper, titanium, iron, cobalt, chromium, tungsten, silver, or a combination thereof. . 22. The lithium secondary battery according to claim 20, wherein the metal that is not alloyed with lithium has holes two-dimensionally or three-dimensionally. 23. The lithium secondary battery according to claim 22, wherein the porosity of the metal not alloyed with lithium is 5 to 50%. 24. The lithium secondary battery according to claim 22, wherein the metal that does not alloy with lithium is a punched metal, felt, expanded, or foam. 25. The metal which does not alloy with lithium,
22. The lithium secondary battery according to claim 20, wherein a cut is provided. 26. The lithium secondary battery according to claim 20, wherein the thickness of the metal that is not alloyed with lithium is 8 to 15 μm. 27. The metal alloyed with lithium is aluminum, tin, indium, zinc, lead, magnesium,
Potassium, sodium, calcium, strontium,
21. The lithium secondary battery according to claim 20, wherein the lithium secondary battery is silicon or a combination thereof. 28. The lithium secondary battery according to claim 20, wherein the porosity of the metal alloyed with lithium is 20 to 80%. 29. The method according to claim 20, wherein the thickness of the metal alloyed with lithium is 10 to 50 μm.
29. The lithium secondary battery according to 27 or 28. 30. The lithium secondary battery according to claim 20, wherein aluminum is used as the current collector of the positive electrode. 31. The lithium secondary battery according to claim 30, wherein the current collector of the positive electrode is a sheet, punched metal, felt, expanded, or foam. 32. A sheet, expanded or punched metal used as a current collector for the positive electrode having a thickness of 15
32. The lithium secondary battery according to claim 31, wherein the thickness of the lithium secondary battery is about 30 m. 33. The lithium secondary battery according to claim 20, wherein lithium nickelate or a material in which nickel is partially substituted with manganese, cobalt, or magnesium is used as the positive electrode active material. 34. The lithium secondary battery according to claim 20, wherein the ratio of the thickness of the negative electrode to the positive electrode is 20 to 50%. 35. A positive electrode for a lithium secondary battery, a metal which does not alloy with lithium as a current collector, and a metal which alloys with lithium is disposed on the surface thereof, and a metal which alloys with lithium by charging / discharging. With the change in volume, the secondary battery formed by winding a negative electrode composed of an electrode structure for a lithium secondary battery in which a metal that does not alloy with lithium used as a current collector is deformed through a separator, has an inner diameter of a battery case. 21. The cross-sectional area obtained by subtracting the total cross-sectional area of the positive electrode, the negative electrode, and the separator from the cross-sectional area of the negative electrode is 0.3 to 1.0 times the cross-sectional area of the metal alloyed with lithium of the negative electrode. The lithium secondary battery according to the above. 36. The separator is made of film-like polypropylene or polyethylene and has a thickness of 15 to
36. The lithium secondary battery according to claim 35, wherein the thickness is 40 [mu] m. 37. A positive electrode for a lithium secondary battery, a metal which does not alloy with lithium as a current collector, and a metal which alloys with lithium is disposed on the surface thereof, and a metal which alloys with lithium by charge / discharge. Along with the change in volume, in a secondary battery obtained by winding a negative electrode composed of an electrode structure for a lithium secondary battery in which a metal that does not alloy with lithium used as a current collector is deformed through a separator, the separator has a film The lithium secondary battery according to claim 20, comprising a nonwoven fabric. 38. The lithium secondary battery according to claim 37, wherein the separator is made of polypropylene or polyethylene and has a thickness of 15 to 50 μm. 39. A positive electrode for a lithium secondary battery, a metal which does not alloy with lithium as a current collector, and a metal which alloys with lithium is disposed on the surface thereof, and a metal which alloys with lithium by charge / discharge. In a secondary battery in which a negative electrode composed of an electrode structure for a lithium secondary battery in which a metal that does not alloy with lithium used as a current collector is deformed due to a change in volume of the current collector, a non-woven fabric is used as a separator at least in a secondary battery. 21. The lithium secondary battery according to claim 20, wherein the electrolyte is a gel. 40. The lithium secondary battery according to claim 39, wherein the separator is made of polypropylene or polyethylene and has a thickness of 15 to 40 μm. 41. The lithium secondary battery according to claim 39, wherein polyethylene oxide, polyvinyl alcohol or polyacrylamide is used as the gelling agent.