AU2016200591B2 - Lead-acid battery - Google Patents
Lead-acid battery Download PDFInfo
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- AU2016200591B2 AU2016200591B2 AU2016200591A AU2016200591A AU2016200591B2 AU 2016200591 B2 AU2016200591 B2 AU 2016200591B2 AU 2016200591 A AU2016200591 A AU 2016200591A AU 2016200591 A AU2016200591 A AU 2016200591A AU 2016200591 B2 AU2016200591 B2 AU 2016200591B2
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- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
-
- 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
- H01M4/14—Electrodes for lead-acid accumulators
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
OF THE DISCLOSURE
A lead-acid battery includes a negative electrode material containing
graphite and barium sulfate. A ratio S/W of an average plate interval S
between a negative electrode plate and a positive electrode plate, to a mass
W of the negative electrode material per one negative electrode plate is 0.01
mm/g or more.
Fig. 1
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Description
Fig. 1
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The present invention relates to a lead-acid battery, and particularly
relates to a lead-acid battery which is used in an environment involving deep
discharge.
With the advent of idling-stop vehicles, lead-acid batteries have been
deeply discharged more often than before. For example, lead-acid batteries
of idling-stop vehicles are based on the premise that they are used in a
partial state of charge (PSOC). Lead-acid batteries for cycle applications
like those for forklift trucks have been used at a deep depth of discharge
(DOD). When a lead-acid battery is used in a partial state of charge, its life
is reduced due to accumulation of lead sulfate in a positive electrode or
sulfation of a negative electrode. In the partial state of charge, agitation of
an electrolyte solution by gas evolution is insufficient, and thus the
electrolyte solution is easily stratified. This further reduces the life of a
lead-acid battery.
Meanwhile, when the lead-acid battery transitions into an
overdischarged state from the partial state of charge because, for example,
the vehicle is left unattended for a long period of time, metal lead passes
through the separator, and thus a permeation short circuit, in which both
positive and negative electrode plates are short-circuited, easily occurs.
The concentration of sulfate ions in the electrolyte solution decreases due to
overdischarge, and correspondingly, the concentration of lead ions in the
electrolyte solution increases. The lead ions are reduced on the negative electrode plate during charge, and metal lead dendrite grows through pores inside the separator, and thus passes through the separator to short-circuit the positive electrode plate and the negative electrode plate.
The applicant proposed improvement of the life of a lead-acid battery
in the PSOC by including graphite in a negative electrode material. For
example, Patent Document 1 (WO 2011/90113) discloses that a negative
electrode material is made to contain 0.02 to 2.20 mass% of graphite, 0.5
mass% of barium sulfate, and 0.02 to 2.20 mass% of carbon black. Patent
Document 2 (WO 2011/52438) discloses that a negative electrode material is
made to contain 0.5 to 3.0 mass% of expanded graphite and 0.6 mass% of
barium sulfate. Among documents other than those by the applicant, for
example, Patent Document 3 (JP5584216 B) discloses that a negative
electrode material is made to contain 1 to 3 mass% of graphite, 0.8 mass% of
barium sulfate, and 0.1 to 2 mass% of carbon black.
Graphite particles form a path for electrons to lead sulfate, and thus
facilitate charge at a negative electrode. The inventors have found, in the
process of conducting studies on improvement of the PSOC life, that graphite
in a negative electrode material causes a permeation short circuit. This can
be because when a graphite particle is exposed to, or protrudes from, a
surface of a negative electrode plate, the exposed portion or the like of the
graphite particle serves as a center of precipitation of metal lead. As a
result, metal lead dendrite may grow from an exposed graphite particle, and
pass through the separator to cause a short circuit. The fact that graphite
in the negative electrode material causes a permeation short circuit was not
known, and was first found by the present inventors.
An object of the present invention is to provide a lead-acid battery
that is: • unlikely to be subjected to a permeation short circuit caused by
graphite or carbon fiber, and
• excellent in life performance in an environment involving deep
discharge, such as a PSOC.
[Means for Solving the Problems]
An aspect of the present invention provides a lead-acid battery
including a negative electrode plate, a positive electrode plate, an electrolyte
solution, and a separator, wherein the negative electrode plate includes a
negative electrode material containing either graphite or carbon fiber, and
barium sulfate, and an average plate interval S between the negative
electrode plate and the positive electrode plate, and a mass W of the negative
electrode material per one negative electrode plate are in a ratio S/W of 0.01
mm/g or more.
Fig. 1 is a sectional view of a part of a lead-acid battery in an
example.
Fig. 2 is a diagram showing a PSOC life test in the example.
Fig. 3 is a characteristic diagram showing the influence of the
content of graphite (Samples 5 to 9 of Table 3).
Fig. 4 is a characteristic diagram showing the influence of the
inter-electrode ratio (Samples 5, 15C, and 16 to 18 of Table 3).
Fig. 5 is a characteristic diagram showing the influence of the
inter-electrode ratio (Samples 5, 19C, 20, 23, and 25 of Table 3).
Fig. 6 is a characteristic diagram showing the influence of the content of barium sulfate (Samples 5, 10C, and 11 to 14 of Table 3).
Fig. 7 is a characteristic diagram showing the influence of the
resistivity of graphite (Samples 26, 27, and 29 of Table 3).
Fig. 8 is a characteristic diagram showing the influence of the
particle size of graphite (Samples 5 and 28 to 30 of Table 3).
Fig. 9 is a characteristic diagram showing the influence of the
content of carbon black (Samples 5 and 41 to 43 of Table 3).
Fig. 10 is a characteristic diagram showing the influence of the oil
absorption capacity of barium sulfate (Samples 5, 54, and 55 of Table 3).
Fig. 11 is a characteristic diagram showing the influence of the
content of silica(SiO 2)in a synthetic resin separator (Samples 5 and 48 to 51
of Table 3).
Fig. 12 is a characteristic diagram showing the influence of the
content of aluminum ions (Samples 5 and 31 to 35 of Table 3).
Fig. 13 is a characteristic diagram showing the influence of the
content of lithium ions (Samples 5 and 36 to 40 of Table 3).
An aspect of the present invention provides a lead-acid battery
including a negative electrode plate, a positive electrode plate, an electrolyte
solution, and a separator, wherein the negative electrode plate includes a
negative electrode material containing either graphite or carbon fiber, and
barium sulfate, and an average plate interval S between the negative
electrode plate and the positive electrode plate, and a mass W of the negative
electrode material per one negative electrode plate are in a ratio S/W of 0.01
mm/g or more.
The graphite may not only be scalelike graphite or expanded graphite of Example, but may also be natural graphite such as scaly graphite or earthy graphite, or artificial graphite, or expansion graphite, etc. Scalelike graphite and expanded graphite are preferable, with scalelike graphite being particularly preferable. Expanded graphite is graphite that has been expanded. Carbon fiber has an effect similar to that of graphite. Carbon fiber to be used has, for example, a length in a range of 5 im or more and 500 im or less.
Graphite or carbon fiber (hereinafter referred to as "graphite or the
like") provides a path for electrons to lead sulfate in the negative electrode
material, and facilitates reduction of the lead sulfate. This improves life
performance in a non-fully charged condition of a lead-acid battery, such as a
PSOC life of a lead-acid battery. On the other hand, it has been found that
inclusion of graphite or the like in the negative electrode material causes a
permeation short circuit to easily occur. It was not known that inclusion of
graphite or the like in the negative electrode material of a lead-acid battery
causes a permeation short circuit to easily occur.
Thus, the present inventors conducted studies on inhibition of
occurrence of a permeation short circuit while graphite or the like is
contained in the negative electrode material to improve the PSOC life. As a
result, it has been found that even when the negative electrode material
contains graphite or the like, a lead-acid battery having excellent PSOC life
performance and excellent permeation short circuit resistance performance
is obtainable when the negative electrode material contains barium sulfate,
and a ratio S/W (hereinafter referred to as "inter-electrode ratio") is 0.01
mm/g or more where S is an average plate interval between the negative
electrode plate and the positive electrode plate, and W is a mass of the
negative electrode material per one negative electrode plate.
Note that elemental barium or a barium compound such as barium
carbonate may be used instead of barium sulfate. This is because elemental
barium or a barium compound added to the negative electrode material
changes to barium sulfate after the addition.
A content of graphite or the like in the negative electrode material of
0.5 mass% or more significantly improves the PSOC life, and is thus
preferred. Moreover, a content of graphite or the like in the negative
electrode material of 1.5 mass% or more especially significantly improves the
PSOC life, and is thus more preferred.
A content of graphite or the like in the negative electrode material of
less than 2.5 mass% can inhibit a permeation short circuit, and is thus
preferred. Moreover, a content of graphite or the like in the negative
electrode material of 2.0 mass% or less can further inhibit a permeation
short circuit, and is thus more preferred.
A content of barium sulfate in the negative electrode material of 0.6
mass% (equivalent to 0.35 mass% of elemental barium) or more has a large
effect of inhibiting a permeation short circuit, and is thus preferred. A
content of barium sulfate in the negative electrode material of 1.2 mass%
(equivalent to 0.7 mass% of elemental barium) or more has an especially
large effect of inhibiting a permeation short circuit, and is thus more
preferred.
A content of barium sulfate in the negative electrode material of 3.5
mass% or less improves the PSOC life, and therefore, the content of barium
sulfate in the negative electrode material is preferably 3.5 mass%
(equivalent to 2.05 mass% of elemental barium) or less. A content of barium
sulfate in the negative electrode material of 3.0 mass% or less significantly
improves the PSOC life, and therefore, the content of barium sulfate in the negative electrode material is more preferably 3.0 mass% (equivalent to 1.75 mass% of elemental barium) or less.
An inter-electrode ratio S/W of 0.02 mm/g or less improves the PSOC
life, and thus the inter-electrode ratio S/W is preferably 0.02 mm/g or less.
An inter-electrode ratio S/W of 0.016 mm/g or less significantly improves the
PSOC life, and is thus more preferred.
Even when the negative electrode material contains graphite or
carbon fiber, and barium sulfate, and the inter-electrode ratio S/W is 0.01
mm/g or more, a permeation short circuit may not be completely inhibited.
Thus, the present inventors have conducted studies on further inhibiting a
permeation short circuit.
An electric resistivity (hereinafter referred to simply as "resistivity")
of graphite or the like in the negative electrode material of 0.01 Q-cm or less
in powder form as measured by a four-terminal method further inhibits a
permeation short circuit. Thus, the resistivity of graphite or the like in the
negative electrode material is preferably 0.01 Q-cm or less.
An average particle size of graphite in the negative electrode
material of 30 pm or more improves the PSOC life, and thus the average
particle size of graphite is preferably 30 pm or more. An average particle
size of graphite of 100 pm or more significantly improves the PSOC life, and
thus the average particle size of graphite is preferably 100 pm or more.
By further including carbon black in the negative electrode material
that contains graphite or the like and barium sulfate, a permeation short
circuit can be further inhibited. The effect of carbon black of inhibiting a
permeation short circuit is noticeable at a content of carbon black in the
negative electrode material of 0.05 mass% or more, and thus the content of
carbon black in the negative electrode material is preferably 0.05 mass% or more. Meanwhile, a content of carbon black in the negative electrode material of more than 1.0 mass% causes the paste of the negative electrode material to be too hard to fill the current collector. Thus, the content of carbon black in the negative electrode material is preferably 1.0 mass% or less.
A content of carbon black in the negative electrode material of 0.1
mass% or more enhances the effect of improving the PSOC life. Thus, the
content of carbon black in the negative electrode material is preferably 0.1
mass% or more.
An oil absorption capacity of barium sulfate in the negative electrode
material of 12 mL/100 g or more can further inhibit a permeation short
circuit. Thus, the oil absorption capacity of barium sulfate in the negative
electrode material is preferably 12 mL/100 g or more. An oil absorption
capacity of barium sulfate in the negative electrode material of 12.5 mL/100
g or more produces a larger effect of inhibiting a permeation short circuit,
and therefore, the oil absorption capacity of barium sulfate in the negative
electrode material is more preferably 12.5 mL/100 g or more.
Use of a separator containing a synthetic resin such as polyolefin,
and a content of silica (SiO 2 ) in the separator of 60 mass% or more can
further inhibit a permeation short circuit. Thus, the separator is preferably
a synthetic resin separator having a content of silica (SiO 2 ) of 60 mass% or
more. A content of silica (SiO2 ) in a synthetic resin separator of 70 mass%
or more can markedly inhibit a permeation short circuit. Thus, the
separator is more preferably a synthetic resin separator having a content of
silica (SiO2 ) of 70 mass% or more. Meanwhile, a content of silica (SiO 2 ) in
the synthetic resin separator of more than 80 mass% reduces the PSOC life,
and therefore, the separator is preferably a synthetic resin separator having a content of silica (SiO 2 ) of 80 mass% or less.
Inclusion of 0.02 mol/L or more of aluminum ions in the electrolyte
solution significantly improves the PSOC life, and thus the concentration of
aluminum ions in the electrolyte solution is preferably 0.02 mol/L or more.
Inclusion of 0.03mol/L or more of aluminum ions in the electrolyte solution
markedly improves the PSOC life, and thus the concentration of aluminum
ions in the electrolyte solution is preferably 0.03 mol/L or more.
Inclusion of aluminum ions in the electrolyte solution can further
inhibit a permeation short circuit. Inclusion of 0.06 mol/L or more of
aluminum ions in the electrolyte solution markedly inhibits a permeation
short circuit. Thus, the concentration of aluminum ions in the electrolyte
solution is preferably 0.06 mol/L or more.
Inclusion of 0.15 mol/L or less of aluminum ions in the electrolyte
solution significantly improves the PSOC life, and thus the concentration of
aluminum ions in the electrolyte solution is preferably 0.15 mol/L or less.
Inclusion of 0.12 mol/L or less of aluminum ions in the electrolyte solution
markedly improves the PSOC life, and thus the concentration of aluminum
ions in the electrolyte solution is preferably 0.12 mol/L or less.
Inclusion of lithium ions in the electrolyte solution can further
inhibit a permeation short circuit. Moreover, inclusion of 0.01 mol/L or
more of lithium ions in the electrolyte solution can markedly inhibit a
permeation short circuit. Thus, the concentration of lithium ions in the
electrolyte solution is preferably 0.01 mol/L or more.
A concentration of lithium ions in the electrolyte solution of 0.02
mol/L or more markedly improves the PSOC life, and thus the concentration
of lithium ions in the electrolyte solution is preferably 0.02 mol/L or less.
A concentration of lithium ions in the electrolyte solution of 0.22 mol/L or less significantly improves the PSOC life, and thus the concentration of lithium ions in the electrolyte solution is preferably 0.22 mol/L or less. A concentration of lithium ions in the electrolyte solution of
0.18 mol/L or less markedly improves the PSOC life, and thus the
concentration of lithium ions in the electrolyte solution is preferably 0.18
mol/L or less.
A lead-acid battery according to the present invention can be used
not only for idling-stop vehicles etc. to be used in a PSOC environment, but
also for cyclic applications of, for example, forklift trucks because of reduced
occurrence of a permeation short circuit when used in a PSOC environment.
In Example, the lead-acid battery is a flooded-type lead-acid battery, but may
also be a valve-regulated lead-acid battery. The lead-acid battery of the
present invention is preferably a flooded-type lead-acid battery. In addition, the lead-acid battery of the present invention is less likely to cause a
permeation short circuit even when it is used in a partial state of charge, and
therefore, is suitable as a lead-acid battery to be used in a partial state of
charge.
Example according to the invention of the present application will be
shown below. In embodying the present invention, the example can be
appropriately changed based on common knowledge of a person skilled in the
art and on disclosures of prior arts. In the example, the negative electrode
material is also referred to as a negative active material, and the positive
electrode material is also referred to as a positive active material. The
negative electrode plate includes a negative electrode current collector
(negative electrode grid) and a negative active material (negative electrode
material), and the positive electrode plate includes a positive electrode
current collector (positive electrode grid) and a positive active material
(positive electrode material). Solid components other than the current collectors belong to the active materials (electrode materials).
[Example]
Graphite, barium sulfate, lignin as a shrink-proofing agent, and
synthetic resin fibers as a reinforcing material were mixed with a lead
powder produced by a ball milling method, and the resulting mixture was
used as the negative active material paste. Carbon black was further
included in the mixture to prepare another negative active material paste.
Hereinafter, a content is expressed in a concentration (mass%) in a formed
negative active material in a fully-charged condition. The term
"fully-charged" refers to a state in which charge has been performed at a
5-hour rate current until the terminal voltage during charge as measured
every 15 minutes exhibits a particular value (+0.01 V) three times in
succession.
The content of graphite was changed in a range of from 0 mass% to
2.5 mass% with respect to the mass of the negative active material in a
fully-charged condition. Although scalelike graphite and expanded
graphite were used as graphite, other graphite such as earthy graphite and
artificial graphite, and carbon fiber may also be used. Among graphite and
carbon fiber, scalelike graphite or expanded graphite is preferred, and
scalelike graphite is particularly preferred. The average particle size of
scalelike graphite was changed in a range of from 5 pm to 300 pm. The
resistivities of scalelike graphite and of expanded graphite as measured by a
four-terminal method were changed in a range of from 0.001 Q-cm to 0.012
Q-cm (resistivities under pressure of 2.5 MPa).
The content of barium sulfate was changed in a range of from 0
mass% to 3.5 mass% with respect to the mass of the negative active material in a fully-charged condition. The oil absorption capacity (oil absorption capacity in accordance with JIS K-5101-13-2:2004) of barium sulfate was changed in a range of from 11.5 mL/100 g to 14.4 mL/ 100g. Barium sulfate has an average primary particle size of, for example, 0.3 pm or more and 2.0 pm or less, and an average secondary particle size of, for example, 1.0 pm or more and 10 pm or less. While the content of lignin was 0.2 mass%, the content is not limited. A synthetic shrink-proofing agent such as a condensate of a sulfonated bisphenol may be used in place of lignin. While the content of the reinforcing material was 0.1 mass%, the content and the type of the synthetic resin fibers are not limited. The method for producing a lead powder, the content of oxygen, and so on are not limited. Other additives such as a water-soluble synthetic polymer may be contained.
The above-mentioned mixture was formed into a paste with water
and sulfuric acid. An expanded type of negative electrode grid (110 mm
(height) x 100 mm (width) x 1.0 mm (thickness)) primarily composed of an
antimony-free Pb-Ca-Sn-based alloy was filled with this paste, which was
then cured and dried. The negative electrode grid may also be a cast grid, a
punched grid, or the like. The mass of the negative active material per one
negative electrode plate was adjusted in a range of 30 g or more and 80 g or
less. The density of the negative active material after formation is
preferably in a range of, for example, 3.6 g/cm 3 or more and 4.0 g/cm 3 or less.
Synthetic resin fibers of a reinforcing material in an amount of 0.1
mass% with respect to the mass of the formed positive active material in a
fully-charged condition were mixed with a lead powder produced by a ball
milling method, and the resulting mixture was formed into a paste with
water and sulfuric acid, and was used as the positive active material paste.
An expanded type of positive electrode grid (110 mm (height) x 100 mm
(width) x 1.2 mm (thickness)) primarily composed of an antimony-free
Pb-Ca-Sn-based alloy was filled with this paste, which was then cured and
dried. The type of the lead powder and production conditions are not
limited. The positive electrode grid may also be a cast grid, a punched grid,
or the like.
An unformed negative electrode plate was wrapped with a
polyethylene separator with ribs protruding from a base, and seven
unformed negative electrode plates and six unformed positive electrode
plates were alternately layered. The negative electrode plates and the
positive electrode plates were connected to one another with a strap to
prepare an element. The thickness of the base of a separator is preferably, for example, 0.15 mm or more and 0.25 mm or less. Six elements connected
in series were placed in a cell chamber of a container, and sulfuric acid with a
specific gravity of 1.230 at 20°C was added to perform formation in the
container, thereby preparing a flooded-type lead-acid battery having a B20
size and a 5-hour rate capacity of 30 Ah. The average plate interval S
(hereinafter sometimes referred to as an "electrode interval" in abbreviation)
between the positive electrode plate and the negative electrode plate was
adjusted in a range of 0.3 mm or more and 1.0 mm or less. The ratio (N/P)
of the mass N of the negative active material to the mass P of the positive
active material per lead-acid battery is preferably, for example, 0.62 or more
and 0.95 or less.
Fig. 1 shows a part of a lead-acid battery 2. Reference numeral 4
denotes a negative electrode plate, reference numeral 6 denotes a positive
electrode plate, reference numeral 8 denotes a separator, and reference
numeral 10 denotes an electrolyte solution mainly composed of sulfuric acid.
The negative electrode plate 4 includes a negative electrode grid 12 and a negative active material 14. The positive electrode plate 6 includes a positive electrode grid 16 and a positive active material 18. The separator 8 is in the form of abagincluding abase 20 andribs 22. A negative electrode is stored in the bag, and the ribs 22 face the positive electrode plate 6 side.
However, the positive electrode plate 6 may be stored in the separator 8 with
the ribs 22 facing the positive electrode plate. The separator is not required
to be in the form of a bag as long as it isolates the positive electrode plate and
the negative electrode plate from each other; the separator may be, for
example, a leaflet-like glass mat or retainer mat. S'is the interval between
plates (interval between the surface of the positive active material and the
surface of the negative active material). The average thereof is the average
plate interval S. Assuming that the direction in which the lugs of the
positive and negative electrode plates protrude is the upside, S'is defined as
the interval between the plates at the top ends of the active material
surfaces of the positive and negative electrode plates.
The average plate interval (electrode interval) S is determined by
subtracting the thickness(es) of the negative electrode plate(s) and the
thickness(es) of the positive electrode plate(s) from the thickness of an
element, and dividing the obtained value by (the total number of plates per
element - 1). The thickness of an element is the length between the outer
ends, along the layering direction, of the plates located at both ends of that
element, that is, the length between the outer active material surfaces, along
the layering direction, of the plates located at both ends of that element.
The thickness of an element, the thickness of a positive electrode plate, and
the thickness of a negative electrode plate are each determined at the top
ends of the active material surfaces of the positive and/or negative electrode
plate(s). In addition, the average plate interval S and the thickness of an element are each a dimension when the element is accommodated in the container, and is in a fully-charged condition.
The content of barium contained in a formed negative active material
is quantitatively determined as follows. The lead-acid battery in a
fully-charged condition is disassembled, and the negative electrode plate is
washed with water, and then dried, to remove the sulfuric acid component.
Thus, the negative active material is collected. The negative active
material is crushed, and hydrogen peroxide water having a concentration of
300 g/L is added thereto in an amount of 20 mL per 100 g of the negative
active material, and (1+3) nitric acid that is obtained by diluting one part by
volume of 60 mass% concentrated nitric acid with 3 parts by volume of
ion-exchange water is further added. The mixture is then heated with
stirring for five hours to allow lead to dissolve in the form of lead nitrate.
Barium sulfate is further dissolved. The concentration of barium in the
resultant solution is quantitatively determined by an atomic absorption
measurement method, and the result is converted into the content of barium
in the negative active material. The content of barium in the negative
active material can then provide the content of barium sulfate in the
negative active material.
The mass of the negative active material per one negative electrode
plate, and the contents of graphite and of carbon black contained in the
formed negative active material are quantitatively determined as follows.
The lead-acid battery 2 in a fully-charged condition is disassembled, and the
negative electrode plate 4 is washed with water, and then dried, to remove
the sulfuric acid component. Thus, the negative active material 14 is
collected, and the mass of the negative active material per one negative
electrode plate is measured. The negative active material is crushed, and hydrogen peroxide water having a concentration of 300 g/L is added thereto in an amount of 20 mL per 100 g of the negative active material, and (1+3) nitric acid that is obtained by diluting 1 part by volume of 60 mass% concentrated nitric acid with 3 parts by volume of ion-exchange water is further added. The mixture is then heated with stirring for five hours to allow lead to dissolve in the form of lead nitrate. Barium sulfate is further dissolved. Filtration is then performed to separate graphite, carbon black, and the reinforcing material.
Solid components obtained by filtration (graphite, carbon black, and
the reinforcing material) are dispersed in water. Using a sieve that retains
the reinforcing material, such as, for example, a sieve having an aperture of
1.4 mm, the dispersion solution is sieved twice, and then washed with water
to remove the reinforcing material, thereby separating carbon black and
graphite.
An organic shrink-proofing agent, such as lignin, is added to the
negative active material paste together with carbon black and graphite.
Due to the surface-active effect of the organic shrink-proofing agent, carbon
black and graphite remain in a non-aggregated state in the negative active
material even after formation. However, since the organic shrink-proofing
agent is dissolved in water and lost in the series of separation operations,
carbon black and graphite are dispersed in water, the organic
shrink-proofing agent is then added, and the mixture is stirred to
disaggregate again the aggregates of carbon black and of graphite, after
which the following separation operation is performed.
The organic shrink-proofing agent is not limited as long as it can be
added to a lead-acid battery. In Example, a lignin sulfonate Vanillex N
(manufactured by NIPPON PAPER INDUSTRIES CO., LTD.) was used. In
Example, 15 g of the organic shrink-proofing agent was added to 100 mL of
water, and a stirring operation was performed.
After the aforementioned operation, carbon black and graphite were
separated from each other by making suspension containing carbon black
and graphite pass through a sieve that does not substantially allow graphite
to pass therethrough, but allows carbon black to pass therethrough. In
Example, a sieve with an aperture of 20 pm was used. Even when graphite
having a particle size of less than this aperture is used, graphite having a
particle size of 3 pm or more causes clogging of the sieve, and thus such
graphite will not substantially pass through the sieve. After this operation, graphite remains on the sieve, and carbon black is contained in the liquid
that has passed through the sieve.
Graphite and carbon black separated in the series of operations are
washed with water and dried, and are then each weighed. Carbon fiber can
be separated in a manner similar to that of graphite.
The average particle size (volume average size) of graphite is
measured by a light scattering method while the separated graphite is
dispersed again in water to which an organic shrink-proofing agent has been
added. A region corresponding to a particle size of less than 3 1m, if any, is
ignored as that of an impurity such as carbon black. The resistivity of
graphite is measured by a four-terminal method during application of a
pressure of 2.5 MPa to a graphite powder that has been washed with water
and dried.
The oil absorption capacity of barium sulfate in the negative active
material is measured as follows. The lead-acid battery 2 is in a
fully-charged condition is disassembled, and the negative electrode plate 4 is
washed with water, and then dried, to remove the sulfuric acid component.
Thus, the negative active material 14 is collected. The negative active
material is crushed, and hydrogen peroxide water having a concentration of
300 g/L is added thereto in an amount of 20 mL per 100 g of the negative
active material, and (1+3) nitric acid that is obtained by diluting 1 part by
volume of 60 mass% concentrated nitric acid with 3 parts by volume of
ion-exchange water is further added. The mixture is then heated with
stirring for five hours to allow lead to dissolve in the form of lead nitrate.
Graphite, carbon black, barium sulfate and the reinforcing material are then
separated by filtration.
The solid components obtained by filtration are dispersed in water.
Using a sieve that retains the reinforcing material, such as a sieve having an
aperture of 1.4 mm, the dispersion solution is sieved twice, and then washed
with water to remove the reinforcing material. Next, the dispersion
solution without the reinforcing material is subjected to centrifugal
separation at 3000 rpm for five minutes. The supernatant and an upper
layer of the precipitate, both of which contain carbon black and graphite, are
discarded, and barium sulfate is extracted from a lower layer of the
precipitate. The barium sulfate extracted is washed with water and dried, and the oil absorption capacity is measured in accordance with JIS
K-5101-13-2:2004.
Aluminum ions and lithium ions in the electrolyte solution are
quantitatively determined by extracting the electrolyte solution, and then
using ICP emission spectrometry.
The content of silica (SiO 2 ) in a separator is quantitatively
determined as follows. First, the lead-acid battery 2 is disassembled to
single out a separator, which is then washed with water and dried, and the
dry weight is measured. Next, the separator is completely burned, and the content of Si in the residue after burning is quantitatively determined using
ICP emission spectrometry. The content of silica (SiO2 ) in the separator is
calculated from the dry weight of the separator and from the content of Si in
the residue after burning.
A permeation short circuit accelerating test and a PSOC life test
were conducted on the lead-acid battery 2 in a fully-charged condition.
Details of the PSOC life test are shown in Fig. 2 and in Table 1. The
denotation "1 CA" means, for example, 30 A for a battery having a 5-hour
rate capacity of 30 Ah. The term 40°C air indicates that the test was
conducted in an air bath at 40°C. The number of cycles until the terminal
voltage reaches 1.2 V/cell in the test pattern in Table 1 is defined as a PSOC
life. Details of the permeation short circuit accelerating test are shown in
Table 2. This test is a test that is conducted under conditions that promote
occurrence of a permeation short circuit. Thus, the rate of occurrence of a
permeation short circuit is significantly higher than that under the actual
conditions of use of the lead-acid battery. Five cycles of the permeation
short circuit accelerating test pattern shown in Table 2 were conducted.
After the 5 cycles, the lead-acid batteries were disassembled to determine
the ratio of lead-acid batteries in which short circuits have occurred
(permeation short circuit occurrence rate). The term 250 C water indicates that the test was conducted in a water bath at 25C. In Tables 1 and 2, CC
discharge, CV charge, and CC charge respectively mean constant current
discharge, constant voltage charge, and constant current charge.
[Table 1] Test conditions Step Details Stop Temperature Current andvoltage condition 1 CC discharge 1 CA 59 sec. 40°C air 2 CC discharge 300 A 1 sec. 40°C air 3 CV charge 2.4 V/cell, max. 50 A 10 sec. 40°C air 4 CC discharge 1 CA 5 sec. 40°C air 5 Repeat steps 3 and 4 5 times 40°C air 6 Repeat steps 1 - 5 50 times 40°C air 7 CV charge 2.4 V/cell, max. 50 A 900 sec. 40°C air 8 Repeat steps 1 - 7 72 times 40°C air 9 Rest 15h 40 0 C air 10 Return to step 1 40 0 Cair
[Table 2] Test conditions Step Details Stop Temperature Current andvoltage condition 1 CC discharge 0.05 CA 1.0 V/cell 25 0 C water
2 Left with Resistance 10 2 28 days 25 0 C water connected 3 CV charge 2.4 V/cell, max. 50 A 10 min. 25 0 C water 4 CC charge 0.05 CA 27 hours 25 0 C water 5 Repeat steps 1 - 4 5 times 25 0 C water
The results of the PSOC life test and of the permeation short circuit
accelerating test are shown in Table 3, and main results are extracted into
Figs. 3 to 13. Data of the PSOC life is shown as a relative value with
respect to the value of the sample 1C set as 1. The graphites shown in Table
3 are as follows.
Graphite 1: scalelike graphite having an average particle size of 100 pm and
a resistivity of 0.001 Q-cm.
Graphite 2: expanded graphite having an average particle size of 30 pm and a resistivity of 0.01 Q-cm.
Graphite 3: expanded graphite having an average particle size of 30 pm and
a resistivity of 0.012 Q-cm.
Graphite 4: scalelike graphite having an average particle size of 5 pm and a
resistivity of 0.001 Q-cm.
Graphite 5: scalelike graphite having an average particle size of 30 pm and a
resistivity of 0.001 Q-cm.
Graphite 6: scalelike graphite having an average particle size of 300 pm and
a resistivity of 0.001 Q-cm.
[Table 3] Graphite Inter-electrode ratio Ba sulfate Al ion Li ion Carbon Silicain Test results _________________ __________ black separator _____
No. Average Amountofnegative Average Inter- Oil PSOC Permeation Content particle Resistivity active material per one plate electrode Contentabsorption Concentration Concentration Content Content life short circuit e (mass%) size (Q-cm) negative electrode interval ratio (mass%) capacity (mol/L) (mol/L) (mass%) (mass%) (ratio occurrence (um) plate (g) (mm) (mm/g) (ml/100g) to 1C rate (%) 1C Not added - - 45 0.7 0.016 0.6 12.5 0 0 0.2 65 1 10 2 Graphite 1 0.5 100 0.001 45 0.7 0.016 0.6 12.5 0 0 0 65 0.85 20 3C Not added - - - 45 0.7 0.016 0.6 12.5 0 0 0 65 0.70 10 4C Not added - - - 45 0.7 0.016 0.6 12.5 0.04 0.06 0.2 65 1.20 20 5 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0 0 0 65 1.26 10 6 Graphite 1 0.3 100 0.001 45 0.7 0.016 2 12.5 0 0 0 65 1.13 0 7 Graphite 1 0.5 100 0.001 45 0.7 0.016 2 12.5 0 0 0 65 1.20 0 8 Graphite 1 2.0 100 0.001 45 0.7 0.016 2 12.5 0 0 0 65 1.27 10 9 Graphite 1 2.5 100 0.001 45 0.7 0.016 2 12.5 0 0 0 65 1.18 30 0C Graphite 1 1.5 100 0.001 45 0.7 0.016 0 12.5 0 0 0 65 1.01 50 11 Graphite 1 1.5 100 0.001 45 0.7 0.016 0.6 12.5 0 0 0 65 1.16 30 12 Graphite 1 1.5 100 0.001 45 0.7 0.016 1.2 12.5 0 0 0 65 1.18 10 13 Graphite 1 1.5 100 0.001 45 0.7 0.016 3 12.5 0 0 0 65 1.29 0 14 Graphite 1 1.5 100 0.001 45 0.7 0.016 3.5 12.5 0 0 0 65 1.18 0 15C Graphite 1 1.5 100 0.001 45 0.3 0.007 2 12.5 0 0 0 65 1.13 50 16 Graphite 1 1.5 100 0.001 45 0.5 0.011 2 12.5 0 0 0 65 1.39 10 17 Graphite 1 1.5 100 0.001 45 0.9 0.020 2 12.5 0 0 0 65 1.13 0 18 Graphite 1 1.5 100 0.001 45 1 0.022 2 12.5 0 0 0 65 1.01 0 19C Graphite 1 1.5 100 0.001 80 0.7 0.009 2 12.5 0 0 0 65 1.24 50 20 Graphite 1 1.5 100 0.001 70 0.7 0.010 2 12.5 0 0 0 65 1.51 10 21 Graphite 1 1.5 100 0.001 60 1 0.017 2 12.5 0 0 0 65 1.50 10 22 Graphite 1 1.5 100 0.001 40 0.5 0.013 2 12.5 0 0 0 65 1.31 10 23 Graphite 1 1.5 100 0.001 40 0.7 0.018 2 12.5 0 0 0 65 1.13 0 24 Graphite 1 1.5 100 0.001 30 0.4 0.013 2 12.5 0 0 0 65 1.30 10 25 Graphite 1 1.5 100 0.001 30 0.7 0.023 2 12.5 0 0 0 65 1.01 0 26 Graphite 2 1.5 30 0.01 45 0.7 0.016 2 12.5 0 0 0 65 1.12 10 27 Graphite 3 1.5 30 0.012 45 0.7 0.016 2 12.5 0 0 0 65 0.88 30 28 Graphite 4 1.5 5 0.001 45 0.7 0.016 2 12.5 0 0 0 65 1.10 0 29 Graphite 5 1.5 30 0.001 45 0.7 0.016 2 12.5 0 0 0 65 1.20 10
Graphite 6 1.5 300 0.001 45 0.7 0.016 2 12.5 0 0 0 65 1.24 10 31 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0.02 0 0 65 1.31 10 32 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0.03 0 0 65 1.45 10 33 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0.06 0 0 65 1.64 0 34 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0.12 0 0 65 1.52 0 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0.15 0 0 65 1.36 0 36 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0 0.01 0 65 1.32 0 37 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0 0.02 0 65 1.46 0 38 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0 0.09 0 65 1.62 0 39 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0 0.18 0 65 1.54 0 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0 0.22 0 65 1.34 0 41 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0 0 0.05 65 1.28 0 42 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0 0 0.1 65 1.32 0 43 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0 0 1 65 1.45 0 44 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0 0 1.2 65 *
* Graphite 1 2 100 0.001 45 0.7 0.016 3 12.5 0 0 0 65 1.31 10 46 Graphite 1 2 100 0.001 45 0.7 0.016 3 12.5 0 0 0.1 65 1.37 0 47 Graphite 1 2 100 0.001 45 0.7 0.016 3 12.5 0 0 1 65 1.50 0 48 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0 0 0 50 1.13 20 49 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0 0 0 60 1.23 10 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0 0 0 70 1.39 0 51 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 12.5 0 0 0 80 1.20 0 52 Graphite 1 2 100 0.001 45 0.7 0.016 3 12.5 0 0 0 60 1.28 20 53 Graphite 1 2 100 0.001 45 0.7 0.016 3 12.5 0 0 0 70 1.44 10 54 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 11.5 0 0 0 65 1.10 15 Graphite 1 1.5 100 0.001 45 0.7 0.016 2 14.4 0 0 0 65 1.30 5 *The paste was hard, and therefore preparation was impossible. 1C, 3C, 4C, 10C, 15C, 19C: comparative examples
Fig. 3 and Table 3 show that inclusion of graphite in the negative
active material improves the PSOC life, that inclusion of 0.5 mass% or more
of graphite significantly improves the PSOC life, and that inclusion of 1.5
mass% or more of graphite markedly improves the PSOC life. Meanwhile, it can be seen that inclusion of graphite in the negative active material
promotes occurrence of a permeation short circuit, while the content of
graphite in the negative active material of less than 2.5 mass% inhibits a
permeation short circuit. A content of graphite in the negative active
material of 2.0 mass% or less has an especially large effect of inhibiting a
permeation short circuit. Since it was not known that graphite in the
negative active material relates to a permeation short circuit, such an effect
was not foreseeable.
Thus, the present inventors conducted studies on inhibition of
occurrence of a permeation short circuit while graphite is included in the
negative active material to improve the PSOC life. As a result, it has been
found that inclusion of graphite and barium sulfate in the negative active
material, and an inter-electrode ratio S/W of 0.01 mm/g or more yield a
lead-acid battery having excellent permeation short circuit resistance
performance, and having PSOC life performance higher than that of a
lead-acid battery not containing graphite or the like in the negative active
material (e.g., samples 5 to 8 of Table 3). It is inferred in general that a
small average plate interval S would cause a permeation short circuit to
easily occur due to the small distance between the positive and negative
electrode plates, thereby producing only a small effect of inhibiting a
permeation short circuit. However, even when the value of S is low, a low
amount W of the negative active material per one negative electrode plate
produces a large effect of inhibiting a permeation short circuit (sample 24 of
Table 3). In contrast, even when the value of S is higher than that of
sample 24, a high value of W produces only a small effect of inhibiting a
permeation short circuit (sample 19C of Table 3). Thus, an effect of
inhibiting a permeation short circuit is not dependent on S or W alone, but
both S and W relate to a permeation short circuit. It is thus important that
the inter-electrode ratio S/W be 0.01 mm/g or more to inhibit a permeation
short circuit.
Without satisfying even any one of a condition in which the negative
active material contains graphite, a condition in which the negative active
material contains barium sulfate, and a condition in which the
inter-electrode ratio S/W is 0.01 mm/g or more, a lead-acid battery having
excellent PSOC life performance and excellent permeation short circuit
resistance performance cannot be obtained. For example, even when the
negative active material contains barium sulfate, and the inter-electrode
ratio S/W is 0.01 mm/g or more, PSOC life performance is low if the negative
active material does not contain graphite (sample 3C of Table 3). In
addition, even when the negative active material contains graphite, and the
inter-electrode ratio S/W is 0.01 mm/g or more, a permeation short circuit
cannot be sufficiently inhibited if the negative active material does not
contain barium sulfate (sample 10C of Table 3). Similarly, even when the
negative active material contains graphite and barium sulfate, a permeation
short circuit cannot be sufficiently inhibited if the inter-electrode ratio S/W is
less than 0.01 mm/g (15C and 19C of Table 3). Thus, concludingly, the
combination of three configurations, including a configuration in which the
negative active material contains graphite, a configuration in which the
negative active material contains barium sulfate, and a configuration in
which the inter-electrode ratio S/W is 0.01 mm/g or more, is required to obtain a lead-acid battery having excellent PSOC life performance and excellent permeation short circuit resistance performance. Since it was not known that barium sulfate in the negative active material relates to occurrence of a permeation short circuit, it is not easy for a person skilled in the art to get an idea to include barium sulfate in the negative active material to inhibit a permeation short circuit. In addition, it was also not known that the inter-electrode ratio S/W relates to occurrence of a permeation short circuit, and therefore, it is also not easy for a person skilled in the art to get an idea to set the inter-electrode ratio S/W to 0.01 mm/g or more to inhibit a permeation short circuit. Moreover, it was not known that inclusion of graphite in the negative active material causes a permeation short circuit to easily occur. Thus, it is very difficult for a person skilled in the art to get an idea of combining inclusion of barium sulfate in the negative active material with setting the inter-electrode ratio S/W to 0.01 mm/g or more to inhibit a permeation short circuit, which occurs more easily by including graphite in the negative active material.
Effects of the inter-electrode ratio S/W are shown in Figs. 4 and 5.
Fig. 4 shows the results when the amount W of the negative active material
per one negative electrode plate was fixed, while the electrode interval
(average plate interval) S was varied. Fig. 5 shows the results when the
electrode interval S was fixed, while the amount W of the negative active
material per one negative electrode plate was varied. The results are
similar between when the electrode interval S was varied and when the
amount W of the negative active material per one negative electrode plate
was varied. The fact that the change in S/W caused by a variation in S and
the change in S/W caused by a variation in W have produced similar results
shows that it is the ratio S/W that has engineering significance, not S or W alone. In addition, Figs. 4 and 5 show that, when the negative active material contains graphite and barium sulfate, the effect of inhibiting a permeation short circuit is completely different between when the inter-electrode ratio S/W is less than 0.01 mm/g and when the inter-electrode ratio S/Wis 0.01 mm/g. Thus, it can be said that an inter-electrode ratio of
0.01 mm/g or more has a meaning as a critical point.
Figs. 4 and 5 show that the PSOC life performance improves when
the inter-electrode ratio S/W is 0.02 mm/g or less. The PSOC life
performance significantly improves when the inter-electrode ratio S/W is
0.16 mm/g or less.
Fig. 6 shows that a content of barium sulfate in the negative active
material of 0.6 mass% or more significantly improves the effect of inhibiting
a permeation short circuit. Since it was not known that barium sulfate in
the negative active material relates to a permeation short circuit, such an
effect was not foreseeable. A content of barium sulfate in the negative
active material of 1.2 mass% or more especially significantly improves the
effect of inhibiting a permeation short circuit. The effect of inhibiting a
permeation short circuit is completely different between when the content of
barium sulfate is less than 1.2 mass% and when the content of barium
sulfate is 1.2 mass% or more. Thus, it can be said that a content of barium
sulfate of 1.2mass% or more has a meaning as a critical point.
Fig. 6 shows that a content of barium sulfate in the negative active
material of 3.5 mass% or less improves the PSOC life performance, and that
a content of barium sulfate in the negative active material of 3.0 mass% or
less significantly improves the PSOC life performance.
Table 3 shows that when the negative active material contains
graphite, a permeation short circuit may not be completely inhibited even when the negative active material contains barium sulfate, and the inter-electrode ratio S/W is 0.01 mm/g or more (e.g., sample 5 of Table 3).
Thus, the present inventors have conducted studies on further inhibiting a
permeation short circuit.
Fig. 7 shows that a resistivity of graphite in the negative active
material of 0.01 Qcm or less further inhibits a permeation short circuit.
Since it was not known that graphite in the negative active material relates
to a permeation short circuit, it was not foreseeable that changing the
resistivity of graphite in the negative active material would improve the
effect of inhibiting a permeation short circuit.
Fig. 8 shows that an average particle size of graphite of 30 pm or
more improves the PSOC life, and an average particle size of graphite of 100
pm or more further improves the PSOC life.
Fig. 9 shows effects of carbon black in the negative active material.
It can be seen that inclusion of carbon black in the negative active material
further inhibits occurrence of a permeation short circuit. It was not known
that carbon black in the negative active material relates to a permeation
short circuit. Therefore, it was not foreseeable that inclusion of carbon
black in the negative active material would improve the effect of inhibiting a
permeation short circuit. In addition, comparison between samples 1 and 3
of Table 3 shows that when the negative active material does not contain
graphite, the effect of inhibiting a permeation short circuit cannot be
obtained even when the negative active material contains carbon black.
Thus, the effect of carbon black of inhibiting a permeation short circuit is
obtained only when the negative active material contains graphite.
The effect of carbon black of inhibiting a permeation short circuit is
noticeable when the content of carbon black in the negative active material is
0.05 mass% or more (Fig. 9). Moreover, a content of carbon black in the
negative electrode material of 0.1 mass% or more produces a larger effect of
improving the PSOC life than when the content of carbon black in the
negative active material is less than 0.1 mass% (Fig. 9). Meanwhile, inclusion of more than 1.0 mass% of carbon black in the negative active
material made the active material paste too hard to fill therewith the
negative electrode current collector.
Fig. 10 shows effects of the oil absorption capacity of barium sulfate
in the negative active material. Fig. 10 shows that an oil absorption
capacity of barium sulfate in the negative active material of 12 mL/100 g or
more further inhibits a permeation short circuit. Since it was not known
that barium sulfate in the negative active material relates to a permeation
short circuit, it was not foreseeable that changing the oil absorption capacity
of barium sulfate in the negative active material would improve the effect of
inhibiting a permeation short circuit. An oil absorption capacity of barium
sulfate in the negative active material of 12.5 mL/100 g or more especially
improves the effect of inhibiting a permeation short circuit.
The separator containing a synthetic resin, such as polyolefin
including polyethylene, contains silica (SiO 2) to provide porosity. The same
applies to other synthetic resin separators. Fig. 11 shows effects of the
content of silica (SiO2 ) in the separator. Fig. 11 shows that the content of
silica (SiO2 ) in the separator of 60 mass% or more can further inhibit a
permeation short circuit. Since it was not known that the content of silica
(SiO2 ) in the separator relates to a permeation short circuit, it was not foreseeable that changing the content of silica (SiO 2 ) in the separator would
improve the effect of inhibiting a permeation short circuit. A content of
silica (SiO2 ) in the separator of 70 mass% or more especially improves the effect of inhibiting a permeation short circuit. Meanwhile, a content of silica (SiO2 ) in the separator of more than 80 mass% reduces the PSOC life
(Fig. 11).
Fig. 12 shows effects of aluminum ions in the electrolyte solution. It
can be seen that the permeation short circuit can be further inhibited by
aluminum ions in the electrolyte solution. The effect of inhibiting a
permeation short circuit by aluminum ions is noticeable when the content of
the aluminum ions is 0.06 mol/L or more. Comparison between samples 1
and 4 of Table 3 shows that when the negative active material does not
contain graphite, the effect of inhibiting a permeation short circuit cannot be
obtained even when the electrolyte solution contains aluminum ions. Thus, the effect of aluminum ions of inhibiting a permeation short circuit is
obtained only when the negative active material contains graphite.
A concentration of aluminum ions in the electrolyte solution of 0.02
mol/L or more significantly improves the PSOC life performance, and a
concentration of aluminum ions in the electrolyte solution of 0.03 mol/L or
more markedly improves the PSOC life performance (Fig. 12). In addition, a concentration of aluminum ions in the electrolyte solution of 0.15 mol/L or
less significantly improves the PSOC life performance, and a concentration
of aluminum ions in the electrolyte solution of 0.12 mol/L or less markedly
improves the PSOC life performance (Fig. 12).
Fig. 13 shows effects of lithium ions. It can be seen that lithium
ions in the electrolyte solution can further inhibit a permeation short circuit.
The effect of inhibiting a permeation short circuit by lithium ions is
noticeable when the content of lithium ions is 0.01 mol/L or more.
Comparison between samples 1 and 4 of Table 3 shows that when the
negative active material does not contain graphite, the effect of inhibiting a permeation short circuit cannot be obtained even when the electrolyte solution contains lithium ions. Thus, the effect of lithium ions of inhibiting a permeation short circuit is obtained only when the negative active material contains graphite.
A concentration of lithium ions in the electrolyte solution of 0.01
mol/L or more significantly improves the PSOC life performance, and a
concentration of lithium ions in the electrolyte solution of 0.02 mol/L or more
markedly improves the PSOC life performance (Fig. 13). In addition, a
concentration of lithium ions in the electrolyte solution of 0.22 mol/L or less
significantly improves the PSOC life performance, and a concentration of
lithium ions in the electrolyte solution of 0.18 mol/L or less markedly
improves the PSOC life performance (Fig. 13).
In Example, a lead-acid battery which is excellent in PSOC life and
suffers little permeation short circuit is obtained, and a glass mat etc. may
be used as a separator to produce a valve-regulated lead-acid battery.
Throughout this specification and the claims which follow, unless the
context requires otherwise, the word "comprise", and variations such as
"comprises" and "comprising", will be understood to imply the inclusion of a
stated integer or step or group of integers or steps but not the exclusion of
any other integer or step or group of integers or steps.
The reference to any prior art in this specification is not, and should
not be taken as, an acknowledgement or any form of suggestion that the
prior art forms part of the common general knowledge in Australia.
Claims (15)
1. A lead-acid battery comprising a negative electrode plate, a positive electrode plate, an electrolyte solution, and a separator, wherein the negative electrode plate includes a negative electrode material containing 0.5 mass% or more and less than 2.5 mass% of graphite, and barium sulfate, and an average plate interval S between the negative electrode plate and the positive electrode plate, and a mass W of the negative electrode material per one negative electrode plate are in a ratio S/W of 0.01 mm/g or more and 0.02 mm/g or less; and the separator has a content of silica (SiO 2 ) of 60 mass% or more, and the average plate interval S between the positive electrode plate and the negative electrode plate is 0.3 mm or more and 1.0 mm or less, and 3 a density of the negative electrode material after formation is 3.6 g/cm or more and 4.0 g/cm 3 or less.
2. A lead-acid battery comprising a negative electrode plate, a positive electrode plate, an electrolyte solution, and a separator, wherein the negative electrode plate includes a negative electrode material containing 0.5 mass% or more and less than 2.5 mass% of graphite, and elemental barium, and an average plate interval S between the negative electrode plate and the positive electrode plate, and a mass W of the negative electrode material per one negative electrode plate are in a ratio S/W of 0.01 mm/g or more and 0.02 mm/g or less; and the separator has a content of silica (SiO 2 ) of 60 mass% or more, and the average plate interval S between the positive electrode plate and the negative electrode plate is 0.3 mm or more and 1.0 mm or less, and a density of the negative electrode material after formation is 3.6 g/cm 3 or more and 4.0 g/cm 3 or less.
3. The lead-acid battery according to claim 1, wherein the negative electrode material contains 0.6 mass% or more of barium sulfate.
4. The lead-acid battery according to claim 3, wherein the negative electrode material contains 1.2 mass% or more of barium sulfate.
5. The lead-acid battery according to any one of claims 1 to 4, wherein the negative electrode material contains carbon black.
6. The lead-acid battery according to claim 2, wherein the negative electrode material contains 0.35 mass% or more of elemental barium.
7. The lead-acid battery according to any one of claims 1 to 6, wherein the separator has a content of silica (SiO 2 ) of 80 mass% or less.
8. The lead-acid battery according to any one of claims 1 to 7, wherein the negative electrode material contains 3.5 mass% or less of barium sulfate.
9. The lead-acid battery according to any one of claims 1 to 8, wherein the graphite has an electric resistivity of 0.01 QAcm or less in powder form as measured by a four-terminal method.
10. The lead-acid battery according to any one of claims 1 to 9, wherein the barium sulfate has an oil absorption capacity of 12 mL/100 g or more.
11. The lead-acid battery according to any one of claims 1 to 10, wherein the electrolyte solution contains aluminum ions.
12. The lead-acid battery according to claim 11, wherein the electrolyte solution contains aluminum ions of 0.02mol/L or more.
13. The lead-acid battery according to any one of claims 1 to 12, wherein the electrolyte solution contains lithium ions.
14. The lead-acid battery according to claim 13, wherein the electrolyte solution contains lithium ions of 0.01mol/L or more.
15. The lead-acid battery according to any one of claims 1 to 14, wherein the graphite is scalelike graphite or expanded graphite.
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| JP2015-029556 | 2015-02-18 | ||
| JP2015029556 | 2015-02-18 | ||
| JP2015248242A JP6136080B2 (en) | 2015-02-18 | 2015-12-21 | Lead acid battery |
| JP2015-248242 | 2015-12-21 |
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| AU2016200591A1 AU2016200591A1 (en) | 2016-09-01 |
| AU2016200591B2 true AU2016200591B2 (en) | 2021-08-05 |
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| JP (2) | JP6136080B2 (en) |
| CN (1) | CN105895911A (en) |
| AU (1) | AU2016200591B2 (en) |
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| JP2753666B2 (en) | 1992-08-07 | 1998-05-20 | 株式会社神戸製鋼所 | Resin-coated steel sheet with excellent electrodeposition coating properties |
| WO2016139855A1 (en) * | 2015-03-05 | 2016-09-09 | 日立化成株式会社 | Lead storage cell |
| JP6338020B2 (en) * | 2015-06-18 | 2018-06-06 | 日立化成株式会社 | Lead acid battery |
| CN109314284A (en) * | 2016-06-08 | 2019-02-05 | 日立化成株式会社 | Lead storage battery |
| WO2018100635A1 (en) * | 2016-11-29 | 2018-06-07 | 日立化成株式会社 | Lead storage battery and production method therefor |
| WO2018199207A1 (en) * | 2017-04-28 | 2018-11-01 | 株式会社Ｇｓユアサ | Lead acid battery |
| DE112018002253T5 (en) * | 2017-04-28 | 2020-01-23 | Gs Yuasa International Ltd. | LEAD ACID BATTERY |
| WO2018199242A1 (en) * | 2017-04-28 | 2018-11-01 | 株式会社Ｇｓユアサ | Lead acid storage battery |
| JP7099448B2 (en) * | 2017-04-28 | 2022-07-12 | 株式会社Ｇｓユアサ | Lead-acid battery |
| WO2018199125A1 (en) * | 2017-04-28 | 2018-11-01 | 株式会社Ｇｓユアサ | Lead acid battery |
| JP7099450B2 (en) * | 2017-04-28 | 2022-07-12 | 株式会社Ｇｓユアサ | Lead-acid battery |
| WO2019021690A1 (en) * | 2017-07-24 | 2019-01-31 | 株式会社Ｇｓユアサ | Lead acid storage battery |
| DE112018003776T5 (en) * | 2017-07-24 | 2020-04-09 | Gs Yuasa International Ltd. | LEAD ACID BATTERY |
| EP3633781B1 (en) * | 2017-07-24 | 2024-04-24 | GS Yuasa International Ltd. | Lead-acid battery |
| CN111279543B (en) * | 2017-10-31 | 2024-11-05 | 株式会社杰士汤浅国际 | Lead acid battery |
| CN111316496A (en) * | 2017-10-31 | 2020-06-19 | 株式会社杰士汤浅国际 | Lead storage battery |
| WO2019188056A1 (en) * | 2018-03-29 | 2019-10-03 | 株式会社Ｇｓユアサ | Lead acid storage battery |
| SG11202102513RA (en) * | 2018-09-25 | 2021-04-29 | Gs Yuasa Int Ltd | Negative electrode for lead-acid battery, and lead-acid battery |
| JP6958693B2 (en) * | 2018-10-10 | 2021-11-02 | 昭和電工マテリアルズ株式会社 | Lead-acid battery |
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Also Published As
| Publication number | Publication date |
|---|---|
| BR102016003138A2 (en) | 2016-08-30 |
| AU2016200591A1 (en) | 2016-09-01 |
| JP2017174822A (en) | 2017-09-28 |
| JP6635346B2 (en) | 2020-01-22 |
| TR201807757T4 (en) | 2018-06-21 |
| JP6136080B2 (en) | 2017-05-31 |
| JP2016154131A (en) | 2016-08-25 |
| CN105895911A (en) | 2016-08-24 |
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