JP2016189296A - Lead acid battery - Google Patents

Abstract

CONSTITUTION: A lead acid battery includes: a positive electrode plate in which a positive electrode current collector body or positive electrode material contains antimony; a negative electrode plate in which a negative electrode material contains synthetic shrink-proofing agent having sulfonate groups; and an adsorption layer for adsorbing antimony ions. The adsorption layer is provided on the surface of the positive electrode plate or the surface of the negative electrode plate, or between the positive electrode plate and the negative electrode plate.EFFECT: An effect of antimony and an effect of synthetic shrink-proofing agent such as bisphenol or the like can be sufficiently drawn by limiting movement of antimony from a positive electrode plate to a negative electrode plate, thereby preventing reduction of a hydrogen overvoltage.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a lead storage battery.

  Patent Document 1 (JP2012-79431A) discloses that when antimony is contained in a positive electrode material of a lead storage battery, softening / dropping of the positive electrode material may be suppressed if predetermined requirements are satisfied. This improves the life of lead-acid batteries that are frequently charged and discharged, such as for idling stop vehicles. Patent Document 2 (JP2014-123525A) discloses that the pore diameter of the negative electrode material can be reduced when the negative electrode material of the lead storage battery contains a sulfonic acid derivative condensate of bisphenols instead of lignin. This means that the high rate discharge performance of the lead storage battery can be improved.

  By the way, there is a problem that antimony moves to the negative electrode plate and reduces hydrogen overvoltage. This results in a decrease in cycle life performance due to liquid reduction, and a large current flows at the end of charging, which causes a short circuit through the dropped positive electrode material particles.

JP2012-79431A JP2014-123525A

  The inventor further found that antimony moved to the negative electrode plate inhibits the effect of a sulfonic acid derivative condensate of bisphenols (hereinafter referred to as bisphenol). Therefore, if the movement of antimony from the positive electrode plate to the negative electrode plate can be restricted, the effect of antimony can be brought out, and at the same time, the decrease in hydrogen overvoltage can be prevented, and the effect of bisphenol can be taken out sufficiently to improve the life performance of the lead storage battery. It should be.

The subject of this invention is
・ Suppressing softening and dropping of the positive electrode material with antimony,
-By restricting the movement of antimony from the positive electrode plate to the negative electrode plate, the synthetic anti-shrink agent and antimony ions are prevented from interacting with each other and the decrease in hydrogen overvoltage is prevented.

  The lead storage battery according to the present invention includes a positive electrode plate in which the positive electrode current collector or the positive electrode material contains antimony, a negative electrode plate in which the negative electrode material contains a synthetic shrinkage-preventing agent, and an adsorption layer that adsorbs antimony ions. The layer is provided on the surface of the negative electrode plate or the positive electrode plate or between the positive electrode plate and the negative electrode plate.

The synthetic shrinking agent is preferably one in which aromatic rings such as phenol or naphthalene are bonded to each other via a methylene group or the like and contain a large amount of a sulfonic acid group or a sulfonyl group. The sulfonyl group (—SO ₂ — group) acts in the same manner as the sulfonic acid group. In a compound in which a sulfonic acid group or the like is introduced into a natural product such as lignin sulfonic acid, it is difficult to make the total of the sulfonyl group and the sulfonic acid group 4000 μmol / g or more. On the other hand, it is easy to introduce 4000 μmol / g or more of a sulfonic acid group or a sulfonyl group into a synthetic polymer in which the monomer contains an aromatic ring. The action of the synthetic anti-shrinking agent is determined by the hydrophilicity and charging due to the sulfonic acid group or sulfonyl group, and the aromatic ring may be phenol or naphthalene. It is not important whether the sulfonic acid is a salt type or an acid type. For example, it is considered that the sulfonic acid changes between an acid type and a salt type due to a change in pH of the electrolytic solution.

  Synthetic shrunk agents are, for example, condensates of bisphenols with formaldehyde, etc., which have a sulfonic acid group or sulfonyl group, and these functional groups are bonded directly to the aromatic ring, but are bonded via a methylene group or the like. May be. In this specification, when these compounds contain a sulfonic acid group, it is called a sulfonic acid derivative condensate of bisphenols, whether a sulfonic acid derivative of bisphenols is condensed, or a bisphenol condensate is sulfonated, etc. It has nothing to do with the manufacturing method. The sulfonic acid derivative of bisphenols is hereinafter simply referred to as “bisphenol”. Also, a formaldehyde condensate of β-naphthalenesulfonic acid (for example, trade name “Demol” from Kao Corporation) can be used.

  According to the inventor's knowledge, the colloidal particle diameter of the anti-shrinking agent is reflected in the pore diameter of the negative electrode material, and the small colloidal particle diameter reduces the pore diameter, thereby improving the high rate discharge performance and the like. In order to reduce the diameter of the colloidal particles, it is effective to prevent the colloidal particles from being associated by electrostatic repulsion and to increase the hydrophilicity by the presence of a large number of ions or strongly polar groups on the surface of the anti-shrinking agent. For this purpose, the total amount of sulfonic acid groups and sulfonyl groups in the anti-shrink agent is increased, for example, preferably 4000 μmol / g to 8000 μmol / g, more preferably 4300 μmol / g to 6000 μmol / g, most preferably 4500 μmol. / g to 6000 μmol / g. In conventional lignin, the concentration of sulfonic acid groups is about 600 μmol / g.

  The effect of the synthetic anti-shrink agent is reduced by antimony moved from the positive electrode plate. This may be because the synthetic anti-shrinkage agent has a large amount of sulfonic acid groups and the like, so that it easily binds and associates with trivalent or pentavalent antimony ions. Then, the colloidal particle diameter increases due to the association, and the average pore diameter of the negative electrode material increases, so it is considered that the high rate discharge performance is lowered. On the other hand, if an adsorption layer of antimony ions is provided, the synthetic anti-shrink agent in the negative electrode material can be protected from antimony ions, and the high-rate discharge performance can be prevented from being lowered, and the reduction of hydrogen overvoltage at the negative electrode plate is limited. it can.

  Preferably, the adsorption layer contains a carbonaceous adsorbent such as activated carbon as an active ingredient. Since activated carbon can adsorb heavy metal ions in the electrolytic solution, it is suitable for capturing antimony ions, and may be granular or fibrous. In particular, the activated carbon in sheet form becomes an adsorption layer as it is. The granular activated carbon is supported on a base material such as a nonwoven fabric with a binder such as a synthetic polymer to form a sheet-like adsorption layer, or is deposited on the surface of the negative electrode plate or the positive electrode plate. And In addition to activated carbon, carbon black or the like can also be used as an adsorbent made of carbonaceous material.

  Metal oxides such as titanium oxide, tin oxide, and rare earth oxides have a property of adsorbing heavy metal ions through hydroxyl groups on the surface and can be used as an adsorbent for antimony ions. A metal oxide that does not dissolve in sulfuric acid electrolyte and has a large surface area is suitable for an adsorption layer of antimony ions, and is supported on a substrate such as a nonwoven fabric to form a sheet, or a negative electrode plate with a binder, It is supported on the surface of a positive electrode plate or the like.

  Preferably, the adsorption layer is composed of a separator that separates the negative electrode plate and the positive electrode plate, and the separator contains an ion exchange resin as an adsorbent for antimony ions. The ion exchange resin can adsorb heavy metal ions and is preferably a cation exchange type resin. When it is supported on a fiber separator such as glass mat or a synthetic resin separator such as polyethylene, it captures antimony ions moving from the positive electrode to the negative electrode. The separator can be used to capture antimony ions. Particularly preferably, the ion exchange resin comprises at least one of a synthetic anti-shrink agent and lignin. These materials have a sulfonic acid group and the like, can capture antimony ions, and have little adverse effect on lead-acid batteries.

This invention has the following features.
1) Antimony on the positive electrode plate improves the light load life performance and idling stop life performance at high temperature by suppressing the softening and falling off of the positive electrode active material.
2) When the total content of the sulfonyl group and the sulfonic acid group in the synthetic anti-shrinkage agent is 4000 μmol / g or more, the average pore diameter of the negative electrode material can be reduced and the low-temperature high-rate discharge performance can be improved.
3) Restrict the movement of antimony from the positive electrode plate to the negative electrode plate with the adsorption layer of antimony ions. Accordingly, it is possible to prevent the antimony from interacting with the synthetic anti-shrink agent of the negative electrode, to lose the effect of the synthetic anti-shrink agent, and to prevent the low-temperature high-rate discharge performance from being lowered.
4) By restricting the movement of antimony to the negative electrode plate, it is possible to prevent liquid reduction due to a decrease in hydrogen overvoltage, and it is possible to prevent the positive electrode active material that has fallen off due to a large current at the end of charging from floating and short-circuiting.
5) As a result, a lead-acid battery that is excellent in light load life and idling stop life and that can maintain low-temperature high-rate discharge performance for a long time can be obtained.
6) Carbon black, graphite and other carbonaceous adsorbents and metal oxide adsorbents adsorb and capture antimony ions, and can effectively limit the movement of antimony ions.
7) For example, when the adsorbent is formed in the form of a film on the surface of the negative electrode plate, the production is simple and the structure is simple.
8) When an ion exchange resin is included in the separator, antimony ions can be captured by the ion exchange resin, and no additional member is required, so the structure of the lead storage battery is simple.
9) When lignin or synthetic anti-shrink agent is used as an ion exchange resin, these are materials that have been proven in lead-acid batteries and have few unexpected side effects.

Main part top view of the lead acid battery of an Example Characteristic diagram showing JIS light load life at 75 ℃ and SBA-IS life Characteristic chart showing the transition of end-of-charge current in JIS light load life test (75 ℃) Characteristic diagram showing changes in low-temperature, high-rate discharge performance before and after 1440 cycles of JIS light load life test at 75 ° C

  Hereinafter, an optimum embodiment of the present invention will be described. In carrying out the present invention, the embodiments can be appropriately changed in accordance with common sense of those skilled in the art and disclosure of prior art. In Examples, the negative electrode material may be referred to as a negative electrode active material, and the positive electrode material may be referred to as a positive electrode active material. The negative electrode plate comprises a negative electrode current collector (negative electrode lattice) and a negative electrode material (negative electrode active material), and the positive electrode plate comprises a positive electrode current collector (positive electrode lattice) and a positive electrode material (positive electrode active material). The solid components other than the current collector belong to the electrode material.

Lead-acid battery structure FIG. 1 shows a lead-acid battery 2 of the embodiment, which may be liquid or control valve type. Reference numeral 4 denotes a negative electrode plate, which is composed of a negative electrode lattice and a negative electrode active material (negative electrode material), and adsorbing sheets 12 are bound to the front and back thereof. Reference numeral 6 denotes a positive electrode plate, which is composed of a positive electrode current collector such as a positive electrode lattice or a cored bar and a positive electrode active material (positive electrode material), 10 is a separator such as microporous polyethylene, and 11 is a rib thereof. Further, 8 is an ear of the negative electrode plate 4, 9 is an ear of the positive electrode plate 6, and the negative electrode plate 4 to the separator 10 are immersed in the electrolytic solution. The separator 10 may wrap the positive electrode plate 6, and the rib 11 may face the positive electrode plate 6 or the negative electrode plate 4.

  The adsorbing sheet 12 is, for example, a synthetic fiber nonwoven fabric in which activated carbon and carbon black are supported by a synthetic polymer binder such as styrene butadiene copolymer, chloroprene, and tetrafluoroethylene, and does not contain carbon black. Only activated carbon may be used. Further, when fibrous activated carbon is formed into a sheet, neither a nonwoven fabric nor a binder is required. Activated carbon is hydrophilic due to the mineral content and surface hydroxyl groups produced during the firing process, and its pores adsorb antimony ions. In addition, in an ion exchange resin in which polyvalent cation exchange groups such as sulfonic acid groups and phosphoric acid groups are introduced into polystyrene or fluororesin, the polystyrene skeleton or fluororesin skeleton is fixed to a nonwoven fabric or the like. Multivalent cation exchange groups adsorb antimony ions.

  Instead of a carbonaceous adsorbent such as activated carbon, metal oxides such as titanium oxide, tin oxide, rare earth oxide, and zeolite may be used as the adsorbent for antimony ions. In addition, compounds that adsorb heavy metal ions stably in sulfuric acid, such as polyphosphoric acid compounds and polytungstic acid compounds, can also be used. The adsorbing sheet 12 may be provided between the negative electrode plate 4 and the positive electrode plate 6, and may be bonded to the surface of the positive electrode plate 6 or may be disposed in the electrolyte together with the separator 10, for example. The adsorption sheet 12 may be any position as long as it can limit the movement of antimony ions from the positive electrode plate 6 to the negative electrode plate 4. Further, an activated carbon adsorbent, a metal oxide adsorbent or the like may be layered on the surface of the electrode plates 4 and 6 with a binder, and the adsorbent may be supported by the electrode plates 4 and 6.

  Instead of providing the adsorption sheet 12, the separator 10 may contain an ion exchange resin to adsorb antimony ions. For example, the separator 10 may be impregnated with a synthetic anti-shrink agent, lignin or the like and dried, or the separator 10 may be a copolymer or mixture of a synthetic resin such as polyethylene and an ion exchange resin. The content of the ion exchange resin in the separator 10 is preferably, for example, 0.05 mass% or more and 5 mass% or less. In addition, you may make a lead storage battery into a control valve type, fix a synthetic anti-shrink agent, a lignin, etc. to a glass mat separator, and may adsorb | suck an antimony ion.

  The positive electrode active material in the positive electrode plate 6 contains antimony in the form of antimony oxide or the like, and the concentration in the positive electrode active material is, for example, 0.01 mass% to 1 mass%, preferably 0.02 mass% to 0.5 mass in terms of antimony metal. % Or less, particularly preferably 0.05 mass% or more and 0.5 mass% or less. Instead of containing antimony in the positive electrode active material, antimony may be introduced into the positive electrode plate 6 by laminating a foil of a Pb—Sb alloy on the positive electrode lattice.

  The negative electrode active material in the negative electrode plate 4 contains a synthetic shrinking agent such as a sulfonic acid derivative condensate of bisphenols (hereinafter simply referred to as “bisphenol”). Instead of bisphenol, a condensate of naphthalene sulfonic acid may be used, and a sulfonyl group may be contained instead of the sulfonic acid group. The synthetic anti-shrinkage agent preferably has a total concentration of sulfonic acid groups and sulfonyl groups of 4000 μmol / g or more and 6000 μmol / g or less. By using a reducing agent having a high total concentration of sulfonic acid groups and sulfonyl groups, the pore diameter of the negative electrode active material is reduced, and high-rate discharge performance and the like are improved. And with the conventional lignin anti-shrink agent, it is difficult to increase the total concentration of sulfonic acid groups and sulfonyl groups. The concentration of the synthetic shrinking agent in the negative electrode active material is preferably 0.01 mass% to 1 mass%, preferably 0.02 mass% to 0.8 mass%, particularly preferably 0.02 mass% to 0.5 mass%.

Production of lead-acid batteries Ball-milled lead powder, synthetic fiber reinforcing material, organic anti-shrink agent, barium sulfate, carbon black, paste with water and sulfuric acid added to antimony-free negative electrode grid, dried and aged And gave. Concentrations in the negative electrode active material are 0.1 mass% for the synthetic fiber reinforcing material, 0.3 mass% for barium sulfate, and 0.15 mass% for carbon black. The method for producing the lead powder is arbitrary, and may further include a known additive such as graphite.

  An antimony-free positive electrode grid was filled with paste containing water and sulfuric acid containing lead powder by a ball mill method, synthetic fiber reinforcing agent and antimony source such as antimony oxide, and dried and aged. The concentration in the positive electrode active material is 0.1 mass% for the synthetic fiber reinforcing material, and the concentration of antimony is shown in each table in terms of metal. The method for producing the lead powder is arbitrary, and heavy metal ions can be captured by the adsorption sheet 12, so that a metal harmful to the negative electrode plate 4 can also be contained in the positive electrode plate 6. A lead-antimony alloy foil (antimony concentration 5 mass%, preferable concentration 1 mass% or more and 20 mass% or less) was laminated on the positive electrode lattice, and an antimony contained in the positive electrode lattice was also produced. In this case, the mass ratio between the total antimony content in the positive electrode plate 6 and the positive electrode active material is 0.01 mass% to 1 mass%, more narrowly 0.02 mass% to 0.5 mass%, particularly 0.05 mass% to 0.5 mass%. The following is preferable.

  A negative electrode plate group and a positive electrode plate group were prepared, and a battery case was formed using sulfuric acid having a specific gravity of 1.280 as an electrolytic solution to obtain a 44B20 type lead acid battery. The electrolytic solution may contain aluminum ions, lithium ions, and the like.

Measurement Method The content of the organic shrinkage agent in the negative electrode active material is measured as follows. The fully charged lead acid battery is disassembled, the negative electrode plate is taken out, the sulfuric acid content is removed by washing with water, and the dry weight is measured. Separate the active material from the negative electrode plate, for example, extract the organic shrunk agent by immersing it in a 1 mol / l NaOH aqueous solution, and use the calibration curve prepared in advance with the absorbance obtained with the UV-visible absorptiometer. Measure the content.

  Further, for example, the S element content (hereinafter simply referred to as “S element content”) of the organic anti-shrinking agent is measured as follows. The organic shrinkage agent NaOH aqueous solution obtained by extraction from the active material is desalted, concentrated and dried. The S element content in the organic shrinkage agent is obtained by converting S element in 0.1 g of the organic shrinkage agent into sulfuric acid by the oxygen combustion flask method, and titrating the eluate with barium perchlorate using Trin as an indicator. Let the measured S element content be total content of a sulfonyl group and a sulfonic acid group.

  An ion exchange resin such as an organic anti-shrink agent in the separator can be detected by an infrared total reflection measurement method. The separator taken out by disassembling the battery is washed with water and dried, the positive electrode side surface of the separator is brought into contact with the prism to reflect infrared light, and the absorption spectrum of infrared light is measured. In this method, the presence of the ion exchange resin can be confirmed without being affected by the organic shrinkage agent derived from the negative electrode plate.

  The content of activated carbon, carbon black, etc. can be measured by centrifugation or the like. When measuring the antimony concentration in the positive electrode active material, take out the positive electrode plate from the fully charged lead acid battery, wash with water and dry, collect the positive electrode active material, dissolve lead and antimony in nitric acid, ICP-AES Quantify antimony content. The antimony concentration in the positive electrode lattice can be measured in the same manner.

  Whether or not a member that did not absorb antimony at the time of disassembly can absorb antimony can be confirmed as follows. By immersing the adsorption layer in a solution saturated with antimony ions and allowing to stand overnight, the adsorption of antimony can be confirmed from the decrease in the concentration of the antimony solution. Note that antimony referred to in this specification refers to an antimony element, and refers to metal antimony, ionized antimony, and an antimony compound.

Performance test The following tests were performed on each battery.
75 ° C light load life test : JIS D 5301: 2006 was changed and the test was conducted in a 75 ° C water bath. Discharge at a constant current of 25A for 240 seconds, then charge 2.47V / cell for a maximum of 25A for 600 seconds and measure the end-of-charge current, discharge every 480 cycles at 300A for 30 seconds, and the terminal voltage at the 30th second Is considered to be the life when 1.2V / cell or less. After reaching the life, the storage battery was disassembled and the antimony concentration in the negative electrode active material was measured.
SBA-IS life test : In accordance with SBA S 0101: 2014, in a 25 ° C air tank, after 31A x 59 seconds of discharge and 300A x 1 second of pulse discharge, 2.33V / cell, charging up to 100A at 60 Repeat for 2 seconds and leave for 40-48 hours every 3600 cycles. And the terminal voltage at the time of pulse discharge of 300A x 1 second is less than 1.2V / cell, and the service life is reached. During the test, water is not replenished until 30,000 cycles.
Low-temperature high-rate discharge test : The time until the terminal voltage decreased to 1 V / cell was measured at a constant current of 150 A at -15 ° C. Furthermore, 1440 cycles of discharging at 25 ° C for 25 seconds at 75 ° C and charging for 600 seconds at a maximum of 25A at 2.47V / cell were performed 1440 cycles.After 1440 cycles, the low-temperature high-rate discharge test was performed again, and the ratio to the initial value was determined. Asked.

In the storage battery used in the test, the adsorption sheet 12 has a thickness of 0.2 mm and a density of 1.5 g / cm ³ , but these values are arbitrary. The lignin anti-shrinkage agent had a sulfonic acid group content of 600 μmol / g, and a bisphenol sulfonic acid condensate had a concentration of 5000 μmol / g. In all tests, water replenishment was performed when the liquid level was below the lower level.

  Tables 1 to 4 and FIG. 2 show the results relative to a comparative example (sample No. 1) in which lignin is used as a shrink reducing agent, the positive electrode active material does not contain antimony, and does not have an adsorption sheet (carbon sheet). To FIG. The composition of the sample is shown in each table, and the unit of concentration is mass% and massppm.

  Table 1 and FIG. 2 show the JIS light load life at 75 ° C. and the SBA-IS life. When the positive electrode plate does not contain antimony, it cannot be said that bisphenol is superior to lignin (sample no. .1 ~ No.4). When the positive electrode plate contained antimony, the life performance was improved. However, in the absence of an adsorbent sheet (carbon sheet), bisphenol had a light load life and was inferior to lignin (Sample Nos. 5, 6, 9, 10). On the other hand, when the positive electrode plate contains antimony and there is an adsorbent sheet, the life performance is improved with a battery containing bisphenol, which exceeds the battery containing lignin even in a light load life (Sample Nos. 8 and 12). ).

  Table 2 shows the antimony concentration in the negative electrode active material after the light load life test, and it can be seen that the accumulation of antimony in the negative electrode active material could be limited by providing the carbon sheet. FIG. 3 shows the transition of the end-of-charge current in the light load life test for samples No. 1 to No. 8, and in the case of No. 5 and 6 where the positive electrode active material contains antimony and no carbon sheet, The current increased gradually. This corresponds to the accumulation of antimony in the negative electrode active material in the absence of the carbon sheet (Table 2), and represents a decrease in hydrogen overvoltage. Even if the positive electrode active material contains antimony, when a carbon sheet is provided, the charging end current is stable over time, which corresponds to the fact that the accumulation of antimony in the negative electrode active material can be suppressed (Table 2).

  In Samples Nos. 9 to 12 in Tables 1 and 2, antimony was included in the surface of the positive electrode lattice, not the positive electrode active material. The results were similar to those obtained when antimony was added to the positive electrode active material in terms of light load life at 75 ° C., SBA-IS life, and antimony accumulation in the negative electrode active material.

  Table 3 and FIG. 4 show the maintenance rate of the low-temperature high-rate discharge performance after 1440 cycles. When bisphenol was used, the maintenance rate was higher than that of lignin (Sample No. 2, 4). However, when the positive electrode plate contained antimony and there was no carbon sheet, the effect of bisphenol could not be confirmed (Sample No. 6). This indicates that the effect of bisphenol is lost due to the interaction between antimony ions and bisphenol, and it is likely that the antimony ions are adsorbed on the surface of the bisphenol particles and cancel the surface charge.

  Table 4 shows the results (sample Nos. 17 to 21) when the bisphenol concentration of the anti-shrinkage agent is changed in the range of 0.01 mass% to 1.0 mass%, and the antimony concentration in the positive electrode active material from 0.01 mass% to 1.0 mass. The result (sample No. 26-29) at the time of changing in the range of% is shown. Furthermore, in place of the carbon sheet, the result when a sulfonic acid derivative condensate of bisphenols (the content of sulfonic acid group is 5000 μmol / g) is contained in a polyethylene separator at a concentration of 0.5 mass% with respect to the separator (sample No. .30,31) are also shown. In addition, a naphthalenesulfonic acid condensate (containing S element as a sulfonic acid group and a content of 5000 μmol / g) instead of bisphenol was able to obtain the same effect as bisphenol (Sample No. 32).

  The bisphenol anti-shrinking agent in the negative electrode active material is effective in the entire range from 0.01 mass% to 1 mass%, but it is understood that 0.02 mass% to 0.8 mass%, particularly 0.02 mass% to 0.5 mass% is preferable. It can be seen that antimony in the positive electrode active material is also effective in the entire range from 0.01 mass% to 1 mass%, but is particularly effective at 0.05 mass% to 0.5 mass%. Therefore, the antimony concentration is preferably 0.02 mass% or more between 0.01 mass% and 0.05 mass%.

  Even when bisphenol was contained in the separator, the same result as that obtained when the carbon sheet was provided was obtained. This indicates that bisphenol in the separator is captured by interacting with antimony ions. And even if it makes a separator contain lignin instead of bisphenol, an antimony ion can be captured similarly.

  After the light load life test, when the amount of the positive electrode active material dropped from the positive electrode plate was measured, the amount of antimony contained was small. The amount of liquid reduction increased when the positive electrode plate contained antimony and no antimony ion adsorption layer was provided.

The embodiment has the following characteristics.
1) The antimony on the positive electrode plate could suppress the softening and falling off of the positive electrode active material.
2) The movement of antimony from the positive electrode plate to the negative electrode plate was restricted by an antimony ion adsorption layer (carbon sheet and bisphenol-containing separator). This prevented the loss of effect due to the interaction between bisphenol and antimony ions.
3) By restricting the movement of antimony from the positive electrode plate to the negative electrode plate with the adsorption layer of antimony ions, it was possible to prevent a decrease in hydrogen overvoltage at the negative electrode. It was also possible to prevent the positive electrode active material that had fallen off due to a large current at the end of charging from floating and short circuiting.
4) As a result, a lead-acid battery that is excellent in light load life and idling stop life and that can maintain low-temperature high-rate discharge performance for a long period of time was obtained.

2 Lead storage battery 4 Negative electrode plate 6 Positive electrode plate 8, 9 Ear 10 Separator 11 Rib 12 Adsorption sheet

Claims (5)

  The positive electrode current collector or the positive electrode material comprises a positive electrode plate containing antimony, the negative electrode material comprises a negative electrode plate containing a synthetic anti-shrink agent, and an adsorption layer that adsorbs antimony ions, and the adsorption layer is a negative electrode plate or a positive electrode A lead-acid battery provided on the surface of the plate or between the positive electrode plate and the negative electrode plate. The lead acid battery according to claim 1, wherein the synthetic anti-shrink agent has a sulfonic acid group and / or a sulfonyl group.   The lead acid battery according to claim 1 or 2, wherein the adsorption layer contains a carbonaceous adsorbent or a metal oxide adsorbent as an active ingredient.   The said adsorption layer is comprised with the separator which isolate | separates a negative electrode plate and a positive electrode plate, and the said separator contains ion-exchange resin as an adsorbent of antimony ion, The Claim 1 or Claim 2 characterized by the above-mentioned. Lead acid battery.   The lead storage battery according to claim 4, wherein the ion exchange resin is made of at least one of a synthetic anti-shrink agent and lignin.

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