CN109565040B - Lead-acid battery - Google Patents
Lead-acid battery Download PDFInfo
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- CN109565040B CN109565040B CN201780047806.8A CN201780047806A CN109565040B CN 109565040 B CN109565040 B CN 109565040B CN 201780047806 A CN201780047806 A CN 201780047806A CN 109565040 B CN109565040 B CN 109565040B
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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
- H01M4/14—Electrodes for lead-acid accumulators
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
Abstract
The invention provides a lead storage battery, which is characterized by comprising a positive electrode plate, a negative electrode plate and an electrolyte, wherein the negative electrode material of the negative electrode plate contains graphite or carbon fiber and barium element with the mass percent of more than 1.1% in terms of barium sulfate, and the positive electrode material of the positive electrode plate contains tin element.
Description
Technical Field
The present invention relates to a lead storage battery.
Background
Lead storage batteries are used in many applications in an incomplete state of charge (PSOC). For example, in order to increase fuel consumption of automobiles, idle-Stop (IS) vehicles have been proposed in which lead storage batteries are used in an undercharge state. In addition to the IS vehicle use, the lead storage battery IS often left in an undercharged state because energy efficiency IS improved to avoid charging the lead storage battery and electric power taken out of the lead storage battery IS increased.
In a lead-acid battery, water is generated at the positive electrode while sulfuric acid is consumed at the bipolar plates during discharge. In addition, sulfuric acid is released from the bipolar plate during charging. Sulfuric acid has a higher specific gravity than water, and therefore tends to accumulate in the lower part of the lead-acid battery, and a phenomenon (stratification) occurs in which the sulfuric acid concentration of the electrolyte is lowered vertically. When the charged amount is sufficient, the electrolyte is stirred by the gas generated from the electrode plate at the final stage of charging, thereby eliminating stratification.
However, in a lead-acid battery used in PSOC, since gas generation due to overcharge is small, it is difficult to eliminate stratification of the electrolytic solution. The charge acceptance is low under the electrode plate having a high sulfuric acid concentration, and sulfation (accumulation of lead sulfate) is performed under the negative electrode plate. In addition, since charge and discharge reactions are concentrated on the upper portion of the positive electrode plate, deterioration of the upper portion of the positive electrode plate is promoted, and the life performance is reduced.
It is known to add graphite to the negative electrode material in order to improve the charge acceptance and improve the life performance of lead storage batteries used in PSOCs.
Patent document 1 describes the following invention: "a lead-acid battery characterized by using a paste-type negative electrode plate in which a paste-type active material made of lead powder as a raw material is held by a current collector made of a lead alloy, wherein the negative electrode active material contains, together with a carbonaceous material, (a) a bisphenol sulfonic acid polymer and (b) sodium lignosulfonate, and the blending amounts of (a) and (b) are as follows. The blending proportion of (a) is 50-80 parts by mass, and the total blending mass of (a) and (b) is 0.05-0.3% by mass relative to the mass of the raw material lead powder of the negative electrode active material, when the total of (a) and (b) is 100 parts by mass. "([ claim 1 ])" and "the lead acid battery according to any one of claims 1 to 3, wherein the negative electrode active material contains, as a carbonaceous material, flake graphite having an average primary particle diameter of 10 μm or more. "([ claim 4 ])" and "the lead-acid battery according to claim 4, wherein the content of the flake graphite is 0.5 to 2.5% by mass based on the mass of the negative electrode active material in a fully charged state. "([ claim 5 ])" and "the lead-acid battery according to claim 5, characterized by containing carbon black in addition to the flake graphite. "([ claim 6 ]).
Patent document 2 describes the following invention: "A shrinkage-preventing agent for a battery paste for a battery plate for a lead-acid battery, which contains barium sulfate, high-concentration carbon and/or graphite, and an organic substance. "(claim 1)" or "the shrinkproof agent according to claim 1, wherein the high concentration of carbon and/or graphite reduces accumulation of lead sulfate on the surface of the negative electrode active material in the lead-acid battery. "(claim 10).
Patent document 3 discloses "an expanding agent for a battery paste, which is characterized by containing barium sulfate, carbon and an organic material, and the organic material is resistant to thermal decomposition. "the invention according to claim 1" describes that "carbon" represents any one of carbon black, activated carbon, graphite, and a mixture thereof. "(paragraph [0029 ]).
In addition, it is known that tin is added to a positive electrode material to specify the density of the positive electrode material in order to improve the performance of a lead-acid battery used in PSOC.
Patent document 4 describes "a liquid lead-acid battery for idling start-stop vehicles, which is characterized by comprising a positive electrode plate composed of a positive electrode active material and a positive electrode grid plate, a negative electrode plate composed of a negative electrode active material and a negative electrode grid plate, a separator for separating the positive electrode plate from the negative electrode plate, and a liquid electrolyte having fluidity and impregnating the positive electrode plate, the negative electrode plate, and the separator, wherein the positive electrode active material has a density of 4.4g/cm in a state of completion of formation3～4.8g/cm3And Sn is contained in an amount of 0.05 to 1.0 mass% in terms of metallic Sn. "(claim 1).
Documents of the prior art
Patent document
Patent document 1: japanese Kohyo publication WO2012/017702
Patent document 2: japanese Kohyo publication No. 2012-501519
Patent document 3: japanese Kokai publication No. 2010-529619
Patent document 4: japanese patent laid-open publication No. 2013-140677
Disclosure of Invention
In a lead-acid battery, if graphite or carbon fibers (hereinafter, sometimes referred to as "graphite or the like") having high conductivity and a particle diameter larger than that of carbon black or the like are contained in a negative electrode material, the life of the lead-acid battery under PSOC conditions (hereinafter, referred to as "PSOC life") can be extended. On the other hand, the present inventors have found for the first time that the negative electrode material containsLead-acid batteries such as graphite are prone to suffer from a penetration short circuit. The reason is not clear, but is presumed as follows. It is presumed that graphite or the like is likely to be partially exposed on the surface of the negative electrode plate because of its larger particle diameter compared with carbon black or the like. Since graphite or the like has high conductivity, when graphite or the like is exposed on the surface of the negative electrode plate, Pb is concentratedly generated in the exposed portion2+Charging reaction of (1). As a result, the locally large dendritic lead grows in a direction of piercing the separator, and a penetration short circuit occurs with the upper portion of the electrode plate, on which the charging current is likely to concentrate, as the center.
In view of the above problems, an object of the present invention is to provide a lead-acid battery having improved PSOC life performance and suppressed occurrence of a crossover short circuit.
A lead-acid battery according to an aspect of the present invention includes a positive electrode plate, a negative electrode plate, and an electrolyte, wherein a negative electrode material of the negative electrode plate contains graphite or carbon fiber and 1.1 mass% or more of barium element in terms of barium sulfate, and a positive electrode material of the positive electrode plate contains tin element.
According to one embodiment of the present invention, a lead-acid battery can be provided in which the occurrence of a crossover short circuit is suppressed while improving PSOC life performance.
Drawings
Fig. 1 is a sectional view of a main part of a lead-acid battery according to an embodiment of the present invention.
FIG. 2 is a characteristic diagram showing the influence of the graphite content (barium content 1.0 mass% in terms of barium sulfate, positive electrode active material density 4.8 g/cm)3 Tin content 0 mass%).
FIG. 3 is a characteristic diagram showing the influence of the barium content (graphite content 1.0 mass%, tin content 0 mass%).
FIG. 4 is a characteristic diagram showing the influence of the barium content and the tin content (graphite content 1.0 mass%, positive electrode active material density 4.2 g/cm)3)。
FIG. 5 is a characteristic diagram showing the influence of the barium content and the tin content (graphite content 1.0 mass%, positive electrode active material density 4.2 g/cm)3)。
Fig. 6 is a characteristic diagram showing the influence of the density of the positive electrode active material (graphite content 1.0 mass%, barium content 1.2 mass% in terms of barium sulfate).
Fig. 7 is a characteristic diagram showing the influence of the density of the positive electrode active material (graphite content 1.0 mass%, barium content 1.0 mass% in terms of barium sulfate).
FIG. 8 is a characteristic diagram showing the influence of the barium content (graphite content: 1.0 mass%, tin content: 0.01 mass%).
FIG. 9 is a characteristic diagram showing the influence of the carbon black content (graphite content: 3.0 mass%, positive electrode active material density: 4.8 g/cm)3)。
FIG. 10 is a characteristic diagram showing the influence of the average particle diameter of graphite (graphite content: 3.0 mass%, barium content 1.2 mass% in terms of barium sulfate, and positive electrode active material density: 4.8 g/cm)3Tin content 0.01 mass%).
Detailed Description
A lead-acid battery according to an aspect of the present invention is characterized in that: the negative electrode material of the negative electrode plate contains graphite or carbon fiber and 1.1 mass% or more of barium element in terms of barium sulfate, and the positive electrode material of the positive electrode plate contains tin element. The details are as follows.
The negative electrode plate is composed of a negative electrode current collector and a negative electrode material, the positive electrode plate is composed of a positive electrode current collector and a positive electrode material, and solid components other than the current collector are the electrode materials. The content of graphite, the content of carbon fiber, the content of barium element, and the content of carbon black are the content (mass%) of the negative electrode material in a fully charged state after formation. The content of tin element is the content (mass%) of the positive electrode material in a fully charged state after formation. The content of barium is a content in terms of barium sulfate, and the content of tin is a content in terms of metallic tin.
In the case of a liquid battery in order to fully charge a lead storage battery, the lead storage battery is charged in a water tank at 25 ℃ with a constant current at a rate of 5 hours until the battery reaches 2.5V/Cell, and then charged with a constant current at a rate of 5 hours for 2 hours. In the case of the valve-regulated battery, constant-current constant-voltage charging was performed at a rate of 2.23V/Cell at a current of 5 hours in a gas tank at 25 ℃ and the charging was terminated when the current value in the constant-voltage charging was 1mCA or less. The 5-hour rate current in this specification is a current value obtained by discharging the lead storage battery at a nominal capacity for 5 hours, and for example, if the lead storage battery is a battery having a nominal capacity of 30Ah, the 5-hour rate current is 6A and 1mCA is 30 mA.
< electrode Material >
As described above, the PSOC life performance of the lead-acid battery including the negative electrode material containing graphite or the like is improved.
The content of graphite or the like in the negative electrode material is preferably 0.5% by mass or more because the PSOC life performance improving effect is large if the content of graphite or the like in the negative electrode material is 0.5% by mass or more. The content of graphite or the like in the negative electrode material is more preferably 1.0 mass% or more because the effect of improving the PSOC lifetime performance is greater if the content of graphite or the like in the negative electrode material is 1.0 mass% or more.
Since the negative electrode current collector is easily filled with the negative electrode material paste if the content of graphite or the like in the negative electrode material is 2.5% by mass or less, the content of graphite or the like in the negative electrode material is preferably 2.5% by mass or less, more preferably 2.0% by mass or less.
Examples of the graphite include flake graphite, scale graphite, soil graphite, expanded graphite, and artificial graphite. Expanded graphite refers to graphite that has been expanded. In addition, carbon fibers may be used instead of graphite. It is considered that graphite and carbon fiber are common in terms of high conductivity and larger than carbon black and the like, and the same effect is also expected in the negative electrode material. The carbon fiber preferably has a length of 5 to 500 μm, and more preferably a length of 10 to 300 μm, for example. The graphite or the like is preferably flake graphite or expanded graphite, and more preferably flake graphite.
If the average particle diameter of graphite is 300 μm or less, the occurrence of short circuit by permeation is less likely, and therefore the average particle diameter of graphite is preferably 300 μm or less. Further, since the PSOC life performance is improved when the average particle diameter of the graphite is 100 μm or more, the average particle diameter of the graphite is preferably 100 μm or more. The average particle diameter of graphite is a value of a particle diameter (D50) having a cumulative volume of 50% in a particle size distribution when analyzed by a laser diffraction particle size distribution measuring apparatus.
By adding graphite or the like to the negative electrode material, PSOC life performance is improved, and on the other hand, a penetration short circuit is likely to occur. It has not been known that a short circuit by permeation is easily caused by adding graphite or the like to a negative electrode material of a lead-acid battery. The present inventors have found that the occurrence of a penetration short circuit can be suppressed by containing 1.1 mass% or more of barium element in terms of barium sulfate together with graphite or the like in a negative electrode material.
The effect of suppressing the penetration short circuit by adding 1.1 mass% or more of barium element in terms of barium sulfate to the negative electrode material together with graphite or the like cannot be expected according to the conventional technical common knowledge. The reason is that: the problem of the occurrence of a penetration short circuit easily occurring due to the incorporation of graphite or the like into the negative electrode material has not been recognized, and the effect of suppressing the occurrence of a penetration short circuit by selecting the amount of barium element to be 1.1 mass% or more in terms of barium sulfate has not been known so far.
The mechanism of action of adding barium to the negative electrode material to suppress the occurrence of the penetration short-circuit is not clear, but is presumed as follows. It is considered that the barium element in the negative electrode material is dispersed almost uniformly in the negative electrode material in the form of barium sulfate, and functions as a nucleation material for lead sulfate at the time of discharge, thereby generating lead sulfate also in the negative electrode material. When lead sulfate is also generated in the negative electrode material, the amount of lead sulfate generated on the surface of the negative electrode plate can be suppressed from increasing. A part of lead sulfate is dissolved to generate lead ions, but if the amount of lead sulfate on the surface of the negative electrode plate is reduced, the concentration of lead ions near the surface of the negative electrode plate is also reduced, and lead ions are less likely to diffuse into the electrolyte between the positive and negative electrode plates. As a result, in the graphite or the like exposed on the surface of the electrode plate, a reduction reaction of lead ions is less likely to occur during charging, and the growth of dendritic lead in the direction of the positive electrode plate from the graphite or the like exposed on the surface of the electrode plate can be suppressed.
When the content of barium element in the negative electrode material is 1.2 mass% or more in terms of barium sulfate, the occurrence of a penetration short circuit can be greatly suppressed. Therefore, the content of barium element in the negative electrode material is preferably 1.2 mass% or more in terms of barium sulfate.
Since PSOC life performance is improved when the content of barium element in the negative electrode material is 3.0 mass% or less in terms of barium sulfate, the content of barium element in the negative electrode material is preferably 3.0 mass% or less in terms of barium sulfate. Since the PSOC life performance is greatly improved when the content of barium element in the negative electrode material is 2.5 mass% or less in terms of barium sulfate, the content of barium element in the negative electrode material is more preferably 2.5 mass% or less in terms of barium sulfate.
In order to make the negative electrode material contain barium element, barium sulfate, barium carbonate, or other barium compounds may be added to the negative electrode material. Even if a simple substance of barium or a barium compound other than barium sulfate is added to the negative electrode material, it is considered that the barium sulfate is obtained after the addition.
Barium sulfate in the negative electrode material preferably has an average secondary particle diameter of 1 to 10 μm, for example. The barium sulfate in the negative electrode material preferably has an average primary particle diameter of 0.3 to 2.0 μm, for example.
When the content of barium element in the negative electrode material is 1.1 mass% or more in terms of barium sulfate and the positive electrode material further contains tin element, the penetration short circuit can be further suppressed. On the other hand, when the content of barium element in the negative electrode material is 1.0 mass% or less in terms of barium sulfate, the effect of suppressing the penetration short circuit due to tin element is not observed even when tin element is contained in the positive electrode material. The tin element in the positive electrode material has not been known to be involved in the penetration short circuit so far. Therefore, it was unexpected that when the negative electrode material contains graphite or the like and contains 1.1 mass% or more of barium element in terms of barium sulfate, the positive electrode material contains tin element, thereby suppressing the penetration short circuit. In addition, when the content of barium element in terms of barium sulfate in the negative electrode material is 1.1% by mass or more and 1.0% by mass or less, the effect of suppressing the penetration short circuit by the tin element clearly changes, and therefore it can be said that it is critical that the content of barium element in the negative electrode material is 1.1% by mass or more in terms of barium sulfate.
When the content of the tin element in the positive electrode material is 0.01 mass% or more, the penetration short circuit can be significantly suppressed, so that the content of the tin element in the positive electrode material is preferably 0.01 mass% or more. As the form of existence of the tin element in the positive electrode material, metals, oxides, sulfates, and the like are considered.
The mechanism of action of suppressing the occurrence of the crossover short by adding tin to the positive electrode material is not clear, but is presumed as follows. It is presumed that since tin has an effect of improving conductivity, when tin is added to the positive electrode material, the charge-discharge reaction in the vertical direction of the positive electrode plate is more uniform, and the concentration of the charge current on the upper portion of the electrode plate is alleviated. When the concentration of the charging current to the upper part of the electrode plate is alleviated, the growth of the dendritic lead on the upper part of the electrode plate is inhibited, and the growth of the dendritic lead on the upper part of the electrode plate and the inhibition effect of the penetration short circuit caused by more than 1.1mass percent of barium sulfate in the negative electrode material play a synergistic role, so that the occurrence of the penetration short circuit is obviously inhibited.
When the negative electrode material contains barium element of 1.1 mass% or more in terms of barium sulfate and graphite or the like, the PSOC life performance is improved when the content of tin element in the positive electrode material is 0.15 mass% or less, as compared with when the positive electrode material does not contain tin element. Therefore, the content of tin element in the positive electrode material is preferably 0.15 mass% or less. On the other hand, when the content of barium element in the negative electrode material is 1.0 mass% or less in terms of barium sulfate, the PSOC life performance is not improved as compared with the case where the positive electrode material does not contain tin element, even if the content of tin element in the positive electrode material is 0.15 mass% or less. It has not been known that when a negative electrode material contains graphite or the like, PSCO life performance is improved by setting the content of barium element in the negative electrode material and the content of tin element in the positive electrode material to specific ranges.
When the negative electrode material contains graphite or the like and barium element in an amount of 1.1 mass% or more in terms of barium sulfate, the PSOC life performance is greatly improved when the content of tin element in the positive electrode material is 0.10 mass% or less, as compared with when the positive electrode material does not contain tin element. Therefore, the content of tin element in the positive electrode material is more preferably 0.10 mass% or less. When the negative electrode material contains graphite or the like and barium element in an amount of 1.1 mass% or more in terms of barium sulfate, the PSOC life performance is further improved when the content of tin element in the positive electrode material is 0.08 mass% or less, which is more preferable. When the negative electrode material contains barium element of 1.1 mass% or more in terms of barium sulfate and graphite or the like, the PSOC life performance is particularly improved when the content of tin element in the positive electrode material is 0.06 mass% or less, which is particularly preferable.
When the negative electrode material contains graphite or the like and barium element in an amount of 1.1 mass% or more in terms of barium sulfate, the PSOC life performance is greatly improved when the content of tin element in the positive electrode material is 0.03 mass% or more, as compared with when the positive electrode material does not contain tin element. Therefore, the content of tin element in the positive electrode material is preferably 0.03 mass% or more.
The effect of improving the PSOC life performance, which is obtained by containing graphite or the like and barium in an amount of 1.1 mass% or more in terms of barium sulfate as the negative electrode material and tin in an amount of 0.15 mass% or less as the positive electrode material, is obtained when the density of the positive electrode material is 3.6g/cm3The above values become large. Therefore, the density of the positive electrode material is preferably 3.6g/cm3The above. On the other hand, when the content of barium element in the negative electrode material is 1.0 mass% or less in terms of barium sulfate, the density of the positive electrode material is set to 3.6g/cm3As described above, the PSOC life performance is not improved as compared with the case where the positive electrode material does not contain tin.
The effect of improving the PSOC life performance, which is obtained by containing graphite or the like and barium in an amount of 1.1 mass% or more in terms of barium sulfate as the negative electrode material and tin in an amount of 0.15 mass% or less as the positive electrode material, is obtained when the density of the positive electrode material is 4.2g/cm3The above becomes larger. Due to the fact thatIn this case, the density of the positive electrode material is more preferably 4.2g/cm3The above. The PSOC life performance improving effect is caused by that the density of the positive electrode material is 4.4g/cm3Since the density of the positive electrode material becomes significantly large, it is particularly preferable that the density of the positive electrode material is 4.4g/cm3The above.
Because the density of the positive electrode material is 5.0g/cm3Hereinafter, since the initial capacity of the lead-acid battery is improved, the density of the positive electrode material is preferably 5.0g/cm3The following.
In the lead-acid battery according to one embodiment of the present invention, the negative electrode material may further contain carbon black. When the negative electrode material contains graphite or the like and 1.1 mass% or more of barium element in terms of barium sulfate and the positive electrode material contains tin element, if carbon black is further contained in the negative electrode material, the penetration short circuit can be further suppressed. On the other hand, when the content of barium element in the negative electrode material is 1.0 mass% or less in terms of barium sulfate, or when the positive electrode material does not contain tin element, even if carbon black is contained in the negative electrode material, the effect of suppressing the penetration short circuit by the carbon black is not obtained.
It is preferable to set the content of carbon black in the negative electrode material to 0.1 mass% or more because the penetration short-circuit can be greatly suppressed. When the content of carbon black in the negative electrode material is 1.0 mass% or less, the negative electrode current collector can be easily filled with the negative electrode material paste. Therefore, the content of carbon black in the negative electrode material is preferably 1.0 mass% or less.
Hereinafter, a lead-acid battery and a method for manufacturing the same according to one embodiment of the present invention will be described in detail in order.
< negative plate >
The unformed negative electrode plate can be produced as follows. First, water and sulfuric acid are added to lead powder to be pasted, thereby obtaining a negative electrode material paste. The negative electrode material paste may further contain reinforcing materials such as graphite, carbon fibers, barium sulfate, carbon black, lignin as a shrinkage inhibitor, synthetic resin fibers, and the like. Instead of barium sulfate, simple barium compounds such as barium and barium carbonate may be used.
The content of lignin is arbitrary, and a synthetic shrinkproof agent such as a condensate of a sulfonated bisphenol may be used instead of lignin. The content of the reinforcing material and the kind of the synthetic resin fiber are arbitrary. The kind and production conditions of the lead powder are arbitrary. The negative electrode material paste may contain other additives, a water-soluble synthetic polymer electrolyte, and the like.
The negative electrode material paste is filled in a negative current collector, and then cured and dried to produce an unformed negative electrode plate. For the negative electrode collector, for example, a mesh plate, a casting plate, a punching plate, or the like can be used.
< Positive plate >
The unformed positive electrode plate can be produced as follows. First, water and sulfuric acid are added to lead powder to be pasted, thereby obtaining a positive electrode material paste. The positive electrode material paste may contain a reinforcing material such as tin sulfate or synthetic resin fibers. The positive electrode material paste is filled in a positive electrode current collector, and then cured and dried to produce an unformed positive electrode plate. The kind and production conditions of the lead powder are arbitrary. Instead of tin sulfate, metallic tin or the like may be used, and tin is supposed to exist as a metal, an oxide, a sulfate compound or the like in the positive electrode material. The density of the formed positive electrode material was adjusted by changing the amount of water added in the preparation of the positive electrode material paste. For example, a mesh grid, a cast grid, a pressed grid, or the like can be used as the positive electrode collector.
< lead storage Battery >
The lead-acid battery can be produced as follows. The unformed negative electrode plates and the unformed positive electrode plates are alternately stacked with separators interposed therebetween, and the unformed negative electrode plates and the unformed positive electrode plates are connected to each other by a common-pole connecting sheet, respectively, to form an electrode plate group. The electrode plate group was housed in a battery chamber of a battery case in a state of being connected in series, and was converted by adding sulfuric acid to produce a lead-acid battery. The lead-acid battery can be produced by assembling a group of electrode plates after chemical conversion of an unformed negative electrode plate and an unformed positive electrode plate. The separator is made of, for example, a synthetic resin, preferably polyolefin, and more preferably polyethylene. In addition, the spacer preferably has a rib protruding from the base. The thickness of the base body of the separator, the total thickness, and the like are arbitrary, and the thickness of the base body of the separator is preferably 0.15mm to 0.25 mm. The spacing between the positive plate and the negative plate is preferably 0.5mm to 1.0 mm. The separator may be formed in a bag shape to surround the positive or negative electrode plate.
Fig. 1 shows a main part of an electrode plate group 1 of a lead-acid battery according to an embodiment of the present invention, 2 being a negative electrode plate, 3 being a positive electrode plate, and 4 being a separator. The negative electrode plate 2 is composed of a negative electrode current collector 21 and a negative electrode material 22, and the positive electrode plate 3 is composed of a positive electrode current collector 31 and a positive electrode material 32. The separator 4 is a bag-like body including a base 41 and a rib 42, and houses the negative electrode plate 2 in the bag, with the rib 42 facing the positive electrode plate 3. However, the rib 42 may be oriented toward the positive electrode plate 3 to house the positive electrode plate 3 in the separator 4, and the separator 4 may not have the rib 42. The separator need not be bag-shaped as long as it separates the positive electrode plate from the negative electrode plate, and for example, a small sheet-shaped glass mat, a fixing mat, or the like may be used.
The content of barium element contained in the resultant negative electrode material was determined as follows. The lead-acid battery in a fully charged state is disassembled, and the negative electrode plate is washed with water and dried to remove a sulfuric acid component, thereby extracting a negative electrode material. The negative electrode material was pulverized, 20mL of a 300g/L hydrogen peroxide solution was added to 100g of the negative electrode material, and nitric acid obtained by diluting 60 mass% concentrated nitric acid with 3 times the volume of ion-exchanged water was further added thereto, and the mixture was heated for 5 hours under stirring to dissolve lead into lead nitrate. Further, barium sulfate was dissolved, and the barium concentration in the obtained aqueous solution was quantified by atomic absorption measurement. The barium content in terms of barium sulfate contained in the negative electrode material was calculated using the barium concentration.
The contents of graphite and carbon black contained in the negative electrode material after formation were determined as follows. The lead-acid battery in a fully charged state is disassembled, and the negative electrode plate is washed with water and dried to remove a sulfuric acid component, thereby extracting a negative electrode material. The negative electrode material was pulverized, 20mL of a 300g/L hydrogen peroxide solution was added to 100g of the negative electrode material, and nitric acid obtained by diluting 60 mass% concentrated nitric acid with 3 times the volume of ion-exchanged water was further added thereto, and the mixture was heated for 5 hours under stirring to dissolve lead into lead nitrate. Further dissolving the barium sulfate. The obtained aqueous solution is filtered to separate solid components such as graphite, carbon black, and reinforcing materials.
Next, the solid content obtained by filtration was dispersed in water. The dispersion was sieved 2 times using a sieve through which the reinforcing material could not pass, and the reinforcing material washed with water was removed, thereby separating carbon black and graphite.
When carbon black and graphite are added to the negative electrode material paste together with an organic shrinkproof agent such as lignin, the carbon black and graphite exist in a state in which aggregates thereof are broken up by the surface active effect of the organic shrinkproof agent even in the negative electrode material after formation. In the above-mentioned series of separation operations, the organic shrinkproof agent was eluted into water and lost, and therefore, after the separated carbon black and graphite were redispersed in water, 15g of vanilex N (manufactured by japan paper company) which is a lignosulfonate as an organic shrinkproof agent was added to 100mL of water and stirred, and the following separation operation was performed in a state where the aggregate of carbon black and graphite was redissolved.
After the above operation, the suspension containing carbon black and graphite was passed through a screen through which carbon black substantially did not pass through graphite, and the two were separated. In this operation, graphite remains on the screen, and the liquid passing through the screen contains carbon black. The graphite and the carbon black separated by the above series of operations were washed with water and dried, respectively, and then the weights thereof were measured. The carbon fibers were also separated in the same manner as graphite, and weighed.
The method for measuring the average particle diameter of graphite is described below. The measurement apparatus used was a laser diffraction particle size distribution measurement apparatus SALD2200 manufactured by Shimadzu corporation. First, graphite was dispersed in a dispersion prepared by mixing water and a surfactant, and the dispersion in which the graphite was dispersed was irradiated with ultrasonic waves for 5 minutes using an ultrasonic cleaner. Next, the dispersion liquid in which graphite was dispersed was introduced into a batch-type measuring cell (back-separation type セル), and stirred for 1 minute. Then, laser light is irradiated to obtain the particle size distribution of graphite. In this particle size distribution, the particle size having a cumulative volume of 50% (D50) was defined as the average particle size in the range of 0.1 μm as the minimum and 1000 μm as the maximum.
The content of tin element in the positive electrode material after formation was determined as follows. The lead-acid battery in a fully charged state is disassembled, and the positive electrode plate is washed with water and dried to remove a sulfuric acid component, and the positive electrode material is extracted. The positive electrode material was pulverized, 20mL of a 300g/L hydrogen peroxide solution was added to 100g of the positive electrode material, and nitric acid obtained by diluting 60 mass% concentrated nitric acid with 3 times the volume of ion-exchanged water was further added thereto, and the mixture was heated for 5 hours under stirring to dissolve lead and tin. The concentration of tin element in the obtained aqueous solution was quantified by ICP emission spectrometry, and the content of tin element in the positive electrode material was calculated.
The density of the positive electrode material is a value of the bulk density of the positive electrode material in a fully charged state after the formation, and is measured in the following manner. The battery after formation was fully charged and then disassembled, and the obtained positive electrode plate was washed with water and dried, thereby removing the electrolyte in the positive electrode plate. Next, the positive electrode material was separated from the positive electrode plate to obtain an uncrushed measurement sample. A sample is put into a measuring container, vacuum-exhausted, then filled with mercury at a pressure of 0.5-0.55 psia, the bulk volume of the positive electrode material is measured, and the mass of the measured sample is divided by the bulk volume to determine the bulk density of the positive electrode material. The volume obtained by subtracting the injection volume of mercury from the volume of the measurement container is defined as the deposition volume.
The lead-acid battery of the present embodiment is excellent in PSOC life performance and is less likely to cause a short circuit due to permeation even when used in a partially charged state, and therefore is suitable for lead-acid batteries used in a partially charged state such as an idling start-stop vehicle lead-acid battery. The lead acid battery of the present embodiment is applicable to lead acid batteries for cycle use such as a forklift in addition to lead acid batteries for idle start/stop vehicles and the like. In the following embodiments, the lead acid battery is of a liquid type, but may be of a valve type. The lead acid battery of the present embodiment is preferably a flooded lead acid battery.
< other embodiment >
The present invention is not limited to the above embodiments, and various modifications and improvements can be made in addition to the above embodiments. For example, the present invention can be implemented as follows.
(1) A lead storage battery is characterized by comprising a positive electrode plate, a negative electrode plate and an electrolyte, wherein the negative electrode material of the negative electrode plate contains graphite or carbon fiber and 1.1 mass% or more of barium element in terms of barium sulfate, and the positive electrode material of the positive electrode plate contains tin element.
(2) The lead-acid battery according to (1), wherein the positive electrode material contains 0.15 mass% or less of tin element.
(3) The lead-acid battery according to (1) or (2), wherein the positive electrode material has a density of 3.6g/cm3The above.
(4) The lead-acid battery according to any one of (1) to (3), wherein the negative electrode material contains carbon black.
(5) The lead-acid battery according to any one of (1) to (4), wherein the negative electrode material contains graphite or carbon fiber in an amount of 0.5 mass% or more.
(6) The lead-acid battery according to any one of (1) to (5), wherein the negative electrode material contains graphite or carbon fiber in an amount of 2.5 mass% or less.
(7) The lead-acid battery according to any one of (1) to (6), wherein the graphite or the carbon fiber is graphite having an average particle diameter of 300 μm or less.
(8) The lead-acid battery according to any one of (1) to (7), wherein the graphite or the carbon fiber is graphite having an average particle diameter of 100 μm or more.
(9) The lead-acid battery according to any one of (1) to (8), wherein the negative electrode material contains 3.0 mass% or less of barium element in terms of barium sulfate.
(10) The lead-acid battery according to any one of (1) to (9), wherein the positive electrode material contains 0.01 mass% or more of tin element.
(11) The method according to any of (1) to (10)The lead-acid battery is characterized in that the density of the positive electrode material is 4.2g/cm3The above.
(12) The lead-acid battery according to any one of (1) to (11), wherein the positive electrode material has a density of 5.0g/cm3The following.
(13) The lead-acid battery according to any one of (1) to (12), wherein the negative electrode material contains graphite or carbon fiber in an amount of 1.0 mass% or more.
(14) The lead-acid battery according to any one of (1) to (13), wherein the negative electrode material contains graphite or carbon fiber in an amount of 2.0 mass% or less.
(15) The lead-acid battery according to any one of (1) to (14), wherein the negative electrode material contains 1.2 mass% or more of barium element in terms of barium sulfate.
(16) The lead-acid battery according to any one of (1) to (15), wherein the negative electrode material contains 2.5 mass% or less of barium element in terms of barium sulfate.
(17) The lead-acid battery according to any one of (1) to (16), wherein the barium element is contained as barium sulfate.
(18) The lead-acid battery according to any one of (1) to (17), wherein the positive electrode material contains 0.10 mass% or less of tin element.
(19) The lead-acid battery according to any one of (1) to (18), wherein the positive electrode material contains 0.08% by mass or less of tin element.
(20) The lead-acid battery according to any one of (1) to (19), wherein the positive electrode material contains 0.06 mass% or less of tin element.
(21) The lead-acid battery according to any one of (1) to (20), wherein the positive electrode material contains 0.03 mass% or more of tin element.
(22) The lead-acid battery according to any one of (1) to (21), wherein the positive electrode material has a density of 4.4g/cm3The above.
(23) The lead-acid battery according to any one of (1) to (22), wherein the negative electrode material contains carbon black in an amount of 0.1 mass% or more.
(24) The lead-acid battery according to any one of (1) to (23), wherein the negative electrode material contains carbon black in an amount of 1.0 mass% or less.
(25) A lead storage battery is characterized by comprising a positive electrode plate, a negative electrode plate and an electrolyte, wherein the negative electrode material of the negative electrode plate contains graphite or carbon fiber and about 1.1 mass% or more of barium element in terms of barium sulfate, and the positive electrode material of the positive electrode plate contains tin element.
(26) The lead-acid battery according to (25), wherein said positive electrode material contains about 0.15 mass% or less of tin element.
(27) The lead-acid battery according to (25) or (26), wherein the positive electrode material has a density of about 3.6g/cm3The above.
(28) The lead-acid battery according to any one of (25) to (27), wherein the negative electrode material contains about 0.5 mass% or more of graphite or carbon fiber.
(29) The lead-acid battery according to any one of (1) to (28), wherein the graphite or the carbon fiber is flake graphite or expanded graphite.
(30) The lead-acid battery according to any one of (1) to (29), wherein the graphite or the carbon fiber is flake graphite.
(31) The lead-acid battery according to any one of (1) to (30), wherein the lead-acid battery is a lead-acid battery used in a partially charged state.
(32) The lead-acid battery according to any one of (1) to (31), wherein the lead-acid battery is a liquid lead-acid battery.
(33) The lead-acid battery according to any one of (1) to (31), wherein the lead-acid battery is a valve regulated lead-acid battery.
(34) The lead-acid battery according to any one of (1) to (33), wherein the lead-acid battery is a lead-acid battery for an idling start-stop vehicle.
(35) A vehicle equipped with the lead-acid battery of any one of (1) to (34).
Examples
The following examples are shown. In practice, the embodiment may be appropriately modified according to common general knowledge of those skilled in the art and the disclosure of the prior art. In the examples, the negative electrode material is sometimes referred to as a negative electrode active material, and the positive electrode material is sometimes referred to as a positive electrode active material.
A lead powder produced by a ball milling method is mixed with a predetermined amount of flaky graphite (average particle diameter (D50) of 10 to 500 μm), a predetermined amount of barium sulfate (average primary particle diameter of 0.79 μm, average secondary particle diameter of 2.5 μm), a predetermined amount of carbon black, a predetermined amount of lignin as a shrinkage inhibitor (content: 0.2 mass%), and synthetic resin fibers as a reinforcing material (content: 0.1 mass%), and gelatinized with water and sulfuric acid to prepare a negative electrode active material paste. The content of the flaky graphite varies within the range of 0 mass% to 3.0 mass%. The content of barium sulfate varies from 1.0% to 4.0% by mass. The content of carbon black varies from 0% by mass to 0.5% by mass.
The prepared negative electrode active material paste was filled in a mesh-type negative electrode grid (height 110 mm. times. width 100 mm. times. thickness 1.0mm) made of a Pb-Ca-Sn alloy containing no antimony, and the paste was aged and dried to prepare an unformed negative electrode plate.
A predetermined amount of tin sulfate and 0.1 mass% of synthetic resin fibers (content: 0.1 mass%) as a reinforcing material were mixed with a lead powder produced by a ball milling method, and the mixture was gelatinized with water and sulfuric acid to prepare a positive electrode active material paste. The content of tin sulfate varies in the range of 0 to 0.3 mass% in terms of metallic tin. The prepared positive electrode active material paste was filled in a mesh-type positive electrode grid (height 110 mm. times. width 100 mm. times. thickness 1.2mm) made of a Pb-Ca-Sn alloy containing no antimony, and aged and dried to prepare an unformed positive electrode plate. The density of the positive electrode active material after formation was adjusted to 3.4g/cm by changing the amount of water added during gelatinization3～5.0g/cm3。
The unformed negative electrode plates were wrapped with a polyethylene separator (average pore diameter 0.1 μm) having ribs protruding from the base, and the unformed negative electrode plates 7 and the unformed positive electrode plates 6 were alternately stacked, and the negative electrode plates and the positive electrode plates were connected to each other by a common-pole connecting sheet, respectively, to prepare an electrode plate group. In the examples, a separator having a substrate thickness of 0.25mm was used, and the positive and negative plates were spaced 0.7mm apart. The 6 electrode plate groups were housed in a cell chamber of a cell casing in a state of being connected in series, and sulfuric acid having a specific gravity of 1.285 was added at 20 ℃ to form a liquid lead storage battery having a 5-hour rate capacity of 30Ah in a size of B20 in the cell casing.
The content of barium element, the content of graphite, the average particle diameter of graphite, and the content of carbon black contained in the negative electrode active material were measured as follows. A sieve having a diameter of 1.4mm was used in the separation of the carbon black and graphite in the negative electrode active material from the reinforcing material. After dispersing the separated carbon black and graphite in water, vanilex N (manufactured by japan paper-making corporation) which is a lignosulfonate was added as an organic shrinkproof agent, and a sieve having a diameter of 20 μm was used to separate the carbon black and the graphite. One of the lead-acid batteries having negative electrode plates of the same composition is selected and measured, and the measurement results are applied to all the lead-acid batteries having negative electrode plates of the same composition. The content of tin element contained in the positive electrode active material and the density of the positive electrode active material were measured as described above. One of these lead-acid batteries was selected and measured for lead-acid batteries having positive electrode plates of the same composition, and the measurement results were applied to all lead-acid batteries having positive electrode plates of the same composition.
The lead-acid battery in a fully charged state was subjected to a PSOC life test and an osmotic short-circuit promotion test. The contents of the PSOC life test are shown in table 1. The 1CA is 30A in the case of a battery having a nominal capacity of 30 Ah. "40 ℃ gas" means that the test is carried out in a 40 ℃ gas cell. The contents of the PSOC life test are as follows. First, a constant current discharge was performed at 1CA for 59 seconds (step 1), and a constant current discharge was performed at 300A for 1 second (step 2). Next, each cell was subjected to constant voltage charging at a voltage of 2.4V (charging current is 50A at maximum) for 10 seconds (step 3), and was subjected to constant current discharging at 1CA for 5 seconds (step 4). The steps 3 and 4 are repeated 5 times in total (step 5), and the steps 1 to 5 are further repeated 50 times in total (step 6). After the end of step 6, the cells were charged at a voltage of 2.4V (charging current is 50A at maximum) for 900 seconds (step 7). The steps 1 to 7 were repeated 72 times in total (step 8), and after a 15-hour pause (step 9), the process was returned to the step 1 (step 10). The number of cycles at the time when the terminal voltage reached 1.2V/Cell was defined as the number of PSOC lifetimes, after repeating steps 1 to 10 until the terminal voltage reached 1.2V/Cell. The cycle of steps 1 to 5 was 1. For example, when the steps 1 to 10 are performed 1 time, the number of cycles is 3600 cycles.
The contents of the penetration short-circuit promoting test are shown in table 2. This test is performed under conditions that promote the occurrence of a penetration short circuit, and the occurrence rate of the penetration short circuit is significantly higher than that under the actual conditions of use of the lead-acid battery. The contents of the penetration short-circuit promotion test are as follows. First, constant current discharge was performed at 0.05CA until the voltage of each cell became 1.0V (step 1). Next, a resistance of 10 Ω was connected between the positive electrode terminal and the negative electrode terminal of the lead-acid battery, and the lead-acid battery was left for 23 hours and 50 minutes (step 2). Then, each cell was subjected to constant voltage charging (charging current 50A at maximum) at a voltage of 2.4V for 10 minutes (step 3). After repeating the steps 2 and 35 times in total (step 4), the lead-acid battery was disassembled and the ratio of the short-circuited lead-acid battery was examined. The expression "water at 25 ℃" means that the test is performed in a water tank at 25 ℃. In tables 1 and 2, CC discharge represents constant current discharge, CV charge represents constant voltage charge, and CC charge represents constant current charge.
[ Table 1]
[ Table 2]
The results of the PSOC life test and the penetration short-circuit promotion test are shown in tables 3 to 10. In tables 3 to 10, the PSOC life count indicates the ratio of the PSOC life counts of the batteries when the PSOC life count of battery a1 in table 3 is 100. The PSOC life ratio indicates a ratio of the number of PSOC lives of each battery to the number of PSOC lives of the battery at the front end of each table.
[ Table 3]
[ Table 4]
[ Table 5]
[ Table 6]
From table 5 and fig. 2, it is understood that the PSOC life performance is improved in the lead-acid battery in which the negative electrode active material contains graphite, as compared with the lead-acid battery in which the same conditions are applied except for the content of graphite. The PSOC service life is greatly improved when the negative active material contains more than 0.5 mass% of graphite, and the PSOC service life is further greatly improved when the negative active material contains more than 1.0 mass% of graphite.
On the other hand, from tables 3 to 6 and fig. 2, it is understood that in the lead-acid battery in which the negative electrode active material contains graphite, a penetration short circuit is more likely to occur as compared with the lead-acid battery in which the same conditions are applied except for the content of graphite. It has not been known that when graphite is contained in the negative electrode active material, a penetration short circuit is likely to occur.
From tables 3 to 6 and fig. 3, it is understood that the penetration short circuit can be suppressed when the negative electrode active material contains 1.1 mass% or more of barium element in terms of barium sulfate. When the negative electrode active material contains 1.2 mass% or more of barium element in terms of barium sulfate, the penetration short circuit can be greatly suppressed.
From tables 3 to 6 and fig. 4, it is understood that when the content of barium element in the negative electrode active material is 1.1 mass% or more in terms of barium sulfate, the penetration short circuit can be greatly suppressed by including tin element in the positive electrode active material. When the content of tin element in the positive electrode active material is 0.01 mass% or more, the penetration short circuit can be significantly suppressed. On the other hand, when the content of barium element in the negative electrode active material is 1.0 mass% or less in terms of barium sulfate, the effect of suppressing the penetration short circuit due to tin element is not obtained even if tin element is contained in the positive electrode active material.
It has not been known that barium element in the negative electrode active material and tin element in the positive electrode active material are involved in the penetration short circuit. Therefore, it is unexpected that when the content of barium element in the negative electrode active material is 1.1 mass% or more in terms of barium sulfate, the penetration short circuit can be significantly suppressed by including tin element in the positive electrode active material. In addition, since the effect of suppressing the penetration short circuit by the tin element clearly changes between the case where the content of the barium element in the negative electrode material is 1.1% by mass or more and the case where the content of the barium element in the negative electrode material is 1.0% by mass or less in terms of barium sulfate, it can be said that the content of the barium element in the negative electrode material is 1.1% by mass or more in terms of barium sulfate has a critical meaning.
From tables 3 to 6 and fig. 5, it is understood that when the content of barium element in the negative electrode active material is 1.1 mass% or more in terms of barium sulfate, the PSOC life performance is improved by making the content of tin element in the positive electrode active material 0.15 mass% or less, as compared with the case where the positive electrode active material does not contain tin element. The PSOC service life performance is greatly improved when the content of the tin element in the positive active material is less than 0.10mass percent, the PSOC service life performance is further greatly improved when the content of the tin element in the positive active material is less than 0.08mass percent, and the PSOC service life performance is particularly greatly improved when the content of the tin element in the positive active material is less than 0.06mass percent. On the other hand, when the content of barium element in the negative electrode active material is 1.0 mass% or less in terms of barium sulfate, the PSOC life performance is not improved even when the content of tin element in the positive electrode active material is 0.15 mass% or less, compared to when the positive electrode active material does not contain tin element.
It has not been known that when the negative electrode material contains graphite or the like, the PSOC life performance is improved by setting the content of the barium element in the negative electrode material and the content of the tin element in the positive electrode material to specific ranges, which is an unexpected result.
From tables 3 to 6 and fig. 6, it is understood that the effect of improving the PSOC life performance obtained by containing graphite and 1.1 mass% or more of barium element in terms of barium sulfate as the negative electrode active material and 0.15 mass% or less of tin element as the positive electrode active material is exhibited when the density of the positive electrode active material is 3.6g/cm3The above values become large. The density of the positive electrode active material was 4.2g/cm3In the above case, the effect of improving the life performance of PSOC becomes further large, and the density of the positive electrode active material is 4.4g/cm3In the above case, the effect of improving the service life performance of the PSOC is remarkably increased. On the other hand, when the content of barium element in the negative electrode active material is 1.0 mass% or less in terms of barium sulfate, the density of the positive electrode active material is set to 3.6g/cm3The PSOC lifetime performance is not improved as above (fig. 7).
From tables 3 to 6 and fig. 8, it is understood that when the content of barium element in the negative electrode active material is 3.0 mass% or less in terms of barium sulfate, the PSOC life performance is improved.
[ Table 7]
Table 7 and fig. 9 show the results obtained when carbon black was added to the negative electrode active material. From table 7 and fig. 9, it is understood that when the negative electrode active material contains graphite and 1.1 mass% or more of barium element in terms of barium sulfate, and the positive electrode active material contains tin element, the penetration short circuit can be further suppressed when the negative electrode active material contains carbon black. When the carbon black content in the negative electrode active material is 0.1 mass% or more, the penetration short circuit can be greatly suppressed. On the other hand, when the content of barium element in the negative electrode active material is 1.0 mass% or less in terms of barium sulfate, or when the positive electrode active material does not contain tin element, the effect of suppressing the penetration short circuit due to carbon black is not obtained.
[ Table 8]
Table 8 and fig. 10 show the results when the average particle size of graphite in the negative electrode active material was changed. From table 8 and fig. 10, it is understood that when the average particle diameter of graphite in the negative electrode active material is 300 μm or less, the penetration short circuit can be suppressed. Further, it is found that when the average particle size of graphite in the negative electrode active material is 100 μm or more, the PSOC life performance is improved.
[ Table 9]
[ Table 10]
Tables 9 and 10 show the results when expanded graphite was contained in the negative electrode active material instead of the flake graphite. From tables 9 and 10, it is understood that the same results are obtained by using expanded graphite instead of the flaky graphite.
In the examples, a flooded lead acid battery with less short circuit penetration was obtained, but a valve regulated lead acid battery may be produced by using a glass mat as the separator.
Industrial applicability
According to the present invention, it IS possible to provide a lead-acid battery with improved PSOC life performance and suppressed occurrence of a crossover short, and therefore, the lead-acid battery IS useful for IS vehicle applications and the like in which the lead-acid battery IS often left in a state of insufficient charge.
Description of the symbols
Electrode plate group of 1 lead storage battery
2 negative plate
3 Positive plate
4 spacer
21 negative electrode current collector
22 negative electrode material
31 positive electrode collector
32 positive electrode material
41 base body
42 ribs.
Claims (12)
1. A lead-acid battery is characterized by comprising a positive electrode plate, a negative electrode plate and an electrolyte,
the negative electrode material of the negative electrode plate contains graphite or carbon fiber and 1.1 to 3.0 mass% of barium element in terms of barium sulfate,
the positive electrode material of the positive electrode plate contains 0.01-0.10 mass% of tin element.
2. The lead-acid battery according to claim 1, wherein the positive electrode material has a density of 3.6g/cm3The above.
3. The lead-acid battery according to claim 1 or 2, characterized in that the negative electrode material contains carbon black.
4. The lead-acid battery according to claim 1 or 2, wherein the negative electrode material contains 0.5 mass% or more of graphite or carbon fiber.
5. The lead-acid battery according to claim 1 or 2, wherein the negative electrode material contains 2.5 mass% or less of graphite or carbon fiber.
6. The lead-acid battery according to claim 1 or 2, wherein the graphite is graphite having an average particle diameter of 300 μm or less.
7. The lead-acid battery according to claim 1 or 2, wherein the graphite is graphite having an average particle diameter of 100 μm or more.
8. The lead storage battery according to claim 1 or 2, wherein the density of the positive electrode material is 4.2g/cm3The above.
9. The lead storage battery according to claim 1 or 2, wherein the density of the positive electrode material is 5.0g/cm3The following.
10. Lead accumulator according to claim 1 or 2, characterized in that it is a lead accumulator used in a partially charged state.
11. Lead accumulator according to claim 1 or 2, characterized in that the lead accumulator is a liquid lead accumulator.
12. A vehicle mounted with the lead-acid battery according to any one of claims 1 to 11.
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| PCT/JP2017/027816 WO2018025837A1 (en) | 2016-08-05 | 2017-08-01 | Lead storage cell |
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| JPWO2018025837A1 (en) | 2019-06-27 |
| WO2018025837A1 (en) | 2018-02-08 |
| JP6844622B2 (en) | 2021-03-17 |
| CN109565040A (en) | 2019-04-02 |
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