WO2022113621A1 - 鉛蓄電池 - Google Patents

鉛蓄電池 Download PDF

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Publication number
WO2022113621A1
WO2022113621A1 PCT/JP2021/039741 JP2021039741W WO2022113621A1 WO 2022113621 A1 WO2022113621 A1 WO 2022113621A1 JP 2021039741 W JP2021039741 W JP 2021039741W WO 2022113621 A1 WO2022113621 A1 WO 2022113621A1
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Prior art keywords
negative electrode
less
lead
group
polymer compound
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English (en)
French (fr)
Japanese (ja)
Inventor
宏樹 籠橋
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GS Yuasa International Ltd
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GS Yuasa International Ltd
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Priority to EP21897597.7A priority Critical patent/EP4231381A4/en
Priority to CN202180079787.3A priority patent/CN116918097A/zh
Priority to JP2022565142A priority patent/JP7677347B2/ja
Publication of WO2022113621A1 publication Critical patent/WO2022113621A1/ja
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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
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/627—Expanders for lead-acid accumulators
    • 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

Definitions

  • the present invention relates to a lead storage battery.
  • Lead-acid batteries are used for various purposes such as in-vehicle use, industrial use, and so on.
  • Lead-acid batteries include a negative electrode plate, a positive electrode plate, a separator (or mat), an electrolytic solution, and the like.
  • Each electrode plate comprises a current collector and an electrode material.
  • Additives may be added to the constituent members of the lead-acid battery from the viewpoint of imparting various functions.
  • Patent Document 1 proposes a lead-acid battery in which a copolymer of propylene oxide and ethylene oxide is added to a negative electrode plate active material in combination with lignin sulfonic acid.
  • Patent Document 2 describes a negative electrode plate for a lead storage battery, which comprises a negative electrode active material containing spongy lead as a main component and a current collector. , Carbon black is contained in 1.0 mass% or more and 2.5 mass% or less and bisphenol condensate is contained in 0.1 mass% or more and 0.9 mass% or less, and the median pore diameter on a volume basis is 0.5 ⁇ m or less and is porous.
  • a negative electrode plate for a lead storage battery characterized in that the degree is 0.22 mL / g or more and 0.4 mL / g or less.
  • Patent Document 3 describes a lead storage battery having a positive electrode having a first surface and a second surface facing the first surface, and a first surface and a second surface facing the first surface. At least one of the positive electrode and the negative electrode and at least one of the positive electrode and the negative electrode, and at least one of the first and second surfaces thereof, which is a negative electrode having the positive electrode and the negative electrode, each of which is immersed in the electrolytic solution.
  • the fiber-attached mat includes a partially covered fiber-attached mat, and the fiber-attached mat includes a plurality of fibers coated with a size composition (a sinking composition), a binder composition (a binding composition), and one or more kinds of fibers.
  • the additive includes a rubber additive, a rubber derivative, an aldehyde, an aldehyde derivative, a metal salt, an aliphatic alcohol ethioxylate (alkenylated alcohol having an OH group at the terminal), an ethylene-propylene oxide block copolymer, and a sulfuric acid.
  • Esters (alkyl sulfates and alkyl ether sulfates), sulfonic acid esters (alkyl and olefin sulfonates), phosphate esters, sulfosuccinates, polyacrylic acids, polyaspartic acid, perfluoroalkyl sulfonic acids, polyvinyl alcohols, lignins, lignin derivatives,
  • the lead storage battery which comprises one or more of a phenol formaldehyde resin, cellulose, and wood flour, wherein the additive reduces water loss in the lead storage battery.
  • Japanese Unexamined Patent Publication No. 60-182662 Japanese Unexamined Patent Publication No. 2014-123525 Japanese Patent Publication No. 2017-525092
  • Lead-acid batteries may be used in an undercharged state called a partially charged state (PSOC).
  • PSOC partially charged state
  • ISS idling stop start
  • PSOC lead-acid batteries installed in idling stop start (ISS) vehicles are used in PSOC.
  • PSOC partially charged state
  • lead sulfate tends to accumulate and the life performance tends to deteriorate.
  • high charge acceptability is required.
  • the pore diameter of the negative electrode material is reduced, the charge acceptability is improved, but the amount of overcharged electricity is increased. Therefore, it is difficult to reduce the amount of overcharged electricity while ensuring high charge acceptability.
  • the lead-acid battery comprises at least one cell comprising a group of plates and an electrolyte.
  • the electrode plate group includes a negative electrode plate, a positive electrode plate, and a separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate comprises a negative electrode material and is provided with a negative electrode material.
  • the negative electrode material contains an organic shrinkage proofing agent and a polymer compound having a peak in the range of 3.2 ppm or more and 3.8 ppm or less in a chemical shift of 1 H-NMR spectrum measured using deuterated chloroform as a solvent.
  • the present invention relates to a lead storage battery in which the median diameter in the volume-based pore distribution of the negative electrode material is 2.15 ⁇ m or less.
  • the lead-acid battery comprises at least one cell comprising a group of plates and an electrolyte.
  • the electrode plate group includes a negative electrode plate, a positive electrode plate, and a separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate comprises a negative electrode material and is provided with a negative electrode material.
  • the negative electrode material contains an organic shrink proofing agent and a polymer compound containing a repeating structure of an oxyC 2-4 alkylene unit.
  • the present invention relates to a lead storage battery in which the median diameter in the volume-based pore distribution of the negative electrode material is 2.15 ⁇ m or less.
  • the smaller the pore diameter of the negative electrode material the better the charge acceptability. This is because the moving distance of lead ions when lead sulfate is reduced is shortened, so that the diffusion rate of lead ions is relatively increased.
  • the pore diameter of the negative electrode material becomes small, the specific surface area of the negative electrode material becomes large, so that a side reaction in which hydrogen is generated from protons during overcharging is promoted. As a result, a large amount of electricity is consumed as a side reaction during overcharging, so that the amount of overcharged electricity increases. As described above, there is a trade-off relationship between the reduction of the amount of overcharged electricity and the improvement of charge acceptability, and it is difficult to achieve both. As the amount of overcharged electricity increases, the amount of hydrogen produced also increases, so that the amount of electrolytic solution decreases significantly.
  • the lead-acid battery includes at least one cell including a group of plates and an electrolytic solution.
  • the electrode plate group includes a negative electrode plate, a positive electrode plate, and a separator interposed between the negative electrode plate and the electrode plate.
  • the negative electrode plate comprises a negative electrode material.
  • the negative electrode material contains an organic shrinkage proofing agent and a polymer compound having a peak in the range of 3.2 ppm or more and 3.8 ppm or less in a chemical shift of 1 H-NMR spectrum measured using deuterated chloroform as a solvent.
  • the median diameter in the volume-based pore distribution of the negative electrode material is 2.15 ⁇ m or less.
  • the peak appearing in the chemical shift range of 3.2 ppm or more and 3.8 ppm or less is derived from the oxyC 2-4 alkylene unit.
  • the lead-acid battery according to another aspect of the present invention includes at least one cell including a group of plates and an electrolytic solution.
  • the electrode plate group includes a negative electrode plate, a positive electrode plate, and a separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate comprises a negative electrode material.
  • Negative electrode materials include organic shrink proofing agents and polymer compounds containing a repeating structure of oxyC 2-4 alkylene units.
  • the median diameter in the volume-based pore distribution of the negative electrode material is 2.15 ⁇ m or less.
  • the median diameter in the volume-based pore distribution may be simply referred to as an average pore diameter.
  • the negative electrode material contains an organic shrinkage proofing agent and a polymer compound as described above, and the average pore diameter of the negative electrode material is set to the above-mentioned specific range. Control to a small range. With such a configuration, it is possible to reduce the amount of overcharged electricity while ensuring high charge acceptability. By suppressing the generation of hydrogen during overcharging, the amount of decrease in the electrolytic solution can be reduced, which is advantageous for extending the life of the lead storage battery.
  • the lead-acid battery according to one aspect and the other aspect of the present invention can reduce the amount of overcharged electricity while ensuring high charge acceptability for the following reasons.
  • the polymer compound has a repeating structure of the oxyC 2-4 alkylene unit, so that it is easy to form a linear structure.
  • the surface of lead in the negative electrode material is thinly and widely covered with the polymer compound. In a wide area of the lead surface, the polymer compound covers the surface of the lead, which increases the hydrogen overvoltage and makes it difficult for side reactions to generate hydrogen during overcharging to occur.
  • the average pore diameter of the negative electrode electrode material is small, the amount of overcharged electricity can be reduced even when the specific surface area is large. Since the effect of reducing the amount of overcharged electricity can be obtained even with a very small amount of the polymer compound, the polymer compound can be present in the vicinity of the lead by containing the polymer compound in the negative electrode electrode material. As a result, it is considered that the oxyC 2-4 alkylene unit exerts a high adsorption action on lead. Further, since the negative electrode material contains the polymer compound, the polymer compound tends to adhere to the surface of lead sulfate generated during discharge, so that the solubility of lead sulfate during charging tends to decrease.
  • the film of the polymer compound covering the surfaces of lead and lead sulfate since the thickness of the film of the polymer compound covering the surfaces of lead and lead sulfate is thin, the film of the polymer compound inhibits the dissolution of lead sulfate and the transfer of electrons when the lead ions are reduced to lead during charging. The degree of lead is reduced. Further, since the polymer compound film is thin and the uneven distribution is suppressed, the steric hindrance of the polymer compound film is small, so that the movement of lead ions in the pores of the negative electrode material is reduced. Therefore, the improved high diffusion rate of lead ions is maintained by controlling the average pore diameter of the negative electrode material to be small. As a result, even when the negative electrode material contains a polymer compound, it is considered that the deterioration of charge acceptability is suppressed.
  • the average pore diameter of the negative electrode material is larger than 2.15 ⁇ m, when the negative electrode material contains a polymer compound, the surface of the lead is covered with the polymer compound, so that the hydrogen overvoltage rises and overcharging occurs. The amount of electricity can be reduced.
  • the specific surface area of the negative electrode material is small due to the large average pore diameter, the film of the polymer compound adhering to the surface of lead sulfate tends to be thick. As a result, the dissolution of lead sulfate is likely to be inhibited during charging, and the reduction reaction from lead ions to lead is also likely to be inhibited. Further, since the average pore diameter of the negative electrode material is large, the diffusion rate of lead ions is also small.
  • the effect of the polymer compound as described above is exhibited by covering the surface of lead with the polymer compound. Therefore, it is important that the polymer compound is present in the vicinity of lead. This makes it possible to effectively exert the effect of the polymer compound. Therefore, it is important that the negative electrode material contains the polymer compound regardless of whether or not the constituent elements of the lead-acid battery other than the negative electrode material contain the polymer compound.
  • the polymer compound may contain an oxygen atom bonded to a terminal group and an -CH 2 -group and / or -CH ⁇ group bonded to the oxygen atom.
  • the integrated value of the peak of 3.2 ppm to 3.8 ppm, the integrated value of the peak of the hydrogen atom of -CH 2 -group bonded to the oxygen atom, and the -CH ⁇ group bonded to the oxygen atom is preferably 85% or more.
  • Such polymer compounds contain a large amount of oxyC 2-4 alkylene unit in the molecule. Therefore, it is considered that the polymer compound is easily adsorbed on lead and further easily has a linear structure, so that the lead surface can be easily covered thinly. Therefore, the amount of overcharged electricity can be reduced more effectively, and the effect of suppressing the decrease in charge acceptability can be further enhanced.
  • the polymer compound having a peak in the chemical shift range of 3.2 ppm to 3.8 ppm preferably contains a repeating structure of an oxyC 2-4 alkylene unit.
  • a polymer compound containing a repeating structure of an oxyC 2-4 alkylene unit it is considered that the polymer compound is more easily adsorbed to lead and easily has a linear structure, so that the lead surface can be easily covered thinly. .. Therefore, the amount of overcharged electricity can be reduced more effectively, and the effect of suppressing the decrease in charge acceptability can be further enhanced.
  • the polymer compound may contain at least one selected from the group consisting of a hydroxy compound having a repeating structure of an oxyC 2-4 alkylene unit, an etherified product of the hydroxy compound, and an esterified product of the hydroxy compound.
  • the hydroxy compound is selected from at least a group consisting of a poly C 2-4 alkylene glycol, a copolymer containing a repeating structure of oxy C 2-4 alkylene, and a poly C 2-4 alkylene oxide adduct of a polyol. It is a kind. When such a polymer compound is used, it is possible to further suppress a decrease in charge acceptability. In addition, the effect of reducing the amount of overcharged electricity is high.
  • the polymer compound may contain a repeating structure of an oxypropylene unit (-O-CH (-CH 3 ) -CH 2- ).
  • a polymer compound is considered to be excellent in the balance between them because it has high adsorptivity to lead but is suppressed from being thickly adhered to the lead surface. Therefore, the amount of overcharged electricity can be reduced more effectively, and the effect of suppressing the decrease in charge acceptability can be further enhanced.
  • the polymer compound has one or more hydrophobic groups, and at least one of the hydrophobic groups may be a long-chain aliphatic hydrocarbon group having 8 or more carbon atoms. Due to the action of such a hydrophobic group, excessive coating of the polymer compound on the lead surface can be suppressed, and the effect of suppressing a decrease in charge acceptability can be further enhanced.
  • the polymer compound preferably contains a repeating structure of oxyethylene units. By including the repeating structure of the oxyethylene unit having high hydrophilicity in the polymer compound, the polymer compound can be selectively adsorbed to lead. By the balance between the hydrophobic group and the hydrophilic group, the amount of overcharged electricity can be reduced more effectively, and the effect of suppressing the decrease in charge acceptability can be further enhanced.
  • the polymer compound has a high adsorptivity to lead and can cover the lead surface thinly. Therefore, even if the content of the polymer compound in the negative electrode material is small, the amount of overcharge electricity is reduced. can do. Further, even if the content of the polymer compound in the negative electrode electrode material is small, a sufficient effect of reducing the amount of overcharged electricity can be ensured, so that it is possible to suppress a decrease in charge acceptability. From the viewpoint of further enhancing the effect of suppressing the decrease in charge acceptability, the content of the polymer compound in the negative electrode electrode material is preferably 400 ppm or less on a mass basis. From the viewpoint of ensuring a higher effect of reducing the amount of overcharged electricity, the content of the polymer compound in the negative electrode electrode material is preferably 8 ppm or more.
  • the polymer compound may be contained in the negative electrode material, and the origin of the polymer compound contained in the negative electrode material is not particularly limited.
  • the polymer compound may be contained in any of the components of the lead-acid battery (for example, the negative electrode plate, the positive electrode plate, the electrolytic solution, and the separator) when the lead-acid battery is manufactured.
  • the polymer compound may be contained in one component or in two or more components (for example, a negative electrode plate and an electrolytic solution).
  • the polymer compound preferably contains a compound having a number average molecular weight (Mn) of 10,000 or less.
  • Mn number average molecular weight
  • the polymer compound preferably contains a polymer compound having Mn of 400 or more. In this case, higher adsorption to lead can be ensured, and the surface of lead can be easily covered with the polymer compound, so that the amount of overcharged electricity can be further reduced.
  • the content of the organic shrinkage barrier in the negative electrode electrode material is preferably 0.005% by mass or more. From the viewpoint of further enhancing the effect of suppressing the decrease in charge acceptability, the content of the organic shrinkage barrier in the negative electrode electrode material is preferably 0.3% by mass or less.
  • the organic shrinkage proofing agent may contain at least a lignin compound.
  • lignin compounds tend to have low charge acceptability. Even when the negative electrode material contains such a lignin compound as an organic shrinkage proofing agent, by adjusting the average pore diameter and using a specific polymer compound, it is possible to suppress a decrease in charge acceptability and achieve high charge acceptability. It will be easier to secure.
  • the bulk density of the negative electrode material is preferably 3.6 g / cm 3 or more.
  • the specific surface area of the negative electrode material is large, the thickness of the polymer compound film formed on the surface of lead sulfate is small. Therefore, the dissolution of lead sulfate during charging is less likely to be hindered, and the deterioration of charge acceptability can be further suppressed.
  • the lead-acid battery may be either a control valve type (sealed type) lead-acid battery (VRLA type lead-acid battery) or a liquid type (vent type) lead-acid battery.
  • the average pore diameter of the negative electrode material, the respective contents of the polymer compound and the organic shrinkage proofing agent in the negative electrode material, and the bulk density of the negative electrode material are determined by the negative electrode plate taken out from the fully charged lead-acid battery. Is asked about.
  • Electrode material Each electrode material of the negative electrode material and the positive electrode material is usually held in the current collector.
  • the electrode material is a portion of the electrode plate excluding the current collector.
  • Members such as mats and pacing papers may be attached to the electrode plate. Since such a member (also referred to as a sticking member) is used integrally with the plate, it is included in the plate.
  • the electrode plate includes a sticking member (mat, pacing paper, etc.)
  • the electrode material is a portion of the electrode plate excluding the current collector and the sticking member.
  • the clad type positive electrode plate includes a plurality of porous tubes, a core metal (spine) inserted in each tube, and a current collecting unit for connecting the plurality of core metal (spine). It includes a positive electrode material filled in a tube into which a spine is inserted, and a spine projector that connects a plurality of tubes.
  • the positive electrode electrode material is a portion of the electrode plate excluding the tube, the core metal (spine), the current collector, and the spine projector.
  • the core metal (spine) and the current collector may be collectively referred to as a positive electrode current collector.
  • the median diameter in the volume-based pore distribution of the negative electrode material is the pore diameter (volume center pore diameter) corresponding to the median value of the integrated pore volume in the volume-based pore distribution obtained by the mercury intrusion method. be.
  • the median diameter in the volume-based pore distribution may be simply referred to as an average pore diameter for convenience.
  • the bulk density of the negative electrode material is a density (g / cm 3 ) obtained by dividing the mass of the negative electrode material by the bulk volume obtained by the mercury intrusion method.
  • the bulk density is determined for a sample of the unground negative electrode material collected from the negative electrode plate taken out from the lead storage battery. The unground sample is collected from the vicinity of the center in the plane direction of the negative electrode plate.
  • the polymer compound satisfies at least one of the following conditions (i) and (ii).
  • Condition (i) The polymer compound has a peak in the range of 3.2 ppm or more and 3.8 ppm or less in the chemical shift of 1 H-NMR spectrum measured using deuterated chloroform as a solvent.
  • Condition (ii) The polymer compound comprises a repeating structure of oxyC 2-4 alkylene units.
  • condition (i) the peak in the range of 3.2 ppm or more and 3.8 ppm or less is derived from the oxyC 2-4 alkylene unit. That is, the polymer compound satisfying the condition (ii) is also a polymer compound satisfying the condition (i).
  • the polymer compound satisfying the condition (i) may contain a repeating structure of a monomer unit other than the oxyC 2-4 alkylene unit, and may have a certain molecular weight.
  • the number average molecular weight (Mn) of the polymer compound satisfying the above (i) or (ii) may be, for example, 300 or more.
  • the oxy C 2-4 alkylene unit is a unit represented by —OR 1 ⁇ (where R 1 indicates a C 2-4 alkylene group).
  • Organic shrinkage proofing agent refers to an organic compound among compounds having a function of suppressing the shrinkage of lead, which is a negative electrode active material, when the lead storage battery is repeatedly charged and discharged.
  • Mn number average molecular weight
  • GPC gel permeation chromatography
  • Weight average molecular weight In the present specification, the weight average molecular weight (Mw) is determined by GPC. The standard substance used when determining Mw is sodium polystyrene sulfonate.
  • the content of the sulfur element in the organic shrinkage proofing agent is X ⁇ mol / g means that the content of the sulfur element contained in 1 g of the organic shrinkage proofing agent is X ⁇ mol / g.
  • the fully charged state of a liquid lead-acid battery is defined by the definition of JIS D 5301: 2019. More specifically, in a water tank at 25 ° C ⁇ 2 ° C, charging is performed every 15 minutes with a current (A) 0.2 times the value described as the rated capacity (value whose unit is Ah). The state in which the lead-acid battery is charged is regarded as a fully charged state until the terminal voltage (V) of No. 1 or the electrolyte density converted into temperature at 20 ° C. shows a constant value with three valid digits three times in a row.
  • V terminal voltage
  • the fully charged state is 0.2 times the current (value with Ah as the unit) described in the rated capacity in the air tank at 25 ° C ⁇ 2 ° C (the unit is Ah).
  • A) constant current constant voltage charging of 2.23 V / cell is performed, and the charging current at the time of constant voltage charging is 0.005 times the value (value with the unit being Ah) described in the rated capacity (A). When it becomes, charging is completed.
  • a fully charged lead-acid battery is a fully charged lead-acid battery.
  • the lead-acid battery may be fully charged after the chemical conversion, immediately after the chemical conversion, or after a lapse of time from the chemical conversion (for example, after the chemical conversion, the lead-acid battery in use (preferably at the initial stage of use) is fully charged. May be).
  • An initial use battery is a battery that has not been used for a long time and has hardly deteriorated.
  • the vertical direction of the lead-acid battery or the component of the lead-acid battery means the vertical direction of the lead-acid battery in the state where the lead-acid battery is used.
  • Each electrode plate of the positive electrode plate and the negative electrode plate is provided with an ear portion for connecting to an external terminal.
  • the ears are provided so as to project laterally to the sides of the plate, but in many lead-acid batteries, the ears are usually made of the plate. It is provided so as to project upward at the top.
  • the negative electrode plate usually includes a negative electrode current collector in addition to the negative electrode material.
  • the negative electrode current collector may be formed by casting lead (Pb) or a lead alloy, or may be formed by processing a lead sheet or a lead alloy sheet. Examples of the processing method include expanding processing and punching processing. It is preferable to use a grid-shaped current collector as the negative electrode current collector because it is easy to support the negative electrode material.
  • the lead alloy used for the negative electrode current collector may be any of Pb—Sb-based alloys, Pb-Ca-based alloys, and Pb-Ca—Sn-based alloys. These leads or lead alloys may further contain, as an additive element, at least one selected from the group consisting of Ba, Ag, Al, Bi, As, Se, Cu and the like.
  • the negative electrode current collector may include a surface layer. The composition of the surface layer and the inner layer of the negative electrode current collector may be different. The surface layer may be formed on a part of the negative electrode current collector. The surface layer may be formed on the selvage portion of the negative electrode current collector. The surface layer of the selvage may contain Sn or Sn alloy.
  • the average pore diameter of the negative electrode material may be 2.15 ⁇ m or less, and may be 2.11 ⁇ m or less. When the average pore diameter exceeds 2.15 ⁇ m, the negative electrode electrode material contains a polymer compound, so that the charge acceptability is significantly reduced.
  • the average pore diameter of the negative electrode material is, for example, 0.95 ⁇ m or more, and may be 0.99 ⁇ m or more or 1 ⁇ m or more. When the average pore diameter of the negative electrode material is in such a range, the pores are less likely to be blocked by lead sulfate generated during discharge, and the discharge performance (for example, 5-hour rate capacity or low-temperature high-rate discharge capacity) is improved. Can be enhanced.
  • the average pore diameter of the negative electrode material is 0.95 ⁇ m or more and 2.15 ⁇ m or less (or 2.11 ⁇ m or less), 0.99 ⁇ m or more and 2.15 ⁇ m or less (or 2.11 ⁇ m or less), or 1 ⁇ m or more and 2.15 ⁇ m or less (or). 2.11 ⁇ m or less) may be used.
  • the type of organic shrinkage proofing agent can be selected, different types of organic shrinkage proofing agents can be used in combination, the sulfur element content of the organic shrinkage proofing agent, the content of the organic shrinkage proofing agent in the negative electrode electrode material, and the negative electrode.
  • the sulfur element content of the organic shrinkage proofing agent can be used in combination
  • the sulfur element content of the organic shrinkage proofing agent can be used in combination
  • the content of the organic shrinkage proofing agent in the negative electrode electrode material can be adjusted.
  • the bulk density of the negative electrode material is, for example, 3.6 g / cm 3 or more, may be 3.7 g / cm 3 or more, 3.8 g / cm 3 or more, or 4.0 g / cm 3 or more. You may. When the bulk density is in such a range, the decrease in charge acceptability can be further suppressed.
  • the bulk density of the negative electrode material is, for example, 5.5 g / cm 3 or less, and may be 5 g / cm 3 or less.
  • the bulk density of the negative electrode electrode material is 3.6 g / cm 3 or more and 5.5 g / cm 3 or less (or 5 g / cm 3 or less), 3.7 g / cm 3 or more and 5.5 g / cm 3 or less (or 5 g / cm). 3 or less), 3.8 g / cm 3 or more, 5.5 g / cm 3 or less (or 5 g / cm 3 or less), or 4.0 g / cm 3 or more, 5.5 g / cm 3 or less (or 5 g / cm 3 or less) It may be.
  • the negative electrode material contains an organic shrinkage proofing agent and the above polymer compound.
  • the negative electrode material further contains a negative electrode active material (specifically, lead or lead sulfate) that develops a capacity by a redox reaction.
  • the negative electrode material may contain at least one selected from the group consisting of carbonaceous materials and other additives. Examples of the additive include, but are not limited to, barium sulfate, fibers (resin fibers, etc.) and the like.
  • the negative electrode active material in the charged state is spongy lead, but the unchemical negative electrode plate is usually produced by using lead powder.
  • the polymer compound has a peak in the range of 3.2 ppm or more and 3.8 ppm or less in the chemical shift of 1 H-NMR spectrum.
  • Such polymer compounds have an oxyC 2-4 alkylene unit.
  • the oxyC 2-4 alkylene unit includes an oxyethylene unit, an oxypropylene unit, an oxytrimethylene unit, an oxy2-methyl-1,3-propylene unit, an oxy1,4-butylene unit, and an oxy1,3-butylene unit. And so on.
  • the polymer compound may have one kind of such oxyC 2-4 alkylene unit, or may have two or more kinds.
  • the polymer compound preferably contains a repeating structure of oxyC 2-4 alkylene units.
  • the repeating structure may contain one type of Oxy-C 2-4 alkylene unit or two or more types of Oxy-C 2-4 alkylene unit.
  • the polymer compound may contain one kind of the above-mentioned repeating structure, or may contain two or more kinds of the above-mentioned repeating structures.
  • Polymer compounds having a repeating structure of oxyC 2-4 alkylene units also include polymer compounds classified as surfactants (more specifically, nonionic surfactants).
  • polymer compound examples include a hydroxy compound having a repeating structure of an oxy C 2-4 alkylene unit (poly C 2-4 alkylene glycol, a copolymer containing a repeating structure of oxy C 2-4 alkylene, and a polyol poly C 2 ). -4 alkylene oxide adducts, etc.), ethers or esters of these hydroxy compounds, and the like.
  • copolymer examples include a copolymer containing different oxyC 2-4 alkylene units.
  • the copolymer may be a block copolymer.
  • the polyol may be any of an aliphatic polyol, an alicyclic polyol, an aromatic polyol, a heterocyclic polyol and the like.
  • Aliphatic polyols, alicyclic polyols (for example, polyhydroxycyclohexane, polyhydroxynorbornane) and the like are preferable, and aliphatic polyols are particularly preferable, from the viewpoint that the polymer compound is thin and easily spreads on the lead surface.
  • the aliphatic polyol include an aliphatic diol and a polyol having more than triol (for example, glycerin, trimethylolpropane, pentaerythritol, sugar or sugar alcohol).
  • Examples of the aliphatic diol include alkylene glycols having 5 or more carbon atoms.
  • the alkylene glycol may be, for example, C 5-14 alkylene glycol or C 5-10 alkylene glycol.
  • Examples of the sugar or sugar alcohol include sucrose, erythritol, xylitol, mannitol, and sorbitol.
  • the sugar or sugar alcohol may have either a chain structure or a cyclic structure.
  • the alkylene oxide corresponds to the oxyC 2-4 alkylene unit of the polymer compound and comprises at least C 2-4 alkylene oxide. From the viewpoint that the polymer compound can easily form a linear structure, the polyol is preferably a diol.
  • the etherified product is composed of a -OH group (a hydrogen atom of the terminal group and an oxygen atom bonded to the hydrogen atom of the terminal group) at least a part of the hydroxy compound having a repeating structure of the above oxyC 2-4 alkylene unit.
  • the —OH group has two etherified —OR groups (in the formula, R 2 is an organic group).
  • R 2 is an organic group.
  • ends of the polymer compound some ends may be etherified, or all ends may be etherified.
  • one end of the main chain of the linear polymer compound may be an ⁇ OH group and the other end may be an ⁇ OR2 group.
  • the esterified product is composed of an OH group (a hydrogen atom of the terminal group and an oxygen atom bonded to the hydrogen atom of the terminal group) at least a part of the hydroxy compound having a repeating structure of the oxyC 2-4 alkylene unit.
  • R 3 is an organic group.
  • some ends may be esterified or all ends may be esterified.
  • Examples of the organic groups R 2 and R 3 include hydrocarbon groups.
  • the hydrocarbon group may have a substituent (eg, a hydroxy group, an alkoxy group, and / or a carboxy group).
  • the hydrocarbon group may be any of an aliphatic, alicyclic, and aromatic group.
  • the aromatic hydrocarbon group and the alicyclic hydrocarbon group may have an aliphatic hydrocarbon group (for example, an alkyl group, an alkenyl group, an alkynyl group) as a substituent.
  • the number of carbon atoms of the aliphatic hydrocarbon group as a substituent may be, for example, 1 to 30, 1 to 20 or 1 to 10, and may be 1 to 6 or 1 to 4. .
  • Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 24 or less carbon atoms (for example, 6 to 24). The number of carbon atoms of the aromatic hydrocarbon group may be 20 or less (for example, 6 to 20), 14 or less (for example, 6 to 14) or 12 or less (for example, 6 to 12).
  • Examples of the aromatic hydrocarbon group include an aryl group and a bisaryl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the bisaryl group include a monovalent group corresponding to bisarene. Examples of the bisarene include biphenyl and bisaryl alkane (for example, bis C 6-10 aryl C 1-4 alkane (2,2-bisphenylpropane, etc.)).
  • Examples of the alicyclic hydrocarbon group include an alicyclic hydrocarbon group having 16 or less carbon atoms.
  • the alicyclic hydrocarbon group may be a crosslinked cyclic hydrocarbon group.
  • the alicyclic hydrocarbon group may have 10 or less or 8 or less carbon atoms.
  • the alicyclic hydrocarbon group has, for example, 5 or more carbon atoms, and may be 6 or more carbon atoms.
  • the number of carbon atoms of the alicyclic hydrocarbon group may be 5 (or 6) or more and 16 or less, 5 (or 6) or more and 10 or less, or 5 (or 6) or more and 8 or less.
  • Examples of the alicyclic hydrocarbon group include a cycloalkyl group (cyclopentyl group, cyclohexyl group, cyclooctyl group, etc.) and a cycloalkenyl group (cyclohexenyl group, cyclooctenyl group, etc.).
  • the alicyclic hydrocarbon group also includes the hydrogenated additive of the above aromatic hydrocarbon group.
  • an aliphatic hydrocarbon group is preferable from the viewpoint that the polymer compound is thin and easily adheres to the lead surface.
  • Aliphatic hydrocarbon groups may be saturated or unsaturated. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a dienyl group having two carbon-carbon double bonds, and a trienyl group having three carbon-carbon double bonds.
  • the aliphatic hydrocarbon group may be linear or branched.
  • the aliphatic hydrocarbon group may have, for example, 30 or less, 26 or less or 22 or less, 20 or less or 16 or less, 14 or less or 10 or less. It may be 8 or less or 6 or less.
  • the lower limit of the number of carbon atoms is 1 or more for an alkyl group, 2 or more for an alkenyl group and an alkynyl group, 3 or more for a dienyl group, and 4 or more for a trienyl group, depending on the type of the aliphatic hydrocarbon group.
  • Alkyl groups and alkenyl groups are particularly preferable from the viewpoint that the polymer compound is thin and easily adheres to the lead surface.
  • alkyl group examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, i-pentyl, and s-pentyl.
  • alkenyl group examples include vinyl, 1-propenyl, allyl, cis-9-heptadecene-1-yl, palmitrail and oleyl.
  • the alkenyl group may be, for example, a C 2-30 alkenyl group or a C 2-26 alkenyl group, a C 2-22 alkenyl group or a C 2-20 alkenyl group, and a C 10-20 alkenyl group. May be.
  • the polymer compounds at least one selected from the group consisting of an etherified product of a hydroxy compound having a repeating structure of an oxyC 2-4 alkylene unit and an esterified product of a hydroxy compound having a repeating structure of an oxy C 2-4 alkylene unit.
  • an etherified product of a hydroxy compound having a repeating structure of an oxyC 2-4 alkylene unit and an esterified product of a hydroxy compound having a repeating structure of an oxy C 2-4 alkylene unit.
  • it is preferable because the effect of suppressing a decrease in charge acceptability can be further enhanced. Further, even when these polymer compounds are used, the amount of overcharged electricity can be reduced.
  • a polymer compound having a repeating structure of an oxypropylene unit, a polymer compound having a repeating structure of an oxyethylene unit, and the like are preferable.
  • the polymer compound may have one or more hydrophobic groups.
  • the hydrophobic group include aromatic hydrocarbon groups, alicyclic hydrocarbon groups, and long-chain aliphatic hydrocarbon groups among the above-mentioned hydrocarbon groups.
  • the long-chain aliphatic hydrocarbon group include aliphatic hydrocarbon groups having 8 or more carbon atoms among the above-mentioned aliphatic hydrocarbon groups (alkyl groups, alkenyl groups, etc.).
  • the aliphatic hydrocarbon group preferably has 12 or more carbon atoms, and more preferably 16 or more carbon atoms.
  • a polymer compound having a long-chain aliphatic hydrocarbon group is preferable because it is unlikely to cause excessive adsorption to lead and the effect of suppressing a decrease in charge acceptability is further enhanced.
  • the polymer compound may be a polymer compound in which at least one of the hydrophobic groups is a long-chain aliphatic hydrocarbon group.
  • the carbon number of the long-chain aliphatic hydrocarbon group may be 30 or less, 26 or less, or 22 or less.
  • the number of carbon atoms of a long-chain aliphatic hydrocarbon group is 8 or more (or 12 or more) 30 or less, 8 or more (or 12 or more) 26 or less, 8 or more (or 12 or more) 22 or less, 10 or more and 30 or less (or 26 or less). ), Or it may be 10 or more and 22 or less.
  • the polymer compound having a hydrophilic group and a hydrophobic group corresponds to a nonionic surfactant.
  • the repeating structure of the oxyethylene unit exhibits high hydrophilicity and can be a hydrophilic group in nonionic surfactants. Therefore, it is preferable that the polymer compound having a hydrophobic group described above contains a repeating structure of an oxyethylene unit.
  • Such a polymer compound can suppress excessive coverage of the surface of lead while selectively adsorbing to lead due to the balance between hydrophobicity and high hydrophilicity due to the repeating structure of the oxyethylene unit. Therefore, such a polymer compound can further enhance the effect of suppressing a decrease in charge acceptability while reducing the amount of overcharged electricity.
  • Such a polymer compound can ensure high adsorptivity to lead even if it has a relatively low molecular weight (for example, Mn is 1000 or less).
  • polyoxypropylene-polyoxyethylene block copolymers etherified compounds of hydroxy compounds having a repeating structure of oxyethylene units, and esterified compounds of hydroxy compounds having a repeating structure of oxyethylene units are nonions.
  • etherified compounds of hydroxy compounds having a repeating structure of oxyethylene units and esterified compounds of hydroxy compounds having a repeating structure of oxyethylene units are nonions.
  • esterified compounds of hydroxy compounds having a repeating structure of oxyethylene units are nonions.
  • a surfactant corresponds to a surfactant.
  • the repeating structure of the oxyethylene unit corresponds to a hydrophilic group
  • the repeating structure of the oxypropylene unit corresponds to a hydrophobic group.
  • Such copolymers are also included in the polymer compound having a hydrophobic group.
  • Examples of the polymer compound having a hydrophobic group and containing a repeating structure of an oxyethylene unit include an etherified product of polyethylene glycol (alkyl ether and the like), an esterified product of polyethylene glycol (carboxylic acid ester and the like), and a polyethylene oxide adduct of the above-mentioned polyol.
  • Examples thereof include ethers (alkyl ethers and the like) of the above, and esterified products (carboxylic acid esters and the like) of polyethylene oxide adducts of the above-mentioned polyols (polyols and higher polyols and the like).
  • polymer compounds include polyethylene glycol oleate, polyethylene glycol dioleate, polyethylene glycol dilaurate, polyethylene glycol distearate, polyoxyethylene coconut oil fatty acid sorbitan, polyoxyethylene sorbitan oleate, and polyoxystearate.
  • examples thereof include ethylene sorbitan, polyoxyethylene lauryl ether, polyoxyethylene tetradecyl ether, and polyoxyethylene cetyl ether.
  • the polymer compound is not limited to these.
  • an esterified product of polyethylene glycol an esterified product of the polyethylene oxide adduct of the above-mentioned polyol, or the like because higher charge acceptability can be ensured and the amount of overcharged electricity can be remarkably reduced.
  • the HLB of the polymer compound is preferably 4 or more, more preferably 4.3 or more, from the viewpoint of further reducing the amount of decrease in the electrolytic solution. From the viewpoint of easily ensuring higher charge acceptability, the HLB of the polymer compound is preferably 18 or less, more preferably 10 or less or 9 or less, still more preferably 8.5 or less.
  • the HLB of the polymer compound may be 4 or more (or 4.3 or more) 18 or less, 4 or more (or 4.3 or more) 10 or less. From the viewpoint of excellent balance between reducing the amount of overcharged electricity and improving charge acceptability, the HLB of the polymer compound is 4 or more (or 4.3 or more) 9 or less, or 4 or more (or 4.3 or more) 8.5. The following is preferable.
  • HLB Hydrophile Lipophile Balance
  • HLB is an abbreviation for Hydrophile Lipophile Balance, and is a numerical value indicating the balance between hydrophobicity and hydrophilicity of a nonionic surfactant.
  • the repeating structure of the oxyC 2-4 alkylene includes at least the repeating structure of the oxypropylene unit.
  • the charge acceptability tends to be lower than in the case of the repeating structure of the oxyethylene unit, but even in this case, high charge acceptability should be ensured while keeping the amount of overcharge electricity low.
  • Polymer compounds containing oxypropylene units have peaks from -CH ⁇ and -CH 2- of the oxypropylene units in the range of 3.2 ppm to 3.8 ppm in a chemical shift of 1 H-NMR spectrum.
  • Such a polymer compound has peaks in the chemical shift of 1 H-NMR spectrum, for example, in the range of 3.2 ppm or more and 3.42 ppm or less, and in the range of 3.42 ppm or more and 3.8 ppm or less. Peaks in the range of 3.2 ppm or more and 3.42 ppm or less are derived from -CH 2- , and peaks in the range of more than 3.42 ppm and 3.8 ppm or less are derived from -CH ⁇ and -CH 2- .
  • Examples of the polymer compound containing at least the repeating structure of the oxypropylene unit include polypropylene glycol, a copolymer containing the repeating structure of the oxypropylene unit, a polypropylene oxide adduct of the above-mentioned polyol, an etherified product or an esterified product thereof.
  • Examples of the copolymer include an oxypropylene-oxyalkylene copolymer (however, the oxyalkylene is C 2-4 alkylene other than oxypropylene).
  • Examples of the oxypropylene-oxyalkylene copolymer include an oxypropylene-oxyethylene copolymer and an oxypropylene-oxytrimethylene copolymer.
  • the oxypropylene-oxyalkylene copolymer may be referred to as a polyoxypropylene-polyoxyalkylene copolymer (for example, a polyoxypropylene-polyoxyethylene copolymer).
  • the oxypropylene-oxyalkylene copolymer may be a block copolymer (for example, a polyoxypropylene-polyoxyethylene block copolymer).
  • Examples of the etherified product include polypropylene glycol alkyl ether, alkyl ether of an oxypropylene-oxyalkylene copolymer (alkyl ether of a polyoxypropylene-polyoxyethylene copolymer, etc.) and the like.
  • esterified product examples include polypropylene glycol ester of carboxylic acid, carboxylic acid ester of oxypropylene-oxyalkylene copolymer (carboxylic acid ester of polyoxypropylene-polyoxyethylene copolymer, etc.) and the like.
  • Examples of the polymer compound containing at least the repeating structure of the oxypropylene unit include polypropylene glycol, polyoxypropylene-polyoxyethylene copolymer (polyoxypropylene-polyoxyethylene block copolymer and the like), polypropylene glycol alkyl ether (above). Alkyl ether (methyl ether, ethyl ether, butyl ether, etc.) in which R 2 is an alkyl having 10 or less carbon atoms (or 8 or less or 6 or less carbon atoms), polyoxyethylene-polyoxypropylene alkyl ether (the above R 2 has carbon atoms).
  • Alkyl ether (butyl ether, hydroxyhexyl ether, etc.) which is an alkyl of 10 or less (or 8 or less or 6 or less), polypropylene glycol carboxylate (the above R 3 is an alkyl having 10 or less carbon atoms (or 8 or less or 6 or less)).
  • polypropylene glycol carboxylate polypropylene glycol acetate, etc.
  • polypropylene oxide adducts of triol or higher polyols polypropylene oxide adducts of glycerin, etc.
  • the polymer compound is not limited to these.
  • the proportion of the oxypropylene unit is, for example, 5 mol% or more, and may be 10 mol% or more or 20 mol% or more.
  • the proportion of the oxypropylene unit is, for example, 100 mol% or less.
  • the proportion of the oxypropylene unit may be 90 mol% or less, 75 mol% or less, 60 mol% or less, 50 mol% or less, or 43 mol% or less.
  • the proportion of the oxypropylene unit is 5 mol% or more and 100 mol% or less (or 90 mol% or less), 10 mol% or more and 100 mol% or less (or 90 mol% or less), 20 mol% or more and 100 mol%.
  • the proportion of the oxypropylene unit is 5 mol% or more and 100 mol% or less (or 90 mol% or less), 10 mol% or more and 100 mol% or less (or 90 mol% or less), 20 mol% or more and 100 mol%.
  • the polymer compound preferably contains a large amount of oxyC 2-4 alkylene unit from the viewpoint of increasing the adsorptivity of the polymer compound to lead and facilitating the formation of a linear structure of the polymer compound.
  • Such polymer compounds include, for example, an oxygen atom attached to a terminal group and an -CH 2 -group and / or -CH ⁇ group attached to an oxygen atom.
  • the integral value of the peak of 3.2 ppm to 3.8 ppm the integral value of the peak of the hydrogen atom of -CH 2- group
  • the integral value of the peak of the hydrogen atom of -CH ⁇ group In the 1 H-NMR spectrum of the polymer compound, the integral value of the peak of 3.2 ppm to 3.8 ppm, the integral value of the peak of the hydrogen atom of -CH 2- group, and the integral value of the peak of the hydrogen atom of -CH ⁇ group.
  • the ratio of the integrated value of the peak of 3.2 ppm to 3.8 ppm and the integrated value of the peak of 3.2 ppm to 3.8 ppm of the integrated value of the peak of 3.2 ppm to 3.8 ppm to the total of the values becomes large.
  • This ratio is, for example, 50% or more, and may be 80% or more. From the viewpoint that the effect of reducing the amount of overcharged electricity is further enhanced and it is easy to secure higher charge acceptability, the above ratio is preferably 85% or more, and more preferably 90% or more.
  • the polymer compound has a -OH group at the end and has -CH 2 -group and / or -CH ⁇ group bonded to the oxygen atom of this -OH group, 1 in the H-NMR spectrum, -CH 2
  • the peaks of the hydrogen atoms of the -group and -CH ⁇ group are in the range of chemical shifts of more than 3.8 ppm and less than 4.0 ppm.
  • the negative electrode material may contain one kind of polymer compound or two or more kinds.
  • the polymer compound may contain, for example, a compound having Mn of 5 million or less, a compound of 3 million or less or 2 million or less, a compound of 500,000 or less or 100,000 or less, and a compound of 50,000 or less or 20,000.
  • the following compounds may be included.
  • the polymer compound preferably contains a compound having a Mn of 10,000 or less, may contain a compound of 5000 or less or 4000 or less, or may contain a compound of 3000 or less or 2500 or less. good.
  • the Mn of such a compound is, for example, 300 or more.
  • the Mn of such a compound is preferably 400 or more or 500 or more, more preferably 1000 or more, still more preferably 1500 or more or 1800 or more.
  • the polymer compound two or more kinds of compounds having different Mns may be used. That is, the polymer compound may have a plurality of Mn peaks in the molecular weight distribution.
  • the Mn of the above compound is 300 or more (or 400 or more) 5 million or less, 300 or more (or 400 or more) 3 million or less, 300 or more (or 400 or more) 2 million or less, 300 or more (or 400 or more) 500,000 or less.
  • the content of the polymer compound in the negative electrode electrode material is, for example, 8 ppm or more and may be 10 ppm or more on a mass basis. From the viewpoint of further enhancing the effect of reducing the amount of overcharged electricity, the content of the polymer compound in the negative electrode electrode material is preferably 20 ppm or more, more preferably 30 ppm or more on a mass basis.
  • the content of the polymer compound in the negative electrode electrode material may be, for example, 1000 ppm or less, less than 1000 ppm, 700 ppm or less, 600 ppm or less, or 500 ppm or less on a mass basis.
  • the content of the polymer compound in the negative electrode electrode material is preferably 400 ppm or less, more preferably 300 ppm or less, and may be 200 ppm or less or 160 ppm or less on a mass basis. , 150 ppm or less, 120 ppm or less, or 100 ppm or less.
  • the content (mass basis) of the polymer compound in the negative electrode electrode material is 8 ppm or more (or 10 ppm or more) 1000 ppm or less, 8 ppm or more (or 10 ppm or more) less than 1000 ppm, 8 ppm or more (or 10 ppm or more) 700 ppm or less, 8 ppm or more (or).
  • Organic shrinkage proofing agents are usually roughly classified into lignin compounds and synthetic organic shrinkage proofing agents. It can be said that the synthetic organic shrinkage proofing agent is an organic shrinkage proofing agent other than the lignin compound.
  • the organic shrinkage proofing agent contained in the negative electrode electrode material include lignin compounds and synthetic organic shrinkage proofing agents.
  • the negative electrode electrode material may contain one kind of organic shrinkage proofing agent, or may contain two or more kinds of organic shrinkage proofing agents.
  • Examples of the lignin compound include lignin and lignin derivatives.
  • Examples of the lignin derivative include lignin sulfonic acid or a salt thereof (alkali metal salt (sodium salt, etc.), etc.).
  • the synthetic organic shrinkage proofing agent is an organic polymer containing a sulfur element, and generally contains a plurality of aromatic rings in the molecule and also contains a sulfur element as a sulfur-containing group.
  • a sulfur-containing group a sulfonic acid group or a sulfonyl group, which is a stable form, is preferable.
  • the sulfonic acid group may be present in acid form or may be present in salt form such as Na salt.
  • At least a lignin compound may be used as the organic shrinkage proofing agent.
  • the charge acceptability tends to be lower than when a synthetic organic shrinkage proofing agent is used.
  • the average pore diameter of the negative electrode electrode material and containing a specific polymer compound in the negative electrode electrode material high charge acceptability can be ensured even when a lignin compound is used as the organic shrinkage proofing agent.
  • the organic shrinkage proofing agent it is also preferable to use a condensate containing at least a unit of an aromatic compound.
  • a condensate include a condensate of an aromatic compound made of an aldehyde compound (such as at least one selected from the group consisting of aldehydes (eg, formaldehyde) and condensates thereof).
  • the organic shrinkage proofing agent may contain a unit of one kind of aromatic compound, or may contain a unit of two or more kinds of aromatic compounds.
  • the unit of the aromatic compound means a unit derived from the aromatic compound incorporated in the condensate.
  • Examples of the aromatic ring contained in the aromatic compound include a benzene ring and a naphthalene ring.
  • the plurality of aromatic rings may be directly bonded or linked by a linking group (for example, an alkylene group (including an alkylidene group), a sulfone group) or the like.
  • Examples of such a structure include a bisarene structure (biphenyl, bisphenylalkane, bisphenylsulfone, etc.).
  • Examples of the aromatic compound include compounds having the above aromatic ring and at least one selected from the group consisting of a hydroxy group and an amino group.
  • the hydroxy group or amino group may be directly bonded to the aromatic ring, or may be bonded as an alkyl chain having a hydroxy group or an amino group.
  • the hydroxy group also includes a salt of the hydroxy group (-OMe).
  • the amino group also includes a salt of the amino group (specifically, a salt with an anion). Examples of Me include alkali metals (Li, K, Na, etc.), Group 2 metals of the periodic table (Ca, Mg, etc.) and the like.
  • aromatic compound examples include bisarene compounds [bisphenol compounds, hydroxybiphenyl compounds, bisarene compounds having an amino group (bisarylalkane compounds having an amino group, bisarylsulfone compounds having an amino group, biphenyl compounds having an amino group, etc.), and the like. Hydroxyarene compounds (hydroxynaphthalene compounds, phenol compounds, etc.), aminoarene compounds (aminonaphthalene compounds, aniline compounds (aminobenzenesulfonic acid, alkylaminobenzenesulfonic acid, etc.), etc.), etc.] are preferable.
  • the aromatic compound may further have a substituent.
  • the organic shrinkage proofing agent may contain one kind of residues of these compounds, or may contain a plurality of kinds.
  • bisphenol compound bisphenol A, bisphenol S, bisphenol F and the like are preferable.
  • organic shrinkage proofing agent a condensate of a bis-alene compound may be used.
  • the condensate preferably contains at least a unit of an aromatic compound having a sulfur-containing group.
  • a condensate containing at least a unit of a bisphenol compound having a sulfur-containing group in order to secure higher charge acceptability.
  • the sulfur-containing group may be directly bonded to the aromatic ring contained in the compound, or may be bonded to the aromatic ring as an alkyl chain having a sulfur-containing group, for example.
  • the sulfur-containing group is not particularly limited, and examples thereof include a sulfonyl group, a sulfonic acid group, or a salt thereof.
  • the organic shrinkage proofing agent for example, a condensation containing at least one selected from the group consisting of a unit of the above-mentioned bisarene compound and a unit of a monocyclic aromatic compound (hydroxyarene compound and / or aminoarene compound, etc.). At least one may be used.
  • the organic shrinkage proofing agent may contain at least a condensate containing a unit of a bisarene compound and a unit of a monocyclic aromatic compound (particularly, a hydroxyarene compound). Examples of such a condensate include a condensate of a bis-alene compound and a monocyclic aromatic compound made of an aldehyde compound.
  • hydroxyarene compound a phenol sulfonic acid compound (such as phenol sulfonic acid or a substitute thereof) is preferable.
  • aminoarene compound aminobenzenesulfonic acid, alkylaminobenzenesulfonic acid and the like are preferable.
  • monocyclic aromatic compound a hydroxyarene compound is preferable.
  • the negative electrode material may contain, for example, an organic shrinkage proofing agent (first organic shrinkage proofing agent) having a sulfur element content of 2000 ⁇ mol / g or more among the above organic shrinkage proofing agents.
  • first organic shrinkage proofing agent include the above-mentioned synthetic organic shrinkage proofing agent (the above-mentioned condensate and the like).
  • the sulfur element content of the first organic shrinkage proofing agent may be 2000 ⁇ mol / g or more, preferably 3000 ⁇ mol / g or more.
  • the upper limit of the sulfur element content of the first organic shrinkage proofing agent is not particularly limited, and from the viewpoint of further enhancing the effect of reducing the amount of overcharged electricity, it is preferably 9000 ⁇ mol / g or less, and more preferably 8000 ⁇ mol / g or less.
  • the sulfur element content of the first organic shrinkage proofing agent is, for example, 2000 ⁇ mol / g or more (or 3000 ⁇ mol / g or more) 9000 ⁇ mol / g or less, or 2000 ⁇ mol / g or more (or 3000 ⁇ mol / g or more) 8000 ⁇ mol / g or less. good.
  • the first organic shrinkage proofing agent contains a condensate containing a unit of an aromatic compound having a sulfur-containing group, and the condensate may contain at least a unit of a bisphenol compound as a unit of the aromatic compound.
  • the weight average molecular weight (Mw) of the first organic shrinkage proofing agent is preferably 7,000 or more.
  • the Mw of the first organic shrinkage proofing agent is, for example, 100,000 or less, and may be 20,000 or less.
  • the negative electrode material can contain, for example, an organic shrinkage proofing agent (second organic shrinkage proofing agent) having a sulfur element content of less than 2000 ⁇ mol / g.
  • second organic shrinkage proofing agent include lignin compounds and synthetic organic shrinkage proofing agents (particularly, lignin compounds) among the above-mentioned organic shrinkage proofing agents.
  • the sulfur element content of the second organic shrinkage proofing agent is preferably 1000 ⁇ mol / g or less, and may be 800 ⁇ mol / g or less.
  • the lower limit of the sulfur element content in the second organic shrinkage proofing agent is not particularly limited, and is, for example, 400 ⁇ mol / g or more.
  • the Mw of the second organic shrinkage proofing agent is, for example, less than 7,000.
  • the Mw of the second organic shrinkage proofing agent is, for example, 3000 or more.
  • the negative electrode material may contain a second organic shrinkage proofing agent in addition to the first organic shrinkage proofing agent.
  • a second organic shrinkage proofing agent in addition to the first organic shrinkage proofing agent.
  • the content of the organic shrinkage proofing agent contained in the negative electrode electrode material is, for example, 0.005% by mass or more, and may be 0.01% by mass or more. When the content of the organic shrinkage proofing agent is in such a range, a high low temperature and high rate discharge capacity can be secured.
  • the content of the organic shrinkage proofing agent is, for example, 1.0% by mass or less, and may be 0.5% by mass or less. From the viewpoint of further enhancing the effect of suppressing the decrease in charge acceptability, the content of the organic shrinkage proofing agent is preferably 0.3% by mass or less, more preferably 0.25% by mass or less, 0.2% by mass or less, or It is more preferably 0.15% by mass or less, and may be 0.12% by mass or less.
  • the content of the organic shrinkage barrier contained in the negative electrode electrode material is 0.005% by mass or more (or 0.01% by mass) 1.0% by mass or less, 0.005% by mass or more (or 0.01% by mass). (More than) 0.5% by mass or less, 0.005% by mass or more (or 0.01% by mass or more) 0.3% by mass or less, 0.005% by mass or more (or 0.01% by mass or more) 0.25% by mass % Or less, 0.005% by mass or more (or 0.01% by mass or more) 0.2% by mass or less, 0.005% by mass or more (or 0.01% by mass or more) 0.15% by mass or less, or 0. It may be 005% by mass or more (or 0.01% by mass or more) and 0.12% by mass or less.
  • Carbonate material As the carbonaceous material contained in the negative electrode electrode material, carbon black, graphite, hard carbon, soft carbon and the like can be used. Examples of carbon black include acetylene black, furnace black, and lamp black. Furness Black also includes Ketjen Black (trade name).
  • the graphite may be any carbonaceous material containing a graphite-type crystal structure, and may be either artificial graphite or natural graphite.
  • the negative electrode material may contain one kind of carbonaceous material, or may contain two or more kinds.
  • the content of the carbonaceous material in the negative electrode electrode material is, for example, 0.05% by mass or more, and may be 0.10% by mass or more.
  • the content of the carbonaceous material is, for example, 5% by mass or less, and may be 3% by mass or less.
  • the content of the carbonaceous material in the negative electrode material is 0.05% by mass or more and 5% by mass or less, 0.05% by mass or more and 3% by mass or less, 0.10% by mass or more and 5% by mass or less, or 0.10. It may be mass% or more and 3 mass% or less.
  • barium sulfate The content of barium sulfate in the negative electrode electrode material is, for example, 0.05% by mass or more, and may be 0.10% by mass or more. The content of barium sulfate in the negative electrode electrode material is, for example, 3% by mass or less, and may be 2% by mass or less.
  • the content of barium sulfate in the negative electrode material is 0.05% by mass or more and 3% by mass or less, 0.05% by mass or more and 2% by mass or less, 0.10% by mass or more and 3% by mass or less, or 0.10% by mass. It may be% or more and 2% by mass or less.
  • the fully charged lead-acid battery is disassembled to obtain the negative electrode plate to be analyzed.
  • the obtained negative electrode plate is washed with water to remove sulfuric acid from the negative electrode plate. Wash with water by pressing the pH test paper against the surface of the negative electrode plate washed with water until it is confirmed that the color of the test paper does not change. However, the time for washing with water shall be within 2 hours.
  • the negative electrode plate washed with water is dried at 60 ⁇ 5 ° C.
  • sample A a sample (hereinafter referred to as sample A) is obtained by separating the negative electrode material from the negative electrode plate. Sample A is pulverized as needed and subjected to analysis.
  • the average pore diameter is measured by a mercury intrusion method. More specifically, the integrated pore volume distribution of sample A is measured using a mercury porosimeter to determine the relationship between the pore diameter and the integrated pore volume. The pore diameter corresponding to the median value of the integrated pore volume is obtained. This pore diameter (that is, the volume center pore diameter) is defined as the median diameter (average pore diameter) in the volume-based pore distribution.
  • the pressure range for measurement is 0.05 psia or more and 30000 psia or less ( ⁇ 0.345 kPa or more and 20700 kPa or less). Further, the pore distribution is obtained in the range where the pore diameter is 17 nm or more and 340 ⁇ m or less.
  • the mercury porosimeter an automatic porosimeter (Autopore IV9505) manufactured by Shimadzu Corporation is used.
  • the bulk density of unground sample A is determined by a mercury intrusion method using a mercury porosimeter.
  • the uncrushed sample A used for measuring the bulk density is collected from the vicinity of the center in the surface direction of the negative electrode plate. The measurement of bulk density will be described more specifically.
  • a predetermined amount of unground sample A is collected and the mass is measured. After putting this sample A into the measuring container of the mercury porosimeter and exhausting it under reduced pressure, the sample A is filled with mercury at a pressure of 0.5 psia or more and 0.55 psia or less ( ⁇ 3.45 kPa or more and 3.79 kPa or less).
  • the bulk density of the negative electrode electrode material is obtained by measuring the bulk volume and dividing the measured mass of the sample A by the bulk volume. The volume obtained by subtracting the mercury injection volume from the volume of the measuring container is defined as the bulk volume.
  • As the mercury porosimeter an automatic porosimeter (Autopore IV9505) manufactured by Shimadzu Corporation is used.
  • the electrode plate group includes one negative electrode plate, the density of the negative electrode electrode material is determined for the negative electrode material collected from the negative electrode plate.
  • the electrode plate group includes two negative electrode plates, the density of the negative electrode electrode material is an average value of the values obtained for the negative electrode material collected from each of the two negative electrode plates.
  • the density of the negative electrode electrode material is the negative electrode electrode material collected from two negative electrode plates arbitrarily selected from the negative electrode plates other than the electrode plates at both ends of the electrode plate group. It is the average value of the values obtained for. However, when two of the three negative electrode plates are the electrode plates at both ends of the electrode plate group, the density of the negative electrode electrode material is determined for the negative electrode material collected from the remaining one negative electrode plate.
  • Chloroform-soluble components are recovered from the chloroform solution in which the polymer compound obtained by extraction is dissolved by distilling off chloroform under reduced pressure.
  • the chloroform-soluble component is dissolved in deuterated chloroform, and the 1 H-NMR spectrum is measured under the following conditions. From this 1 H-NMR spectrum, a peak with a chemical shift in the range of 3.2 ppm or more and 3.8 ppm or less is confirmed. Further, the type of oxyC 2-4 alkylene unit is specified from the peak in this range.
  • V 1 From the 1 H-NMR spectrum, the integral value (V 1 ) of the peaks in which the chemical shift exists in the range of 3.2 ppm or more and 3.8 ppm or less is obtained.
  • V 2 the sum of the integrated values of the peaks in the 1 H-NMR spectrum
  • the integral value of the peak in the 1 H-NMR spectrum when the integral value of the peak in the 1 H-NMR spectrum is obtained, two points in the 1 H-NMR spectrum having no significant signal so as to sandwich the corresponding peak are determined, and these two points are determined.
  • Each integrated value is calculated using the straight line connecting the intervals as the baseline. For example, for a peak in which the chemical shift is in the range of 3.2 ppm to 3.8 ppm, the straight line connecting the two points of 3.2 ppm and 3.8 ppm in the spectrum is used as the baseline. For example, for a peak in which the chemical shift exceeds 3.8 ppm and exists in the range of 4.0 ppm or less, the straight line connecting the two points of 3.8 ppm and 4.0 ppm in the spectrum is used as the baseline.
  • the obtained mixture is analyzed by thermal decomposition GC-MS under the following conditions to identify the hydrophobic group contained in the esterified product.
  • Analyzer High-performance general-purpose gas chromatogram GC-2014 manufactured by Shimadzu Corporation Column: DEGS (diethylene glycol succinate) 2.1m Oven temperature: 180-120 ° C Injection port temperature: 240 ° C Detector temperature: 240 ° C Carrier gas: He (flow rate: 50 mL / min) Injection volume: 1 ⁇ L to 2 ⁇ L
  • Na and Ma averaged the Na and Ma values of each monomer unit using the molar ratio (mol%) of each monomer unit contained in the repeating structure, respectively. The value.
  • the integrated value of the peak in the 1 H-NMR spectrum is obtained by using the data processing software "ALICE” manufactured by JEOL Ltd.
  • the infrared spectroscopic spectrum measured using the sample B of the organic shrinkage proofing agent thus obtained the ultraviolet visible absorption spectrum measured by diluting the sample B with distilled water or the like and measuring with an ultraviolet visible absorptiometer, and the sample B being used as heavy water or the like.
  • the first organic shrinkage proofing agent and the second organic shrinkage proofing agent are separated from the above extract as follows. First, the extract is measured by infrared spectroscopy, NMR, and / or GC-MS to determine whether or not it contains a plurality of organic shrink proofing agents. Next, the molecular weight distribution is measured by GPC analysis of the extract, and if a plurality of organic shrink-proofing agents can be separated by molecular weight, the organic shrinkage-proofing agents are separated by column chromatography based on the difference in molecular weight.
  • one of the organic shrinkage proofing agents is separated by a precipitation separation method by utilizing the difference in solubility which differs depending on the type of functional group and / or the amount of functional groups of the organic shrinkage proofing agent.
  • one of the organic shrink-proofing agents is aggregated and separated by adding a sulfuric acid aqueous solution to a mixture in which the above extract is dissolved in a NaOH aqueous solution and adjusting the pH of the mixture.
  • the insoluble component is removed by filtration from the mixture obtained by dissolving the separated product in the aqueous NaOH solution again as described above.
  • the remaining solution after separating one of the organic shrink proofing agents is concentrated.
  • the obtained concentrate contains the other organic shrink-proofing agent, and the insoluble component is removed from the concentrate by filtration as described above.
  • the structural formula of the organic shrinkage proofing agent cannot be specified exactly, so that the same organic shrinkage proofing is applied to the calibration curve.
  • the agent may not be available.
  • calibration is performed using an organic shrink-proof agent extracted from the negative electrode of the battery and a separately available organic polymer having a similar shape in the ultraviolet-visible absorption spectrum, the infrared spectroscopic spectrum, the NMR spectrum, and the like. By creating a line, the content of the organic shrink-proofing agent is measured using the ultraviolet-visible absorption spectrum.
  • GPC device Build-up GPC system SD-8022 / DP-8020 / AS-8020 / CO-8020 / UV-8020 (manufactured by Tosoh Corporation)
  • Standard substance: Na polystyrene sulfonate (Mw 275,000, 35,000, 12,500, 7,500, 5,200, 1,680)
  • a carbonaceous material and components other than barium sulfate are removed from the dispersion liquid using a sieve.
  • the dispersion liquid is suction-filtered using a membrane filter whose mass has been measured in advance, and the membrane filter is dried together with the filtered sample in a dryer at 110 ° C. ⁇ 5 ° C.
  • the filtered sample is a mixed sample of a carbonaceous material and barium sulfate.
  • the mass of the sample C (M m ) is measured by subtracting the mass of the membrane filter from the total mass of the dried mixed sample (hereinafter referred to as sample C) and the membrane filter.
  • the sample C is put into a crucible together with a membrane filter and incinerated at 1300 ° C. or higher.
  • the remaining residue is barium oxide.
  • the mass of barium oxide is converted into the mass of barium sulfate to obtain the mass of barium sulfate ( MB ).
  • the mass of the carbonaceous material is calculated by subtracting the mass MB from the mass M m .
  • the negative electrode plate can be formed by applying or filling a negative electrode paste to a negative electrode current collector, aging and drying to produce an unchemical negative electrode plate, and then forming an unchemical negative electrode plate.
  • the negative electrode paste is, for example, a lead powder, a polymer compound, and, if necessary, at least one selected from the group consisting of an organic shrinkage proofing agent, a carbonaceous material, and other additives, and water and sulfuric acid (or an aqueous solution of sulfuric acid). ) Is added and kneaded to produce. At the time of aging, it is preferable to ripen the unchemical negative electrode plate at a temperature higher than room temperature and high humidity.
  • Chemical formation can be performed by charging the electrode plate group in a state where the electrode plate group including the unchemical negative electrode plate is immersed in the electrolytic solution containing sulfuric acid in the electric tank of the lead storage battery. However, the chemical formation may be performed before assembling the lead-acid battery or the electrode plate group. The formation produces spongy lead.
  • the positive electrode plate of a lead storage battery can be classified into a paste type, a clad type and the like. Either a paste type or a clad type positive electrode plate may be used.
  • the paste type positive electrode plate includes a positive electrode current collector and a positive electrode material. The configuration of the clad type positive electrode plate is as described above.
  • the positive electrode current collector may be formed by casting lead (Pb) or a lead alloy, or may be formed by processing a lead sheet or a lead alloy sheet. Examples of the processing method include expanding processing and punching processing. It is preferable to use a grid-shaped current collector as the positive electrode current collector because it is easy to support the positive electrode material.
  • the positive electrode current collector may include a surface layer.
  • the composition of the surface layer and the inner layer of the positive electrode current collector may be different.
  • the surface layer may be formed on a part of the positive electrode current collector.
  • the surface layer may be formed only on the lattice portion, the ear portion, or the frame bone portion of the positive electrode current collector.
  • the positive electrode material contained in the positive electrode plate contains a positive electrode active material (lead dioxide or lead sulfate) that develops a capacity by a redox reaction.
  • the positive electrode material may contain other additives, if necessary.
  • the unchemical paste type positive electrode plate is obtained by filling a positive electrode current collector with a positive electrode paste, aging and drying.
  • the positive electrode paste is prepared by kneading lead powder, additives, water, and sulfuric acid.
  • lead powder or slurry-like lead powder is filled in a porous tube into which a core metal (spine) connected by a current collector is inserted, and a plurality of tubes are connected to each other (spine projector). ) Is formed. Then, a positive electrode plate is obtained by forming these unchemical positive electrode plates.
  • Chemical formation can be performed by charging the electrode plate group in a state where the electrode plate group including the unchemical positive electrode plate is immersed in the electrolytic solution containing sulfuric acid in the electric tank of the lead storage battery. However, the chemical formation may be performed before assembling the lead-acid battery or the electrode plate group.
  • a separator can be arranged between the negative electrode plate and the positive electrode plate.
  • As the separator at least one selected from a non-woven fabric and a microporous membrane is used.
  • Nonwoven fabric is a mat that is entwined without weaving fibers, and is mainly composed of fibers.
  • the non-woven fabric for example, 60% by mass or more of the non-woven fabric is formed of fibers.
  • the fiber glass fiber, polymer fiber (polyolefin fiber, acrylic fiber, polyester fiber (polyethylene terephthalate fiber, etc.), etc.), pulp fiber, and the like can be used. Of these, glass fiber is preferable.
  • the nonwoven fabric may contain components other than fibers (for example, acid-resistant inorganic powder, polymer as a binder) and the like.
  • the microporous film is a porous sheet mainly composed of components other than fiber components.
  • a composition containing a pore-forming agent is extruded into a sheet and then the pore-forming agent is removed to form pores. It is obtained by.
  • the microporous membrane is preferably composed of a material having acid resistance, and a microporous membrane mainly composed of a polymer component is preferable.
  • the polymer component polyolefin (polyethylene, polypropylene, etc.) is preferable.
  • the pore-forming agent include at least one selected from the group consisting of polymer powders and oils.
  • the separator may be composed of, for example, only a non-woven fabric or only a microporous membrane. Further, the separator may be a laminate of a non-woven fabric and a microporous film, a material obtained by laminating different or similar materials, or a material in which irregularities are engaged with different or similar materials, as required.
  • the separator may be in the shape of a sheet or in the shape of a bag.
  • a sheet-shaped separator may be sandwiched between the positive electrode plate and the negative electrode plate.
  • the electrode plate may be arranged so as to sandwich the electrode plate with one sheet-shaped separator in a bent state.
  • the positive electrode plate sandwiched between the bent sheet-shaped separators and the negative electrode plate sandwiched between the bent sheet-shaped separators may be overlapped, and one of the positive electrode plate and the negative electrode plate may be sandwiched between the bent sheet-shaped separators. , May be overlapped with the other electrode plate.
  • the sheet-shaped separator may be bent in a bellows shape, and the positive electrode plate and the negative electrode plate may be sandwiched between the bellows-shaped separators so that the separator is interposed between them.
  • the separator may be arranged so that the bent portion is along the horizontal direction of the lead storage battery (for example, the bent portion is parallel to the horizontal direction), or along the vertical direction. (For example, the separator may be arranged so that the bent portion is parallel to the vertical direction).
  • recesses are alternately formed on both main surface sides of the separator.
  • the positive electrode plate is formed only in the concave portion on one main surface side of the separator.
  • a negative electrode plate is arranged (that is, a double separator is interposed between the adjacent positive electrode plate and the negative electrode plate).
  • the separator is arranged so that the bent portion is along the vertical direction of the lead storage battery, the positive electrode plate can be accommodated in the recess on one main surface side and the negative electrode plate can be accommodated in the recess on the other main surface side (that is,).
  • the separator can be in a single interposition between the adjacent positive electrode plate and the negative electrode plate).
  • the bag-shaped separator may accommodate a positive electrode plate or a negative electrode plate.
  • the electrolytic solution is an aqueous solution containing sulfuric acid, and may be gelled if necessary.
  • the electrolytic solution may contain the above-mentioned polymer compound.
  • the electrolytic solution may contain a cation (for example, a metal cation) and / or an anion (for example, an anion other than the sulfate anion (for example, a phosphate ion)), if necessary.
  • a cation for example, a metal cation
  • an anion for example, an anion other than the sulfate anion (for example, a phosphate ion)
  • the metal cation include at least one selected from the group consisting of Na ion, Li ion, Mg ion, and Al ion.
  • the specific gravity of the electrolytic solution in a fully charged lead storage battery at 20 ° C. is, for example, 1.20 or more, and may be 1.25 or more.
  • the specific gravity of the electrolytic solution at 20 ° C. is 1.35 or less, preferably 1.32 or less.
  • the specific gravity of the electrolytic solution at 20 ° C. may be 1.20 or more and 1.35 or less, 1.20 or more and 1.32 or less, 1.25 or more and 1.35 or less, or 1.25 or more and 1.32 or less. ..
  • the lead-acid battery can be obtained by a manufacturing method including a step of accommodating a group of plates and an electrolytic solution in a cell chamber of an electric tank.
  • Each cell of the lead-acid battery includes a group of plates and an electrolytic solution housed in each cell chamber.
  • the electrode plate group is assembled by laminating the positive electrode plate, the negative electrode plate, and the separator so that the separator is interposed between the positive electrode plate and the negative electrode plate prior to the accommodation in the cell chamber.
  • the positive electrode plate, the negative electrode plate, the electrolytic solution, and the separator are each prepared prior to assembling the electrode plate group.
  • the method for manufacturing a lead-acid battery may include, if necessary, a step of forming at least one of a positive electrode plate and a negative electrode plate after a step of accommodating a group of electrode plates and an electrolytic solution in a cell chamber.
  • Each electrode plate in the electrode plate group may be one plate or two or more plates.
  • the electrode plate group includes two or more negative electrode plates
  • the average pore diameter of the negative electrode electrode material is in the above range in at least one negative electrode plate
  • the negative electrode electrode material contains an organic shrinkage proofing agent and the above polymer compound. If the above condition is satisfied, the effect of suppressing the decrease in charge acceptability of the negative electrode plate can be obtained, and the effect of reducing the amount of overcharged electricity can be obtained according to the number of such negative electrode plates.
  • the above) preferably satisfies the above conditions.
  • the ratio of the negative electrode plates satisfying the above conditions is 100% or less. All of the negative electrode plates included in the electrode plate group may satisfy the above conditions.
  • the lead-acid battery has two or more cells
  • at least a group of electrode plates of some cells may be provided with a negative electrode plate that satisfies the above conditions.
  • 50% or more (more preferably 80% or more or 90% or more) of the number of cells contained in the lead storage battery 50% or more (more preferably 80% or more or 90% or more) of the number of cells contained in the lead storage battery.
  • the ratio of the cells including the electrode plate group including the negative electrode plate satisfying the above conditions is 100% or less. It is preferable that all of the electrode plates included in the lead storage battery are provided with a negative electrode plate that satisfies the above conditions.
  • FIG. 1 shows the appearance of an example of a lead storage battery according to an embodiment of the present invention.
  • the lead-acid battery 1 includes an electric tank 12 for accommodating a plate group 11 and an electrolytic solution (not shown).
  • the inside of the electric tank 12 is partitioned into a plurality of cell chambers 14 by a partition wall 13.
  • One electrode plate group 11 is housed in each cell chamber 14.
  • the opening of the battery case 12 is closed by a lid 15 including a negative electrode terminal 16 and a positive electrode terminal 17.
  • the lid 15 is provided with a liquid spout 18 for each cell chamber. At the time of refilling water, the liquid spout 18 is removed and the refilling liquid is replenished.
  • the liquid spout 18 may have a function of discharging the gas generated in the cell chamber 14 to the outside of the battery.
  • the electrode plate group 11 is configured by laminating a plurality of negative electrode plates 2 and positive electrode plates 3 via a separator 4, respectively.
  • the bag-shaped separator 4 accommodating the negative electrode plate 2 is shown, but the form of the separator is not particularly limited.
  • the negative electrode shelf portion 6 for connecting the plurality of negative electrode plates 2 in parallel is connected to the through connection body 8, and the positive electrode shelf portion for connecting the plurality of positive electrode plates 3 in parallel is connected.
  • 5 is connected to the positive electrode column 7.
  • the positive electrode column 7 is connected to the positive electrode terminal 17 outside the lid 15.
  • the negative electrode column 9 is connected to the negative electrode shelf portion 6, and the penetration connecting body 8 is connected to the positive electrode shelf portion 5.
  • the negative electrode column 9 is connected to the negative electrode terminal 16 outside the lid 15.
  • Each through-connecting body 8 passes through a through-hole provided in the partition wall 13 and connects the electrode plates 11 of the adjacent cell chambers 14 in series.
  • the positive electrode shelf 5 is formed by welding the ears provided on the upper part of each positive electrode plate 3 by a cast-on-strap method or a burning method.
  • the negative electrode shelf portion 6 is also formed by welding the selvage portions provided on the upper portions of the negative electrode plates 2 as in the case of the positive electrode shelf portion 5.
  • the lid 15 of the lead storage battery has a single structure (single lid), but is not limited to the case shown in the illustrated example.
  • the lid 15 may have, for example, a double structure including an inner lid and an outer lid (or upper lid).
  • the lid having a double structure may be provided with a reflux structure between the inner lid and the outer lid for returning the electrolytic solution to the inside of the battery (inside the inner lid) from the reflux port provided on the inner lid.
  • each of the overcharged electricity amount and the charge acceptability is evaluated by the following procedure.
  • the rated voltage of the test battery used for the evaluation is 2V / cell, and the rated 5-hour rate capacity is 32Ah.
  • the lead-acid batteries according to one aspect of the present invention are summarized below.
  • the lead-acid battery comprises at least one cell comprising a group of plates and an electrolyte.
  • the electrode plate group includes a negative electrode plate, a positive electrode plate, and a separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate comprises a negative electrode material and is provided with a negative electrode material.
  • the negative electrode material contains an organic shrinkage proofing agent and a polymer compound having a peak in the range of 3.2 ppm or more and 3.8 ppm or less in a chemical shift of 1 H-NMR spectrum measured using deuterated chloroform as a solvent.
  • a lead-acid battery having a median diameter (average pore diameter) of 2.15 ⁇ m or less in a volume-based pore distribution of the negative electrode material.
  • the polymer compound contains an oxygen atom bonded to a terminal group and an -CH 2 -group and / or -CH ⁇ group bonded to the oxygen atom.
  • the integral value of the peak, the integral value of the peak of the -CH2 -group hydrogen atom, and the integral value of the peak of the -CH ⁇ group hydrogen atom account for the sum of the peak.
  • the ratio of the integrated values may be 50% or more, 80% or more, 85% or more, or 90% or more.
  • the polymer compound may contain a repeating structure of an oxyC 2-4 alkylene unit.
  • the lead-acid battery comprises at least one cell comprising a group of plates and an electrolyte.
  • the electrode plate group includes a negative electrode plate, a positive electrode plate, and a separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate comprises a negative electrode material and is provided with a negative electrode material.
  • the negative electrode material contains an organic shrink proofing agent and a polymer compound containing a repeating structure of an oxyC 2-4 alkylene unit.
  • a lead-acid battery having a median diameter (average pore diameter) of 2.15 ⁇ m or less in a volume-based pore distribution of the negative electrode material.
  • the average pore diameter of the negative electrode electrode material may be 2.11 ⁇ m or less.
  • the average pore diameter of the negative electrode electrode material may be 0.95 ⁇ m or more, 0.99 ⁇ m or more, or 1 ⁇ m or more.
  • the bulk density of the negative electrode material is 3.6 g / cm 3 or more, 3.7 g / cm 3 or more, and 3.8 g / cm 3 or more. Alternatively, it may be 4.0 g / cm 3 or more.
  • the bulk density of the negative electrode electrode material may be 5.5 g / cm 3 or less or 5 g / cm 3 or less.
  • the polymer compound has Mn of 5 million or less, 3 million or less, 2 million or less, 500,000 or less, 100,000 or less, 50,000 or less, 20,000 or less. It may contain compounds of 10,000 or less, 5000 or less, 4000 or less, 3000 or less, or 2500 or less.
  • the polymer compound may contain a compound having Mn of 300 or more, 400 or more, 500 or more, 1000 or more, 1500 or more, or 1800 or more. ..
  • the polymer compound is a hydroxy compound having a repeating structure of an oxyC 2-4 alkylene unit, an etherified product of the hydroxy compound, and the hydroxy compound. Containing at least one selected from the group consisting of esterified compounds,
  • the hydroxy compound is at least one selected from the group consisting of a poly C 2-4 alkylene glycol, a copolymer containing a repeating structure of oxy C 2-4 alkylene, and a poly C 2-4 alkylene oxide adduct of a polyol. There may be.
  • the polymer compound may contain a repeating structure of an oxypropylene unit.
  • the polymer compound is polypropylene glycol, a polyoxypropylene-polyoxyethylene copolymer (polyoxypropylene-polyoxyethylene block copolymer, etc.), or a polypropylene glycol alkyl ether (the above R 2 ).
  • a polyoxypropylene-polyoxyethylene copolymer polyoxypropylene-polyoxyethylene block copolymer, etc.
  • a polypropylene glycol alkyl ether the above R 2 .
  • polypropylene glycol carboxylate (Or 8 or less or 6 or less) alkyl ethers (butyl ether, hydroxyhexyl ether, etc.), polypropylene glycol carboxylate (R 3 above is an alkyl having 10 or less carbon atoms (or 8 or less or 6 or less)). It may contain at least one selected from the group consisting of polypropylene glycol carboxylate (such as polypropylene glycol acetate) and polypropylene oxide adducts of triol or higher polyols (such as polypropylene oxide adducts of glycerin).
  • polypropylene glycol carboxylate such as polypropylene glycol acetate
  • polypropylene oxide adducts of triol or higher polyols such as polypropylene oxide adducts of glycerin.
  • the proportion of the oxypropylene unit in the polymer compound may be 5 mol% or more, 10 mol% or more, or 20 mol% or more.
  • the proportion of the oxypropylene unit in the polymer compound is 100 mol% or less, 90 mol% or less, 75 mol% or less, 60 mol% or less, 50 mol% or less, or It may be 43 mol% or less.
  • the polymer compound has one or more hydrophobic groups, and at least one of the hydrophobic groups has 8 or more carbon atoms. It may be a long-chain aliphatic hydrocarbon group.
  • the carbon number of the long-chain aliphatic hydrocarbon group may be 12 or more or 16 or more.
  • the carbon number of the long-chain aliphatic hydrocarbon group may be 30 or less, 26 or less, or 22 or less.
  • the polymer compound may contain a repeating structure of oxyethylene units.
  • the polymer compound is an etherified product of polyethylene glycol (alkyl ether or the like), an esterified product of polyethylene glycol (carboxylic acid ester or the like), or an etherified product of a polyethylene oxide adduct of the polyol (alkyl ether). Etc.), and at least one selected from the group consisting of esterified products (such as carboxylic acid esters) of polyethylene oxide adducts of polyols (such as polyols of triol or higher).
  • esterified products such as carboxylic acid esters
  • the polymer compound is polyethylene glycol oleate, polyethylene glycol dioleate, polyethylene glycol dilaurate, polyethylene glycol distearate, polyoxyethylene coconut oil fatty acid sorbitan, polyoxy oleate. It may contain at least one selected from the group consisting of ethylene sorbitan, polyoxyethylene sorbitan stearate, polyoxyethylene lauryl ether, polyoxyethylene tetradecyl ether, and polyoxyethylene cetyl ether.
  • the HLB of the polymer compound may be 4 or more, or 4.3 or more.
  • the HLB of the polymer compound may be 18 or less, 10 or less, 9 or less, or 8.5 or less.
  • the content of the polymer compound in the negative electrode electrode material is 8 ppm or more, 10 ppm or more, 20 ppm or more, or 30 ppm or more on a mass basis. You may.
  • the content of the polymer compound in the negative electrode electrode material is 1000 ppm or less, less than 1000 ppm, 700 ppm or less, 600 ppm or less, 500 ppm or less on a mass basis. , 400 ppm or less, 300 ppm or less, 200 ppm or less, 160 ppm or less, 150 ppm or less, 120 ppm or less, or 100 ppm or less.
  • the content of the organic shrinkage-proofing agent in the negative electrode electrode material is 0.005% by mass or more, or 0.01% by mass or more. May be good.
  • the content of the organic shrinkage-proofing agent in the negative electrode electrode material is 1.0% by mass or less, 0.5% by mass or less, 0.3. It may be 0% by mass or less, 0.25% by mass or less, 0.2% by mass or less, 0.15% by mass or less, or 0.12% by mass or less.
  • the organic shrinkage proofing agent (or the negative electrode electrode material) is the first organic shrinkage proofing agent having a sulfur element content of 2000 ⁇ mol / g or more or 3000 ⁇ mol / g or more. It may contain an agent.
  • the sulfur element content of the first organic shrinkage proofing agent may be 9000 ⁇ mol / g or less, or 8000 ⁇ mol / g or less.
  • the Mw of the first organic shrinkage proofing agent may be 7,000 or more.
  • the Mw of the first organic shrinkage proofing agent may be 100,000 or less, or 20,000 or less.
  • the organic shrinkage proofing agent (or the negative electrode electrode material) may contain a second organic shrinkage proofing agent having a sulfur element content of less than 2000 ⁇ mol / g. ..
  • the sulfur element content of the second organic shrinkage proofing agent may be 1000 ⁇ mol / g or less, or 800 ⁇ mol / g or less.
  • the sulfur element content of the second organic shrinkage proofing agent may be 400 ⁇ mol / g or more.
  • the Mw of the second organic shrinkage proofing agent may be less than 7,000.
  • the Mw of the second organic shrinkage proofing agent may be 3000 or more.
  • the organic shrinkage proofing agent (or the negative electrode material) may contain at least a lignin compound.
  • the negative electrode material may further contain a carbonaceous material.
  • the content of the carbonaceous material in the negative electrode material may be 0.05% by mass or more, or 0.10% by mass or more.
  • the content of the carbonaceous material in the negative electrode electrode material may be 5% by mass or less, or 3% by mass or less.
  • the negative electrode material may further contain barium sulfate.
  • the content of the barium sulfate in the negative electrode electrode material may be 0.05% by mass or more, or 0.10% by mass or more.
  • the content of the barium sulfate in the negative electrode electrode material may be 3% by mass or less, or 2% by mass or less.
  • the specific gravity of the electrolytic solution in the fully charged lead-acid battery at 20 ° C. may be 1.20 or more or 1.25 or more.
  • the specific gravity of the electrolytic solution in the fully charged lead-acid battery at 20 ° C. may be 1.35 or less or 1.32 or less.
  • Lead-acid batteries E1 to E27, R1 to R3 and C1 to C5 >> (1) Preparation of lead-acid battery (a) Preparation of negative electrode plate
  • Raw lead powder, barium sulfate, carbon black, the polymer compound shown in the table, and the organic shrinkage proofing agent shown in the table are mixed with an appropriate amount of sulfuric acid aqueous solution.
  • To obtain a negative electrode paste the contents of each of the polymer compound and the organic shrink-proofing agent in the negative electrode electrode material, which are obtained by the above-mentioned procedure, are the values shown in the table, and the content of barium sulfate is 0.6% by mass.
  • Each component is mixed so that the content of carbon black is 0.3% by mass.
  • the concentration and amount of the sulfuric acid aqueous solution are adjusted so that the bulk density of the negative electrode material obtained by the above-mentioned procedure becomes the value shown in the table.
  • the negative electrode paste is filled in the mesh portion of the expanded lattice made of Pb—Ca—Sn alloy and aged and dried to obtain an unchemicald negative electrode plate.
  • E1 Lignin: Sodium lignin sulfonate (sulfur element content 600 ⁇ mol / g, Mw5500)
  • E2 Polybisphenol: A formaldehyde-based condensate of a bisphenol compound having a sulfonic acid group introduced (sulfur element content 5000 ⁇ mol / g, Mw9600).
  • E3 Polybisphenol: A formaldehyde-based condensate of a bisphenol compound having a sulfonic acid group introduced (sulfur element content 3000 ⁇ mol / g, Mw9000).
  • (E4) Polybisphenol: A formaldehyde-based condensate of a bisphenol compound having a sulfonic acid group introduced (sulfur element content 8000 ⁇ mol / g, Mw9200).
  • (E5) Polybisphenol: A formaldehyde-based condensate of a bisphenol compound having a sulfonic acid group introduced (sulfur element content 3000 ⁇ mol / g, Mw9600).
  • (E6) Polybisphenol: A formaldehyde-based condensate of a bisphenol compound having a sulfonic acid group introduced (sulfur element content 8000 ⁇ mol / g, Mw9600).
  • the test battery has a rated voltage of 2 V / cell and a rated 5-hour rate capacity of 32 Ah.
  • the electrode plate group of the test battery is composed of seven positive electrode plates and seven negative electrode plates.
  • the negative electrode plate is housed in a bag-shaped separator formed of a microporous polyethylene film, and is alternately laminated with the positive electrode plate to form a group of electrode plates.
  • a group of electrode plates is housed in a polypropylene electric tank together with an electrolytic solution (sulfuric acid aqueous solution) and chemically formed in the electric tank to produce a liquid-type lead-acid battery.
  • the specific gravity of the electrolytic solution in a fully charged lead-acid battery at 20 ° C. is 1.28.
  • the oxyethylene unit is in the range of the chemical shift of 3.2 ppm or more and 3.8 ppm or less in the 1 H-NMR spectrum of the polymer compound measured by the above-mentioned procedure. A peak derived from -CH 2- is observed.
  • the 1 H-NMR spectrum of the polymer compound measured by the above procedure shows that the oxypropylene unit is in the range of a chemical shift of 3.2 ppm or more and 3.42 ppm or less.
  • (B) Charge acceptability Using the fully charged test battery, measure the amount of electricity at the 10th second according to the procedure described above. The charge acceptability of each lead-acid battery is evaluated by the ratio when the electric energy of the lead-acid battery C1 at the 10th second is 100.
  • the results are shown in Tables 1 to 3.
  • the table also shows the value of the ratio (A) / (B) of the charge acceptability evaluation result (A) to the overcharge electricity amount evaluation result (B). Note that (A) / (B) in the table is a value obtained by multiplying the actual ratio (A) / (B) by 100.
  • Lead-acid batteries E1 to E27 are examples.
  • Lead-acid batteries R1 to R3 are reference examples.
  • Lead-acid batteries C1 to C5 are comparative examples.
  • the average pore diameter of the negative electrode material is as small as 2.15 ⁇ m or less, if a polymer compound is used for the negative electrode material, the amount of overcharged electricity can be significantly reduced and high charge acceptability can be ensured.
  • E1 to E8 and C1 to C5 high values of (A) / (B) exceeding 100 can be obtained, and both high charge acceptability and low overcharge electricity amount can be achieved at the same time.
  • the reason why the amount of overcharge electricity is reduced in E1 to E8 is that the negative electrode material contains a polymer compound, the surface of the lead is thinly covered with the polymer compound over a wide area, and the hydrogen overvoltage rises to overcharge.
  • the content of the organic shrinkage barrier in the negative electrode electrode material is preferably 0.005% by mass or more, more preferably 0.01% by mass or more. From the viewpoint of easily ensuring higher charge acceptability, the content of the organic shrinkage barrier in the negative electrode electrode material is preferably 0.3% by mass or less, more preferably 0.25% by mass or less or 0.2% by mass or less. It is preferable, and it is more preferably 0.15% by mass or less or 0.12% by mass or less.
  • the Mn of the etherified or esterified product shown in Table 2 is the Mn of the etherified or esterified product used for preparing the negative electrode material.
  • the content of the polymer compound in the negative electrode electrode material is preferably 10 ppm or more, more preferably 20 ppm or more or 30 ppm or more, from the viewpoint of enhancing the effect of reducing the amount of overcharged electricity.
  • the content of the polymer compound in the negative electrode electrode material is preferably 400 ppm or less, more preferably 300 ppm or less or 200 ppm or less, further preferably 160 ppm or less or 150 ppm or less, and 120 ppm or less. Alternatively, it may be 100 ppm or less.
  • the lead-acid battery according to one aspect and the other aspect of the present invention is suitable for use in an idling stop vehicle as, for example, a lead-acid battery for IS that is charged and discharged under PSOC conditions.
  • the lead-acid battery can be suitably used, for example, as a power source for starting a vehicle (automobile, motorcycle, etc.) and an industrial power storage device (for example, a power source for an electric vehicle (forklift, etc.)). It should be noted that these are merely examples, and the use of the lead storage battery is not limited to these.
  • Negative electrode plate 3 Positive electrode plate 4: Separator 5: Positive electrode shelf part 6: Negative electrode shelf part 7: Positive electrode pillar 8: Through connection body 9: Negative electrode pillar 11: Electrode plate group 12: Electric tank 13: Bulk partition 14: Cell chamber 15: Lid 16: Negative electrode terminal 17: Positive electrode terminal 18: Liquid spout

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
PCT/JP2021/039741 2020-11-27 2021-10-28 鉛蓄電池 Ceased WO2022113621A1 (ja)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
US12097261B2 (en) 2021-05-07 2024-09-24 Kymera Therapeutics, Inc. CDK2 degraders and uses thereof

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JPS60182662A (ja) 1984-02-28 1985-09-18 Japan Storage Battery Co Ltd 鉛蓄電池
JPH09147869A (ja) * 1995-11-17 1997-06-06 Shin Kobe Electric Mach Co Ltd 鉛蓄電池
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JP2014123525A (ja) 2012-12-21 2014-07-03 Gs Yuasa Corp 鉛蓄電池用負極板及びその製造方法
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WO2020241878A1 (ja) * 2019-05-31 2020-12-03 株式会社Ｇｓユアサ 鉛蓄電池
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JPS5147237A (https=) * 1974-10-18 1976-04-22 Yuasa Battery Co Ltd
JPS60182662A (ja) 1984-02-28 1985-09-18 Japan Storage Battery Co Ltd 鉛蓄電池
JPH09147869A (ja) * 1995-11-17 1997-06-06 Shin Kobe Electric Mach Co Ltd 鉛蓄電池
CN101937996A (zh) * 2010-08-26 2011-01-05 风帆股份有限公司 电动助力车用胶体铅酸蓄电池负极铅膏及制备方法
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12097261B2 (en) 2021-05-07 2024-09-24 Kymera Therapeutics, Inc. CDK2 degraders and uses thereof

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JP7677347B2 (ja) 2025-05-15
CN116918097A (zh) 2023-10-20

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