WO2022113635A1 - 鉛蓄電池 - Google Patents

鉛蓄電池 Download PDF

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Publication number
WO2022113635A1
WO2022113635A1 PCT/JP2021/039832 JP2021039832W WO2022113635A1 WO 2022113635 A1 WO2022113635 A1 WO 2022113635A1 JP 2021039832 W JP2021039832 W JP 2021039832W WO 2022113635 A1 WO2022113635 A1 WO 2022113635A1
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Prior art keywords
lead
negative electrode
electrode material
group
positive electrode
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English (en)
French (fr)
Japanese (ja)
Inventor
由梨 北田
一樹 関家
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GS Yuasa International Ltd
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GS Yuasa International Ltd
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Priority to US18/038,743 priority Critical patent/US12586821B2/en
Priority to JP2022565152A priority patent/JP7687348B2/ja
Publication of WO2022113635A1 publication Critical patent/WO2022113635A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • H01M10/121—Valve regulated lead acid batteries [VRLA]
    • 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
    • H01M4/14—Electrodes for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/604—Polymers containing aliphatic main chain 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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.
  • Lead-acid batteries include liquid-type lead-acid batteries and control valve-type lead-acid batteries.
  • the liquid lead-acid battery is an open-type lead-acid battery including an electric tank, a group of plates housed in the electric tank, and an electrolytic solution.
  • the control valve type lead-acid battery is a sealed lead-acid battery including a positive electrode plate, a negative electrode plate, a group of electrode plates including a fine glass mat separator (retainer mat) interposed between the positive electrode plate and the negative electrode plate, and an electrolytic solution.
  • the control valve type lead-acid battery uses a principle called an oxygen cycle in which an electrolytic solution is held in a separator and oxygen gas generated in a positive electrode plate is reduced to water in a negative electrode plate.
  • additives may be added to the constituent members of the lead-acid battery.
  • Patent Document 1 describes a polymer compound containing any of polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid, or an ester thereof having a degree of polymerization of 30 or more and 3000 or less, or a colloid with the polymer compound.
  • a lead storage battery characterized in that any of the barium sulfate particles is contained in the electrolytic solution and / or the electrode active material molded body.
  • a positive electrode plate holding a positive electrode active material containing barium is formed, and the converted positive electrode plate contains barium of 10 ppm or more and 1000 ppm or less on average per sheet after the chemical conversion.
  • the active material density of the electrode plate is 3.1 g / cc or more and 4.2 g / cc or less on average per sheet
  • the barium content is X
  • the active material density is Y.
  • lead sulfate In lead-acid batteries, lead sulfate is produced when self-discharge occurs. Lead sulfate generated by self-discharge is difficult to be reduced during charging. When the accumulation of lead sulfate becomes remarkable, sulfation occurs in which the accumulated lead sulfate is inactivated, and the life performance is deteriorated. Therefore, lead-acid batteries are required to suppress self-discharge. Further, in the control valve type lead-acid battery, since the amount of the electrolytic solution is smaller than that of the active material, the specific gravity of the electrolytic solution decreases as the self-discharge progresses, which tends to lead to a voltage decrease.
  • the first aspect of the present invention is a control valve type lead-acid battery.
  • 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 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 positive electrode plate comprises a positive electrode material and is provided with a positive electrode material.
  • the density of the positive electrode material relates to a lead storage battery having a density of 3.70 g / cm 3 or more and 4.65 g / cm 3 or less.
  • the second aspect of the present invention is a control valve type lead-acid battery.
  • 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 a polymer compound containing a repeating structure of oxyC 2-4 alkylene units.
  • the positive electrode plate comprises a positive electrode material and is provided with a positive electrode material.
  • the density of the positive electrode material relates to a lead storage battery having a density of 3.70 g / cm 3 or more and 4.65 g / cm 3 or less.
  • the progress of the self-discharge reaction is relatively slow, so the crystal structure of lead sulfate produced during self-discharge on the negative electrode plate tends to grow and become dense.
  • Such lead sulfate has low activity and is difficult to be reduced during charging. Therefore, even if the lead-acid battery is charged after self-discharge, it tends to be in a state where lead sulfate is accumulated as it is. If the lead-acid battery is repeatedly charged and discharged in such a state, the accumulation of lead sulfate progresses, sulfation occurs, and the life performance of the lead-acid battery deteriorates. For example, in small mobility such as a motorcycle, the self-discharge of the mounted lead-acid battery tends to proceed because the period of non-use may continue depending on the season.
  • the lead-acid battery according to the first aspect of the present invention is a control valve type lead-acid battery, which includes at least one cell including a plate group 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.
  • the negative electrode material contains 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 positive electrode plate comprises a positive electrode material.
  • the density of the positive electrode material is 3.70 g / cm 3 or more and 4.65 g / cm 3 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 the second aspect of the present invention is a control valve type lead-acid battery, and includes at least one cell including a plate group 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.
  • the negative electrode material contains a polymer compound containing a repeating structure of oxyC 2-4 alkylene units.
  • the positive electrode plate comprises a positive electrode material.
  • the density of the positive electrode material is 3.70 g / cm 3 or more and 4.65 g / cm 3 or less.
  • the negative electrode electrode material contains the polymer compound as described above, and the density of the positive electrode material is controlled to the above-mentioned specific range. With such a configuration, the self-discharge of the lead storage battery can be remarkably reduced. By reducing self-discharge, it is advantageous for extending the life of lead-acid batteries.
  • the density of the positive electrode material is about 3.66 g / cm 3 .
  • the density of the positive electrode material is large and the self-discharge reaction is reduced.
  • the amount of oxygen gas generated from the positive electrode plate is reduced.
  • the negative electrode plate when oxygen gas is absorbed and water is generated, a side reaction in which PbO is generated from Pb occurs. PbO produces lead sulfate by reacting with the electrolytic solution.
  • the amount of oxygen gas generated from the positive electrode plate is reduced, the amount of PbO generated is also reduced, so that the reaction in which lead sulfate is generated is also reduced. As a result, self-discharge is reduced.
  • the polymer compound contained in the negative electrode material has a repeating structure of the oxyC 2-4 alkylene unit, it is easy to form a linear structure. Therefore, in the negative electrode material, the surface of the lead is thinly and widely covered with the polymer compound. It will be. As a result, the oxygen gas absorption reaction itself in the negative electrode plate is reduced, so that self-discharge is reduced.
  • the effect of the polymer compound as described above on the negative electrode material 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, whereby the effect of the polymer compound can be effectively exerted. 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 endothermic reaction of oxygen gas in the negative electrode plate is further reduced, and self-discharge can be reduced more effectively.
  • 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 endothermic reaction of oxygen gas in the negative electrode plate is further reduced, and self-discharge can be reduced more effectively.
  • 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.
  • 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 endothermic reaction of oxygen gas in the negative electrode plate is further reduced, and self-discharge can be reduced more effectively.
  • the polymer compound may contain a repeating structure of an oxypropylene unit (-O-CH (-CH 3 ) -CH 2- ).
  • the density of the positive electrode material is 3.70 g / cm 3 as compared with the case where the repeating structure of the oxyethylene unit (-O-CH 2 -CH 2- ) is contained.
  • self-discharge tends to increase.
  • the negative electrode material contains a polymer compound containing the repeating structure of the oxypropylene unit, self-discharge can be suppressed low by controlling the density of the positive electrode material.
  • 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 is suppressed, and uneven distribution of the polymer compound is suppressed.
  • 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. The balance between hydrophobic and hydrophilic groups ensures high adsorption to lead and suppresses uneven distribution of polymer compounds, further reducing self-discharge and achieving high low-temperature high-rate (HR) discharge performance. Can be secured.
  • the polymer compound has 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, self-discharge can be reduced. Can be done. From the viewpoint of further reducing self-discharge, the content of the polymer compound in the negative electrode electrode material is preferably 10 ppm or more on a mass basis. From the viewpoint of ensuring higher low-temperature HR discharge performance, the content of the polymer compound in the negative electrode electrode material is preferably 370 ppm or less on a mass basis.
  • 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 negative electrode material may contain a condensate of a bis-alene compound. Condensations of bis-alene compounds are generally classified as synthetic organic shrink proofing agents. In general, when the negative electrode material contains a condensate of a bis-alene compound, the specific surface area of the negative electrode material increases, so that the hydrogen overvoltage tends to be low. However, in the lead-acid battery according to the first aspect and the second aspect of the present invention, the negative electrode material contains a polymer compound and the density of the positive electrode material is controlled within a specific range. Even when it contains an object, the hydrogen overvoltage can be increased to keep the self-discharge low. Further, even when the negative electrode material contains a lignin compound, self-discharge can be suppressed to a low level.
  • the negative electrode material may contain a carbonaceous material.
  • the content of the carbonaceous material in the negative electrode electrode material is preferably 0.1% by mass or more.
  • the self-discharge tends to increase as the hydrogen overvoltage decreases.
  • the self-discharge can be suppressed to a low level by controlling the density of the positive electrode material while the negative electrode material contains the polymer compound.
  • the content of the carbonaceous material in the negative electrode material is preferably 1.2% by mass or less from the viewpoint of further enhancing the effect of reducing self-discharge by easily adsorbing the polymer compound to lead.
  • the lead-acid batteries on the first side surface and the second side surface are suitable for small mobility applications.
  • the use of lead-acid batteries is not limited to small mobility applications.
  • the control valve type lead acid battery is sometimes called a closed type lead acid battery (or VRLA type lead acid battery).
  • the content of the polymer compound in the negative electrode electrode material and the density of the positive electrode material are determined for the negative electrode plate or the positive electrode plate taken out from the lead storage battery in a fully charged state.
  • 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 density of the positive electrode material is a density (g / cm 3 ) obtained by dividing the mass of the positive electrode material by the bulk volume obtained by the mercury intrusion method. The density is determined for a sample of the unmilled positive electrode material taken from the positive 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 positive 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).
  • a condensate of a bis-alene compound is a condensate containing a unit of the bis-alene compound.
  • the unit of the bis-alene compound means a unit derived from the bis-alene compound incorporated in the condensate.
  • a bis-alene compound is a compound in which two sites each having an aromatic ring are linked via a single bond or a linking group.
  • 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 fully charged state of the control valve type lead-acid battery is a current (A) 0.2 times the value (value with Ah as the unit) described in the rated capacity in an air tank at 25 ° C ⁇ 2 ° C.
  • A 0.2 times the value (value with Ah as the unit) described in the rated capacity in an air tank at 25 ° C ⁇ 2 ° C.
  • 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.
  • Small mobility refers to motorcycles and power sports vehicles. Small mobility includes, for example, motorcycles, tricycles, buggies (including both three-wheeled and four-wheeled), water skis, snowmobiles, and all-terrain vehicles.
  • the small mobility is equipped with a lead storage battery for the small mobility together with the engine.
  • the lead-acid battery used or mounted on small mobility means a lead storage battery included in the scope of application of IEC60095-7: 2019 and the scope of application of JIS D 5302: 2004. ..
  • 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 negative electrode material contains 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 organic shrink proofing agents, 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. From the viewpoint that the polymer compound is thin and easily spreads on the lead surface, an aliphatic polyol, an alicyclic polyol (for example, polyhydroxycyclohexane, polyhydroxynorbornane) and the like are preferable, and an aliphatic polyol is particularly preferable.
  • 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, sorbitol and the like.
  • 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.
  • Hydrocarbon groups also include hydrocarbon groups having substituents (eg, hydroxy groups, alkoxy groups, and / or carboxy groups).
  • 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.), a cycloalkenyl group (cyclohexenyl group, cyclooctenyl group, etc.) and the like.
  • 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. It is preferable to use it because self-discharge can be further reduced. Further, among such polymer compounds, a polymer compound having a repeating structure of an oxypropylene unit, a polymer compound having a repeating structure of an oxyethylene unit, or the like is 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.), preferably 12 or more, and 16 or more. Is more preferable.
  • a polymer compound having a long-chain aliphatic hydrocarbon group is preferable because it is unlikely to cause excessive adsorption to lead and it is easy to secure higher low-temperature HR discharge performance while suppressing self-discharge to a low level.
  • 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. Due to the balance between hydrophobicity and high hydrophilicity due to the repeating structure of the oxyethylene unit, such a polymer compound can suppress excessive coverage of the surface of lead while selectively adsorbing to lead. It is possible to secure higher low-temperature HR discharge performance while suppressing self-discharge to a low level. 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.
  • the polymer compound having a hydrophobic group preferably contains a repeating structure of an oxyethylene unit. Due to the balance between hydrophobicity and high hydrophilicity due to the repeating structure of the oxyethylene unit, such a polymer compound can suppress excessive coverage of the surface of lead while selectively adsorbing to lead. It is possible to secure higher low-temperature HR discharge performance while suppressing self-discharge to a low level. 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).
  • 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 self-discharge can be further reduced and higher low-temperature HR discharge performance can be ensured.
  • the HLB of the polymer compound is preferably 4 or more or 4.3 or more from the viewpoint of further reducing self-discharge.
  • the HLB of the polymer compound is, for example, 18 or less.
  • the HLB of the polymer compound is preferably 10 or less or 9 or less, and 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 and 4 or more (or 4.3 or more) 10 or less. From the viewpoint of excellent balance between reduction of self-discharge and improvement of low-temperature HR discharge performance, 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 is an abbreviation for Hydrophile Lipophile Balance, and is a numerical value representing the balance between hydrophobicity and hydrophilicity of a nonionic surfactant.
  • the repeating structure of Oxy C 2-4 alkylene contains at least the repeating structure of the oxypropylene unit.
  • the self-discharge tends to increase as compared with the case of the repeating structure of the oxyethylene unit, but even in this case, the self-discharge can be kept low by controlling the density of the positive electrode material. can.
  • 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. Since the electron densities around the nuclei of hydrogen atoms in these groups are different, the peaks are split.
  • 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 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 -CH 2 -group hydrogen atom, and the integral value of the peak of -CH ⁇ group hydrogen atom In the 1 H-NMR spectrum of a polymer compound, the integral value of the peak of 3.2 ppm to 3.8 ppm, the integral value of the peak of -CH 2 -group hydrogen atom, and the integral value of the peak of -CH ⁇ group hydrogen atom.
  • the ratio of the integrated value of the peak of 3.2 ppm to 3.8 ppm to the total value becomes large.
  • This ratio is, for example, 50% or more, and may be 80% or more. From the viewpoint of further reducing self-discharge, the above ratio is preferably 85% or more, 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 1 million or less or 100,000 or less, or a compound of 20000 or less. From the viewpoint of ensuring higher charge acceptability, the polymer compound preferably contains a compound having a Mn of 10,000 or less, may contain a compound of 5000 or less or 3000 or less, or may contain a compound of 2500 or less or 2000 or less. good.
  • the Mn of such a compound may be 300 or more, 400 or more, or 500 or more.
  • the polymer compound two or more kinds of compounds having different Mns may be used. That is, the polymer compound may be a polymer compound having a plurality of Mn peaks in the distribution of molecular weight.
  • the Mn of the above compounds is 3 or more and 5 million or less (or 1 million or less), 4 or more and 5 million or less (or 1 million or less), 5 or more and 5 million or less (or 1 million or less), and 300 or more and 100,000 or less (or).
  • the content of the polymer compound in the negative electrode electrode material is, for example, 8 ppm or more on a mass basis. From the viewpoint of further reducing self-discharge, the content of the polymer compound in the negative electrode electrode material is preferably 10 ppm or more, preferably 20 ppm or more, and 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, 500 ppm or less, 450 ppm or less, or 420 ppm or less on a mass basis. From the viewpoint of easily ensuring higher low-temperature HR discharge performance, the content of the polymer compound in the negative electrode electrode material is preferably 370 ppm or less, and may be 350 ppm or less on a mass basis.
  • 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) 500 ppm or less, 8 ppm or more (or 10 ppm or more) 450 ppm or less, 8 ppm or more (or).
  • Organic shrinkage proofing agent is 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.
  • 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.
  • Examples of 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 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.
  • the negative electrode material contains a condensate of a bis-alene compound (such as a condensate of an aldehyde compound)
  • self-discharge tends to increase, but the negative electrode material contains a polymer compound and the density of the positive electrode material is specified. By controlling the range, self-discharge can be suppressed to a low level.
  • 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 is used, high high-temperature durability can be obtained, which is advantageous in ensuring excellent life performance.
  • a condensate of a naphthalene compound having a sulfur-containing group and at least one selected from the group consisting of a hydroxy group and an amino group is used. It is also preferable.
  • 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 content of sulfur element in the organic shrinkage proofing agent is X ⁇ mol / g means that the content of sulfur element contained in 1 g of the organic shrinkage proofing agent is X ⁇ mol / g.
  • 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. From the viewpoint of further enhancing the effect of reducing the amount of overcharged electricity, the sulfur element content of the first organic shrinkage proofing agent 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 electrode material may contain a first organic shrinkage proofing agent and a second organic shrinkage proofing agent.
  • first organic shrinkage proofing agent and the second organic shrinkage proofing agent are used in combination, the mass ratios thereof can be arbitrarily selected.
  • the content of the organic shrinkage barrier contained in the negative electrode electrode material is, for example, 0.005% by mass or more, 0.01% by mass or more, or 0.1% by mass or more.
  • 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.
  • 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). It may be 0.5% by mass or less, or 0.1% by mass or more and 1.0% by mass or less (or 0.5% 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 0.1% by mass or more.
  • the content of the carbonaceous material in the negative electrode electrode material is, for example, 5% by mass or less, and may be 3% by mass or less. From the viewpoint of further reducing self-discharge, the content of the carbonaceous material in the negative electrode electrode material is preferably 1.2% by mass or less.
  • the content of carbonaceous material in the negative electrode 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 (or 1.2% by mass or less), and 0.1% by mass or more. It may be 5% by mass or less, or 0.1% by mass or more and 3% by mass or less (or 1.2% by 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.
  • a fully charged lead-acid battery is disassembled to obtain a 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. for about 6 hours in a reduced pressure environment. If the negative electrode plate contains a sticking member, the sticking member is removed as necessary.
  • sample A hereinafter referred to as sample A
  • 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.
  • 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.
  • an electrode plate group including an unchemical negative electrode plate and an electrolytic solution containing sulfuric acid are housed in an electric tank of a lead storage battery, and the electrode plate group is charged in a state where the electrolytic solution is soaked in the electrode plate group. It can be done by doing.
  • 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 density of the positive electrode material is 3.70 g / cm 3 or more, and may be 3.72 g / cm 3 or more.
  • the density of the positive electrode material is preferably 3.74 g / cm 3 or more.
  • the density of the positive electrode material is 4.65 g / cm 3 or less, and may be 4.5 g / cm 3 or less.
  • the density of the positive electrode material is preferably 4.40 g / cm 3 or less, and more preferably 4.30 g / cm 3 or less.
  • the density of the positive electrode material is 3.70 g / cm 3 or more and 4.65 g / cm 3 or less (or 4.5 g / cm 3 or less), 3.72 g / cm 3 or more and 4.65 g / cm 3 or less (or 4. 5 g / cm 3 or less) 3.74 g / cm 3 or more 4.65 g / cm 3 or less (or 4.5 g / cm 3 or less) 3.70 g / cm 3 or more 4.40 g / cm 3 or less (or 4.
  • 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.
  • a positive electrode plate is obtained by forming these unchemical positive electrode plates.
  • an electrode plate group including an unchemical positive electrode plate and an electrolytic solution containing sulfuric acid are housed in an electric tank of a lead storage battery, and the electrode plate group is charged in a state where the electrolytic solution is soaked in the electrode plate group. It can be done by doing. However, the chemical formation may be performed before assembling the lead-acid battery or the electrode plate group.
  • the density is determined by the mercury intrusion method using a mercury porosimeter. More specifically, first, a predetermined amount of uncrushed sample D is collected and the mass is measured. After putting this sample D into the measuring container of the mercury porosimeter and exhausting it under reduced pressure, the sample D 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 density of the positive electrode electrode material is obtained by measuring the bulk volume and dividing the measured mass of the sample D 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.
  • the mercury porosimeter an automatic porosimeter (Autopore IV9505) manufactured by Shimadzu Corporation is used.
  • the density of the positive electrode electrode material is determined for the positive electrode material collected from the positive electrode plate.
  • the density of the positive electrode material is an average value of the values obtained for the positive electrode material collected from each of the two positive electrode plates.
  • the density of the positive electrode electrode material is the positive electrode material collected from two positive electrode plates arbitrarily selected from the positive electrode plates other than the electrode plates at both ends of the electrode plate group. It is the average value of the obtained values.
  • the density of the positive electrode electrode material is determined for the positive electrode material collected from the remaining one positive electrode plate.
  • Electrode-acid batteries usually include a separator interposed between the negative electrode plate and the positive electrode plate.
  • the separator is composed of a non-woven fabric.
  • Nonwoven fabric is a mat that is entwined without weaving fibers, and is mainly composed of fibers. In the non-woven fabric, for example, 60% by mass or more of the non-woven fabric is formed of fibers.
  • the non-woven fabric may contain components other than fibers, such as acid-resistant inorganic powder (for example, silica powder, glass powder, diatomaceous earth), a polymer as a binder, and the like.
  • the fiber glass fiber, organic fiber, etc. can be used.
  • the organic fiber a fiber material insoluble in the electrolytic solution is used.
  • the organic fiber include polymer fiber (polyolefin fiber, acrylic fiber, polyester fiber (polyethylene terephthalate fiber and the like), etc.), pulp fiber and the like.
  • the non-woven fabric preferably contains at least glass fiber.
  • Nonwoven fabric containing glass fiber is also referred to as AGM (Absorbed Glass Mat) separator.
  • the non-woven fabric may contain glass fibers and organic fibers. The ratio of the glass fiber to the total fiber constituting the non-woven fabric is preferably 60% by mass or more.
  • the separator may be composed of only non-woven fabric.
  • the separator is a laminate of a non-woven fabric and a microporous membrane, a laminated non-woven fabric and a different or similar material, or a non-woven fabric and a different or similar material engaged with each other. It may be a thing or 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. can get.
  • the microporous membrane is preferably composed of a material having acid resistance, and is preferably microporous mainly composed of a polymer component.
  • 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 thickness of the separator interposed between the negative electrode plate and the positive electrode plate may be selected according to the distance between the electrodes.
  • the number of separators may be selected according to the number of poles.
  • 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 included in one cell may be one plate or two or more plates.
  • the negative electrode material contains the above polymer compound in at least one negative electrode plate, and the positive electrode material of the cell is used. It is preferable that the condition that the density is in the above range is satisfied. In this case, the effect of reducing self-discharge can be obtained according to the number of the negative electrode plates. From the viewpoint of further reducing self-discharge, 50% or more (more preferably 80% or more or 90% or more) of the number of negative electrode plates included in the electrode plate group is a negative electrode plate containing the above polymer compound. preferable. The ratio of the negative electrode plate containing the above polymer compound to the negative electrode plates included in the electrode plate group is 100% or less. All of the negative electrode plates included in the electrode plate group may be negative electrode plates containing the above polymer compound.
  • the electrode plate group of the cells for which the density of the positive electrode material is determined may be provided with the negative electrode plate containing the above polymer compound.
  • the density of the positive electrode material is in the above range and the polymer is in the above range in 50% or more (more preferably 80% or more or 90% or more) of the number of cells contained in the lead storage battery.
  • the density of the positive electrode material is in the above range, and the ratio of the cells including the electrode plate group including the negative electrode plate containing the polymer compound is 100% or less.
  • all of the electrode plate groups included in the lead storage battery include the electrode plate group including the negative electrode plate containing the polymer compound and the density of the positive electrode electrode material is in the above range.
  • FIG. 1 is a cross-sectional view schematically showing the structure of an example of a control valve type lead-acid battery.
  • the lead-acid battery 1 includes a battery case 10 that houses an electrode plate group 11 and an electrolytic solution (not shown). The upper opening of the battery case 10 is closed by the lid 12.
  • 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.
  • an ear portion (not shown) for collecting electricity is provided so as to project upward.
  • An ear portion (not shown) for collecting electricity is also provided on the upper portion of each of the plurality of positive electrode plates 3 so as to project upward.
  • the ears of the negative electrode plate 2 are connected and integrated by a negative electrode strap (not shown).
  • the selvage portions of the positive electrode plates 3 are also connected and integrated by a positive electrode strap (not shown).
  • the negative electrode strap is connected to a negative electrode column (not shown) which is an external terminal
  • the positive electrode strap is connected to a positive electrode column (not shown) which is an external terminal.
  • the electric tank 10 is divided into a plurality of (three in the illustrated example) cell chambers 10R independently of each other, and one electrode plate group 11 is housed in each cell chamber 10R.
  • the lid 12 includes an independent exhaust valve 13 for each cell chamber 10R. When the internal pressure of the cell chamber 10R exceeds a predetermined upper limit value, the exhaust valve 13 opens and the gas is directly discharged from the cell chamber 10R to the outside. When the internal pressure of the cell chamber 10R is equal to or less than the upper limit, oxygen generated in the positive electrode plate 3 is reduced by the negative electrode plate 2 in the same cell chamber 10R to generate water.
  • FIG. 1 shows the case of each cell exhaust type, but the lid has a collective exhaust chamber that communicates with each cell chamber, and the number of collective exhaust chambers is smaller than the number of cell chambers (for example, one). It may be a collective exhaust type provided with.
  • each of the self-discharge and the low-temperature HR discharge performance is evaluated by the following procedure.
  • the rated voltage of the test battery used for the evaluation is 12V, and the rated 10-hour rate capacity is 5Ah.
  • the lead-acid batteries according to one aspect of the present invention are summarized below.
  • a control valve type 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 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 positive electrode plate comprises a positive electrode material and is provided with a positive electrode material.
  • a lead-acid battery having a density of the positive electrode material of 3.70 g / cm 3 or more and 4.65 g / cm 3 or less.
  • 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 85% 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 a polymer compound containing a repeating structure of oxyC 2-4 alkylene units.
  • the positive electrode plate comprises a positive electrode material and is provided with a positive electrode material.
  • a lead-acid battery having a density of the positive electrode material of 3.70 g / cm 3 or more and 4.65 g / cm 3 or less.
  • the density of the positive electrode material may be 3.72 g / cm 3 or more, or 3.74 g / cm 3 or more.
  • the density of the positive electrode material is 4.5 g / cm 3 or less, 4.40 g / cm 3 or less, or 4.30 g / cm 3 or less. It may be.
  • 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, 500 ppm or less, 450 ppm or less, 420 ppm or less, 370 ppm or less on a mass basis. , Or 350 ppm or less.
  • the polymer compound has Mn of 5 million or less, 1 million or less, 100,000 or less, 20000 or less, 10000 or less, 5000 or less, 3000 or less, 2500 or less.
  • the following or 2000 or less compounds may be included.
  • the polymer compound may contain a compound having Mn of 300 or more, 400 or more, or 500 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 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 an oxyethylene unit.
  • 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 negative electrode electrode material may contain an organic shrinkage proofing agent.
  • the negative electrode electrode material (or the organic shrinkage proofing agent) may contain a lignin compound.
  • the negative electrode electrode material (or the organic shrinkage proofing agent) may contain a condensate of a bis-alene compound.
  • the content of the organic shrinkage-proofing agent in the negative electrode electrode material is 0.005% by mass or more, 0.01% by mass or more, or 0. It may be 1% by mass or more.
  • the content of the organic shrinkage-proofing agent in the negative electrode electrode material is 1.0% by mass or less, or 0.5% by mass or less. May be good.
  • the negative electrode material may contain a carbonaceous material.
  • the content of the carbonaceous material in the negative electrode material may be 0.05% by mass or more, or 0.1% by mass or more.
  • the content of the carbonaceous material in the negative electrode electrode material may be 5% by mass or less, 3% by mass or less, or 1.2% by mass or less. ..
  • the negative electrode material may 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.
  • the lead storage battery may be used for small mobility.
  • Lead-acid batteries E1 to E34, R1 to R8, and C1 to C12 >> (1) Preparation of lead-acid battery (a) Preparation of negative electrode plate A suitable amount of sulfuric acid is added to lead powder as a raw material, a polymer compound shown in the table, an organic shrinkage proofing agent, a carbonaceous material (carbon black), and barium sulfate. Mix with aqueous solution to give negative paste. At this time, the contents of the polymer compound, the organic shrink-proofing agent, and the carbonaceous material in the negative electrode electrode material, which are all obtained by the above-mentioned procedure, are the values shown in the table, and the content of barium sulfate is 0.4.
  • 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.
  • the Mn required by the above-mentioned procedure for polypropylene glycol as a polymer compound is 2000.
  • the Mn of polyethylene glycol oleic acid ester and polyethylene glycol dilauric acid ester used in the preparation of the negative electrode material is 500 and 630, respectively.
  • E1 Lignin: Sodium lignin sulfonate (sulfur element content 600 ⁇ mol / g, Mw5500)
  • E2 Bisphenol condensate: A formaldehyde-based condensate of a bisphenol compound having a sulfonic acid group introduced (sulfur element content 3330 ⁇ mol / g, Mw9600).
  • the concentration and amount of the sulfuric acid aqueous solution used for preparing the positive electrode paste are adjusted so that the density of the positive electrode material obtained by the above procedure becomes the value shown in the table.
  • the test battery has a rated voltage of 12 V and a rated 10-hour rate capacity of 5 Ah.
  • the electrode plate group of the test battery is composed of three positive electrode plates and four negative electrode plates. The positive electrode plate and the negative electrode plate are alternately laminated with a separator interposed therebetween to form a group of electrode plates.
  • the electrode plates are housed in a polypropylene electric tank together with an electrolytic solution (sulfuric acid aqueous solution) and sealed with a lid. A fine glass mat is used as the separator.
  • a control valve type lead-acid battery is manufactured by forming a group of electrode plates in an electric tank. Due to the chemical formation, the lead-acid battery becomes fully charged.
  • the specific gravity of the electrolytic solution in a fully charged lead-acid battery at 20 ° C. is 1.32.
  • 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.
  • Evaluation 1 Self-discharge The self-discharge of the produced lead-acid battery is evaluated by the procedure described above. The self-discharge of each lead-acid battery is evaluated by the ratio when the self-discharge of the lead-acid battery C1 is 100%. The smaller this ratio, the less self-discharge and the better.
  • Tables 1-5 The results are shown in Tables 1-5.
  • Table 2 also shows the HLB of the polymer compound.
  • Table 1, Table 2, Table 4 and Table 5 show the difference in self-discharge from the lead-acid battery C1 as the self-discharge improvement rate.
  • E1 to E34 are examples.
  • R1 to R8 are reference examples.
  • C1 to C12 are comparative examples.
  • the effect of reducing self-discharge by changing the density of the positive electrode material from 3.66 g / cm 3 to 3.70 to 4.65 g / cm 3 is 2 to 10%. ..
  • the effect of reducing self-discharge by using the negative electrode plate provided with the negative electrode material containing 320 ppm of polypropylene glycol as a polymer compound on a mass basis is 12%.
  • the self-discharge is further reduced from the self-discharge estimated from each of the density of the positive electrode material and the use of the polymer compound, and a synergistic effect is obtained.
  • the density of the positive electrode material is preferably 3.74 g / cm 3 or more. From the same viewpoint, the density of the positive electrode material is preferably 4.40 g / cm 3 or less.
  • 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 on a mass basis. From the viewpoint of ensuring higher low-temperature HR discharge performance, the content of the polymer compound in the negative electrode electrode material is preferably 370 ppm or less, more preferably 350 ppm or less on a mass basis.
  • control valve type lead-acid battery is suitable for small mobility, idling stop (Idle Reduction) vehicle applications, industrial batteries, and the like. It should be noted that these uses are merely examples and are not limited to these uses.
  • Control valve type lead acid battery 2 Negative electrode plate 3: Positive electrode plate 4: Separator 11: Electrode plate group 10: Electric tank 10R: Cell chamber 12: Cover 13: Exhaust valve

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