WO2022113624A1 - 鉛蓄電池 - Google Patents

鉛蓄電池 Download PDF

Info

Publication number
WO2022113624A1
WO2022113624A1 PCT/JP2021/039744 JP2021039744W WO2022113624A1 WO 2022113624 A1 WO2022113624 A1 WO 2022113624A1 JP 2021039744 W JP2021039744 W JP 2021039744W WO 2022113624 A1 WO2022113624 A1 WO 2022113624A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
electrode plate
negative electrode
lead
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/039744
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
千紘 大林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GS Yuasa International Ltd
Original Assignee
GS Yuasa International Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GS Yuasa International Ltd filed Critical GS Yuasa International Ltd
Priority to EP21897600.9A priority Critical patent/EP4254549A4/en
Priority to JP2022565145A priority patent/JP7747004B2/ja
Publication of WO2022113624A1 publication Critical patent/WO2022113624A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a lead storage battery.
  • Lead-acid batteries are used for various purposes such as in-vehicle use, industrial use, and so on.
  • Lead-acid batteries include a negative electrode plate, a positive electrode plate, a separator (or mat), an electrolytic solution, and the like.
  • Each electrode plate comprises a current collector and an electrode material.
  • additives may be added to the constituent members of the lead-acid battery.
  • 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.
  • Patent Document 2 uses polyoxyperfluoroethylenephenylamine represented by a specific chemical formula as the depolarizing agent in a negative electrode plate for a lead storage battery in which a paste-type active material containing a shrink-proofing agent is filled in a current collector.
  • a negative electrode plate for a lead storage battery characterized in that the polyoxyperfluoroethylenephenylamine is contained in an amount of 0.005 to 3% by weight based on the paste-type active material.
  • a bag-shaped separator may be used in addition to a sheet or mat-shaped separator.
  • Patent Document 3 describes a lead-calcium-tin (Pb-Ca-Sn) alloy containing 0.05 to 0.07% by weight of calcium (Ca) and 0.75 to 1.0% by weight of tin (Sn).
  • a positive electrode plate filled with a paste-like active material is folded into a U-shape with a microporous polyethylene film, vertically parallel ribs are provided inside, and mechanical irregularities are provided on both the left and right ends for crimping.
  • the positive electrode current collector stretches due to corrosion. Therefore, if the positive electrode plate is housed in the bag-shaped separator, it will reach the end of its life due to a short circuit caused by the breakage of the separator. In particular, in the high temperature cycle test, the elongation of the positive electrode current collector becomes remarkable, so that when the positive electrode plate is housed in the bag-shaped separator, the life performance is greatly deteriorated. On the other hand, it was clarified that when the positive electrode plate was housed in the bag-shaped separator, the life performance in the deep discharge cycle test was improved.
  • the first aspect of the present disclosure is a 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 bag-shaped separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate comprises a negative electrode current collector and a negative electrode material.
  • the positive electrode plate comprises a positive electrode current collector and a positive 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 current collector contains Sn and contains Sn.
  • the bag-shaped separator relates to a lead storage battery having ribs protruding toward the positive electrode plate and accommodating the positive electrode plate.
  • the second aspect of the present invention is a lead storage 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 bag-shaped separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate comprises a negative electrode current collector and a negative electrode material.
  • the positive electrode plate comprises a positive electrode current collector and a positive electrode material.
  • the negative electrode material contains a polymer compound containing a repeating structure of oxyC 2-4 alkylene units.
  • the positive electrode current collector contains Sn and contains Sn.
  • the bag-shaped separator relates to a lead storage battery having ribs protruding toward the positive electrode plate and accommodating the positive electrode plate.
  • the lead-acid battery according to the first aspect of the present invention is a 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 bag-shaped separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate comprises a negative electrode current collector and a negative electrode material.
  • the positive electrode plate comprises a positive electrode current collector and a positive 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 current collector contains Sn.
  • the bag-shaped separator has ribs protruding toward the positive electrode plate and houses the positive electrode plate.
  • 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 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 bag-shaped separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate comprises a negative electrode current collector and a negative electrode material.
  • the positive electrode plate comprises a positive electrode current collector and a positive electrode material.
  • the negative electrode material contains a polymer compound containing a repeating structure of oxyC 2-4 alkylene units.
  • the positive electrode current collector contains Sn.
  • the bag-shaped separator has ribs protruding toward the positive electrode plate and houses the positive electrode plate.
  • the negative electrode electrode material contains the polymer compound as described above, and the positive electrode plate provided with the positive electrode current collector containing Sn is directed toward the positive electrode plate. It is housed in a bag-shaped separator having a protruding rib. With such a configuration, excellent life performance can be ensured in both the deep discharge cycle test and the high temperature cycle test.
  • the lead-acid batteries of the first aspect and the second aspect of the present invention can secure excellent life performance in both the deep discharge cycle test and the high temperature cycle test for the following reasons.
  • the separator may be provided with ribs protruding toward the positive electrode plate. The electrolytic solution convects in the space formed between the positive electrode plate and the separator by the ribs.
  • the electrolytic solution having a high concentration of sulfate ions passes through the space between the separator and the positive electrode plate and reaches the bottom of the electric tank further below the electrode plate. It becomes easy to settle.
  • the positive electrode plate is housed in the bag-shaped separator. As a result, even if the electrolytic solution having a high concentration of sulfate ions settles through the space between the positive electrode plate and the separator, the bottom of the bag-shaped separator prevents further downward settling.
  • the elongation of the positive electrode plate due to the corrosion of the positive electrode current collector becomes remarkable.
  • the positive electrode current collector contains Sn
  • the corrosion of the positive electrode current collector is reduced by the action of Sn deposited at the grain boundaries of lead.
  • the negative electrode material contains a polymer compound
  • the hydrogen overvoltage in the negative electrode plate rises, and the charging current value can be lowered when constant voltage charging is performed. This makes it difficult for the corrosion of the positive electrode current collector to proceed.
  • the polymer compound eluted from the negative electrode plate adheres to the separator, it acts as an antioxidant, reduces the oxidative deterioration of the separator, and makes the separator less likely to be damaged.
  • the corrosion of the positive electrode current collector is synergistically reduced and the oxidative deterioration of the separator is reduced, so that the life performance in the high temperature cycle test can be synergistically improved.
  • the Sn content in the positive electrode current collector is preferably 0.5% by mass or more.
  • the Sn content in the positive electrode current collector is preferably less than 3% by mass.
  • the Sn content is in such a range, the influence of elongation due to corrosion of the positive electrode current collector is likely to become apparent.
  • the negative electrode electrode material to contain the polymer compound, the high temperature cycle test is performed even though the positive electrode plate provided with the positive electrode current collector having a Sn content of less than 3% by mass is housed in the bag-shaped separator. High life performance can be ensured.
  • the effect of the polymer compound that raises the hydrogen overvoltage 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, since the hydrogen overvoltage can be increased and the decrease in charge acceptability can be suppressed, the life performance in the deep discharge cycle test and the high temperature cycle test can be further improved.
  • 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, since the hydrogen overvoltage can be increased and the decrease in charge acceptability can be suppressed, the life performance in the deep discharge cycle test and the high temperature cycle test can be further improved.
  • 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 effect of increasing the hydrogen overvoltage is further enhanced, and the decrease in charge acceptability can be suppressed, so that higher life performance in the deep discharge cycle test and the high temperature cycle test can be ensured. Can be done.
  • the polymer compound may contain a repeating structure of an oxypropylene unit (-O-CH (-CH 3 ) -CH 2- ). Such a polymer compound tends to have lower charge acceptability as compared with the case where it contains a repeating structure of an oxyethylene unit (-O-CH 2 -CH 2- ), but the positive electrode current collector contains Sn.
  • the polymer compound has one or more hydrophobic groups, and at least one of the hydrophobic groups may be a long-chain aliphatic hydrocarbon group having 8 or more carbon atoms. Due to the action of such a hydrophobic group, excessive coating of the polymer compound on the lead surface can be suppressed, and the effect of suppressing a decrease in charge acceptability can be further enhanced.
  • the polymer compound preferably contains a repeating structure of oxyethylene units. By including the repeating structure of the oxyethylene unit having high hydrophilicity, it can be selectively adsorbed to lead. The balance between the hydrophobic group and the hydrophilic group can increase the hydrogen overvoltage and suppress the decrease in charge acceptability, so that the life performance in the deep discharge cycle test and the high temperature cycle test can be further improved.
  • the HLB of the polymer compound is preferably 4 or more and 9 or less.
  • the balance between hydrophobicity and hydrophilicity can increase the hydrogen overvoltage and suppress the decrease in charge acceptability, so that the life performance in the deep discharge cycle test and the high temperature cycle test can be further improved.
  • the polymer compound has a high adsorptivity to lead and can cover the lead surface thinly. Therefore, even if the content of the polymer compound in the negative electrode material is small, the hydrogen overvoltage is increased. It is possible to suppress a decrease in charge acceptability. From the viewpoint of further enhancing the effect of suppressing the decrease in charge acceptability and ensuring higher life performance in the deep discharge cycle test, the content of the polymer compound in the negative electrode electrode material is preferably 550 ppm or less on a mass basis. .. From the viewpoint of enhancing the effect of increasing the hydrogen overvoltage and ensuring higher life performance in the high temperature cycle test, the content of the polymer compound in the negative electrode material is preferably 5 ppm or more.
  • the polymer compound may be contained in the negative electrode material, and the origin of the polymer compound contained in the negative electrode material is not particularly limited.
  • the polymer compound may be contained in any of the components of the lead-acid battery (for example, the negative electrode plate, the positive electrode plate, the electrolytic solution, and the separator) when the lead-acid battery is manufactured.
  • the polymer compound may be contained in one component or in two or more components (for example, a negative electrode plate and an electrolytic solution).
  • the lead-acid battery may be either a control valve type (sealed type) lead-acid battery (VRLA type lead-acid battery) or a liquid type (vent type) lead-acid battery.
  • the content of the polymer compound in the negative electrode electrode material and the content of Sn in the positive electrode current collector are determined for the negative electrode plate or the positive electrode plate taken out from the fully charged lead-acid battery.
  • 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 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).
  • HLB Hydrophile Lipofile Balance
  • P polymer compound
  • Mn number average molecular weight
  • GPC gel permeation chromatography
  • the fully charged state of a liquid lead-acid battery is defined by the definition of JIS D 5301: 2019. More specifically, in a water tank at 25 ° C ⁇ 2 ° C, charging is performed every 15 minutes with a current (A) 0.2 times the value described as the rated capacity (value whose unit is Ah). The state in which the lead-acid battery is charged is regarded as a fully charged state until the terminal voltage (V) of No. 1 or the electrolyte density converted into temperature at 20 ° C. shows a constant value with three valid digits three times in a row.
  • V terminal voltage
  • the fully charged state is 0.2 times the current (value with Ah as the unit) described in the rated capacity in the air tank at 25 ° C ⁇ 2 ° C (the unit is Ah).
  • A) constant current constant voltage charging of 2.23 V / cell is performed, and the charging current at the time of constant voltage charging is 0.005 times the value (value with the unit being Ah) described in the rated capacity (A). When it becomes, charging is completed.
  • a fully charged lead-acid battery is a fully charged lead-acid battery.
  • the lead-acid battery may be fully charged after the chemical conversion, immediately after the chemical conversion, or after a lapse of time from the chemical conversion (for example, after the chemical conversion, the lead-acid battery in use (preferably at the initial stage of use) is fully charged. May be).
  • An initial use battery is a battery that has not been used for a long time and has hardly deteriorated.
  • the vertical direction of the lead-acid battery or the component of the lead-acid battery means the vertical direction of the lead-acid battery in the state where the lead-acid battery is used.
  • Each electrode plate of the positive electrode plate and the negative electrode plate is provided with an ear portion for connecting to an external terminal.
  • the ears are provided so as to project laterally to the sides of the plate, but in many lead-acid batteries, the ears are usually made of the plate. It is provided so as to project upward at the top.
  • the negative electrode plate usually includes a negative electrode current collector in addition to the negative electrode material.
  • the negative electrode current collector may be formed by casting lead (Pb) or a lead alloy, or may be formed by processing a lead sheet or a lead alloy sheet. Examples of the processing method include expanding processing and punching processing. It is preferable to use a grid-shaped current collector as the negative electrode current collector because it is easy to support the negative electrode material.
  • the lead alloy used for the negative electrode current collector may be any of Pb—Sb-based alloys, Pb-Ca-based alloys, and Pb-Ca—Sn-based alloys. These leads or lead alloys may further contain, as an additive element, at least one selected from the group consisting of Ba, Ag, Al, Bi, As, Se, Cu and the like.
  • the negative electrode current collector may include a surface layer. The composition of the surface layer and the inner layer of the negative electrode current collector may be different. The surface layer may be formed on a part of the negative electrode current collector. The surface layer may be formed on the selvage portion of the negative electrode current collector. The surface layer of the selvage may contain Sn or Sn alloy.
  • the 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, and sorbitol.
  • the sugar or sugar alcohol may have either a chain structure or a cyclic structure.
  • the alkylene oxide corresponds to the oxyC 2-4 alkylene unit of the polymer compound and comprises at least C 2-4 alkylene oxide. From the viewpoint that the polymer compound can easily form a linear structure, the polyol is preferably a diol.
  • the etherified product is composed of a -OH group (a hydrogen atom of the terminal group and an oxygen atom bonded to the hydrogen atom of the terminal group) at least a part of the hydroxy compound having a repeating structure of the above oxyC 2-4 alkylene unit.
  • the —OH group has two etherified —OR groups (in the formula, R 2 is an organic group).
  • R 2 is an organic group.
  • ends of the polymer compound some ends may be etherified, or all ends may be etherified.
  • one end of the main chain of the linear polymer compound may be an ⁇ OH group and the other end may be an ⁇ OR2 group.
  • the esterified product is composed of an OH group (a hydrogen atom of the terminal group and an oxygen atom bonded to the hydrogen atom of the terminal group) at least a part of the hydroxy compound having a repeating structure of the oxyC 2-4 alkylene unit.
  • R 3 is an organic group.
  • some ends may be esterified or all ends may be esterified.
  • Examples of the organic groups R 2 and R 3 include hydrocarbon groups.
  • the hydrocarbon group may have a substituent (eg, a hydroxy group, an alkoxy group, and / or a carboxy group).
  • the hydrocarbon group may be any of an aliphatic, alicyclic, and aromatic group.
  • the aromatic hydrocarbon group and the alicyclic hydrocarbon group may have an aliphatic hydrocarbon group (for example, an alkyl group, an alkenyl group, an alkynyl group) as a substituent.
  • the number of carbon atoms of the aliphatic hydrocarbon group as a substituent may be, for example, 1 to 30, 1 to 20 or 1 to 10, and may be 1 to 6 or 1 to 4. .
  • Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 24 or less carbon atoms (for example, 6 to 24). The number of carbon atoms of the aromatic hydrocarbon group may be 20 or less (for example, 6 to 20), 14 or less (for example, 6 to 14) or 12 or less (for example, 6 to 12).
  • Examples of the aromatic hydrocarbon group include an aryl group and a bisaryl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the bisaryl group include a monovalent group corresponding to bisarene. Examples of the bisarene include biphenyl and bisaryl alkane (for example, bis C 6-10 aryl C 1-4 alkane (2,2-bisphenylpropane, etc.)).
  • Examples of the alicyclic hydrocarbon group include an alicyclic hydrocarbon group having 16 or less carbon atoms.
  • the alicyclic hydrocarbon group may be a crosslinked cyclic hydrocarbon group.
  • the alicyclic hydrocarbon group may have 10 or less or 8 or less carbon atoms.
  • the alicyclic hydrocarbon group has, for example, 5 or more carbon atoms, and may be 6 or more carbon atoms.
  • the number of carbon atoms of the alicyclic hydrocarbon group may be 5 (or 6) or more and 16 or less, 5 (or 6) or more and 10 or less, or 5 (or 6) or more and 8 or less.
  • Examples of the alicyclic hydrocarbon group include a cycloalkyl group (cyclopentyl group, cyclohexyl group, cyclooctyl group, etc.) and a cycloalkenyl group (cyclohexenyl group, cyclooctenyl group, etc.).
  • the alicyclic hydrocarbon group also includes the hydrogenated additive of the above aromatic hydrocarbon group.
  • an aliphatic hydrocarbon group is preferable from the viewpoint that the polymer compound is thin and easily adheres to the lead surface.
  • Aliphatic hydrocarbon groups may be saturated or unsaturated. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a dienyl group having two carbon-carbon double bonds, and a trienyl group having three carbon-carbon double bonds.
  • the aliphatic hydrocarbon group may be linear or branched.
  • the aliphatic hydrocarbon group may have, for example, 30 or less, 26 or less or 22 or less, 20 or less or 16 or less, 14 or less or 10 or less. It may be 8 or less or 6 or less.
  • the lower limit of the number of carbon atoms is 1 or more for an alkyl group, 2 or more for an alkenyl group and an alkynyl group, 3 or more for a dienyl group, and 4 or more for a trienyl group, depending on the type of the aliphatic hydrocarbon group.
  • Alkyl groups and alkenyl groups are particularly preferable from the viewpoint that the polymer compound is thin and easily adheres to the lead surface.
  • alkyl group examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, i-pentyl, and s-pentyl.
  • alkenyl group examples include vinyl, 1-propenyl, allyl, cis-9-heptadecene-1-yl, palmitrail and oleyl.
  • the alkenyl group may be, for example, a C 2-30 alkenyl group or a C 2-26 alkenyl group, a C 2-22 alkenyl group or a C 2-20 alkenyl group, and a C 10-20 alkenyl group. May be.
  • the polymer compounds at least one selected from the group consisting of an etherified product of a hydroxy compound having a repeating structure of an oxyC 2-4 alkylene unit and an esterified product of a hydroxy compound having a repeating structure of an oxy C 2-4 alkylene unit.
  • an etherified product of a hydroxy compound having a repeating structure of an oxyC 2-4 alkylene unit and an esterified product of a hydroxy compound having a repeating structure of an oxy C 2-4 alkylene unit.
  • it is preferable because it is possible to further suppress a decrease in charge acceptability and further enhance the life performance in a high temperature cycle test. Further, even when these polymer compounds are used, the effect of increasing the hydrogen overvoltage can be ensured.
  • 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.).
  • the aliphatic hydrocarbon group preferably has 12 or more carbon atoms, and more preferably 16 or more carbon atoms.
  • a polymer compound having a long-chain aliphatic hydrocarbon group is preferable because it is unlikely to cause excessive adsorption to lead and the effect of suppressing a decrease in charge acceptability is further enhanced.
  • the polymer compound may be a polymer compound in which at least one of the hydrophobic groups is a long-chain aliphatic hydrocarbon group.
  • the carbon number of the long-chain aliphatic hydrocarbon group may be 30 or less, 26 or less, or 22 or less.
  • the number of carbon atoms of the 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 it to lead. , Hydrogen overvoltage can be increased, and the effect of suppressing a decrease in charge acceptability can be further enhanced. Such a polymer compound can ensure high adsorptivity to lead even if it has a relatively low molecular weight (for example, Mn is 1000 or less).
  • polyoxypropylene-polyoxyethylene block copolymers etherified compounds of hydroxy compounds having a repeating structure of oxyethylene units, and esterified compounds of hydroxy compounds having a repeating structure of oxyethylene units are nonions.
  • etherified compounds of hydroxy compounds having a repeating structure of oxyethylene units and esterified compounds of hydroxy compounds having a repeating structure of oxyethylene units are nonions.
  • esterified compounds of hydroxy compounds having a repeating structure of oxyethylene units are nonions.
  • a surfactant corresponds to a surfactant.
  • the repeating structure of the oxyethylene unit corresponds to a hydrophilic group
  • the repeating structure of the oxypropylene unit corresponds to a hydrophobic group.
  • Such copolymers are also included in the polymer compound having a hydrophobic group.
  • Examples of the polymer compound having a hydrophobic group and containing a repeating structure of an oxyethylene unit include an etherified product of polyethylene glycol (alkyl ether, etc.), an esterified product of polyethylene gucol (carboxylic acid ester, etc.), and the addition of polyethylene oxide to the above-mentioned polyol.
  • Examples thereof include ether compounds of substances (alkyl ethers and the like), esters of polyethylene oxide adducts of the above-mentioned polyols (polyols of triol or higher, etc.) (carboxylic acid esters, etc.).
  • 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, but are not limited to, ethylene sorbitan, polyoxyethylene lauryl ether, polyoxyethylene tetradecyl ether, and polyoxyethylene cetyl ether.
  • an esterified product of polyethylene glycol an esterified product of the polyethylene oxide adduct of the above-mentioned polyol, or the like because higher charge acceptability can be ensured and the effect of increasing the hydrogen overvoltage can be obtained.
  • the polymer compounds classified as surfactants have an HLB of 4 or more from the viewpoint that the effect of increasing the hydrogen overvoltage is enhanced and it is easy to secure higher life performance in the high temperature cycle test.
  • the HLB of the polymer compound is preferably 18 or less, more preferably 10 or less or 9 or less, and 8.5 or less. Is more preferable.
  • the HLB of the polymer compound may be 4 or more (or 4.3 or more) 18 or less, 4 or more (or 4.3 or more) 10 or less. From the viewpoint of excellent balance between the life performance in the high temperature cycle life test and the life performance in the deep discharge cycle test, 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). Above) 8.5 or less is preferable.
  • the repeating structure of Oxy C 2-4 alkylene contains at least the repeating structure of the oxypropylene unit.
  • the charge acceptability tends to be lower than when the repeating structure of the oxyethylene unit is included, but even in this case, high life performance in the deep discharge cycle test and the high temperature cycle test should be ensured. Can be done.
  • 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 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 the 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 that the effect of increasing the hydrogen overvoltage is further enhanced and it is easy to secure higher charge acceptability, the above ratio is preferably 85% or more, and more preferably 90% or more.
  • the polymer compound has a -OH group at the end and has -CH 2 -group and / or -CH ⁇ group bonded to the oxygen atom of this -OH group, 1 in the H-NMR spectrum, -CH 2
  • the peaks of the hydrogen atoms of the -group and -CH ⁇ group are in the range of chemical shifts of more than 3.8 ppm and less than 4.0 ppm.
  • the negative electrode material may contain one kind of polymer compound or two or more kinds.
  • the polymer compound may contain, for example, a compound having Mn of 5 million or less, a compound of 1 million or less or 100,000 or less, or a compound of 20000 or less. From the viewpoint of ensuring higher discharge performance, the polymer compound preferably contains a compound having a Mn of 10,000 or less, and 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. .. From the viewpoint that the effect of increasing the hydrogen overvoltage can be easily obtained, the Mn of such a compound may be 300 or more, 400 or more, or 500 or more. As the polymer compound, two or more kinds of compounds having different Mns may be used. That is, the polymer compound may have a plurality of Mn peaks in the molecular weight distribution.
  • the Mn of the above 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, 5 ppm or more and may be 10 ppm or more on a mass basis. From the viewpoint of increasing the hydrogen overvoltage and ensuring higher life performance in the high temperature cycle test, the content of the polymer compound in the negative electrode electrode material is preferably 20 ppm or more, preferably 30 ppm or more, on a mass basis. More preferably, it may be 70 ppm or more or 100 ppm or more. The content of the polymer compound in the negative electrode electrode material may be, for example, 1000 ppm or less, less than 1000 ppm, 800 ppm or less, 700 ppm or less, or 600 ppm or less on a mass basis.
  • the content of the polymer compound in the negative electrode electrode material is preferably 550 ppm or less or 500 ppm or less on a mass basis. ..
  • the content of the polymer compound in the negative electrode material is 5 ppm or more (or 10 ppm or more) 1000 ppm or less, 5 ppm or more (or 10 ppm or more) less than 1000 ppm, 5 ppm or more (or 10 ppm or more) 800 ppm or less, 5 ppm or more (or) on a mass basis.
  • 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 charge acceptability tends to be lower than when a synthetic organic shrinkage proofing agent is used.
  • the negative electrode material contains a specific polymer compound, the decrease in charge acceptability is suppressed even when the lignin compound is used as the organic shrinkage proofing agent.
  • the organic shrinkage proofing agent it is also preferable to use a condensate containing at least a unit of an aromatic compound.
  • a condensate include a condensate of an aromatic compound made of an aldehyde compound (such as at least one selected from the group consisting of aldehydes (eg, formaldehyde) and condensates thereof).
  • the organic shrinkage proofing agent may contain a unit of one kind of aromatic compound, or may contain a unit of two or more kinds of aromatic compounds.
  • the unit of the aromatic compound means a unit derived from the aromatic compound incorporated in the condensate.
  • Examples of the aromatic ring contained in the aromatic compound include a benzene ring and a naphthalene ring.
  • the plurality of aromatic rings may be directly bonded or linked by a linking group (for example, an alkylene group (including an alkylidene group), a sulfone group) or the like.
  • Examples of such a structure include a bisarene structure (biphenyl, bisphenylalkane, bisphenylsulfone, etc.).
  • Examples of the aromatic compound include compounds having the above aromatic ring and at least one selected from the group consisting of a hydroxy group and an amino group.
  • the hydroxy group or amino group may be directly bonded to the aromatic ring, or may be bonded as an alkyl chain having a hydroxy group or an amino group.
  • the hydroxy group also includes a salt of the hydroxy group (-OMe).
  • the amino group also includes a salt of the amino group (specifically, a salt with an anion). Examples of Me include alkali metals (Li, K, Na, etc.), Group 2 metals of the periodic table (Ca, Mg, etc.) and the like.
  • the 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 condensate preferably contains at least a unit of an aromatic compound having a sulfur-containing group. Above all, it is advantageous to use a condensate containing at least a unit of a bisphenol compound having a sulfur-containing group in order to secure higher charge acceptability.
  • the sulfur-containing group may be directly bonded to the aromatic ring contained in the compound, or may be bonded to the aromatic ring as an alkyl chain having a sulfur-containing group, for example.
  • the sulfur-containing group is not particularly limited, and examples thereof include a sulfonyl group, a sulfonic acid group, or a salt thereof.
  • the organic shrinkage proofing agent for example, a condensation containing at least one selected from the group consisting of a unit of the above-mentioned bisarene compound and a unit of a monocyclic aromatic compound (hydroxyarene compound and / or aminoarene compound, etc.). At least one may be used.
  • the organic shrinkage proofing agent may contain at least a condensate containing a unit of a bisarene compound and a unit of a monocyclic aromatic compound (particularly, a hydroxyarene compound). Examples of such a condensate include a condensate of a bis-alene compound and a monocyclic aromatic compound made of an aldehyde compound.
  • hydroxyarene compound a phenol sulfonic acid compound (such as phenol sulfonic acid or a substitute thereof) is preferable.
  • aminoarene compound aminobenzenesulfonic acid, alkylaminobenzenesulfonic acid and the like are preferable.
  • monocyclic aromatic compound a hydroxyarene compound is preferable.
  • the content of the organic shrinkage proofing agent contained in the negative electrode electrode material is, for example, 0.005% by mass or more, and may be 0.01% by mass or more. When the content of the organic shrink proofing agent is in such a range, high discharge performance can be ensured.
  • 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 or 0.2% 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 0.005% by mass or more (or 0.01% by mass or more) and 0.2% by mass or less.
  • Carbonate material As the carbonaceous material contained in the negative electrode electrode material, carbon black, graphite, hard carbon, soft carbon and the like can be used. Examples of carbon black include acetylene black, furnace black, and lamp black. Furness Black also includes Ketjen Black (trade name).
  • the graphite may be any carbonaceous material containing a graphite-type crystal structure, and may be either artificial graphite or natural graphite.
  • the negative electrode material may contain one kind of carbonaceous material, or may contain two or more kinds.
  • the content of the carbonaceous material in the negative electrode electrode material is, for example, 0.05% by mass or more, and may be 0.10% by mass or more.
  • the content of the carbonaceous material is, for example, 5% by mass or less, and may be 3% by mass or less.
  • the content of the carbonaceous material in the negative electrode material is 0.05% by mass or more and 5% by mass or less, 0.05% by mass or more and 3% by mass or less, 0.10% by mass or more and 5% by mass or less, or 0.10. It may be mass% or more and 3 mass% or less.
  • barium sulfate The content of barium sulfate in the negative electrode electrode material is, for example, 0.05% by mass or more, and may be 0.10% by mass or more. The content of barium sulfate in the negative electrode electrode material is, for example, 3% by mass or less, and may be 2% by mass or less.
  • the content of barium sulfate in the negative electrode material is 0.05% by mass or more and 3% by mass or less, 0.05% by mass or more and 2% by mass or less, 0.10% by mass or more and 3% by mass or less, or 0.10% by mass. It may be% or more and 2% by mass or less.
  • 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 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.
  • a carbonaceous material and components other than barium sulfate are removed from the dispersion liquid using a sieve.
  • the dispersion liquid is suction-filtered using a membrane filter whose mass has been measured in advance, and the membrane filter is dried together with the filtered sample in a dryer at 110 ° C. ⁇ 5 ° C.
  • the filtered sample is a mixed sample of a carbonaceous material and barium sulfate.
  • the mass of the sample C (M m ) is measured by subtracting the mass of the membrane filter from the total mass of the dried mixed sample (hereinafter referred to as sample C) and the membrane filter.
  • the sample C is put into a crucible together with a membrane filter and incinerated at 1300 ° C. or higher.
  • the remaining residue is barium oxide.
  • the mass of barium oxide is converted into the mass of barium sulfate to obtain the mass of barium sulfate ( MB ).
  • the mass of the carbonaceous material is calculated by subtracting the mass MB from the mass M m .
  • the negative electrode plate can be formed by applying or filling a negative electrode paste to a negative electrode current collector, aging and drying to produce an unchemical negative electrode plate, and then forming an unchemical negative electrode plate.
  • the negative electrode paste is, for example, a lead powder, a polymer compound, and, if necessary, at least one selected from the group consisting of an organic shrinkage proofing agent, a carbonaceous material, and other additives, and water and sulfuric acid (or an aqueous solution of sulfuric acid). ) Is added and kneaded to produce. At the time of aging, it is preferable to ripen the unchemical negative electrode plate at a temperature higher than room temperature and high humidity.
  • Chemical formation can be performed by charging the electrode plate group in a state where the electrode plate group including the unchemical negative electrode plate is immersed in the electrolytic solution containing sulfuric acid in the electric tank of the lead storage battery. However, the chemical formation may be performed before assembling the lead-acid battery or the electrode plate group. The formation produces spongy lead.
  • the paste type positive electrode plate includes a positive electrode current collector and a positive electrode material.
  • 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 positive electrode current collector may be formed by casting a lead alloy containing Sn, or may be formed by processing a lead alloy sheet containing Sn. 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 Sn content in the positive electrode current collector is preferably less than 3% by mass, more preferably 2.5% by mass or less, and may be 1.8% by mass or less or 1.6% by mass or less.
  • the Sn content in such a range When the Sn content is in such a range, the elongation amount due to the corrosion of the positive electrode current collector tends to be large, but even in this case, excellent life performance in the high temperature cycle test can be ensured. can. It is also advantageous from the viewpoint of low cost. From the viewpoint of ensuring higher life performance in the high temperature cycle test, the Sn content in the positive electrode current collector is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, or 0.8% by mass or more. preferable.
  • the Sn content in the negative electrode current collector is 0.5% by mass or more and less than 3% by mass (or 2.5% by mass or less), 0.7% by mass or more and less than 3% by mass (or 2.5% by mass or less). ), 0.8% by mass or more and less than 3% by mass (or 2.5% by mass or less), 0.5% by mass or more and 1.8% by mass or less (or 1.6% by mass or less), 0.7% by mass or more It may be 1.8% by mass or less (or 1.6% by mass or less), or 0.8% by mass or more and 1.8% by mass or less (or 1.6% by mass or less).
  • Examples of the lead alloy constituting the positive electrode current collector include Pb-Sn-based alloys and Pb-Ca-Sn-based alloys.
  • the lead alloy may further contain at least one selected from the group consisting of Ba, Ag, Al, Bi, As, Se, Cu and the like as an additive element.
  • the positive electrode current collector may have 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 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. Then, a positive electrode plate is obtained by forming an unchemical positive electrode plate.
  • Chemical formation can be performed by charging the electrode plate group in a state where the electrode plate group including the unchemical positive electrode plate is immersed in the electrolytic solution containing sulfuric acid in the electric tank of the lead storage battery. However, the chemical formation may be performed before assembling the lead-acid battery or the electrode plate group.
  • the positive electrode material Prior to the quantitative analysis of Sn, the positive electrode material is removed from the positive electrode plate taken out from the lead storage battery to obtain a positive electrode current collector, and a part of the positive electrode current collector is collected to prepare a sample for analysis. .. More specifically, after applying vibration to the positive electrode plate to cause the positive electrode material to fall off from the positive electrode collector, a ceramic knife is used to remove the positive electrode material remaining around the positive electrode collector. , A part of the metal glossy part of the positive electrode current collector is collected as a sample. After measuring the mass of the collected sample, an aqueous solution is obtained by mixing with tartaric acid and dilute nitric acid. Hydrochloric acid is added to the aqueous solution to precipitate lead chloride, which is filtered and the filtrate is collected. Using this filtrate, the Sn content in the positive electrode current collector is determined by the following procedure.
  • the quantification of Sn contained in the positive electrode current collector is analyzed according to the lead separation inductively coupled plasma emission spectroscopy described in JIS H2105: 1955. More specifically, the Sn concentration in the above-mentioned filtrate is analyzed by a calibration curve method using an ICP emission spectroscopic analyzer, and from the Sn concentration and the mass of the collected sample, Sn in the positive electrode current collector is used. Content is required.
  • ICP emission spectroscopic analyzer ICPS-8000 manufactured by Shimadzu Corporation is used.
  • the bag-shaped separator is configured to accommodate the positive electrode plate. By superimposing the positive electrode plate and the negative electrode plate housed in the bag-shaped separator, the separator is interposed between the positive electrode plate and the negative electrode plate.
  • a non-woven fabric may be used, but at least a microporous membrane is preferably used.
  • the non-woven fabric is a mat that is entwined without weaving fibers, and is mainly composed of fibers.
  • the non-woven fabric for example, 60% by mass or more of the non-woven fabric is formed of fibers.
  • the fiber include glass fiber, polymer fiber (polyolefin fiber, acrylic fiber, polyester fiber (polyethylene terephthalate fiber and the like), etc.), pulp fiber and the like.
  • the non-woven fabric may contain components other than fibers, such as an acid-resistant inorganic powder, a polymer as a binder, and the like.
  • the microporous membrane is a porous sheet (or film) mainly composed of non-fiber components.
  • the microporous membrane is preferably composed of a material having acid resistance, and a microporous membrane mainly composed of a polymer component is preferable.
  • the microporous membrane may contain a filler.
  • Polyolefins polyethylene, polypropylene, etc.
  • the separator contains polyolefin, it is prone to oxidative deterioration.
  • the polymer compound eluted from the negative electrode material adheres to the separator and acts as an antioxidant, oxidative deterioration is suppressed even when a separator containing polyolefin is used, and high life performance in high temperature cycle tests is ensured. Can be done.
  • the separator may be composed of, for example, only a microporous membrane. Further, the separator may be a laminate of a non-woven fabric and a microporous membrane, if necessary.
  • the bag-shaped separator has at least a rib protruding toward the positive electrode plate.
  • the electrolytic solution having a high concentration of sulfate ions tends to settle in the space formed between the bag-shaped separator and the positive electrode plate by such ribs.
  • the separator can be used. Subsidence below the bottom is hindered and stratification is reduced.
  • the bag-shaped separator has a base portion having a first surface on the positive electrode plate side and a second surface on the negative electrode plate side, and ribs (first ribs) protruding from the first surface toward the positive electrode plate. It is equipped with.
  • the bag-shaped separator usually has a plurality of first ribs on the first surface.
  • the average thickness of the base portion is, for example, 0.1 mm or more, preferably 0.15 mm or more.
  • the strength of the separator is increased, which is more advantageous from the viewpoint of reducing damage to the separator.
  • the average thickness of the base portion is, for example, 0.3 mm or less.
  • the average height of the first rib is, for example, 0.3 mm or more, preferably 0.4 mm or more.
  • the electrolytic solution having a high concentration of sulfate ions tends to settle in the space formed between the separator and the positive electrode plate by the first rib.
  • stratification can be effectively reduced and high life performance in the high temperature cycle test can be ensured.
  • oxidative deterioration of the separator can be suppressed.
  • the average height of the first rib is, for example, 1.0 mm or less, and may be 0.7 mm or less.
  • the first rib is formed at least in a region facing the positive electrode plate (preferably a region in which the positive electrode material is present) at such an average height.
  • the average height of the first rib may be 0.3 mm or more (or 0.4 mm or more) 1.0 mm or less, or 0.3 mm or more (or 0.4 mm or more) 0.7 mm or less.
  • the bag-shaped separator may be provided with a rib (second rib) protruding from the second surface toward the negative electrode plate.
  • a rib second rib
  • the average height of the second rib is preferably lower than the average height of the first rib, and it is more preferable that the bag-shaped separator does not have the second rib.
  • the average height of the second rib is, for example, 0.3 mm or less, and may be 0.1 mm or less.
  • the average thickness of the base and the average height of the ribs are obtained for a separator that has been taken out of a fully charged lead-acid battery, washed, and dried under a pressure lower than atmospheric pressure.
  • the average thickness of the base portion is obtained by measuring and averaging the thickness of the base portion at five arbitrarily selected points in the cross-sectional photograph of the separator.
  • the average height of the first rib is obtained by averaging the heights of the first ribs measured at 10 arbitrarily selected points of the first rib on the first surface of the base portion.
  • the height of the first rib means the distance from the first surface of the base portion to the top of the first rib at a predetermined position of the first rib.
  • the first rib is placed at a predetermined position from the highest position on the first surface of the base portion.
  • the distance to the top of the rib is the height of the first rib.
  • the average height of the second rib is obtained according to the case of the first rib.
  • the height of the second rib refers to the distance from the second surface of the base portion to the top of the second rib at a predetermined position of the second rib, as in the case of the first rib.
  • a resin composition containing a pore-forming agent and a polymer component is extruded into a sheet, and then the pore-forming agent is removed to form pores in a matrix of polymer components to form a sheet. It is obtained by bending and crimping the ends to form a bag.
  • the ribs may be formed, for example, during extrusion molding, or may be formed by pressing with a roller having a groove corresponding to the ribs after forming into a sheet or after removing the pore-forming agent.
  • a filler it is added, for example, to the resin composition.
  • the pore-forming agent include at least one selected from the group consisting of polymer powders and oils.
  • the electrolytic solution is an aqueous solution containing sulfuric acid, and may be gelled if necessary.
  • the electrolytic solution may contain the above-mentioned polymer compound.
  • the electrolytic solution may contain a cation (for example, a metal cation) and / or an anion (for example, an anion other than the sulfate anion (for example, a phosphate ion)), if necessary.
  • a cation for example, a metal cation
  • an anion for example, an anion other than the sulfate anion (for example, a phosphate ion)
  • the metal cation include at least one selected from the group consisting of Na ion, Li ion, Mg ion, and Al ion.
  • the specific gravity of the electrolytic solution in a fully charged lead storage battery at 20 ° C. is, for example, 1.20 or more, and may be 1.25 or more.
  • the specific gravity of the electrolytic solution at 20 ° C. is 1.35 or less, preferably 1.32 or less.
  • the specific gravity of the electrolytic solution at 20 ° C. may be 1.20 or more and 1.35 or less, 1.20 or more and 1.32 or less, 1.25 or more and 1.35 or less, or 1.25 or more and 1.32 or less. ..
  • the lead-acid battery can be obtained by a manufacturing method including a step of accommodating a group of plates and an electrolytic solution in a cell chamber of an electric tank.
  • Each cell of the lead-acid battery includes a group of plates and an electrolytic solution housed in each cell chamber.
  • the electrode plate group is assembled by laminating the positive electrode plate, the negative electrode plate, and the separator so that the separator is interposed between the positive electrode plate and the negative electrode plate prior to the accommodation in the cell chamber.
  • the positive electrode plate, the negative electrode plate, the electrolytic solution, and the separator are each prepared prior to assembling the electrode plate group.
  • the method for manufacturing a lead-acid battery may include, if necessary, a step of forming at least one of a positive electrode plate and a negative electrode plate after a step of accommodating a group of electrode plates and an electrolytic solution in a cell chamber.
  • Each electrode plate in the electrode plate group may be one plate or two or more plates.
  • the electrode plate group includes two or more negative electrode plates, if at least one negative electrode plate satisfies the condition (condition a) that the above polymer compound is contained, the number of such negative electrode plates is increased. Therefore, the effect of improving the charge acceptability can be obtained, and the effect of increasing the hydrogen overvoltage can be obtained. From the viewpoint of further suppressing the decrease in charge acceptability and easily obtaining the effect of increasing the hydrogen overvoltage, 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 preferably a negative electrode plate that satisfies the condition a.
  • the ratio of the negative electrode plates satisfying the condition a is 100% or less. All of the negative electrode plates included in the electrode plate group may be negative electrode plates satisfying the condition a.
  • the electrode plate group includes two or more positive electrode plates
  • the number of positive electrode plates included in the electrode plate group from the viewpoint of reducing the elongation of the positive electrode current collector and ensuring higher life performance in the high temperature cycle test.
  • 50% or more (more preferably 80% or more or 90% or more) of the above satisfies the condition (condition b) that the positive electrode current collector containing Sn is provided and is housed in the bag-shaped separator provided with the first rib. It is preferably a positive electrode plate.
  • the ratio of the positive electrode plates satisfying the condition b is 100% or less. All of the positive electrode plates included in the electrode plate group may be positive electrode plates satisfying the condition b.
  • the electrode plate group of at least a part of the cells may be a electrode plate group including a negative electrode plate satisfying the condition a and a positive electrode plate satisfying the condition b.
  • 50% or more (more preferably 80% or more or 90% or more) of the number of cells contained in the lead storage battery is used. It is preferable to include a group of electrode plates including a negative electrode plate satisfying the condition a and a positive electrode plate satisfying the condition b.
  • the ratio of the cells including the electrode plate group including the negative electrode plate satisfying the condition a and the positive electrode plate satisfying the condition b is 100% or less. It is preferable that all of the electrode plates included in the lead storage battery are electrode plates including a negative electrode plate satisfying the condition a and a positive electrode plate satisfying the condition b.
  • FIG. 1 shows the appearance of an example of a lead storage battery according to an embodiment of the present invention.
  • the lead-acid battery 1 includes an electric tank 12 for accommodating a plate group 11 and an electrolytic solution (not shown).
  • the inside of the electric tank 12 is partitioned into a plurality of cell chambers 14 by a partition wall 13.
  • One electrode plate group 11 is housed in each cell chamber 14.
  • the opening of the battery case 12 is closed by a lid 15 including a positive electrode terminal 16 and a negative electrode terminal 17.
  • the lid 15 is provided with a liquid spout 18 for each cell chamber. At the time of refilling water, the liquid spout 18 is removed and the refilling liquid is replenished.
  • the liquid spout 18 may have a function of discharging the gas generated in the cell chamber 14 to the outside of the battery.
  • the electrode plate group 11 is configured by alternately laminating a plurality of negative electrode plates 3 and a plurality of positive electrode plates 2 via a separator 4.
  • the separator 4 has a bag shape, and the positive electrode plates 2 are packaged one by one.
  • the positive electrode shelf portion 6 for connecting the ear portions 2a of the plurality of positive electrode plates 2 in parallel is connected to the through connection body 8, and the ear portions of the plurality of negative electrode plates 3 are connected.
  • the negative electrode shelf portion 5 that connects 3a in parallel is connected to the negative electrode column 7.
  • the negative electrode column 7 is connected to the negative electrode terminal 17 outside the lid 15.
  • the positive electrode column 9 is connected to the positive electrode shelf 6 and the through-connecting body 8 is connected to the negative electrode shelf 5.
  • the positive electrode column 9 is connected to the positive electrode terminal 16 outside the lid 15.
  • Each through-connecting body 8 passes through a through-hole provided in the partition wall 13 and connects the electrode plates 11 of the adjacent cell chambers 14 in series.
  • the positive electrode shelf portion 6 is formed by welding the selvage portions 2a provided on the upper part of each positive electrode plate 2 by a cast-on-strap method or a burning method.
  • the negative electrode shelf portion 5 is also formed by welding the selvage portions 3a provided on the upper portions of the negative electrode plates 3 to each other, as in the case of the positive electrode shelf portion 6.
  • the lid 15 of the lead storage battery has a single structure (single lid), but is not limited to the case shown in the illustrated example.
  • the lid 15 may have, for example, a double structure including an inner lid and an outer lid (or upper lid).
  • the lid having a double structure may be provided with a reflux structure between the inner lid and the outer lid for returning the electrolytic solution to the inside of the battery (inside the inner lid) from the reflux port provided on the inner lid.
  • the life performance in each of the deep discharge cycle test and the high temperature cycle test is evaluated by the following procedure.
  • the increase in hydrogen overvoltage in the negative electrode plate is evaluated based on the amount of overcharged electricity.
  • the amount of overcharged electricity is measured by the following procedure.
  • Life performance in deep discharge cycle test A deep discharge cycle test is performed at a discharge depth of 50% (DOD 50%), and the life performance is evaluated by the end-of-discharge voltage.
  • DOD 50% a deep discharge cycle test is performed at a discharge depth of 50%
  • a lead-acid battery having a rated voltage of 2 V / cell and having 7 positive electrode plates and 8 negative electrode plates per cell is used.
  • the fully charged lead-acid battery is repeatedly discharged and charged at 40 ° C. ⁇ 2 ° C. under the following conditions.
  • the end-of-discharge voltage at the time of DOD 50% discharge in each cycle is measured and monitored.
  • the life is defined as the time when the voltage at the time of DOD 50% discharge falls below 1.67 V / cell. Life performance is evaluated based on the number of cycles at the time of life.
  • Discharge Discharge for 2 hours with a constant current of Y ⁇ In (A) (DOD 50%).
  • Charging Charge at a constant voltage of 2.6 V / cell with a maximum current of Y ⁇ In (A) for 5 hours.
  • In (A) is a current value (A) obtained by dividing the rated n time rate capacity (Ah) of the lead storage battery by n.
  • Y n / 4.
  • the upper part (the part within 10 mm below the liquid level of the electrolytic solution) and the lower part (upper from the lower end of the negative electrode plate) in the battery case of the lead-acid battery after the test.
  • the electrolytic solution is collected and the specific gravity is measured.
  • the high temperature cycle test is performed in accordance with SAE J2801 (high temperature stability test). More specifically, the test is performed under the conditions shown in Table 1. At this time, the discharge end voltage, the charge end current, and the open circuit voltage (OCV) of the step 20 are measured and monitored for each charge / discharge cycle. The time point at which at least one of the following conditions (a) to (c) is satisfied is defined as the life. Life performance is evaluated based on the number of cycles at the time of life. For the test, a lead-acid battery having a rated voltage of 12 V and having 7 positive electrode plates and 8 negative electrode plates per cell is used. (A) Each discharge end voltage becomes 7.2 V or less. (B) Each charge end current exceeds 15 A. (C) The OCV of step 20 becomes less than 12.0V.
  • a lead-acid battery having a rated voltage of 2 V / cell and having 7 positive electrode plates and 8 negative electrode plates per cell is used for measuring the amount of overcharged electricity.
  • the amount of overcharged electricity (charged electricity amount-discharged electricity amount) in each cycle up to 1220 cycles is totaled to obtain the integrated value (Ah) of the overcharged electricity amount, and the overcharged electricity amount is evaluated based on this integrated value. do.
  • the lead-acid batteries according to one aspect of the present invention are summarized below.
  • the lead-acid battery comprises at least one cell comprising a group of plates and an electrolyte.
  • the electrode plate group includes a negative electrode plate, a positive electrode plate, and a bag-shaped separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate comprises a negative electrode current collector and a negative electrode material.
  • the positive electrode plate comprises a positive electrode current collector and a positive 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 current collector contains Sn and contains Sn.
  • the bag-shaped separator is a lead storage battery having a rib (first rib) protruding toward the positive electrode plate and accommodating the positive electrode plate.
  • 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 bag-shaped separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate comprises a negative electrode current collector and a negative electrode material.
  • the positive electrode plate comprises a positive electrode current collector and a positive electrode material.
  • the negative electrode material contains a polymer compound containing a repeating structure of oxyC 2-4 alkylene units.
  • the positive electrode current collector contains Sn and contains Sn.
  • the bag-shaped separator is a lead storage battery having ribs protruding toward the positive electrode plate and accommodating the positive electrode plate.
  • 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 Sn content in the positive electrode current collector is 0.5% by mass or more, 0.7% by mass or more, or 0.8% by mass. It may be% or more.
  • the Sn content in the positive electrode current collector is less than 3% by mass, 2.5% by mass or less, 1.8% by mass or less, Alternatively, it may be 1.6% by mass 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. , Or may contain less than 2000 compounds.
  • 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 an esterified product of the hydroxy compound.
  • Including at least one selected from the group consisting of 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 contains the hydroxy compound.
  • the hydroxy compound may contain a repeating structure of an oxypropylene unit.
  • examples of the polymer compound include polypropylene glycol, polyoxypropylene-polyoxyethylene copolymer (polyoxypropylene-polyoxyethylene block copolymer, etc.), polypropylene glycol alkyl ether ( R2 above). Is an alkyl having 10 or less carbon atoms (or 8 or less or 6 or less), such as an alkyl ether (methyl ether, ethyl ether, butyl ether, etc.), polyoxyethylene-polyoxypropylene alkyl ether (R 2 is 10 or less carbon atoms).
  • 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. At least one of the hydrophobic groups may be a long-chain aliphatic hydrocarbon group having 8 or more carbon atoms.
  • 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 comprises at least one selected from the group consisting of the etherified product and the esterified product.
  • Each of the etherified product and the esterified product 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 polymer content in the negative electrode electrode material is 5 ppm or more, 10 ppm or more, 20 ppm or more, 30 ppm or more, 70 ppm or more, or 100 ppm on a mass basis. It may be the above.
  • the polymer content in the negative electrode electrode material is 1000 ppm or less, less than 1000 ppm, 800 ppm or less, 700 ppm or less, 600 ppm or less, 550 ppm or less on a mass basis. , Or 500 ppm or less.
  • the negative electrode electrode material may further contain an organic shrinkage proofing agent.
  • the content of the organic shrinkage barrier in the negative electrode electrode material may be 0.005% by mass or more, or 0.01% by mass or more.
  • the content of the organic shrinkage barrier in the negative electrode electrode material is 1.0% by mass or less, 0.5% by mass or less, or 0.2% by mass or less. May be good.
  • the negative electrode material may further contain a carbonaceous material.
  • the content of the carbonaceous material in the negative electrode material may be 0.05% by mass or more, or 0.10% by mass or more.
  • the content of the carbonaceous material in the negative electrode electrode material may be 5% by mass or less, or 3% by mass or less.
  • the negative electrode material may further contain barium sulfate.
  • the content of the barium sulfate in the negative electrode electrode material may be 0.05% by mass or more, or 0.10% by mass or more.
  • the content of the barium sulfate in the negative electrode electrode material may be 3% by mass or less, or 2% by mass or less.
  • the average height of the first rib may be, for example, 0.3 mm or more, or 0.4 mm or more.
  • the average height of the first rib may be 1.0 mm or less, or 0.7 mm or less.
  • the bag-shaped separator includes a base portion having a first surface on the positive electrode plate side and a second surface on the negative electrode plate side, and the first rib. May project from the first surface toward the positive electrode plate.
  • the average thickness of the base portion may be 0.1 mm or more or 0.15 mm.
  • the average thickness of the base portion may be 0.3 mm or less.
  • the bag-shaped separator may be provided with a rib (second rib) protruding from the second surface toward the negative electrode plate, and the second rib may be provided. It does not have to be provided.
  • the average height of the second rib may be 0.3 mm or less or 0.1 mm or less.
  • Lead-acid batteries E1 to E16, R1 to R5, and C1 to C4 >> (1) Preparation of lead-acid battery (a) Preparation of negative electrode plate Lead powder as a raw material, polymer compounds shown in Tables 2 to 4, sodium lignin sulfonate, carbonaceous material (carbon black), and barium sulfate are used. , Mix with an appropriate amount of sulfuric acid aqueous solution to obtain a negative electrode paste. At this time, the content of the polymer compound in the negative electrode electrode material obtained by the above-mentioned procedure is the value shown in the table, the content of sodium lignin sulfonate is 0.1% by mass, and the content of carbon black is contained.
  • 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 oxyethylene unit is in the range of the chemical shift of 3.2 ppm or more and 3.8 ppm or less in the 1 H-NMR spectrum of the polymer compound measured by the above-mentioned procedure. A peak derived from -CH 2- is observed.
  • the 1 H-NMR spectrum of the polymer compound measured by the above procedure shows that the oxypropylene unit is in the range of a chemical shift of 3.2 ppm or more and 3.42 ppm or less.
  • (B) Preparation of positive electrode plate The lead powder as a raw material is mixed with an aqueous sulfuric acid solution to obtain a positive electrode paste.
  • the positive electrode paste is filled in the mesh portion of the expanded lattice made of Pb or Pb alloy as the positive electrode current collector and aged and dried to obtain an unchemical positive electrode plate.
  • the Pb alloy constituting the positive electrode current collector a Pb—Ca—Sn-based alloy is used.
  • the content of Sn in the positive electrode current collector made of Pb which is obtained by the above-mentioned procedure, is 0% by mass
  • the content of Sn in the positive electrode current collector made of Pb—Ca—Sn alloy is 0% by mass. Is 0.8% by mass or 1.6% by mass.
  • (C) Preparation of test battery As a test battery used for evaluating the life performance and the amount of overcharged electricity in the deep discharge cycle test, a lead storage battery having a rated voltage of 2 V / cell and a rated capacity of 30 Ah is manufactured. As a test battery used for evaluating the service life performance in the high temperature cycle test, a lead storage battery having a rated voltage of 12 V and a rated capacity of 59 Ah is manufactured.
  • the electrode plate group is composed of 7 positive electrode plates and 8 negative electrode plates. One electrode plate of the positive electrode plate and the negative electrode plate is housed in a bag-shaped separator and alternately laminated with the other electrode plate to form a group of electrode plates.
  • a bag-shaped separator formed of a polyethylene microporous membrane having ribs protruding toward the positive electrode plate is used.
  • the average thickness of the base portion of the bag-shaped separator is 0.25 mm, and the average height of the ribs is 0.55 mm.
  • the electrode plates shown in Tables 2 to 4 are housed in a bag-shaped separator.
  • the electrode plate group is housed in a polypropylene electric tank together with an electrolytic solution (sulfuric acid aqueous solution), and chemical formation is performed in the electric tank to produce a liquid-type lead-acid battery. Due to the chemical formation, the lead-acid battery is almost fully charged.
  • the specific gravity of the electrolytic solution at 20 ° C. in a fully charged lead-acid battery is 1.28.
  • (B) Life performance in high temperature cycle test Using the test battery, the life performance in the high temperature cycle test is evaluated by the procedure described above. The life performance of each lead-acid battery in the deep discharge cycle test is evaluated by the ratio when the number of cycles at the time when the lead-acid battery C1 reaches the end of its life is 100. The larger this ratio is, the better the life performance is.
  • (C) Overcharged electricity amount Using the test battery, measure the integrated value of the overcharged electricity amount by the procedure described above. The overcharged electricity amount of each lead storage battery is evaluated at a ratio when the integrated value (Ah) of the overcharged electricity amount of the lead storage battery C1 is 100.
  • Tables 2 to 4 also show the Sn content in the positive electrode current collector.
  • Table 4 also shows the polymer compounds Mn and HLB.
  • Mn of polypropylene glycol (PPG) is Mn obtained by the above-mentioned procedure.
  • the Mn of the etherified and esterified polyethylene glycol is the Mn of the esterified or etherified material used in the preparation of the negative electrode material.
  • a part of the data in Table 2 is excerpted and shown in Table 3.
  • E1 to E16 are examples.
  • R1 to R5 are reference examples.
  • C1 to C4 are comparative examples.
  • the life performance in the deep discharge cycle test is improved, but the life performance in the high temperature cycle test is lowered as compared with the case where the negative electrode plate is housed. (Comparison between C1 and C2).
  • the life performance in the high temperature cycle test is improved to some extent while maintaining the high life performance in the deep discharge cycle test (comparison between C2 and C3 and C4).
  • the life performance in the deep discharge cycle test is improved to some extent by containing the polymer compound in the negative electrode material, but the life performance in the high temperature cycle test is lowered (C2 and R3). Contrast).
  • the results of the life performance in the deep discharge cycle test correspond to the difference in the density of the electrolytic solution, and it is suggested that the difference in the density is small and the life performance in the deep discharge cycle test is improved when the stratification is suppressed. There is.
  • the content of the polymer compound in the negative electrode electrode material is preferably 20 ppm or more or 30 ppm or more, and even 70 ppm or more or 100 ppm or more. good. From the viewpoint of ensuring higher life performance in the deep discharge cycle test, 550 ppm or less or 500 ppm or less is preferable.
  • the Sn content in the positive electrode current collector is as small as less than 3% by mass, the growth of the positive electrode current collector is usually remarkable, and the service life performance in the high temperature cycle test is lowered. However, even if the Sn content is in such a range, excellent life performance in the high temperature cycle test can be ensured as shown in Table 2 (E1 to E11). From the viewpoint of ensuring higher life performance in the high temperature cycle test, the Sn content in the positive electrode current collector is preferably 0.5% by mass or more, preferably 0.7% by mass or more or 0.8% by mass or more. More preferred.
  • HLB is 4 or more (or 4.3 or more) 9 or less, or 4 or more (or 4.3 or more) 8.5 or less. preferable.
  • the lead-acid battery according to the first aspect and the second aspect of the present invention can be suitably used as, for example, a power source for starting a vehicle (automobile, motorcycle, etc.), a power source for an industrial power storage device such as an electric vehicle (forklift, etc.). .. It should be noted that these uses are merely examples and are not limited to these uses.
  • Electrode plate group 12 Electric tank 13: Partition 14: Cell chamber 15: Lid 16: Positive electrode terminal 17: Negative electrode terminal 18: Liquid spout

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
PCT/JP2021/039744 2020-11-27 2021-10-28 鉛蓄電池 Ceased WO2022113624A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP21897600.9A EP4254549A4 (en) 2020-11-27 2021-10-28 LEAD-ACID BATTERY
JP2022565145A JP7747004B2 (ja) 2020-11-27 2021-10-28 鉛蓄電池

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-197587 2020-11-27
JP2020197587 2020-11-27

Publications (1)

Publication Number Publication Date
WO2022113624A1 true WO2022113624A1 (ja) 2022-06-02

Family

ID=81755776

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/039744 Ceased WO2022113624A1 (ja) 2020-11-27 2021-10-28 鉛蓄電池

Country Status (3)

Country Link
EP (1) EP4254549A4 (https=)
JP (1) JP7747004B2 (https=)
WO (1) WO2022113624A1 (https=)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5147237A (https=) * 1974-10-18 1976-04-22 Yuasa Battery Co Ltd
JPS60182662A (ja) * 1984-02-28 1985-09-18 Japan Storage Battery Co Ltd 鉛蓄電池
JPH05307949A (ja) 1992-04-30 1993-11-19 Matsushita Electric Ind Co Ltd 鉛蓄電池
JPH09147874A (ja) 1995-11-24 1997-06-06 Shin Kobe Electric Mach Co Ltd 鉛蓄電池用負極板及び鉛蓄電池
JPH09147869A (ja) * 1995-11-17 1997-06-06 Shin Kobe Electric Mach Co Ltd 鉛蓄電池
JP2000149981A (ja) 1998-11-02 2000-05-30 Jec Service Kk 鉛蓄電池および鉛蓄電池用添加剤
CN101937996A (zh) * 2010-08-26 2011-01-05 风帆股份有限公司 电动助力车用胶体铅酸蓄电池负极铅膏及制备方法
WO2019087683A1 (ja) * 2017-10-31 2019-05-09 株式会社Ｇｓユアサ 鉛蓄電池
WO2020241878A1 (ja) * 2019-05-31 2020-12-03 株式会社Ｇｓユアサ 鉛蓄電池

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5147237A (https=) * 1974-10-18 1976-04-22 Yuasa Battery Co Ltd
JPS60182662A (ja) * 1984-02-28 1985-09-18 Japan Storage Battery Co Ltd 鉛蓄電池
JPH05307949A (ja) 1992-04-30 1993-11-19 Matsushita Electric Ind Co Ltd 鉛蓄電池
JPH09147869A (ja) * 1995-11-17 1997-06-06 Shin Kobe Electric Mach Co Ltd 鉛蓄電池
JPH09147874A (ja) 1995-11-24 1997-06-06 Shin Kobe Electric Mach Co Ltd 鉛蓄電池用負極板及び鉛蓄電池
JP2000149981A (ja) 1998-11-02 2000-05-30 Jec Service Kk 鉛蓄電池および鉛蓄電池用添加剤
CN101937996A (zh) * 2010-08-26 2011-01-05 风帆股份有限公司 电动助力车用胶体铅酸蓄电池负极铅膏及制备方法
WO2019087683A1 (ja) * 2017-10-31 2019-05-09 株式会社Ｇｓユアサ 鉛蓄電池
WO2020241878A1 (ja) * 2019-05-31 2020-12-03 株式会社Ｇｓユアサ 鉛蓄電池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4254549A4

Also Published As

Publication number Publication date
EP4254549A4 (en) 2024-09-11
JP7747004B2 (ja) 2025-10-01
EP4254549A1 (en) 2023-10-04
JPWO2022113624A1 (https=) 2022-06-02

Similar Documents

Publication Publication Date Title
WO2020241878A1 (ja) 鉛蓄電池
JP7173322B2 (ja) 鉛蓄電池
WO2022113633A1 (ja) 鉛蓄電池
JP7501528B2 (ja) 鉛蓄電池
JP7677347B2 (ja) 鉛蓄電池
JP7661978B2 (ja) 鉛蓄電池
WO2022113624A1 (ja) 鉛蓄電池
JP7718427B2 (ja) 鉛蓄電池
JP7786391B2 (ja) 鉛蓄電池
JP7757982B2 (ja) 鉛蓄電池
JP7694582B2 (ja) 鉛蓄電池
WO2020241883A1 (ja) 鉛蓄電池
JP7819461B2 (ja) 鉛蓄電池
JP7798037B2 (ja) 鉛蓄電池
JP7687348B2 (ja) 鉛蓄電池
WO2020241886A1 (ja) 鉛蓄電池
JP7679841B2 (ja) 鉛蓄電池
JP7452538B2 (ja) 鉛蓄電池
JP2022085747A (ja) 鉛蓄電池
JP2025039251A (ja) 液式鉛蓄電池
JP2022085749A (ja) 鉛蓄電池
WO2022113628A1 (ja) 鉛蓄電池
JP2022085745A (ja) 鉛蓄電池
WO2020241879A1 (ja) 鉛蓄電池
JP2022085746A (ja) 鉛蓄電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21897600

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022565145

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2021897600

Country of ref document: EP

Effective date: 20230627