WO2020241883A1 - 鉛蓄電池 - Google Patents

鉛蓄電池 Download PDF

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Publication number
WO2020241883A1
WO2020241883A1 PCT/JP2020/021480 JP2020021480W WO2020241883A1 WO 2020241883 A1 WO2020241883 A1 WO 2020241883A1 JP 2020021480 W JP2020021480 W JP 2020021480W WO 2020241883 A1 WO2020241883 A1 WO 2020241883A1
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Prior art keywords
positive electrode
negative electrode
lead
less
polymer compound
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PCT/JP2020/021480
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English (en)
French (fr)
Japanese (ja)
Inventor
泰紀 溝口
宏樹 籠橋
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GS Yuasa International Ltd
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GS Yuasa International Ltd
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Priority to GB2115811.8A priority Critical patent/GB2597869B/en
Priority to US17/608,870 priority patent/US11735742B2/en
Priority to CN202080040487.XA priority patent/CN113994521A/zh
Priority to JP2021521914A priority patent/JP7528932B2/ja
Publication of WO2020241883A1 publication Critical patent/WO2020241883A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—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
    • H01M10/121—Valve regulated lead acid batteries [VRLA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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 and industrial use.
  • Lead-acid batteries include a negative electrode plate, a positive electrode plate, a separator (or mat), an electrolytic solution, and the like.
  • Additives may be added to the constituent members of the lead-acid battery from the viewpoint of imparting various functions.
  • Patent Document 1 proposes a lead-acid battery characterized in that a copolymer of propylene oxide and ethylene oxide is added to a negative electrode plate active material in combination with lignin sulfonate.
  • Patent Document 2 is characterized in that an activator containing an organic polymer is sealed in a small airtight container having a dehiscence mechanism into an electric tank, and the small airtight container is attached to the electric tank or a lid. Storage batteries have been proposed.
  • Patent Document 3 includes a plurality of fibers coated with a size composition, a binder composition, and one or more kinds of additives, and the additives include rubber additives, rubber derivatives, aldehydes, and metal salts.
  • the additive comprises one or more of ethylene-propylene oxide block copolymer, sulfuric acid ester, sulfonic acid ester, phosphoric acid ester, polyacrylic acid, polyvinyl alcohol, lignin, phenol aldehyde resin, cellulose, wood flour and the like. Fiber-attached mats that can function to reduce water loss in lead storage batteries have been proposed.
  • Patent Document 4 describes a control valve type lead-acid battery having a positive electrode current collector, a positive electrode active material, a negative electrode current collector, a negative electrode active material, and a liquid retaining material.
  • the positive electrode current collector is a rolled sheet of a lead alloy.
  • the average layer spacing of the layered current collector structure in the cross section in the thickness direction of the current collector is 25 ⁇ m or more and 180 ⁇ m or less, and the positive electrode current collector is Pb-Ca-Sn. It is composed of an alloy, and when the Ca content is x and the Sn content is y in mass% units, 0.03 ⁇ x ⁇ 0.09 and 9.16x + 0.525 ⁇ y ⁇ 2.0.
  • the corrosion resistance of the positive electrode current collector has a large effect on the life of the float when charging.
  • the standby lead-acid battery is continuously charged at a constant voltage, so that the positive electrode is easily exposed to a noble potential and corrosion of the positive electrode current collector is likely to proceed.
  • One aspect of the present invention includes a positive electrode plate, a negative electrode plate, an electrolytic solution, and a polymer compound
  • the positive electrode plate includes a positive electrode current collector and a positive electrode material
  • the negative electrode plate is a negative electrode collector.
  • the electric body and the negative electrode electrode material are provided, and the Ca content of the positive electrode current collector is 0.13% by mass or less, and the polymer compound is 3.2 ppm or more in a chemical shift of 1 H-NMR spectrum.
  • the present invention relates to a lead storage battery having a peak in the range of 8 ppm or less.
  • Another aspect of the present invention includes a positive electrode plate, a negative electrode plate, an electrolytic solution, and a polymer compound, the positive electrode plate comprises a positive electrode current collector and a positive electrode material, and the negative electrode plate comprises a negative electrode.
  • the lead is provided with a current collector and a negative electrode material, the positive electrode current collector has a Ca content of 0.13% by mass or less, and the polymer compound contains a repeating structure of an oxyC 2-4 alkylene unit. Regarding storage batteries.
  • FIG. 2 is a cross-sectional view taken along the line IIB-IIB of the lead-acid battery of FIG. 2A.
  • the lead-acid battery according to the embodiment of the present invention includes a positive electrode plate, a negative electrode plate, an electrolytic solution, and a polymer compound.
  • the positive electrode plate includes a positive electrode current collector and a positive electrode material.
  • the negative electrode plate includes a negative electrode current collector and a negative electrode material.
  • the Ca content of the positive electrode current collector is 0.13% by mass or less.
  • 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.
  • the polymeric compound comprises a repeating structure of oxyC 2-4 alkylene units.
  • the peak appearing in the range of 3.2 ppm or more and 3.8 ppm or less in the 1 H-NMR spectrum is derived from the oxyC 2-4 alkylene unit.
  • these polymer compounds are collectively referred to simply as "polymer compounds”.
  • the 1 H-NMR spectrum is measured using deuterated chloroform as a solvent.
  • the battery life during float charging is significantly improved.
  • the polymer compound has the effect of increasing the hydrogen overvoltage in the negative electrode plate and suppressing the decomposition reaction of water during float charging. Further, as the hydrogen overvoltage of the negative electrode plate rises, the positive electrode potential at the time of float charging shifts to a low level. Therefore, it is advantageous in suppressing corrosion of the positive electrode current collector. Further, when the Ca content of the positive electrode current collector is 0.13% by mass or less, corrosion of the positive electrode current collector is further suppressed.
  • the reason why the battery life during float charging is remarkably improved is that among the effects on the battery life, the influence of corrosion of the positive electrode current collector is small and the influence of the decrease in the electrolytic solution is relatively large. It is inferred that.
  • the progress of decrease of the electrolytic solution is usually slow.
  • the presence of the polymer compound suppresses the decomposition reaction of water in the negative electrode plate, so that the decrease in the electrolytic solution is more gradual. From the above, it is considered that the battery life, which is mainly due to the decrease in the electrolytic solution, cannot be easily reached. That is, even when the same positive electrode plate is used, the life of the lead-acid battery containing the polymer compound is significantly improved as compared with the lead-acid battery containing no polymer compound.
  • the Ca content of the positive electrode current collector is 0.07% by mass or less, the synergistic effect of improving the corrosion resistance of the positive electrode current collector and suppressing the decrease of the electrolytic solution by the polymer compound is enhanced, and the battery life is extended. Greatly improved.
  • the polymer compound is used and the Ca content of the positive electrode current collector is less than 0.01% by mass, the battery life is further significantly improved.
  • the Ca content of the positive electrode current collector is less than 0.01% by mass, corrosion starting from the grain boundaries of the metal crystal grains (so-called grain boundary corrosion) is less likely to proceed, so that the effect of improving battery life is remarkable. It is thought that it will be.
  • the improvement in the corrosion resistance of the positive electrode current collector by reducing the Ca content is not so remarkable. Nevertheless, the improvement in life during float charging is remarkable. The reason is not clear, but it is thought that the influence of the polymer compound becomes more remarkable.
  • a positive electrode current collector having a Ca content of more than 0.13% by mass is used, the influence of corrosion of the positive electrode current collector is extremely large among the effects on the battery life, and when a polymer compound is used. Even so, the effect of improving the life is not seen.
  • the lead alloy constituting the positive electrode current collector or the positive electrode current collector may further contain Sn from the viewpoint of improving the corrosion resistance of the positive electrode current collector, for example, Pb-Ca-. It may be composed of a Sn alloy.
  • the positive electrode current collector may contain Sn, but when the Ca content is 0.13% by mass or less, the Sn content is preferably 3.0% by mass or less. When the Ca content is less than 0.01% by mass, the Sn content is preferably 0.5% by mass or less, more preferably less than 0.01% by mass.
  • the decomposition reaction of water is greatly affected by the reduction reaction of hydrogen ions at the interface between lead and the electrolytic solution.
  • the water decomposition reaction is reduced because the surface of lead, which is the negative electrode active material, is covered with the polymer compound, which raises the hydrogen overvoltage and causes a side reaction in which hydrogen is generated from protons during overcharging. It is thought that it is hindered. Therefore, in order to enhance the effect of suppressing the decomposition reaction of water during float charging, it is preferable that the polymer compound is contained in at least the negative electrode material.
  • the polymer compound has an oxyC 2-4 alkylene unit, it is easy to form a linear structure, so that it is difficult to stay in the negative electrode material and it is expected that the polymer compound is easily diffused into the electrolytic solution.
  • the negative electrode material contains a very small amount of polymer compound, the effect of reducing the decomposition reaction of water during float charging can be obtained.
  • the oxyC 2-4 alkylene unit exerts a high adsorption action on lead.
  • the polymer compound contained in the negative electrode material exhibits the effect of reducing the decomposition reaction of water during float charging even in a very small amount. This suggests that the polymer compound is thinly spread on the surface of lead and suppresses the reduction reaction of hydrogen ions in a wide range of the lead surface. This is consistent with the fact that polymer compounds tend to have a linear structure. By suppressing the decomposition reaction of water during float charging, it is possible to reduce liquid reduction, which is advantageous for extending the life of lead-acid batteries.
  • an aqueous sulfuric acid solution is used as the electrolytic solution. Therefore, when an organic additive (oil, polymer, organic shrink-proofing agent, etc.) is contained in the negative electrode material, it elutes into the electrolytic solution and becomes lead. It becomes difficult to balance with adsorption. For example, if an organic additive having low adsorptivity to lead is used, it is likely to elute into the electrolytic solution. On the other hand, when an organic additive having high adsorptivity to lead is used, it becomes difficult to attach the organic additive thinly to the surface of lead, and the organic additive tends to be unevenly distributed in the pores of lead.
  • an organic additive oil, polymer, organic shrink-proofing agent, etc.
  • 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 peaks of 3.2 ppm ⁇ 3.8 ppm, and the integral value of the peak, -CH 2 bonded to an oxygen atom - and the integral value of the peak of the hydrogen atoms of the group, an oxygen atom The ratio of the peak of the hydrogen atom of the -CH ⁇ group bonded to the group to the integrated value 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 lead surface is easily covered thinly by easily adsorbing to lead and easily forming a linear structure.
  • 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 it becomes easier to adsorb to lead and it becomes easier to thinly cover the lead surface by easily taking a linear structure.
  • a polymer compound is defined to have a repeating unit of oxyC 2-4 alkylene unit and / or have a number average molecular weight (Mn) of 500 or more.
  • the oxyC 2-4 alkylene unit is a unit represented by —OR 1 ⁇ (R 1 represents a C 2-4 alkylene group).
  • Polymeric compounds include at least one selected from the group consisting of esters of hydroxy compounds having a repeating structure of ethers of hydroxy compounds, and oxy C 2-4 alkylene unit having a repeating structure oxy C 2-4 alkylene unit It may be.
  • 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 C 2-4 alkylene oxide adduct of a polyol.
  • the repeating structure of the oxyC 2-4 alkylene unit may include at least the repeating structure of the oxypropylene unit (-O-CH (-CH 3 ) -CH 2- ). It is considered that such a polymer compound has a high adsorptivity to lead, yet easily spreads thinly on the lead surface, and has an excellent balance between them. Therefore, the effect of suppressing the decomposition reaction of water during float charging is enhanced.
  • the polymer compound has high adsorptivity to lead and can cover the lead surface thinly. Therefore, even if the content of the polymer compound in the negative electrode material is small, a wide range of the lead surface can be obtained. Can suppress the reduction reaction of hydrogen ions.
  • the content of the polymer compound in the negative electrode electrode material is preferably 5 ppm or more in terms of mass ratio (that is, based on mass), and may be 15 ppm or more.
  • the content of the polymer compound in the negative electrode material is preferably 400 ppm or less, and may be 250 ppm or less in terms of mass ratio.
  • the content of the polymer compound in the negative electrode electrode material is preferably 5 ppm or more and 400 ppm or less in terms of mass ratio, and may be 5 ppm or more and 250 ppm or less, 15 ppm or more and 400 ppm or less, and 15 ppm or more and 250 ppm or less.
  • the polymer compound may be contained in the electrolytic solution.
  • the concentration of the polymer compound in the electrolytic solution may be, for example, 500 ppm or less, more than 8 ppm, 400 ppm or less, or 15 ppm or more and 360 ppm or less in terms of mass ratio. Even when the electrolytic solution contains a polymer compound, the effect of improving the life during float charging can be obtained by controlling the Ca content of the positive electrode current collector to 0.13% by mass or less.
  • the polymer compound preferably contains a compound having an Mn of at least 500 or more.
  • the adsorptivity to lead is enhanced, the effect of suppressing the reduction reaction of hydrogen ions is further enhanced, and the hydrogen gas collides with the negative electrode material.
  • the resulting structural change in the negative electrode active material can also be suppressed.
  • the polymer compound is preferably contained in the negative electrode material, but when the lead-acid battery is manufactured, it is included in any of the components of the lead-acid battery (for example, the negative electrode plate, the positive electrode plate, the electrolytic solution, and / or the separator). It may be contained.
  • 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 content of the polymer compound in the negative electrode material and the concentration of the polymer compound in the electrolytic solution shall be obtained for the fully charged lead-acid battery, respectively.
  • the lead-acid battery may be either a control valve type (sealed type) lead-acid battery or a liquid type (vent type) lead-acid battery.
  • the fully charged state of the liquid lead-acid battery is defined by the definition of JIS D 5301: 2006. More specifically, electrolysis of a lead-acid battery with a current (A) 0.2 times the value described as the rated capacity (Ah), which is measured every 15 minutes and converted to the terminal voltage during charging or 20 ° C.
  • a fully charged state is defined as a state in which the liquid density is charged three times in a row until it shows a constant value with three significant figures.
  • the fully charged state is a current (A) that is 0.2 times the value described as the rated capacity (Ah) in an air tank at 25 ° C. ⁇ 2 ° C.
  • a constant current constant voltage charge of .23 V / cell is performed, and the charge is completed when the charge current at the time of constant voltage charge becomes 0.005 times the value described as the rated capacity (Ah).
  • the numerical value described as the rated capacity is a numerical value in which the unit is Ah.
  • the unit of current set based on the numerical value described as the rated capacity is A.
  • 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 number average molecular weight Mn is determined by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the standard substance used to determine Mn is polyethylene glycol.
  • the negative electrode plate usually includes a negative electrode current collector in addition to the negative electrode material.
  • the negative electrode electrode material is a negative electrode plate obtained by removing the negative electrode current collector. Members such as mats and pacing papers may be attached to the negative electrode plate. Since such a member (pasting member) is used integrally with the negative electrode plate, it is included in the negative electrode plate.
  • the negative electrode material is the one excluding the negative electrode current collector and the sticking member.
  • 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 negative electrode lattice 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 alloy, Pb-Ca-based alloy, and Pb-Ca-Sn-based alloy. These leads or lead alloys 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 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 the selvage portion of the negative electrode current collector. The surface layer of the selvage portion may contain Sn or a Sn alloy.
  • 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 unchemicald negative electrode plate, and then forming an unchemicald negative electrode plate.
  • the negative electrode paste is prepared by adding water and sulfuric acid to lead powder, an organic shrink-proofing agent, and various additives as necessary, and kneading them. At the time of aging, it is preferable to ripen the unchemicald negative electrode plate at a temperature higher than room temperature and high humidity.
  • the negative electrode material contains the above polymer compound.
  • the negative electrode material further contains a negative electrode active material (lead or lead sulfate) that develops a capacity by a redox reaction.
  • the negative electrode material may contain shrink-proofing agents, carbonaceous materials, and / or 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 unchemicald 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 oxyC 2-4 alkylene unit, or may contain 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 repeating structures.
  • 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 C 2- of a polyol. (4 alkylene oxide adduct, etc.), etherified products or esterified products of these hydroxy compounds, and the like.
  • copolymer examples include a copolymer containing different oxyC 2-4 alkylene units, a poly C 2-4 alkylene glycol alkyl ether, a poly C 2-4 alkylene glycol ester of a carboxylic acid, and the like.
  • 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, etc.) and the like are preferable, and an aliphatic polyol is particularly preferable.
  • the aliphatic polyol include an aliphatic diol and a polyol above triol (for example, glycerin, trimethylolpropane, pentaerythritol, sugar alcohol, etc.).
  • Examples of the aliphatic diol include alkylene glycol having 5 or more carbon atoms.
  • Alkylene glycol for example, be a C 5 ⁇ 14 alkylene glycol or C 5-10 alkylene glycol.
  • sugar alcohols include erythritol, xylitol, mannitol, sorbitol and the like.
  • the alkylene oxide adduct of the polyol 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 easily has a linear structure, the polyol is preferably a diol.
  • the etherified product is composed of at least a part of the terminal -OH group (hydrogen atom of the terminal group and the oxygen atom bonded to the hydrogen atom) of the hydroxy compound having the repeating structure of the above oxyC 2-4 alkylene unit. -OH group) having etherified -OR 2 group (wherein, 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. For example, in one end of the main chain is -OH groups of a linear polymer compound, the other end may be an -OR 2 group.
  • the esterified product is composed of at least a part of a terminal-OH group (a hydrogen atom of the terminal group and an oxygen atom bonded to the hydrogen atom) 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, etc.) as a substituent.
  • the number of carbon atoms of the aliphatic hydrocarbon group as a substituent may be, for example, 1 to 20, 1 to 10, or 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 number of carbon atoms of the alicyclic hydrocarbon group may be 10 or less or 8 or less.
  • the number of carbon atoms of the alicyclic hydrocarbon group is, for example, 5 or more, and may be 6 or more.
  • the number of carbon atoms of the alicyclic hydrocarbon group may be 5 (or 6) or more and 16 or less, 5 (or 6) or more and 10 or less, or 5 (or 6) or more and 8 or less.
  • Examples of the alicyclic hydrocarbon group include a cycloalkyl group (cyclopentyl group, cyclohexyl group, cyclooctyl group, etc.), a cycloalkenyl group (cyclohexenyl group, cyclooctenyl group, etc.) and the like.
  • the alicyclic hydrocarbon group also includes the hydrogenated additive of the above aromatic hydrocarbon group.
  • an aliphatic hydrocarbon group is preferable from the viewpoint that the polymer compound is thin and easily adheres to the lead surface.
  • the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and a dienyl group.
  • the aliphatic hydrocarbon group may be linear or branched chain.
  • the number of carbon atoms of the aliphatic hydrocarbon group may be, 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, and 3 or more for a dienyl group, depending on the type of 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, s-pentyl, Examples thereof include 3-pentyl, t-pentyl, n-hexyl, 2-ethylhexyl, n-octyl, n-decyl, i-decyl, lauryl, myristyl, cetyl, stearyl and behenyl.
  • alkenyl group examples include vinyl, 1-propenyl, allyl, palmitrail, oleyl and the like.
  • 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. It may be.
  • esters of hydroxy compounds having a repeating structure of ethers of hydroxy compounds and / or oxy-C 2-4 alkylene unit having a repeating structure oxy C 2-4 alkylene unit, higher reduction solution
  • the suppressing effect can be ensured.
  • the negative electrode material may contain one kind of polymer compound or two or more kinds.
  • the repeating structure of oxyC 2-4 alkylene includes at least the repeating structure of the oxypropylene unit.
  • 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 such a polymer compound include polypropylene glycol, a copolymer containing a repeating structure of oxypropylene, a propylene oxide adduct of the above-mentioned polyol, and an etherified product or an esterified product thereof.
  • Examples of the copolymer include an oxypropylene-oxyalkylene copolymer (where oxyalkylene is C 2-4 alkylene other than oxypropylene), polypropylene glycol alkyl ether, polypropylene glycol ester of carboxylic acid and the like.
  • Examples of the oxypropylene-oxyalkylene copolymer include an oxypropylene-oxyethylene copolymer and an oxypropylene-oxytrimethylene copolymer.
  • the oxypropylene-oxyalkylene copolymer may be a block copolymer.
  • the proportion of the oxypropylene unit is, for example, 5 mol% or more, and may be 10 mol% or more or 20 mol% or more.
  • the polymer compound preferably contains a large amount of oxyC 2-4 alkylene unit from the viewpoint of increasing the adsorptivity to lead and facilitating the formation of a linear structure.
  • Such polymer compounds include, for example, an oxygen atom attached to a terminal group and an -CH 2 -group and / or -CH ⁇ group attached to an oxygen atom.
  • the ratio of the peak of hydrogen atom to the integral value of the peak becomes large.
  • This ratio is, for example, 50% or more, may be 85% or more, and more preferably 90% or more.
  • the polymer compound having an -OH group at the terminal, -CH 2 bonded to an oxygen atom of the -OH group - if having a group or -CH ⁇ group the 1 H-NMR spectrum, -CH 2 - group
  • the peak of the hydrogen atom of the -CH ⁇ group has a chemical shift in the range of more than 3.8 ppm and 4.0 ppm or less.
  • the polymer compound may contain a compound having a Mn of 500 or more, a compound having a Mn of 600 or more, or a compound having a Mn of 1000 or more.
  • the Mn of such a compound is, for example, 20000 or less, and may be 15000 or less or 10000 or less.
  • the Mn of the above compound is preferably 5000 or less, and may be 4000 or less or 3500 or less, in that the polymer compound is easily retained in the negative electrode material and spreads thinner on the lead surface.
  • the Mn of the above compounds is 500 or more (or 600 or more) 20000 or less, 500 or more (or 600 or more) 15000 or less, 500 or more (or 600 or more) 10000 or less, 500 or more (or 600 or more) 5000 or less, 500 or more ( Or 600 or more) 4000 or less, 500 or more (or 600 or more) 3500 or less, 1000 or more and 20000 or less (or 15000 or less), 1000 or more and 10000 or less (or 5000 or less), or 1000 or more and 4000 or less (or 3500 or less). May be good.
  • the polymer compound preferably contains a compound having at least Mn of 1000 or more.
  • the Mn of such a compound may be 1000 or more and 20000 or less, 1000 or more and 15000 or less, or 1000 or more and 10000 or less.
  • the Mn of the above compound is preferably 1000 or more and 5000 or less, may be 1000 or more and 4000 or less, and is 1000 or more and 3500 or less in that the compound can be easily retained in the negative electrode material and spreads thinner on the lead surface. May be good.
  • the battery life during float charging in a high temperature environment can be significantly improved.
  • two or more compounds having different Mns may be used. That is, the polymer compound may have a plurality of Mn peaks in the distribution of molecular weight.
  • the content of the polymer compound in the negative electrode electrode material may be, for example, 5 ppm or more, or 50 ppm or more, on a mass basis.
  • the content (mass basis) of the polymer compound in the negative electrode electrode material is, for example, 400 ppm or less, 360 ppm or less, 350 ppm or less, or 250 ppm or less.
  • the content of the polymer compound is 400 ppm or less, the surface of lead is suppressed from being excessively covered with the polymer compound.
  • the negative electrode material can include a shrink-proofing agent.
  • an organic shrink proofing agent is preferable.
  • the organic shrinkage proofing agent lignins and / or synthetic organic shrinkage proofing agents may be used.
  • lignins include lignin and lignin derivatives.
  • the lignin derivative include lignin sulfonic acid or a salt thereof (alkali metal salt (sodium salt, etc.), etc.).
  • Organic shrink proofing agents are usually roughly classified into lignins and synthetic organic shrink proofing agents. It can be said that the synthetic organic shrinkage proofing agent is an organic shrinkage proofing agent other than lignins.
  • 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 element as a sulfur-containing group.
  • the sulfur-containing groups a sulfonic acid group or a sulfonyl group in a stable form is preferable.
  • the sulfonic acid group may be present in the acid form or in the salt form such as the Na salt.
  • the negative electrode material may contain one type of shrink-proofing agent, or may contain two or more types.
  • the organic shrinkage proofing agent it is 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 an aldehyde (for example, formaldehyde) and / or a condensate thereof).
  • the organic shrink 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.
  • the organic shrinkage proofing agent one synthesized by a known method may be used, or a commercially available product may be used.
  • a condensate containing a unit of an aromatic compound can be obtained, for example, by reacting an aromatic compound with an aldehyde compound.
  • an aromatic compound containing a sulfur element for example, bisphenol S
  • an organic shrinkage proofing agent containing a sulfur element can be obtained.
  • the sulfur element content in the organic shrink-proofing agent can be adjusted by adjusting the amount of sulfites and / or the amount of aromatic compounds containing sulfur elements. When other raw materials are used, it can be obtained according to this method.
  • 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, etc.).
  • Examples of such a structure include a bisarene structure (biphenyl, bisphenylalkane, bisphenylsulfone, etc.).
  • Examples of the aromatic compound include the above-mentioned compounds having an aromatic ring and a hydroxy group and / or 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 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 (salt with an anion). Examples of Me include alkali metals (Li, K, Na, etc.) and Group 2 metals of the periodic table (Ca, Mg, etc.).
  • 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.), Hydroxyarene compounds (hydroxynaphthalene compounds, phenol compounds, etc.), aminoarene compounds (aminonaphthalene compounds, aniline compounds (aminobenzenesulfonic acid, alkylaminobenzenesulfonic acid, etc.), etc.) are preferable.
  • Aromatic compounds are further substituents.
  • the organic shrinkage proofing agent may contain one or more residues of these compounds.
  • 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.
  • a condensate containing at least a unit of a bisphenol compound having a sulfur-containing group when used, the effect of suppressing a decrease in low-temperature HR discharge performance after a high-temperature light load test can be enhanced.
  • 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 the above-mentioned unit of a bisalene compound and a unit of a monocyclic aromatic compound (such as a hydroxyarene compound and / or an aminoarene compound). At least one may be used.
  • the organic shrink-proofing agent may contain at least a condensate containing a unit of a bisalene compound and a unit of a monocyclic aromatic compound (particularly, a hydroxyarene compound). Examples of such a condensate include a condensate of a bisarene compound and a monocyclic aromatic compound with an aldehyde compound.
  • hydroxyarene compound a phenol sulfonic acid compound (phenol sulfonic acid or a substitute thereof, etc.) 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 shrink-proofing agent contained in the negative electrode electrode material is, for example, 0.01% by mass or more, and may be 0.05% by mass or more.
  • the content of the organic shrink proofing agent is, for example, 1.0% by mass or less, and may be 0.5% by mass or less.
  • the content of the organic shrink-proofing agent contained in the negative electrode electrode material is 0.01 to 1.0% by mass, 0.05 to 1.0% by mass, 0.01 to 0.5% by mass, or 0.05 to 0.05. It may be 0.5% by mass.
  • Carbonaceous material As the carbonaceous material contained in the negative electrode material, carbon black, graphite, hard carbon, soft carbon and the like can be used. Examples of carbon black include acetylene black, ketjen black, furnace black, and lamp black.
  • the graphite may be any carbonaceous material containing a graphite-type crystal structure, and may be either artificial graphite or natural graphite. As the carbonaceous material, one kind may be used alone, or two or more kinds may be combined.
  • the content of the carbonaceous material in the negative 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 may be 0.05 to 5% by mass, 0.05 to 3% by mass, 0.10 to 5% by mass, or 0.10 to 3% by mass. ..
  • 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 3% by mass or less, and may be 2% by mass or less. These lower limit values and upper limit values can be arbitrarily combined.
  • the content of barium sulfate in the negative electrode electrode material may be 0.05 to 3% by mass, 0.05 to 2% by mass, 0.10 to 3% by mass, or 0.10 to 2% by mass.
  • Chloroform-soluble components are recovered by distilling off chloroform under reduced pressure from the chloroform solution in which the polymer compound obtained by extraction is dissolved.
  • the chloroform-soluble component is dissolved in deuterated chloroform, and the 1 H-NMR spectrum is measured under the following conditions. From this 1 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.
  • 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 (V 2 ).
  • the straight line connecting the intervals is used as the baseline.
  • the straight line connecting the two points of 3.2 ppm and 3.8 ppm in the spectrum is used as the baseline.
  • the straight line connecting the two points of 3.8 ppm and 4.0 ppm in the spectrum is used as the baseline.
  • N a is a value obtained by averaging using a molar ratio of each monomer unit contained in the structure repeated N a value of each monomer unit (mol%), M a is the monomer It is determined according to the type of unit.
  • 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 positive electrode plate of the lead storage battery includes a positive electrode current collector and a positive electrode material.
  • the positive electrode material is held in the positive electrode current collector.
  • the positive electrode material contains a positive electrode active material (lead dioxide or lead sulfate) whose capacity is developed by a redox reaction.
  • the positive electrode material may contain other additives, if necessary.
  • the positive electrode electrode material is a positive electrode plate obtained by removing a positive electrode current collector.
  • the positive electrode current collector may be formed by casting lead (Pb) or a lead alloy, or may be formed by processing a lead sheet or a lead alloy sheet. Examples of the processing method include expanding processing and punching processing. It is preferable to use a grid-shaped current collector as the positive electrode current collector because it is easy to support the positive electrode material.
  • the positive electrode current collector may be formed of pure lead, but when a lead alloy is used, for example, a Pb—Ca alloy, a Pb—Sn alloy, a Pb—Ca—Sn alloy or the like may be used. ..
  • 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 include a surface layer. The composition of the surface layer and the inner layer of the positive electrode current collector may be different. The surface layer may be formed on a part of the positive electrode current collector. The surface layer may be formed only on the lattice portion of the positive electrode current collector, only the ear portion, or only the frame bone portion.
  • the unchemicald 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.
  • the Ca content of the positive electrode current collector or the lead alloy constituting the positive electrode current collector may be, for example, 0 to 0.13% by mass, 0 to 0.13% by mass or less, and 0 to 0.07% by mass. It may be%, and it may be 0 to 0.01% by mass (or less than 0.01% by mass).
  • the Sn content of the positive electrode current collector or the lead alloy constituting the positive electrode current collector may be, for example, 0 to 3.0% by mass, 0 to 0.5% by mass or less, and 0 to 0.01% by mass. % (Or less than 0.01% by mass) may be used.
  • the Sn content is preferably 0.5% by mass or less, and may be less than 0.01% by mass.
  • the positive electrode current collector contains Ca
  • the corrosion resistance of the alloy constituting the positive electrode current collector is improved by including Sn.
  • the positive electrode current collector contains 0.01% by mass or more of Ca
  • the lower limit of the Sn content of the positive electrode current collector may be 0.5% by mass.
  • the positive electrode plate may be attached to the positive electrode plate. Since such a member (pasting member) is used integrally with the positive electrode plate, it is included in the positive electrode plate. Further, when the positive electrode plate includes such a member, the positive electrode electrode material is a paste type positive electrode plate obtained by removing the positive electrode current collector and the sticking member from the positive electrode plate.
  • the positive electrode plate can be formed by applying or filling a positive electrode paste to a positive electrode current collector, aging and drying to produce an unchemicald negative electrode plate, and then forming an unchemicald positive electrode plate.
  • the positive electrode paste is prepared by adding additives to lead powder as needed, and further adding water and sulfuric acid and kneading them. At the time of aging, it is preferable to ripen the unchemical positive electrode plate at a temperature higher than room temperature and high humidity.
  • the quantification of Sn and Ca contained in the positive electrode current collector can be analyzed according to, for example, the lead separation inductively coupled plasma emission spectroscopy described in JIS H2105.
  • JIS H2105. When analyzing the content of elements contained in the positive electrode current collector of the positive electrode plate taken out from the lead storage battery, first vibrate the positive electrode plate to remove the positive electrode material from the positive electrode current collector, and then use a ceramic knife. The positive electrode material remaining around the positive electrode current collector is removed, and a part of the positive electrode current collector having a metallic luster is collected as a sample. The collected sample is decomposed with tartaric acid and dilute nitric acid to obtain an aqueous solution.
  • Hydrochloric acid is added to the aqueous solution to precipitate lead chloride, which is filtered and the filtrate is collected.
  • an ICP emission spectroscopic analyzer for example, ICPS-8000 manufactured by Shimadzu Corporation
  • the Sn and Ca concentrations in the filtrate are analyzed by the calibration curve method, and the Sn content and Ca per mass of the positive electrode current collector are analyzed. Convert to content.
  • the negative electrode plate and the positive electrode plate are formed by immersing the electrode plate group including the unchemicald negative electrode plate and the positive electrode plate in the electrolytic solution containing sulfuric acid in the battery case of the lead storage battery, respectively. Can be done by charging. However, the chemical conversion may be carried out before assembling the lead-acid battery or the electrode plate group. Due to the chemical formation, spongy lead is produced in the negative electrode plate, and lead dioxide is produced in the positive electrode plate.
  • the separator may be in the shape of a sheet or in the shape of a bag.
  • a sheet-shaped separator may be sandwiched between the positive electrode plate and the negative electrode plate.
  • the electrode plate may be arranged so as to sandwich the electrode plate with one sheet-shaped separator in a bent state.
  • the positive electrode plate sandwiched between the bent sheet-shaped separators and the negative electrode plate sandwiched between the bent sheet-shaped separators may be overlapped, and one of the positive electrode plate and the negative electrode plate may be sandwiched between the bent sheet-shaped separators. , May be overlapped with the other electrode plate.
  • the sheet-shaped separator may be bent in a bellows shape, and the positive electrode plate and the negative electrode plate may be sandwiched between the bellows-shaped separators so that the separator is interposed between them.
  • the separator may be arranged so that the bent portion is along the horizontal direction of the lead storage battery (for example, the bent portion is parallel to the horizontal direction), and is along the vertical direction. (For example, the separator may be arranged so that the bent portion is parallel to the vertical direction).
  • recesses are alternately formed on both main surface sides of the separator.
  • the positive electrode plate is formed only in the recess on one main surface side of the separator.
  • a negative electrode plate is arranged (that is, a double separator is interposed between the adjacent positive electrode plate and the negative electrode plate).
  • a separator may be provided in a single layer between the adjacent positive electrode plate and the negative electrode plate.
  • the bag-shaped separator may accommodate a positive electrode plate or a negative electrode plate.
  • the vertical direction of the electrode plate means the vertical direction of the lead storage battery in the vertical direction.
  • 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 concentration of the polymer compound in the electrolytic solution may be, for example, 500 ppm or less, 300 ppm or less, or 200 ppm or less on a mass basis.
  • the concentration of the polymer compound in the electrolytic solution may be 1 ppm or more or 5 ppm or more on a mass basis.
  • the concentration of the polymer compound in the electrolytic solution is determined by adding chloroform to a predetermined amount (m 1 (g)) of electrolytic solution taken out from a ready-made fully charged lead-acid battery, mixing the mixture, and allowing it to stand to separate into two layers. After that, only the chloroform layer is taken out. After repeating this operation several times, chloroform is distilled off under reduced pressure to obtain a chloroform-soluble component. An appropriate amount of chloroform-soluble matter is dissolved in deuterated chloroform together with TCE 0.0212 ⁇ 0.0001 g, and 1 1 H-NMR spectrum is measured.
  • the electrolyte may optionally include cations (eg, metal cations such as sodium ions, lithium ions, magnesium ions, and / or aluminum ions) and / or anions (eg, anions other than sulfate anions such as phosphate ions). ) May be included.
  • cations eg, metal cations such as sodium ions, lithium ions, magnesium ions, and / or aluminum ions
  • anions eg, anions other than sulfate anions such as phosphate ions.
  • the specific gravity of the electrolytic solution in a fully charged lead-acid 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. These lower limit values and upper limit values can be arbitrarily combined.
  • 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 assembling the lead-acid battery by accommodating the positive electrode plate, the negative electrode plate, and the electrolytic solution in the battery case.
  • the separator is usually arranged so as to be interposed between the positive electrode plate and the negative electrode plate.
  • the step of assembling the lead-acid battery may include a step of accommodating the positive electrode plate, the negative electrode plate, and the electrolytic solution in the battery case, and then, if necessary, a step of forming the positive electrode plate and / or the negative electrode plate.
  • the positive electrode plate, the negative electrode plate, the electrolytic solution, and the separator are each prepared before being housed in the battery case.
  • FIG. 1 is a perspective view schematically showing an example in which the lid of the lead storage battery according to the embodiment of the present invention is removed.
  • 2A is a front view of the lead-acid battery of FIG. 1
  • FIG. 2B is a cross-sectional view taken along the line IIB-IIB of FIG. 2A.
  • the lead-acid battery 1 includes a battery case 10 that houses a electrode plate group 11 and an electrolytic solution (not shown).
  • the electrode plate group 11 is formed by laminating a plurality of negative electrode plates 2 and positive electrode plates 3 via a separator 4, respectively.
  • An ear portion (not shown) for collecting electricity is provided above each of the plurality of negative electrode plates 2.
  • An ear portion (not shown) for collecting electricity is also provided on the upper portion of each of the plurality of positive electrode plates 3 so as to project upward.
  • the ears of the negative electrode plate 2 are connected and integrated by the negative electrode strap 5a.
  • the ears of the positive electrode plates 3 are also connected and integrated by the positive electrode strap 5b.
  • the negative electrode column 6a is fixed to the negative electrode strap 5a
  • the positive electrode column 6b is fixed to the positive electrode strap 5b.
  • ⁇ Battery life when charging high temperature float> As the test battery, a control valve type lead-acid battery having a nominal voltage of 2 V and a rated capacity of 50 Ah / 10 hr is used. Float charging is performed under a constant voltage condition of 2.23 V / cell in an environment of 60 ° C. ⁇ 2 ° C., and a 10-hour rate capacity test is performed every month at 25 ° C. ⁇ 2 ° C. In the 10-hour rate capacity test, the test battery is discharged until it reaches 1.8 V / cell with a current (A) of 0.1 times the value described as the rated capacity (Ah), and then 120% of the discharge capacity. Performs recovery charging of the amount of electricity.
  • A current
  • the life period is the test period until the battery capacity becomes 80% or less of the rated capacity. By multiplying the life period at 60 ° C. by a predetermined index, it can be converted into the life period at 25 ° C.
  • the guideline is as follows. Lifespan at 60 ° C 12 months or more: Expected life at 25 ° C 11-12 years Lifespan at 60 ° C 16 months or more: Expected life at 25 ° C 15 years or more Lifespan at 60 ° C 22 months or more: 25 Expected life at °C 20 years or more
  • Amount of overcharged electricity Measure the total amount of electricity charged when high-temperature float charging of 2.23 V / cell is performed for one month.
  • (B) Corrosion amount of positive electrode current collector The test battery is subjected to high temperature float charging for 1 month, 8 months or 11 months, after which the lead storage battery is disassembled, the positive electrode current collector is taken out from the positive electrode plate, and the positive electrode plate is removed. After cutting around the center in the vertical direction, the cut surface is polished, the cross-sectional area of the polished cross-sectional portion having metallic luster is measured, and the difference from the cross-sectional area of the positive electrode current collector before the test. Is calculated as a percentage as the amount of corrosion.
  • (D) Liquid reduction rate High-temperature float charging of the test battery is performed for 1 month, 8 months or 11 months, and then the amount of mass loss before and after the test of the sample battery is measured, and the amount of mass loss is tested before the test. The difference from the mass of the electrolytic solution contained in the battery is calculated as a percentage as the liquid reduction rate.
  • the lead-acid batteries according to one aspect of the present invention are summarized below.
  • a positive electrode plate, a negative electrode plate, an electrolytic solution, and a polymer compound are provided.
  • the positive electrode plate includes a positive electrode current collector and a positive electrode material.
  • the negative electrode plate includes a negative electrode current collector and a negative electrode material.
  • the Ca content of the positive electrode current collector is 0.13% by mass or less.
  • the polymer compound is a lead-acid battery 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.
  • the Ca content of the positive electrode current collector may be, for example, 0.07% by mass or less.
  • the Ca content of the positive electrode current collector may be, for example, less than 0.01% by mass, and the Sn content may be, for example, 0.5% by mass or less. Just do it.
  • the Ca content of the positive electrode current collector may be, for example, less than 0.01% by mass, and the Sn content may be, for example, less than 0.01% by mass. ..
  • the content of the polymer compound in the negative electrode material is, for example, a mass ratio. It may be 400 ppm or less.
  • the content of the polymer compound in the negative electrode material may be, for example, 5 ppm or more in terms of mass ratio.
  • a positive electrode plate, a negative electrode plate, an electrolytic solution, and a polymer compound are provided.
  • the positive electrode plate includes a positive electrode current collector and a positive electrode material.
  • the negative electrode plate includes a negative electrode current collector and a negative electrode material.
  • the positive electrode current collector has a Ca content of 0.13% by mass or less.
  • the polymer compound is a lead-acid battery containing a repeating structure of oxyC 2-4 alkylene units.
  • the Ca content of the positive electrode current collector may be, for example, 0.07% by mass or less.
  • the Ca content of the positive electrode current collector may be, for example, less than 0.01% by mass, and the Sn content may be, for example, 0.5% by mass or less. Just do it.
  • the Ca content of the positive electrode current collector may be, for example, less than 0.01% by mass, and the Sn content may be, for example, less than 0.01% by mass. ..
  • (11) In any one of the above (7) to (10), when at least the negative electrode material contains the polymer compound, the content of the polymer compound in the negative electrode material is, for example, a mass ratio. It may be 400 ppm or less.
  • the content of the polymer compound in the negative electrode material may be, for example, 5 ppm or more in terms of mass ratio.
  • the lead storage battery may be a control valve type.
  • Lead-acid batteries A1 to A7 and R1 to R6 >> (1) Preparation of Lead-acid Battery Using the negative electrode material having a polypropylene glycol (PPG) content and the positive electrode current collector having a Ca content and a Sn content shown in Table 1 below, the following (a) )-(C), lead-acid batteries A1 to A7 and R1 to R6 were assembled. A1 to A7 correspond to Examples, and R1 to R6 correspond to Comparative Examples.
  • PPG polypropylene glycol
  • the content of the polymer compound in the negative electrode material which is obtained by the procedure described above, is the value shown in Table 1, the content of barium sulfate is 1.5% by mass, and the content of carbon black.
  • Each component is mixed so that the content is 0.3% by mass and the content of the organic shrink-proofing agent is 0.1% by mass.
  • the negative electrode paste is filled in the mesh portion of a cast lattice made of a Pb—Ca—Sn alloy, which is a negative electrode current collector, and aged and dried to obtain an unchemicald negative electrode plate.
  • (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 a cast lattice made of a Pb-Ca—Sn alloy or the like and aged and dried to obtain an unchemicald positive electrode plate.
  • the Ca content and Sn content of the positive electrode current collector (that is, Pb-Ca-Sn alloy or the like here) obtained by the procedure described above are the values shown in Table 1.
  • a control valve type lead-acid battery having a nominal voltage of 2V and a rated capacity of 50Ah / 10hr is manufactured.
  • the electrode plate group of the test battery is composed of five positive electrode plates and six negative electrode plates sandwiching the positive electrode plates.
  • a positive electrode plate and a negative electrode plate are laminated with a glass fiber non-woven fabric separator interposed therebetween to form a group of electrode plates.
  • a group of electrode plates is housed in a polypropylene electric tank together with an electrolytic solution (sulfuric acid aqueous solution) and chemically formed in the electric tank to prepare a liquid lead-acid battery.
  • the specific gravity of the electrolytic solution after chemical conversion is 1.28 (20 ° C. conversion).
  • the integrated value of the peaks of 3.2 ppm ⁇ 3.8 ppm, and the integral value of the peak, -CH 2 bonded to an oxygen atom - and the integral value of the peak of the hydrogen atoms of the group is 98.1%.
  • the life period is as short as 8 months regardless of the presence or absence of the polymer compound. ..
  • the amount of overcharged electricity of the battery R6 in which the negative electrode material contains the polymer compound in the first month is significantly lower than that of the battery R5.
  • the life period is remarkably improved as the Ca content decreases. Comparing the batteries R1 to R4 having a Ca content of 0.13% by mass or less, the life period is increased by 7 months from 11 months to 18 months. Further, by reducing the Sn content as the Ca content decreases, the life period is further extended.
  • the life period is increased by 14 months from 13 months to 27 months. That is, the degree of improvement in the life period is remarkable due to the presence of the polymer compound. More specifically, when comparing the batteries R4 and A7 having a Ca content of 0.13% by mass, there is a difference of 2 months in the life period (11 months for R4, 13 months for A7) depending on the presence or absence of the polymer compound. Can be seen.
  • Table 4 shows that when a polymer compound is used, the amount of corrosion of the positive electrode current collector tends to decrease and the rate of decrease of the electrolytic solution tends to decrease. In addition, based on the results in Tables 1 and 2, it is suggested that the decrease in the reduction rate of the electrolytic solution has a great influence on the battery life. It can be understood that when the polymer compound of the negative electrode material becomes 400 ppm, the accumulation of lead sulfate on the positive electrode plate becomes remarkable. It is understood that this is because the charging current during float charging is lower than the self-discharge rate of the positive electrode material.
  • Table 6 also shows that when a polymer compound is used, the amount of corrosion of the positive electrode current collector tends to decrease and the liquid reduction rate of the electrolytic solution tends to decrease, and the reduction of the liquid reduction rate is particularly remarkable. Is. Based on the results in Tables 1 and 2, it is considered that the reduction in the reduction rate of the electrolytic solution is largely related to the remarkable improvement in the life period when the Ca content is low.
  • the lead-acid battery according to the present invention can be applied to, for example, a control valve type lead-acid battery, and specifically, can be used as a stationary industrial power storage device, a vehicle starting power source, an auxiliary power source, or the like. It should be noted that these uses are merely examples and are not limited to these uses.
  • Electrode tank 11 Electrode plate group

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GB2115811.8A GB2597869B (en) 2019-05-31 2020-05-29 Lead-acid battery
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CN202080040487.XA CN113994521A (zh) 2019-05-31 2020-05-29 铅蓄电池
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