WO2020241882A1 - 鉛蓄電池 - Google Patents

鉛蓄電池 Download PDF

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Publication number
WO2020241882A1
WO2020241882A1 PCT/JP2020/021479 JP2020021479W WO2020241882A1 WO 2020241882 A1 WO2020241882 A1 WO 2020241882A1 JP 2020021479 W JP2020021479 W JP 2020021479W WO 2020241882 A1 WO2020241882 A1 WO 2020241882A1
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Prior art keywords
positive electrode
negative electrode
lead
current collector
polymer compound
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PCT/JP2020/021479
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English (en)
French (fr)
Japanese (ja)
Inventor
泰如 ▲浜▼野
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 US17/614,886 priority Critical patent/US11658347B2/en
Priority to JP2021521913A priority patent/JP7173322B2/ja
Priority to EP20813250.6A priority patent/EP3975307A4/en
Priority to CN202080038772.8A priority patent/CN113892208A/zh
Publication of WO2020241882A1 publication Critical patent/WO2020241882A1/ja
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • 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
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0473—Filling tube-or pockets type electrodes; Applying active mass in cup-shaped terminals
    • H01M4/0478—Filling tube-or pockets type electrodes; Applying active mass in cup-shaped terminals with dispersions, suspensions or pastes
    • 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 proposes that the expanded lattice body of the positive electrode plate of the control valve type lead-acid battery is composed of a Pb-Ca-Sn alloy containing 1.2% by mass to 1.8% by mass of Sn. ..
  • the slit portion is mechanically pulled to expand and extend, it is necessary to pay attention to the tensile strength and the elongation rate of the rolled lead alloy sheet.
  • the Sn concentration in the rolled lead alloy sheet is increased to 1.2% by mass or more for the purpose of improving the trickle life of the lead storage battery, the tensile strength of the rolled lead alloy sheet is improved, the elongation rate is lowered, and slits are formed. When the portion is expanded to form the mesh portion, the mesh portion is cut or cracks occur.
  • Japanese Unexamined Patent Publication No. 60-182662 Japanese Unexamined Patent Publication No. 2000-149980 Special Table 2017-525092 Japanese Unexamined Patent Publication No. 2003-34687
  • the positive electrode current collector containing Pb—Sb alloy increases the overvoltage when charging the lead storage battery, so that the decomposition reaction of water contained in the electrolytic solution is suppressed.
  • the positive electrode current collector containing Pb—Sb alloy increases the overvoltage when charging the lead storage battery, so that the decomposition reaction of water contained in the electrolytic solution is suppressed.
  • the float is charged in a high temperature environment, it is difficult to sufficiently suppress the decomposition reaction of water even when a positive electrode current collector containing Sn is used, the amount of charging electricity increases, and the positive electrode current collector Corrosion reaction proceeds. If the corrosion reaction continues, the positive electrode current collector may break, making it difficult to charge and discharge.
  • 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 positive electrode current collector contains an electric body and a negative electrode material
  • the positive electrode current collector contains 0.95% by mass or more of Sn
  • the polymer compound has a chemical shift of 3.2 ppm or more and 3.8 ppm in a 1 H-NMR spectrum. It relates to a lead storage battery having a peak in the following range.
  • 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 present invention relates to a lead storage battery comprising a current collector and a negative electrode material, the positive electrode current collector containing 0.95% by mass or more of Sn, and the polymer compound containing a repeating structure of an oxyC 2-4 alkylene unit. ..
  • 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 positive electrode current collector contains 0.95% by mass or more of Sn.
  • 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 effect of suppressing corrosion of the positive electrode current collector during float charging in a high temperature environment is remarkably enhanced, and the durability performance of the lead storage battery is remarkably improved. More specifically, when Sn is contained in the positive electrode current collector, the effect of suppressing corrosion of the positive electrode current collector during float charging in a high temperature environment is gradually improved as the Sn content increases. The improvement effect tends to be gradually saturated.
  • the lead-acid battery contains a polymer compound
  • the Sn content in the positive electrode current collector is 0.95% by mass or more
  • the effect of suppressing corrosion of the positive electrode current collector during float charging in a high temperature environment is effective. It is remarkably enhanced, and the durability performance of the lead storage battery is remarkably improved.
  • the polymer compound increases the negative electrode overvoltage, which reduces the charging current value during float charging, which is advantageous in suppressing corrosion of the positive electrode current collector.
  • the polymer compound is a crystal of the positive electrode current collector. It is considered that this is because it acts on the Sn compound precipitated at the grain boundary.
  • 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. As a result, the amount of electricity charged during float charging is reduced, which is advantageous in suppressing corrosion of the positive electrode current collector. Further, the reason why the improvement in durability performance becomes remarkable when the Sn content of the positive electrode current collector is 0.95% by mass or more is probably due to the Sn compound in which the polymer compound is precipitated at the grain boundaries of the positive electrode current collector. It is considered that the intergranular corrosion is suppressed by adhering and filling the corroded part of the grain boundaries. When the Sn content in the positive electrode current collector is 0.95% by mass or more, it is considered that the amount of Sn compounds precipitated at the grain boundaries increases, and the effect of suppressing grain boundary corrosion by the polymer compounds becomes remarkable.
  • the Sn content of the lead alloy constituting the positive electrode current collector since Sn is expensive, it is desired to reduce the Sn content of the lead alloy constituting the positive electrode current collector. Further, when the Sn content of the lead alloy increases, the elongation amount of the lead alloy decreases, so that the processability and productivity of the positive electrode current collector are lowered, and defects such as cracks are likely to occur. Therefore, there is a limit to increasing the Sn content of the lead alloy.
  • the upper limit of the Sn content of the positive electrode current collector that can ensure sufficient workability is, for example, less than 3.0% by mass, preferably 2.5% by mass or less, and Sn from the viewpoint of ensuring higher workability.
  • the content is preferably 1.8% by mass or less. Further, from the viewpoint of more remarkably suppressing corrosion of the positive electrode current collector during float charging in a high temperature environment, the Sn content of the positive electrode current collector is preferably 1.1% by mass or more.
  • the positive electrode current collector may be further composed of a Pb-Ca-Sn alloy containing Ca.
  • the Ca content of the positive electrode current collector is preferably 0.17% by mass or less, more preferably 0.13 parts by mass or less, and 0.10 parts by mass. It may be less than or equal to, 0.07% by mass or less, and 0.05% by mass or less.
  • the Ca content of the positive electrode current collector may be, for example, 0.01% by mass or more, and 0.03% by mass or more. It may be.
  • the action of the polymer compound on the negative electrode plate will be described in more detail.
  • 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 hydrogen overvoltage rises, the side reaction of hydrogen generation from protons during overcharging is inhibited, and the water decomposition reaction is reduced. .. Therefore, in order to enhance the effect of suppressing the amount of electricity charged during float charging, it is preferable to include at least the polymer compound in 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 amount of electricity charged 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 amount of electricity charged 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 reducing the amount of electricity charged during float charging, it is possible to reduce the amount of 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 leads to lead. It becomes difficult to balance with the adsorption of. For example, when an organic additive having a low adsorptivity to lead is used, it becomes easy to elute into the electrolytic solution, and it becomes difficult to reduce the amount of electricity charged during float charging. 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 organic additive When the organic additive is unevenly distributed in the pores of lead, the movement of ions (lead ion, sulfate ion, etc.) is hindered by the steric hindrance of the unevenly distributed organic additive. Therefore, the low temperature high rate (HR) discharge performance is also lowered. If the content of the organic additive is increased in order to ensure a sufficient effect of reducing the amount of electricity charged during float charging, the movement of ions in the pores is further inhibited, and the low temperature HR discharge performance is also lowered. Become.
  • the lead surface is covered with the polymer compound in a thinly spread state as described above. Therefore, as compared with the case of using other organic additives, even if the content in the negative electrode electrode material is small, the effect of sufficiently reducing the amount of electricity charged during float charging can be sufficiently ensured. Further, since the polymer compound thinly covers the lead surface, it is difficult to inhibit the elution of lead sulfate generated during discharge during charging, and it is possible to suppress a decrease in charge acceptability. Therefore, it is possible to suppress a decrease in charge acceptability while reducing the amount of charge electricity during float charging. Since the uneven distribution of the polymer compound in the pores of lead is suppressed, the ions can easily move, and the deterioration of the low temperature HR discharge performance can be suppressed.
  • 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 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. Therefore, it is possible to more effectively reduce the amount of electricity charged during float charging.
  • 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 decomposition reaction of water during float charging is likely to be suppressed, and the amount of charging electricity can be reduced more effectively.
  • 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 (for example, 500 ppm or less). The amount of electricity charged during float charging can be reduced. Further, even if the content is small, the effect of reducing the amount of electricity charged during float charging can be ensured, so that the decrease in charge acceptability can be suppressed.
  • the polymer compound slightly eluted from the negative electrode material is considered to have high adsorptivity to the Sn compound precipitated at the grain boundaries of the positive electrode current collector. From the viewpoint of sufficiently suppressing corrosion of the positive electrode current collector even in a high temperature environment, the content of the polymer compound in the negative electrode material is preferably 5 ppm or more.
  • 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, negative electrode plate, positive electrode plate, electrolytic solution, and / or 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 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 of the control valve type lead-acid battery means that the lead-acid battery after chemical conversion has a current of 0.2 times the value described as the rated capacity (Ah) in an air tank at 25 ° C ⁇ 2 ° C (Ah).
  • A constant current constant voltage charging of 2.23 V / cell is performed, and charging is completed when the charging current at the time of constant voltage charging becomes 0.005 times the value described as the rated capacity.
  • 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 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 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 thickness of the sticking member is included in the thickness of the separator.
  • 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, of charge acceptance This is preferable because the effect of suppressing the decrease can be further enhanced. Further, even when these polymer compounds are used, a high liquid reduction 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 in that the effect of reducing the amount of charging electricity during float charging can be further enhanced.
  • 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 should contain a large amount of oxyC 2-4 alkylene unit from the viewpoint of enhancing the adsorptivity to lead and the Sn compound precipitated at the grain boundaries of the positive current collector and facilitating the linear structure. Is preferable.
  • 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, and may be 80% or more. From the viewpoint of further enhancing the effect of reducing the amount of electricity charged during float charging and further enhancing the effect of suppressing the decrease in charge acceptability and / or low-temperature HR discharge performance, the above ratio is preferably 85% or more, preferably 90% or more. Is more preferable.
  • 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 because the polymer compound can be easily retained in the negative electrode material, spread thinly on the lead surface, and easily adhere to the Sn compound precipitated at the crystal grain boundaries of the positive electrode current collector. It may be 4000 or less or 3500 or less.
  • 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 point that the compound is easily retained in the negative electrode material, spreads thinly on the lead surface, and the polymer compound is appropriately eluted from the negative electrode material and easily adheres to the Sn compound precipitated at the crystal grain boundary of the positive electrode current collector.
  • the Mn of the above compound is preferably 1000 or more and 5000 or less, and may be 1000 or more and 4000 or less, or 1000 or more and 3500 or less.
  • the corrosion reaction of the positive electrode current collector during float charging in a high temperature environment can be suppressed more remarkably.
  • structural changes in the negative electrode active material due to collision of hydrogen gas with the negative electrode active material can also be suppressed. Therefore, it is possible to enhance the effect of suppressing the deterioration of the low temperature HR discharge performance after the high temperature light load test.
  • the compound having Mn as described above easily moves into the negative electrode material even when it is contained in the electrolytic solution, the compound can be replenished in the negative electrode material, and from this viewpoint as well, the negative electrode electrode It is easy to retain the compound in the material.
  • the polymer compound 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, 50 ppm or more, or 250 ppm or more on a mass basis.
  • the hydrogen generation voltage can be easily increased, the effect of reducing the amount of electricity charged during float charging can be further enhanced, and the grain boundaries of the positive current collector can be reached. It is easy to attach the polymer compound to the precipitated Sn compound.
  • the content (mass basis) of the polymer compound in the negative electrode electrode material is, for example, 500 ppm or less, 360 ppm or less, or 350 ppm or less.
  • the content of the polymer compound is 500 ppm or less, the surface of lead is suppressed from being excessively covered with the polymer compound, so that the deterioration of the low temperature HR discharge performance can be effectively suppressed.
  • These lower limit value and upper limit value can be arbitrarily combined.
  • the content (mass basis) of the polymer compound in the negative electrode material may be 5 ppm or more and 500 ppm or less, 50 ppm or more and 500 ppm or less, 250 ppm or more and 500 ppm or less, 5 ppm or more and 250 ppm or less, and 50 ppm or more and 250 ppm or less.
  • 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 compounds 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.
  • the aromatic compound may further have a substituent.
  • the organic shrinkage proofing agent may contain one type of residues of these compounds, or may contain a plurality of types.
  • 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.
  • the lead-acid battery after chemical conversion is fully charged and then disassembled to obtain a negative electrode plate to be analyzed.
  • the obtained negative electrode plate is washed with water to remove sulfuric acid from the negative electrode plate.
  • the washing with water is carried out by pressing the pH test paper against the surface of the negative electrode plate washed with water until it is confirmed that the color of the test paper does not change. However, the time for washing with water shall be within 2 hours.
  • the negative electrode plate washed with water is dried at 60 ⁇ 5 ° C. for about 6 hours in a reduced pressure environment. If the attached member is included after drying, the attached member is removed from the negative electrode plate by peeling.
  • sample A a sample (hereinafter, also referred to as sample A) is obtained by separating the negative electrode material from the negative electrode plate.
  • Sample A is pulverized as needed and subjected to analysis.
  • (1-1) Qualitative Analysis of Polymer Compound 150.0 ⁇ 0.1 mL of chloroform is added to 100.0 ⁇ 0.1 g of pulverized sample A, and the mixture is stirred at 20 ⁇ 5 ° C. for 16 hours to extract the polymer compound. .. Then, the solid content is removed by filtration.
  • 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 a lead storage battery can be classified into a paste type, a clad type and the like.
  • the paste-type positive electrode plate 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 electrode material is the positive electrode plate from which the positive electrode current collector is removed.
  • the clad type positive electrode plate is a positive electrode filled in a plurality of porous tubes, a core metal inserted in each tube, a current collector connecting the plurality of core metals, and a tube in which the core metal is inserted. It comprises an electrode material and a coupling that connects a plurality of tubes.
  • the positive electrode material is the one excluding the tube, the core metal, the current collector, and the collective punishment.
  • the core metal and the current collector may be collectively referred to as a positive electrode current collector.
  • 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 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 lead alloy used for the positive electrode current collector may be a Pb—Sn alloy, a Pb—Ca—Sn alloy, or the like.
  • 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 upper limit of the Sn content of the positive electrode current collector is, for example, less than 3.0% by mass and 2.5% by mass. % Or less is preferable, and the Sn content is preferably 1.8% by mass or less from the viewpoint of ensuring higher workability. Further, from the viewpoint of more remarkably suppressing the corrosion of the positive electrode current collector during float charging in a high temperature environment, the Sn content of the positive electrode current collector is 0.95% by mass or more, 1.1% by mass. The above is preferable.
  • the Sn content of the positive electrode current collector is, for example, 0.95% by mass or more and less than 3.0% by mass, and may be 1.1% by mass or more and less than 3.0% by mass. It may be 95% by mass or more and 2.5% by mass or less, 1.1% by mass or more and 2.5% by mass or less, and 0.95% by mass or more and 1.8% by mass or less. It may be 1.1% by mass or more and 1.8% by mass or less.
  • the positive electrode current collector contains Ca, the workability of the lead alloy is improved and the productivity of the positive electrode current collector is improved.
  • the Ca content of the positive electrode current collector is preferably 0.17% by mass or less, more preferably 0.13 parts by mass or less, and 0.10 parts by mass or less. It may be 0.07% by mass or less, and may be 0.05% by mass or less.
  • the Ca content of the positive electrode current collector may be, for example, 0.01% by mass or more, and 0.03% by mass or more. It may be.
  • the Ca content of the positive electrode current collector is, for example, 0.01% by mass or more and 0.17% by mass or less, and may be 0.01% by mass or more and 0.13% by mass or less, 0.01% by mass. As mentioned above, it may be 0.10 mass% or less, 0.01 mass% or more, 0.07 mass% or less, 0.01 mass% or more, 0.05 mass% or less, 0.03 mass% or more, It may be 0.17% by mass or less, 0.03% by mass or more, 0.13% by mass or less, 0.03% by mass or more, 0.10% by mass or less, 0.03% by mass or more, 0. It may be 07% by mass or less, 0.03% by mass or more, and 0.05% by mass or less.
  • 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 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 unchemical paste type positive electrode plate is obtained by filling the positive electrode current collector with the positive electrode paste, aging and drying.
  • the positive electrode paste is prepared by kneading lead powder, additives, water, and sulfuric acid.
  • the unchemical clad type positive electrode plate is formed by filling a porous tube into which a core metal connected by a current collector is inserted with lead powder or slurry-like lead powder, and connecting a plurality of tubes in a collective punishment. Will be done. Then, a positive electrode plate is obtained by forming these unchemical positive electrode plates.
  • the positive electrode plate can be formed, for example, 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 may be, for example, more than 8 ppm and 500 ppm or less, 15 ppm or more and 300 ppm or less, and 15 ppm or more and 200 ppm or less on a mass basis. Even when the amount of the polymer compound contained in the negative electrode material and the electrolytic solution is small in this way, by controlling the Sn content of the positive electrode current collector to 0.95% by mass or more, the amount of electricity charged during float charging Is reduced, and the effect of suppressing corrosion of the positive electrode current collector can be obtained.
  • the polymer compound preferably contains a compound having an Mn of at least 500 or more.
  • the adsorptivity to lead is enhanced, so that the effect of reducing the amount of electricity charged during float charging is further enhanced.
  • the concentration of the polymer compound in the electrolytic solution is 100 ppm or more.
  • the polymer compound preferably contains at least a compound having Mn of 1000 or more and 5000 or less.
  • a polymer compound having a Mn of 5000 or less is easily dissolved in an electrolytic solution and easily moves in the electrolytic solution. Therefore, the polymer compound moves into the positive electrode plate (positive electrode current collector) or the negative electrode electrode material to charge electricity during float charging. The effect of reducing the amount can be further enhanced.
  • a polymer compound having Mn of 1000 or more is considered to have higher adsorptivity to lead, and the effect of reducing the amount of electricity charged during float charging can be further enhanced.
  • the structural change of the negative electrode material gradually progresses, and the polymer compound tends to easily elute from the negative electrode plate.
  • the electrolytic solution contains a polymer compound having a certain concentration, the elution of the polymer compound from the negative electrode plate can be suppressed, the polymer compound can be retained in the negative electrode electrode material, and the polymer compound can be contained in the electrolytic solution.
  • the negative electrode plate can be replenished.
  • 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 storage battery can be obtained by a manufacturing method including a step of assembling a lead storage battery by accommodating a positive electrode plate, a negative electrode plate, and an electrolytic solution in an electric tank.
  • 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 shows the appearance of an example of a lead storage battery according to an embodiment of the present invention.
  • the lead-acid battery 1 for automobiles includes an electric tank 12 that houses a electrode plate group 11 and an electrolytic solution (not shown).
  • the inside of the electric tank 12 is partitioned into a plurality of cell chambers 14 by a partition wall 13.
  • One electrode plate group 11 is housed in each cell chamber 14.
  • the opening of the battery case 12 is closed by a lid 15 including a negative electrode terminal 16 and a positive electrode terminal 17.
  • the lid 15 is provided with a liquid spout 18 for each cell chamber. At the time of rehydration, the liquid spout 18 is removed and the rehydration 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 formed by laminating a plurality of negative electrode plates 2 and positive electrode plates 3 with a separator 4 interposed therebetween.
  • the bag-shaped separator 4 that accommodates the negative electrode plate 2 is shown, but the form of the separator is not particularly limited.
  • the negative electrode shelf portion 6 for connecting the plurality of negative electrode plates 2 in parallel is connected to the through connecting body 8, and the positive electrode shelf portion for connecting the plurality of positive electrode plates 3 in parallel. 5 is connected to the positive electrode column 7.
  • the positive electrode column 7 is connected to the positive electrode terminal 17 outside the lid 15.
  • the negative electrode column 9 is connected to the negative electrode shelf 6, and the through connector 8 is connected to the positive electrode shelf 5.
  • the negative electrode column 9 is connected to the negative electrode terminal 16 outside the lid 15.
  • Each through-connecting body 8 passes through a through-hole provided in the partition wall 13 and connects the electrode plates 11 of the adjacent cell chambers 14 in series.
  • the positive electrode shelf 5 is formed by welding the ears provided on the upper part of each positive electrode plate 3 by a cast-on strap method or a burning method.
  • the negative electrode shelf portion 6 is also formed by welding the ear portions provided on the upper portions of the negative electrode plates 2 as in the case of the positive electrode shelf portion 5.
  • the lid 15 of the lead storage battery has a single structure (single lid), but is not limited to the case shown in the illustrated example.
  • the lid 15 may have, for example, a double structure including an inner lid and an outer lid (or upper lid).
  • the lid having a double structure is 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. May be good.
  • ⁇ High temperature float durability> Prepare two lead-acid batteries with the same measurement target.
  • One of the lead-acid batteries is immersed in a water tank at 75 ° C. ⁇ 3 ° C., and a constant voltage charge of 2.5 V / cell (that is, high temperature float charge) is performed for 30 days.
  • the lead-acid battery is disassembled, the positive electrode current collector is taken out from the positive electrode plate, and the corrosive layer is removed with an aqueous solution in which mannitol, hydrazine and sodium hydroxide are dissolved.
  • the mass W1 of the positive electrode current collector after removing the corroded layer is measured.
  • the other lead-acid battery is disassembled without performing high-temperature float charging, the positive electrode current collector is taken out from the positive electrode plate, and the mass W0 of the positive electrode current collector having no corrosive layer is measured.
  • the difference between W0 and W1 was calculated as the amount of corrosion, and the reciprocal was indexed as the high temperature float durability performance. The larger the amount of corrosion, the smaller the reciprocal (exponent). The larger the index value, the better the durability performance.
  • 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 positive electrode current collector contains 0.95% by mass or more of Sn.
  • 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 Sn content in the positive electrode current collector may be, for example, less than 3% by mass.
  • the positive electrode current collector may further contain Ca.
  • At least the negative electrode material contains the polymer compound.
  • the content of the polymer compound in the negative electrode material may be, for example, 5 to 500 ppm by mass ratio.
  • the number average molecular weight of the polymer compound may be, for example, 500 or more.
  • 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 contains 0.95% by mass or more of Sn.
  • the polymer compound is a lead-acid battery containing a repeating structure of oxyC 2-4 alkylene units.
  • the Sn content in the positive electrode current collector may be, for example, less than 3% by mass.
  • the positive electrode current collector may further contain Ca.
  • the content of the polymer compound in the negative electrode material may be, for example, 5 to 500 ppm by mass ratio.
  • the number average molecular weight of the polymer compound may be, for example, 500 or more.
  • Lead-acid batteries A1 to A15 and R1 to R13 >> (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 Sn content shown in Table 1 below, the following (a) to (c) ), The lead-acid batteries A1 to A15 and R1 to R13 were assembled. A1 to A15 correspond to Examples, and R1 to R13 correspond to Comparative Examples.
  • PPG polypropylene glycol
  • (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—Ca—Sn alloy and aged and dried to obtain an unchemicald positive electrode plate.
  • the Sn content of the positive electrode current collector that is, Pb—Ca—Sn alloy here
  • the Ca content of the Pb—Ca—Sn alloy is 0.09% by mass.
  • the test battery has a rated voltage of 2V and a rated 5-hour rate capacity of 32Ah.
  • the electrode plate group of the test battery is composed of seven positive electrode plates and seven negative electrode plates.
  • the negative electrode plate is housed in a bag-shaped separator and laminated with the positive electrode plate to form a group of electrode plates.
  • a group of electrode plates is housed in a polypropylene electric tank together with an electrolytic solution (sulfuric acid aqueous solution) and chemically formed in the electric tank to 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%.
  • FIG. 2 graphically shows the relationship between the Sn content of the positive electrode current collector and the high temperature float durability. From Tables 2A to 2D and FIG. 2, when the Sn content of the positive electrode current collector is 0.95% by mass or more, the improvement in high temperature float durability performance due to the inclusion of the polymer compound in the negative electrode electrode material becomes remarkable. Can be understood. In particular, when the Sn content of the positive electrode current collector is in the range of 1.10% by mass to 1.80% by mass, the durability performance is remarkably improved regardless of the content of the polymer compound (PPG) in the negative electrode material.
  • PPG polymer compound
  • Batteries A16, A17 and R14, R15 Similar to the above, the lead-acid battery A16, except that the Sn content of the positive electrode current collector was 1.10% by mass or 0.60% by mass and the PPG content in the negative electrode material was 500 ppm or 750 ppm. Lead-acid batteries R14 and R15 of A17 and Comparative Examples were prepared and evaluated in the same manner.
  • Table 3 shows the results together with excerpts from Tables 2A to 2D when the Sn content is 1.10% by mass or 0.60% by mass. From Table 3, it can be easily understood that the behavior of durability performance due to the addition of PPG to the negative electrode material differs greatly depending on whether the Sn content of the positive electrode current collector is higher than 0.95% by mass or lower than 0.95% by mass. ..
  • Batteries A18-A21 The lead-acid batteries A18 to A21 of Examples were produced and evaluated in the same manner as the batteries A12 of Examples except that the number average molecular weight of the polymer compounds contained in the negative electrode electrode material was changed as shown in Table 4. The results are shown in Table 4.
  • the number average molecular weight Mn of the polymer compound may be 500 or more, but from the viewpoint of improving the high temperature float durability performance, 1000 or more is preferable, and the larger the Mn is up to 2500 or more (for example, about 3000). It can be seen that the durability performance is also improved. However, when Mn exceeds 2500, the improvement in durability performance is saturated. It is presumed that this is because when Mn becomes larger than a certain level, it becomes difficult for the polymer compound to elute from the negative electrode material, and the amount of the polymer compound adhering to the Sn compound precipitated at the crystal grain boundaries of the positive electrode current collector decreases. ..
  • the lead-acid battery according to the present invention can be suitably used as, for example, a power source for starting a vehicle (automobile, motorcycle, etc.) or an industrial power storage device for an electric vehicle (forklift, etc.). It should be noted that these uses are merely examples and are not limited to these uses.

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EP20813250.6A EP3975307A4 (en) 2019-05-31 2020-05-29 Lead storage battery
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JP7643017B2 (ja) * 2020-11-27 2025-03-11 株式会社Ｇｓユアサ 制御弁式鉛蓄電池
WO2023210513A1 (ja) * 2022-04-26 2023-11-02 株式会社Ｇｓユアサ 鉛蓄電池およびその製造方法、および使用方法

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