WO2022113623A1 - 鉛蓄電池 - Google Patents

鉛蓄電池 Download PDF

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Publication number
WO2022113623A1
WO2022113623A1 PCT/JP2021/039743 JP2021039743W WO2022113623A1 WO 2022113623 A1 WO2022113623 A1 WO 2022113623A1 JP 2021039743 W JP2021039743 W JP 2021039743W WO 2022113623 A1 WO2022113623 A1 WO 2022113623A1
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Prior art keywords
lead
negative electrode
less
group
electrode plate
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English (en)
French (fr)
Japanese (ja)
Inventor
泰如 ▲浜▼野
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GS Yuasa International Ltd
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GS Yuasa International Ltd
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Priority to EP21897599.3A priority Critical patent/EP4228051A4/en
Priority to JP2022565144A priority patent/JP7661978B2/ja
Priority to CN202180079759.1A priority patent/CN116615815A/zh
Publication of WO2022113623A1 publication Critical patent/WO2022113623A1/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
    • H01M4/62—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
    • 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
    • H01M10/08—Selection of materials as electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/627—Expanders for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H01M2300/0011—Sulfuric acid-based
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a lead storage battery.
  • Lead-acid batteries are used for various purposes such as in-vehicle use, industrial use, and so on.
  • Lead-acid batteries include a negative electrode plate, a positive electrode plate, a separator (or mat), an electrolytic solution, and the like.
  • Additives may be added to the constituent members of the lead-acid battery from the viewpoint of imparting various functions.
  • Patent Document 1 describes a group of electrode plates in which a negative electrode plate in which a negative electrode active material is filled in a negative electrode current collector and a positive electrode plate in which a positive electrode active material is filled in a positive electrode current collector are laminated via a separator.
  • a liquid lead-acid battery having a configuration in which it is housed in an electric tank together with an electrolytic solution, is charged intermittently, and is discharged to a load at a high rate in a partially charged state.
  • at least a carbonaceous conductive material and an organic compound that suppresses the coarsening of the negative electrode active material due to charging and discharging are added to the negative electrode active material, and the positive electrode plate has a unit electrode plate group volume [cm].
  • the total surface area [m 2 ] of the positive electrode active material per 3 ] is configured to be in the range of 3.5 to 15.6 [m 2 / cm 3 ], and in addition, cations are contained in the electrolytic solution.
  • a lead storage battery characterized by the addition of a compound selected from a system flocculant, a cationic surfactant, and a phosphoric acid.
  • Patent Document 2 proposes an electrolytic solution for a lead storage battery containing an ammonium compound represented by a specific formula (I).
  • Patent Document 3 proposes a lead-acid battery in which a copolymer of propylene oxide and ethylene oxide is added to a negative electrode plate and a substance in combination with lignin sulfonate.
  • Patent Document 4 proposes a rechargeable electrochemical cell that is subjected to a plurality of charge cycles and discharge cycles. Each charge cycle has a charge unit corresponding to gassing charge in which gas is generated in the cell and a charge unit lower than gassing charge.
  • the electrochemical cell is a water-soluble electrolyte that supports the current between the positive and negative electrodes and the electrodes, and is an inactivating inhibitor that is placed in the electrolyte and a barrier that inhibits gassing charging. With its constituents bonded to the negative electrode, for forming.
  • the inactivated inhibitory means is activated by a charging unit corresponding to the gassing charge so that the inactivated inhibitor inhibits the gassing charge and limits gas generation in the cell.
  • Patent Document 4 describes quaternary ammonium such as alkyldimethylbenzylammonium chloride as an inactivating inhibitory means.
  • Patent Document 6 mainly describes a coordination agent of 2.5 to 4% by weight, a complexing agent of 2.5 to 4% by weight, a catalyst of 0.01 to 0.5% by weight, and a stabilizer of 2.3 to 3.8% by weight.
  • We are proposing an electrolyte.
  • the complexing agent is sodium carboxymethyl cellulose or polyacrylamide
  • the stabilizer is an alkali containing lithium sulfate or lithium ion
  • the defoaming agent is glycerin polyoxyethylene polyoxypropylene ether or tributyl phosphate.
  • the modifier is sodium hydroxide or potassium hydroxide, or sodium carbonate
  • the coordinator is nanofumed silica with a diameter of 8-15 nm
  • the catalyst is sodium amide or sodium metal 99.5. be.
  • Patent Document 7 proposes a lead storage battery including a combination of a positive electrode plate made of a porous substrate made of a Pb—Ca based alloy filled with a positive electrode active material containing calcium and an electrolytic solution containing aluminum ions. ..
  • Lead-acid batteries may be used in an undercharged state called a partially charged state (PSOC).
  • PSOC partially charged state
  • ISS idling stop start
  • the lead-acid battery is repeatedly charged and discharged by PSOC, lead sulfate tends to accumulate and the life performance tends to deteriorate.
  • high charge acceptability is required.
  • the charge acceptability is high, the reduction reaction of hydrogen ions at the time of overcharging is also remarkable, so that the amount of overcharged electricity is large and the electrolytic solution is significantly reduced.
  • the lead-acid battery comprises at least one cell comprising a group of plates and an electrolyte.
  • the electrode plate group includes a positive electrode plate, a negative electrode plate, and a separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate comprises a negative electrode material and is provided with a negative electrode material.
  • the negative electrode material contains at least one additive selected from the group consisting of a surfactant, a polymer compound having a repeating structure of an oxyC 2-4 alkylene unit, and a surfactant, and an organic shrinkage proofing agent.
  • the electrolytic solution contains metal ions and contains metal ions.
  • the metal ion contains at least one component selected from the group consisting of lithium ion, sodium ion, and aluminum ion.
  • the total concentration of the components in the electrolytic solution is 0.02 mol / L or more.
  • the present invention relates to a lead storage battery in which the concentration of each of the components in the electrolytic solution is 0.35 mol / L or less.
  • the reaction during overcharging is greatly affected by the reduction reaction of hydrogen ions at the interface between lead and the electrolytic solution.
  • the negative electrode material of the lead storage battery contains an organic additive
  • the organic additive adheres to the surface of lead, which is an active material.
  • the reduction reaction of hydrogen ions is less likely to occur, so that the amount of overcharged electricity tends to decrease.
  • the organic additive also adheres to the surface of lead sulfate generated during discharge, making it difficult for lead sulfate to elute during charging, and thus the charge acceptability is lowered.
  • an aqueous sulfuric acid solution is generally used as the electrolytic solution, so if an organic additive (oil, polymer, organic shrink-proofing agent, etc.) is contained in the negative electrode material, it will elute into the electrolytic solution and lead. It becomes difficult to balance with the adsorption of. For example, when an organic additive having low adsorptivity to lead is used, it becomes easy to elute into the electrolytic solution, and it becomes difficult to reduce the amount of overcharged electricity. 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 lead surface, 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 charge / discharge reaction is likely to be inhibited.
  • the content of the organic additive is increased in order to secure a sufficient effect of reducing the amount of overcharged electricity, the movement of ions in the pores is further inhibited, so that the charge / discharge reaction is further inhibited.
  • the charge acceptability is lowered and the discharge performance is lowered.
  • the lead-acid battery includes at least one cell including a group of plates and an electrolytic solution.
  • the electrode plate group includes a positive electrode plate, a negative electrode plate, and a separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate comprises a negative electrode material.
  • the negative electrode electrode material is an additive (hereinafter referred to as a first additive) selected from the group consisting of a surfactant and a polymer compound having a repeating structure of an oxyC 2-4 alkylene unit, and an organic shrinkage barrier. Including agents.
  • the electrolytic solution contains metal ions.
  • the metal ion contains at least one component (hereinafter referred to as a first component) selected from the group consisting of lithium ion, sodium ion, and aluminum ion.
  • a first component selected from the group consisting of lithium ion, sodium ion, and aluminum ion.
  • the total concentration of the first component in the electrolytic solution is 0.02 mol / L or more.
  • the concentration of each of the first components in the electrolytic solution is 0.35 mol / L or less.
  • the combination of a negative electrode plate provided with a negative electrode material containing an organic shrinkage proofing agent and a first additive and an electrolytic solution containing the first component at the above concentration is high.
  • the amount of overcharged electricity can be reduced while ensuring charge acceptability.
  • the amount of decrease in the electrolytic solution can be reduced.
  • the lead-acid battery according to one aspect of the present invention can reduce the amount of overcharged electricity while ensuring relatively high charge acceptability for the following reasons.
  • the first additive has a high adsorptivity to lead due to the repeating structure of the oxyC 2-4 alkylene unit or the presence of the hydrophilic group of the surfactant.
  • hydrogen sulfate ions are adsorbed on the lead surface in the negative electrode material, but the anionic property of the hydrogen sulfate ions is relaxed by the action of the first component. This effect is believed to be more pronounced when the first additive has a hydrophobic group. Therefore, it is considered that the adsorptivity of the first additive to the lead surface is further enhanced.
  • the first additive has a repeating structure of the oxyC 2-4 alkylene unit, it is easy to take a linear structure.
  • the surfactant can suppress excessive coating on the lead surface by the action of the hydrophobic group and is amphipathic, it is considered that aggregation is unlikely to occur. Therefore, a wide area of the surface of lead will be thinly and widely covered with the first additive. As a result, the hydrogen overvoltage rises, and side reactions that generate hydrogen during overcharging are less likely to occur, so that the amount of overcharged electricity can be reduced. Even when the negative electrode material contains a very small amount of the first additive, the effect of reducing the amount of overcharged electricity can be obtained. Therefore, by containing the first additive in the negative electrode material, it is placed in the vicinity of lead. It can be present, which is considered to exert a high adsorption action of the first additive on lead.
  • the effect of reducing the amount of overcharged electricity is exhibited by covering the surface of lead in the negative electrode material with the first additive. Therefore, it is important that the first additive is present in the vicinity of lead in the negative electrode material, whereby the effect of the first additive can be effectively exerted. Therefore, it is important that the negative electrode material contains the first additive regardless of whether or not the first additive is contained in the components of the lead storage battery other than the negative electrode material.
  • the organic additive adheres not only to the lead surface but also to the surface of lead sulfate generated during discharge, so that the solubility of lead sulfate during charging tends to decrease. be.
  • the first additive since the thickness of the coating film of the first additive covering the surfaces of lead and lead sulfate is thin, the first additive is capable of dissolving lead sulfate and transferring electrons when reducing lead ions to lead during charging. The degree of inhibition by the coating is reduced. Further, since the coating film of the first additive is thin and the uneven distribution is suppressed, the steric hindrance caused by the coating film of the first additive is reduced, so that the movement of lead ions in the pores of the negative electrode material may be hindered.
  • the high diffusion rate of lead ions is maintained.
  • the negative electrode material contains the first additive which is an organic additive and the organic shrinkage barrier, it is possible to reduce the inhibition of the charge / discharge reaction.
  • the electrolytic solution contains the first component in a specific content, the crystal growth of lead sulfate on the negative electrode plate during discharge becomes difficult to proceed, so that the coarsening of lead sulfate is suppressed.
  • the electrolytic solution contains the first component, the adsorbability of the first additive to the surface of lead sulfate is lowered due to the presence of the first component existing in the vicinity of lead sulfate.
  • the coating of the first additive on lead sulfate is further reduced.
  • a high diffusion rate of lead ions can be ensured, coarsening of lead sulfate can be suppressed, and excessive coating of the first additive on lead sulfate is suppressed, thereby achieving high charge acceptability. It is thought that it can be secured.
  • the lead storage battery of one aspect of the present invention coarsening of lead sulfate is suppressed and high charge acceptability can be obtained.
  • the accumulation of lead sulfate is reduced, and the progress of sulfation in which the accumulated lead sulfate is inactivated can be suppressed. Therefore, high PSOC life performance can be ensured.
  • the electrolytic solution contains the first component having a specific concentration
  • the negative electrode electrode material contains an organic shrinkage proofing agent and does not contain the first additive
  • a certain degree of charge acceptability and PSOC life performance should be ensured. Can be done. However, the effect of reducing the amount of overcharged electricity cannot be obtained. Further, even when the negative electrode material contains the organic shrinkage proofing agent and the first additive, if the electrolytic solution does not contain the first component, the amount of overcharged electricity can be reduced to some extent, but the charge acceptability is high. It is reduced and the PSOC life performance is almost unchanged or reduced.
  • a negative electrode plate provided with a negative electrode material containing an organic shrinkage proofing agent and a first additive is combined with an electrolytic solution containing the first component at a specific concentration. Therefore, as described above, the charge acceptability can be greatly improved while reducing the amount of overcharged electricity. In addition, the PSOC life performance can be significantly improved.
  • the electrolytic solution containing the first component having a specific concentration is combined with the negative electrode plate containing the negative electrode material containing the organic shrinkage proofing agent and not containing the first additive, and the organic shrinkage proofing agent and the first.
  • the negative electrode plate provided with the negative electrode material containing the organic shrinkage proofing agent and the first additive and the electrolytic solution containing the first component at a specific concentration are combined to overcharge.
  • a synergistic effect can be obtained in reducing the amount of electricity and improving charge acceptability and PSOC life performance.
  • the adsorption of the first additive to the lead surface itself tends to be hindered.
  • the concentration of each of the first components in the electrolytic solution as described above, the amount of overcharged electricity to the lead surface can be suppressed to a low level.
  • the first component preferably contains at least one of lithium ion and sodium ion and aluminum ion. In this case, charge acceptability and PSOC life performance can be further improved. In addition, the amount of overcharged electricity can be further reduced.
  • the first component preferably contains at least lithium ions and aluminum ions.
  • the first additive preferably contains a compound having a repeating structure of an oxypropylene unit (-O-CH (-CH 3 ) -CH 2- ). Further, such a compound may not contain a repeating structure of an oxyethylene unit (-O-CH 2 -CH 2- ). In these cases, the charge acceptability and PSOC life performance are further enhanced, and the amount of overcharged electricity is further reduced. Since the compound containing the repeating structure of the oxypropylene unit easily forms a linear structure, it is considered that the amount of overcharged electricity is reduced by covering the lead surface thinly and widely. Further, the repeating structure of the oxypropylene unit is more hydrophobic than the repeating structure of the oxyethylene unit.
  • the compound having a repeating structure of the oxypropylene unit preferably has a number average molecular weight (Mn) of 1000 or more and 10000 or less.
  • Mn number average molecular weight
  • the first additive easily stays in the negative electrode material, and the amount of overcharged electricity can be further reduced. Further, the effect of suppressing the uneven distribution of the first additive on the lead surface is enhanced, so that the charge acceptability and the PSOC life performance can be further improved.
  • the first additive contains a sulfur element
  • the first additive tends to be easily adsorbed on the surface of lead sulfate due to the action of the first component existing in the vicinity of lead sulfate. Therefore, it is preferable that the first additive does not contain a sulfur element. As a result, the adsorption of the first additive on lead sulfate can be reduced, so that it becomes easier to secure higher charge acceptability and PSOC life performance.
  • the surfactant contains a cationic surfactant.
  • the cationic surfactant preferably contains a quaternary ammonium salt type cationic surfactant. Since the cationic surfactant has a cationic hydrophilic group, in the absence of the first component, it exhibits high adsorption to the lead surface due to the action of lead and hydrogen sulfate ions present in the vicinity of lead sulfate, and discharges. It tends to adhere to the surface of lead sulfate that is sometimes produced.
  • the action of the first component relaxes the adsorptivity of the cationic surfactant to the lead surface, and makes it easy to cover a wide range of the lead surface thinly and widely. Further, the cationic surfactant electrically repels the first component existing in the vicinity of lead sulfate, and the adsorption of the cationic surfactant on lead sulfate is further reduced. Therefore, it is possible to obtain higher charge acceptability and PSOC life performance while keeping the amount of overcharged electricity low.
  • Cationic surfactants are generally classified into amine salt type or quaternary ammonium salt type.
  • the cationic surfactant preferably contains a quaternary ammonium salt (in other words, a quaternary ammonium salt type cationic surfactant).
  • a quaternary ammonium salt When a quaternary ammonium salt is used, high charge acceptance and PSOC life performance can be obtained, and due to the high cationicity of the hydrophilic group, it exhibits higher adsorption to the lead surface than the amine salt, so that it is overcharged. The amount of electricity can be further reduced.
  • the negative electrode material may contain a carbonaceous material.
  • the first additive may have at least one hydrophobic group and a hydrophilic group. At least one of the hydrophobic groups may be a long-chain aliphatic hydrocarbon group having 8 or more carbon atoms. Due to the action of the long-chain aliphatic hydrocarbon group having 8 or more carbon atoms, the adsorptivity of the first additive to the lead surface is alleviated, and excessive coating is alleviated. Further, since the first additive is easily adsorbed on the carbonaceous material, the uneven distribution of the first additive on the surface of lead sulfate is reduced. Therefore, it becomes easy to secure higher charge acceptability and PSOC life performance while keeping the amount of overcharge electricity low.
  • the organic shrinkage proofing agent preferably contains a condensate of a bis-alene compound.
  • Bisareene compounds are generally classified as synthetic organic shrink proofing agents.
  • the specific surface area of the negative electrode material increases, so that the amount of overcharged electricity tends to increase.
  • the organic shrinkage proofing agent is used. Even when contains a condensate of a bis-alene compound, the amount of overcharged electricity can be kept low.
  • the condensate of the bis-alene compound the uneven distribution of the organic shrink-proofing agent is reduced as compared with the lignin compound, so that higher charge acceptability and PSOC life performance can be easily obtained.
  • the lead-acid battery may be either a control valve type (sealed type) lead-acid battery (VRLA type lead-acid battery) or a liquid type (vent type) lead-acid battery.
  • Electrode material Each electrode material of the negative electrode material and the positive electrode material is usually held in the current collector.
  • the electrode material is a portion of the electrode plate excluding the current collector.
  • Members such as mats and pacing papers may be attached to the electrode plate. Since such a member (also referred to as a sticking member) is used integrally with the plate, it is included in the plate.
  • the electrode plate includes a sticking member (mat, pacing paper, etc.)
  • the electrode material is a portion of the electrode plate excluding the current collector and the sticking member.
  • the clad type positive electrode plate includes a plurality of porous tubes, a core metal (spine) inserted in each tube, and a current collecting unit for connecting the plurality of core metal (spine). It includes a positive electrode material filled in a tube into which a spine is inserted, and a spine projector that connects a plurality of tubes.
  • the positive electrode electrode material is a portion of the electrode plate excluding the tube, the core metal (spine), the current collector, and the spine projector.
  • the core metal (spine) and the current collector may be collectively referred to as a positive electrode current collector.
  • the oxyC 2-4 alkylene unit contained in the polymer compound is a unit represented by —OR 1 ⁇ (where R 1 represents a C 2-4 alkylene group).
  • the polymer compound may have a repeating structure of oxyC 2-4 alkylene unit, and Mn is not particularly limited.
  • the number average molecular weight (Mn) of the polymer compound may be 300 or more.
  • the content of the sulfur element in the organic shrinkage proofing agent is X ⁇ mol / g means that the content of the sulfur element contained in 1 g of the organic shrinkage proofing agent is X ⁇ mol / g.
  • the condensate of bis-alene compound is a condensate containing a unit of bis-alene compound.
  • the unit of the bis-alene compound means a unit derived from the bis-alene compound incorporated in the condensate.
  • a bis-alene compound is a compound in which two sites each having an aromatic ring are linked via a single bond or a linking group.
  • Mn number average molecular weight
  • GPC gel permeation chromatography
  • the concentration of each of the first components in the electrolytic solution means the concentration of individual ions of lithium ion, sodium ion and aluminum ion.
  • the total concentration of the first component in the electrolytic solution is the total concentration of the above-mentioned individual ions.
  • the electrolytic solution contains lithium ions, sodium ions and aluminum ions, the total concentration of these ions is the total concentration of the first component.
  • the fully charged state is 0.2 times the current (value with Ah as the unit) described in the rated capacity in the air tank at 25 ° C ⁇ 2 ° C (the unit is Ah).
  • A) constant current constant voltage charging of 2.23 V / cell is performed, and the charging current at the time of constant voltage charging is 0.005 times the value (value with the unit being Ah) described in the rated capacity (A). When it becomes, charging is completed.
  • a fully charged lead-acid battery is a fully charged lead-acid battery.
  • the lead-acid battery may be fully charged after the chemical conversion, immediately after the chemical conversion, or after a lapse of time from the chemical conversion (for example, after the chemical conversion, the lead-acid battery in use (preferably at the initial stage of use) is fully charged. May be).
  • An initial use battery is a battery that has not been used for a long time and has hardly deteriorated.
  • the vertical direction of the lead-acid battery or the component of the lead-acid battery means the vertical direction of the lead-acid battery in the state where the lead-acid battery is used.
  • Each electrode plate of the positive electrode plate and the negative electrode plate is provided with an ear portion for connecting to an external terminal.
  • the ears are provided so as to project laterally to the sides of the plate, but in many lead-acid batteries, the ears are usually made of the plate. It is provided so as to project upward at the top.
  • the negative electrode plate usually includes a negative electrode current collector in addition to the negative electrode material.
  • the negative electrode current collector may be formed by casting lead (Pb) or a lead alloy, or may be formed by processing a lead sheet or a lead alloy sheet. Examples of the processing method include expanding processing and punching processing. It is preferable to use a grid-shaped current collector as the negative electrode current collector because it is easy to support the negative electrode material.
  • the lead alloy used for the negative electrode current collector may be any of Pb—Sb-based alloys, Pb-Ca-based alloys, and Pb-Ca—Sn-based alloys. These leads or lead alloys may further contain, as an additive element, at least one selected from the group consisting of Ba, Ag, Al, Bi, As, Se, Cu and the like.
  • the negative electrode current collector may include a surface layer. The composition of the surface layer and the inner layer of the negative electrode current collector may be different. The surface layer may be formed on a part of the negative electrode current collector. The surface layer may be formed on the selvage portion of the negative electrode current collector. The surface layer of the selvage may contain Sn or Sn alloy.
  • the negative electrode material contains a first additive and an organic shrink proofing agent.
  • the negative electrode material further contains a negative electrode active material (specifically, lead or lead sulfate) that develops a capacity by a redox reaction.
  • the negative electrode material may contain at least one selected from the group consisting of carbonaceous materials and additives other than the first additive.
  • Additives other than the first additive may be referred to as the second additive. Examples of the second additive include, but are not limited to, barium sulfate, fibers (resin fibers, etc.) and the like.
  • the negative electrode active material in the charged state is spongy lead, but the unchemical negative electrode plate is usually produced by using lead powder.
  • the first additive is at least one selected from the group consisting of a polymer compound having a repeating structure of an oxyC 2-4 alkylene unit and a surfactant.
  • Polymer compounds having a repeating structure of oxyC 2-4 alkylene units also include polymer compounds classified as surfactants (more specifically, nonionic surfactants).
  • polymer compound examples of the oxyC 2-4 alkylene unit contained in the polymer compound include oxyethylene unit, oxypropylene unit, oxytrimethylene unit, oxy2-methyl-1,3-propylene unit, oxy1,4-butylene unit, and oxy1,. Examples include 3-butylene unit.
  • the polymer compound may have one kind of such oxyC 2-4 alkylene unit, or may have two or more kinds.
  • Such a polymer compound has a peak derived from an oxyC 2-4 alkylene unit in the range of 3.2 ppm or more and 3.8 ppm or less in a chemical shift of 1 H-NMR spectrum measured using deuterated chloroform as a solvent. show.
  • the repeating structure of the oxyC 2-4 alkylene unit may contain one kind of oxy C 2-4 alkylene unit or may contain two or more kinds of oxy C 2-4 alkylene units.
  • the polymer compound may contain one kind of the above-mentioned repeating structure, or may contain two or more kinds of the above-mentioned repeating structures.
  • polymer compound examples include a hydroxy compound having a repeating structure of an oxy C 2-4 alkylene unit (poly C 2-4 alkylene glycol, a copolymer containing a repeating structure of oxy C 2-4 alkylene, and a polyol poly C 2 ). -4 alkylene oxide adducts, etc.), ethers or esters of these hydroxy compounds.
  • copolymer examples include a copolymer containing different oxyC 2-4 alkylene units.
  • the copolymer may be a block copolymer.
  • the polyol may be any of an aliphatic polyol, an alicyclic polyol, an aromatic polyol, a heterocyclic polyol and the like. From the viewpoint that the polymer compound is thin and easily spreads on the lead surface, an aliphatic polyol, an alicyclic polyol (for example, polyhydroxycyclohexane, polyhydroxynorbornane) and the like are preferable, and an aliphatic polyol is particularly preferable.
  • the aliphatic polyol include an aliphatic diol and a polyol having more than triol (for example, glycerin, trimethylolpropane, pentaerythritol, sugar or sugar alcohol).
  • Examples of the aliphatic diol include alkylene glycols having 5 or more carbon atoms.
  • the alkylene glycol may be, for example, C 5-14 alkylene glycol or C 5-10 alkylene glycol.
  • Examples of the sugar or sugar alcohol include sucrose, erythritol, xylitol, mannitol, and sorbitol.
  • the sugar or sugar alcohol may have either a chain structure or a cyclic structure.
  • the alkylene oxide corresponds to the oxyC 2-4 alkylene unit of the polymer compound and comprises at least C 2-4 alkylene oxide. From the viewpoint that the polymer compound can easily form a linear structure, the polyol is preferably a diol.
  • the etherified product is composed of a -OH group (a hydrogen atom of the terminal group and an oxygen atom bonded to the hydrogen atom of the terminal group) at least a part of the hydroxy compound having a repeating structure of the above oxyC 2-4 alkylene unit.
  • the —OH group has two etherified —OR groups (in the formula, R 2 is an organic group).
  • R 2 is an organic group.
  • ends of the polymer compound some ends may be etherified, or all ends may be etherified.
  • one end of the main chain of the linear polymer compound may be an ⁇ OH group and the other end may be an ⁇ OR2 group.
  • the esterified product is composed of an OH group (a hydrogen atom of the terminal group and an oxygen atom bonded to the hydrogen atom of the terminal group) at least a part of the hydroxy compound having a repeating structure of the oxyC 2-4 alkylene unit.
  • R 3 is an organic group.
  • some ends may be esterified or all ends may be esterified.
  • Examples of the organic groups R 2 and R 3 include hydrocarbon groups.
  • the hydrocarbon group may have a substituent (eg, a hydroxy group, an alkoxy group, and / or a carboxy group).
  • the hydrocarbon group may be any of an aliphatic, alicyclic, and aromatic group.
  • the aromatic hydrocarbon group and the alicyclic hydrocarbon group may have an aliphatic hydrocarbon group (for example, an alkyl group, an alkenyl group, an alkynyl group) as a substituent.
  • the number of carbon atoms of the aliphatic hydrocarbon group as a substituent may be, for example, 1 to 30, 1 to 20 or 1 to 10, and may be 1 to 6 or 1 to 4. .
  • Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 24 or less carbon atoms (for example, 6 to 24). The number of carbon atoms of the aromatic hydrocarbon group may be 20 or less (for example, 6 to 20), 14 or less (for example, 6 to 14) or 12 or less (for example, 6 to 12).
  • Examples of the aromatic hydrocarbon group include an aryl group and a bisaryl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the bisaryl group include a monovalent group corresponding to bisarene. Examples of the bisarene include biphenyl and bisaryl alkane (for example, bis C 6-10 aryl C 1-4 alkane (2,2-bisphenylpropane, etc.)).
  • Examples of the alicyclic hydrocarbon group include an alicyclic hydrocarbon group having 16 or less carbon atoms.
  • the alicyclic hydrocarbon group may be a crosslinked cyclic hydrocarbon group.
  • the alicyclic hydrocarbon group may have 10 or less or 8 or less carbon atoms.
  • the alicyclic hydrocarbon group has, for example, 5 or more carbon atoms, and may be 6 or more carbon atoms.
  • the number of carbon atoms of the alicyclic hydrocarbon group may be 5 (or 6) or more and 16 or less, 5 (or 6) or more and 10 or less, or 5 (or 6) or more and 8 or less.
  • Examples of the alicyclic hydrocarbon group include a cycloalkyl group (cyclopentyl group, cyclohexyl group, cyclooctyl group, etc.) and a cycloalkenyl group (cyclohexenyl group, cyclooctenyl group, etc.).
  • the alicyclic hydrocarbon group also includes the hydrogenated additive of the above aromatic hydrocarbon group.
  • an aliphatic hydrocarbon group is preferable from the viewpoint that the polymer compound is thin and easily adheres to the lead surface.
  • Aliphatic hydrocarbon groups may be saturated or unsaturated. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a dienyl group having two carbon-carbon double bonds, and a trienyl group having three carbon-carbon double bonds.
  • the aliphatic hydrocarbon group may be linear or branched.
  • the aliphatic hydrocarbon group may have, for example, 30 or less, 26 or less or 22 or less, 20 or less or 16 or less, 14 or less or 10 or less. It may be 8 or less or 6 or less.
  • the lower limit of the number of carbon atoms is 1 or more for an alkyl group, 2 or more for an alkenyl group and an alkynyl group, 3 or more for a dienyl group, and 4 or more for a trienyl group, depending on the type of the aliphatic hydrocarbon group.
  • Alkyl groups and alkenyl groups are particularly preferable from the viewpoint that the polymer compound is thin and easily adheres to the lead surface.
  • alkyl group examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, i-pentyl, and s-pentyl.
  • alkenyl group examples include vinyl, 1-propenyl, allyl, cis-9-heptadecene-1-yl, palmitrail and oleyl.
  • the alkenyl group may be, for example, a C 2-30 alkenyl group or a C 2-26 alkenyl group, a C 2-22 alkenyl group or a C 2-20 alkenyl group, and a C 10-20 alkenyl group. May be.
  • the polymer compounds at least one selected from the group consisting of an etherified product of a hydroxy compound having a repeating structure of an oxyC 2-4 alkylene unit and an esterified product of a hydroxy compound having a repeating structure of an oxy C 2-4 alkylene unit.
  • an etherified product of a hydroxy compound having a repeating structure of an oxyC 2-4 alkylene unit and an esterified product of a hydroxy compound having a repeating structure of an oxy C 2-4 alkylene unit.
  • it is preferable because the effect of suppressing a decrease in charge acceptability can be further enhanced. Further, even when these polymer compounds are used, the amount of overcharged electricity can be reduced.
  • a polymer compound having a repeating structure of an oxypropylene unit, a polymer compound having a repeating structure of an oxyethylene unit, or the like is preferable.
  • the polymer compound may have one or more hydrophobic groups.
  • the hydrophobic group include aromatic hydrocarbon groups, alicyclic hydrocarbon groups, and long-chain aliphatic hydrocarbon groups among the above-mentioned hydrocarbon groups.
  • the long-chain aliphatic hydrocarbon group include aliphatic hydrocarbon groups having 8 or more carbon atoms among the above-mentioned aliphatic hydrocarbon groups (alkyl groups, alkenyl groups, etc.).
  • the aliphatic hydrocarbon group preferably has 12 or more carbon atoms, and more preferably 16 or more carbon atoms.
  • a polymer compound having a long-chain aliphatic hydrocarbon group is preferable because it is unlikely to cause excessive adsorption to lead and the effect of suppressing a decrease in charge acceptability is further enhanced.
  • the polymer compound may be a polymer compound in which at least one of the hydrophobic groups is a long-chain aliphatic hydrocarbon group.
  • the carbon number of the long-chain aliphatic hydrocarbon group may be 30 or less, 26 or less, or 22 or less.
  • the number of carbon atoms of a long-chain aliphatic hydrocarbon group is 8 or more (or 12 or more) 30 or less, 8 or more (or 12 or more) 26 or less, 8 or more (or 12 or more) 22 or less, 10 or more and 30 or less (or 26 or less). ), Or it may be 10 or more and 22 or less.
  • polyoxypropylene-polyoxyethylene block copolymers etherified compounds of hydroxy compounds having a repeating structure of oxyethylene units, and esterified compounds of hydroxy compounds having a repeating structure of oxyethylene units are nonions.
  • etherified compounds of hydroxy compounds having a repeating structure of oxyethylene units and esterified compounds of hydroxy compounds having a repeating structure of oxyethylene units are nonions.
  • esterified compounds of hydroxy compounds having a repeating structure of oxyethylene units are nonions.
  • a surfactant corresponds to a surfactant.
  • the repeating structure of the oxyethylene unit corresponds to a hydrophilic group
  • the repeating structure of the oxypropylene unit corresponds to a hydrophobic group.
  • Such copolymers are also included in the polymer compound having a hydrophobic group.
  • Examples of the polymer compound having a hydrophobic group and containing a repeating structure of an oxyethylene unit include an etherified product of polyethylene glycol (alkyl ether and the like), an esterified product of polyethylene glycol (carboxylic acid ester and the like), and a polyethylene oxide adduct of the above-mentioned polyol.
  • Examples thereof include ethers (alkyl ethers and the like) of the above, and esterified products (carboxylic acid esters and the like) of polyethylene oxide adducts of the above-mentioned polyols (polyols and higher polyols and the like).
  • polymer compounds include polyethylene glycol oleate, polyethylene glycol dioleate, polyethylene glycol dilaurate, polyethylene glycol distearate, polyoxyethylene coconut oil fatty acid sorbitan, polyoxyethylene sorbitan oleate, and polyoxystearate.
  • examples thereof include ethylene sorbitan, polyoxyethylene lauryl ether, polyoxyethylene tetradecyl ether, and polyoxyethylene cetyl ether.
  • the polymer compound is not limited to these.
  • an esterified product of polyethylene glycol an esterified product of the polyethylene oxide adduct of the above-mentioned polyol, or the like because higher charge acceptability can be ensured and the amount of overcharged electricity can be remarkably reduced.
  • the first additive may contain a polymer compound containing a repeating structure of an oxypropylene unit.
  • Polymer compounds containing oxypropylene units have peaks from -CH ⁇ and -CH 2- of the oxypropylene units in the range of 3.2 ppm to 3.8 ppm in a chemical shift of 1 H-NMR spectrum. Since the electron densities around the nuclei of hydrogen atoms in these groups are different, the peaks are split.
  • Such a polymer compound has peaks in the chemical shift of 1 H-NMR spectrum, for example, in the range of 3.2 ppm or more and 3.42 ppm or less, and in the range of 3.42 ppm or more and 3.8 ppm or less. Peaks in the range of 3.2 ppm or more and 3.42 ppm or less are derived from -CH 2- , and peaks in the range of more than 3.42 ppm and 3.8 ppm or less are derived from -CH ⁇ and -CH 2- .
  • Examples of the polymer compound containing at least the repeating structure of the oxypropylene unit include polypropylene glycol, a copolymer containing the repeating structure of the oxypropylene unit, a polypropylene oxide adduct of the above-mentioned polyol, an etherified product or an esterified product thereof.
  • Examples of the copolymer include an oxypropylene-oxyalkylene copolymer (however, the oxyalkylene is C 2-4 alkylene other than oxypropylene).
  • Examples of the oxypropylene-oxyalkylene copolymer include an oxypropylene-oxyethylene copolymer and an oxypropylene-oxytrimethylene copolymer.
  • the oxypropylene-oxyalkylene copolymer may be referred to as a polyoxypropylene-polyoxyalkylene copolymer (for example, a polyoxypropylene-polyoxyethylene copolymer).
  • the oxypropylene-oxyalkylene copolymer may be a block copolymer (for example, a polyoxypropylene-polyoxyethylene block copolymer).
  • Examples of the etherified product include polypropylene glycol alkyl ether, alkyl ether of an oxypropylene-oxyalkylene copolymer (alkyl ether of a polyoxypropylene-polyoxyethylene copolymer, etc.) and the like.
  • esterified product examples include polypropylene glycol ester of carboxylic acid, carboxylic acid ester of oxypropylene-oxyalkylene copolymer (carboxylic acid ester of polyoxypropylene-polyoxyethylene copolymer, etc.) and the like.
  • Examples of the polymer compound containing at least the repeating structure of the oxypropylene unit include polypropylene glycol, polyoxypropylene-polyoxyethylene copolymer (polyoxypropylene-polyoxyethylene block copolymer and the like), polypropylene glycol alkyl ether (above). Alkyl ether (methyl ether, ethyl ether, butyl ether, etc.) in which R 2 is an alkyl having 10 or less carbon atoms (or 8 or less or 6 or less carbon atoms), polyoxyethylene-polyoxypropylene alkyl ether (the above R 2 has carbon atoms).
  • Alkyl ether (butyl ether, hydroxyhexyl ether, etc.) which is an alkyl of 10 or less (or 8 or less or 6 or less), polypropylene glycol carboxylate (the above R 3 is an alkyl having 10 or less carbon atoms (or 8 or less or 6 or less)).
  • polypropylene glycol carboxylate polypropylene glycol acetate, etc.
  • polypropylene oxide adducts of triol or higher polyols polypropylene oxide adducts of glycerin, etc.
  • the polymer compound is not limited to these.
  • the proportion of the oxypropylene unit is, for example, 5 mol% or more, and may be 10 mol% or more or 20 mol% or more.
  • the proportion of the oxypropylene unit is, for example, 100 mol% or less.
  • the polymer compound having the repeating structure of the oxypropylene unit is also preferable when it does not contain the repeating structure of the oxyethylene unit.
  • a first additive containing at least polypropylene glycol is used, excellent effects are likely to be obtained.
  • the first additive may contain one kind of polymer compound or two or more kinds.
  • the polymer compound may contain, for example, a compound having Mn of 5 million or less, a compound of 1 million or less, a compound of 100,000 or less, and a compound of 50,000 or less or 20,000 or less.
  • the polymer compound preferably contains a compound having a Mn of 10,000 or less, and is preferably 9000 or less or 8000 or less. May contain the compound of.
  • the Mn of such a compound may be 300 or more, 400 or more, or 500 or more.
  • the Mn of such a compound is preferably 1000 or more, and more preferably 1500 or more.
  • the polymer compound two or more kinds of compounds having different Mns may be used. That is, the polymer compound may be a polymer compound having a plurality of Mn peaks in the distribution of molecular weight.
  • the Mn of the polymer compound having the repeating structure of the oxypropylene unit may be in such a range.
  • the Mn of the above compounds is 300 or more (or 400 or more) 5 million or less, 300 or more (or 400 or more) 1 million or less, 300 or more (or 400 or more) 100,000 or less, 300 or more (or 400 or more) 50,000 or less, 300 or more (or 400 or more) 20000 or less, 300 or more (or 400 or more) 10000 or less, 300 or more (or 400 or more) 9000 or less, 300 or more (or 400 or more) 8000 or less, 500 or more (or 1000 or more) 5 million or less , 500 or more (or 1000 or more) 1 million or less, 500 or more (or 1000 or more) 100,000 or less, 500 or more (or 1000 or more) 50,000 or less, 500 or more (or 1000 or more) 20000 or less, 500 or more (or 1000 or more) 10,000 or less, 500 or more (or 1000 or more) 9000 or less, 500 or more (or 1000 or more) 8000 or less, 1500 or more and 5 million or less, 1500 or more and 1 million or less, 1500 or more and 100,000 or
  • surfactant examples include a cationic surfactant, a nonionic surfactant, an anionic surfactant, and an amphoteric surfactant.
  • Surfactants contain hydrophilic and hydrophobic groups.
  • the hydrophobic group of the surfactant is a functional group having a higher hydrophobicity than the hydrophilic group.
  • the first additive may contain one type of surfactant, or may contain two or more types in combination.
  • a typical nonionic surfactant is a compound having a repeating structure of an oxyethylene unit and a hydrophobic group, and the description of the polymer compound can be referred to.
  • a fatty acid ester of a polyol such as a polyol (such as a sugar or a sugar alcohol exemplified for a polymer compound)
  • anionic surfactant include carboxylates, sulfonates, sulfates and the like.
  • the amphoteric tenside include an amino acid type amphoteric tenside agent and a betaine type amphoteric tenside agent.
  • the surfactant preferably contains a cationic surfactant from the viewpoint of easily ensuring higher charge acceptability and PSOC life performance while keeping the amount of overcharge electricity low. Further, from the same viewpoint, it is also preferable to use a surfactant containing the above-mentioned nonionic surfactant.
  • Cationic surfactants are classified into amine salt type and quaternary ammonium salt type according to the type of hydrophilic group.
  • cationic surfactants the amine salt moiety or the quaternary ammonium salt moiety corresponds to a hydrophilic group.
  • the hydrophilic group may be present in a salt state or may be present in a cationic state.
  • the type of anion forming the salt is not particularly limited, and examples thereof include a halide ion and an anion derived from an inorganic acid. Examples of the halide ion include fluoride ion, chloride ion, bromide ion, and iodide ion.
  • Examples of the inorganic acid corresponding to the anion derived from the inorganic acid include hydrohalogenated acid (hydrogen hydrochloride, hydrobromic acid, etc.) or oxo acid (sulfuric acid, phosphoric acid, etc.).
  • hydrohalogenated acid hydrogen hydrochloride, hydrobromic acid, etc.
  • oxo acid sulfuric acid, phosphoric acid, etc.
  • the cationic surfactant has one or more hydrophobic groups in one molecule.
  • the hydrophobic group include the hydrocarbon group described for the polymer compound or the hydrophobic group.
  • the number of hydrophobic groups in the cationic surfactant may be one or more, and may be two or more or three or more.
  • Amine salt-type cationic surfactants can usually have one or more and three or less hydrophobic groups per nitrogen atom of the amine salt.
  • a quaternary ammonium salt type cationic surfactant may usually have four hydrophobic groups per nitrogen atom of the ammonium salt.
  • At least one of the hydrophobic groups of the cationic surfactant is a long-chain aliphatic hydrocarbon group having 8 or more carbon atoms.
  • a long-chain aliphatic hydrocarbon group having 8 or more carbon atoms in a cationic surfactant may be referred to as a first hydrophobic group.
  • the cationic surfactant may have one or more hydrophobic groups (also referred to as a second hydrophobic group) other than the first hydrophobic group.
  • the cationic surfactant may have one first hydrophobic group or two or more in one molecule.
  • the kind of at least two first hydrophobic groups may be the same, and all the first hydrophobic groups are different. May be.
  • the upper limit of the number of first hydrophobic groups in the cationic surfactant is not particularly limited.
  • the number of first hydrophobic groups is, for example, 3 or less, and may be 2 or less.
  • the number of primary hydrophobic groups is, for example, 4 or less, and may be 3 or less or 2 or less.
  • the number of first hydrophobic groups contained in one molecule of the cationic surfactant is, for example, 1 to 3, may be 1 to 2, or may be 2 to 3.
  • the number of primary hydrophobic groups contained in one molecule of the cationic surfactant is, for example, 1 to 4 in the quaternary ammonium salt type, and may be 1 to 3 or 1 to 2 or 2 to 2. It may be 4 or 2 to 3.
  • the cationic surfactant may have one second hydrophobic group or two or more.
  • the kind of at least two second hydrophobic groups may be the same, and all the second hydrophobic groups may be different.
  • the upper limit of the number of the second hydrophobic groups is not particularly limited, and may be, for example, 2 or less in the amine salt type, and may be, for example, 3 or less or 2 or less in the quaternary ammonium salt type.
  • the total number of first and second hydrophobic groups in one molecule does not exceed 3 for the amine salt type and 4 for the quaternary ammonium salt type per nitrogen atom. It will not be exceeded.
  • the first hydrophobic group is preferably an alkyl group or an alkenyl group.
  • the carbon number of the first hydrophobic group is, for example, 30 or less.
  • the carbon number of the first hydrophobic group is preferably 26 or less, more preferably 24 or less or 22 or less, from the viewpoint that it is easy to secure high adsorptivity of the cationic surfactant to the lead surface due to the balance with the hydrophilic group.
  • the negative electrode electrode material may contain a carbonaceous material, but when the carbon number of the long-chain aliphatic hydrocarbon group is 26 or less (for example, 24 or less or 22 or less), a cationic surfactant is used. However, the adsorption on the carbonaceous material is reduced, and the adsorption on the lead surface is likely to occur. Therefore, the amount of overcharged electricity can be further reduced.
  • the second hydrophobic group examples include the hydrocarbon groups described for polymer compounds.
  • the hydrocarbon group may be a hydrocarbon group having a substituent (for example, an alkoxy group).
  • the hydrocarbon group may be any of an aliphatic, alicyclic, and aromatic group.
  • the aliphatic hydrocarbon group is selected as a substituent from the group consisting of an aromatic hydrocarbon group (eg, phenyl group, trill group, naphthyl group) and an alicyclic hydrocarbon group (eg, cyclopentyl group, cyclohexyl group). May have at least one of them.
  • Examples of the aliphatic hydrocarbon group having such a substituent include a benzyl group, a phenethyl group and a cyclohexylmethyl group.
  • the carbon number of the aromatic hydrocarbon group and the alicyclic hydrocarbon group as the substituent is, for example, 5 or more and 20 or less, and may be 6 or more and 12 or less.
  • the aromatic hydrocarbon group and the alicyclic hydrocarbon group may each have an aliphatic hydrocarbon group (for example, an alkyl group, an alkenyl group, an alkynyl group) as a substituent.
  • the number of carbon atoms of the aliphatic hydrocarbon group as a substituent may be, for example, 1 to 30, 1 to 20 or 1 to 10, and may be 1 to 6 or 1 to 4. ..
  • the description of the hydrocarbon group for the polymer compound can be referred to.
  • alkyl group as the second hydrophobic group examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, neopentyl and i. -Pentyl, s-pentyl, 3-pentyl, t-pentyl, n-hexyl can be mentioned.
  • alkenyl group examples include vinyl, 1-propenyl, and allyl.
  • the cationic surfactant preferably contains at least a quaternary ammonium salt type cationic surfactant.
  • the cationic surfactant may contain an amine salt type cationic surfactant in addition to the quaternary ammonium salt type cationic surfactant.
  • Examples of the quaternary ammonium salt type cationic surfactant include tetraalkylammonium salts and alkylbenzalkonium chloride.
  • Examples of the tetraalkylammonium salt include a cationic surfactant having one first hydrophobic group (octyltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, etc.) and two first hydrophobic groups.
  • Examples thereof include cationic surfactants (such as distearyldimethylammonium chloride).
  • a cationic surfactant having four second hydrophobic groups such as tetramethylammonium chloride
  • alkylbenzalkonium chloride examples include stearylbenzyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, and stearylbenzalkonium chloride.
  • amine salt type cationic surfactant examples include n-octylamine hydrochloride, dodecylamine hydrochloride and the like. These are merely examples, and cationic surfactants are not limited to these specific examples.
  • the first additive may contain one kind of cationic surfactant, or may contain two or more kinds.
  • the Mn of the nonionic surfactant can be selected from the range of Mn described for the polymer compound. From the viewpoint of ensuring higher charge acceptability, the nonionic surfactant preferably contains a compound having Mn of 10,000 or less.
  • the content of the first additive in the negative electrode electrode material is, for example, 8 ppm or more on a mass basis. From the viewpoint of further enhancing the effect of reducing the amount of overcharged electricity, the content of the first additive in the negative electrode electrode material is preferably 10 ppm or more or 50 ppm or more, more preferably 100 ppm or more, and 300 ppm or more or 400 ppm on a mass basis. It may be the above.
  • the content of the first additive in the negative electrode electrode material may be, for example, 10,000 ppm or less, 6000 ppm or less, 5000 ppm or less, 1000 ppm or less, or 700 ppm or less on a mass basis.
  • the content of the first additive in the negative electrode electrode material is 8 ppm or more (or 10 ppm or more) 10000 ppm or less, 8 ppm or more (or 10 ppm or more) 6000 ppm or less, 8 ppm or more (or 10 ppm or more) 5000 ppm or less, 8 ppm or more on a mass basis.
  • Organic shrinkage proofing agents are usually roughly classified into lignin compounds and synthetic organic shrinkage proofing agents. It can be said that the synthetic organic shrinkage proofing agent is an organic shrinkage proofing agent other than the lignin compound.
  • the organic shrinkage proofing agent contained in the negative electrode electrode material include lignin compounds and synthetic organic shrinkage proofing agents.
  • the negative electrode electrode material may contain one kind of organic shrinkage proofing agent, or may contain two or more kinds of organic shrinkage proofing agents.
  • Examples of the lignin compound include lignin and lignin derivatives.
  • Examples of the lignin derivative include lignin sulfonic acid or a salt thereof (alkali metal salt (sodium salt, etc.), etc.).
  • the synthetic organic shrinkage proofing agent is an organic polymer containing a sulfur element, and generally contains a plurality of aromatic rings in the molecule and also contains a sulfur element as a sulfur-containing group.
  • a sulfur-containing group a sulfonic acid group or a sulfonyl group, which is a stable form, is preferable.
  • the sulfonic acid group may be present in acid form or may be present in salt form such as Na salt.
  • At least a lignin compound may be used as the organic shrinkage proofing agent.
  • Lignin compounds tend to have lower charge acceptability than synthetic organic shrink proofing agents.
  • the negative electrode electrode material contains the first additive, high charge acceptability can be ensured even when a lignin compound is used as the organic shrinkage proofing agent.
  • the organic shrinkage proofing agent it is also preferable to use a condensate containing at least a unit of an aromatic compound.
  • a condensate include a condensate of an aromatic compound made of an aldehyde compound (such as at least one selected from the group consisting of aldehydes (eg, formaldehyde) and condensates thereof).
  • the organic shrinkage proofing agent may contain a unit of one kind of aromatic compound, or may contain a unit of two or more kinds of aromatic compounds.
  • the unit of the aromatic compound means a unit derived from the aromatic compound incorporated in the condensate.
  • Examples of the aromatic ring contained in the aromatic compound include a benzene ring and a naphthalene ring.
  • the plurality of aromatic rings may be directly bonded or linked by a linking group (for example, an alkylene group (including an alkylidene group), a sulfone group) or the like.
  • Examples of such a structure include a bisarene structure (biphenyl, bisphenylalkane, bisphenylsulfone, etc.).
  • Examples of the aromatic compound include compounds having the above aromatic ring and at least one selected from the group consisting of a hydroxy group and an amino group.
  • the hydroxy group or amino group may be directly bonded to the aromatic ring, or may be bonded as an alkyl chain having a hydroxy group or an amino group.
  • the hydroxy group also includes a salt of the hydroxy group (-OMe).
  • the amino group also includes a salt of the amino group (specifically, a salt with an anion). Examples of Me include alkali metals (Li, K, Na, etc.), Group 2 metals of the periodic table (Ca, Mg, etc.) and the like.
  • aromatic compound examples include bisarene compounds [bisphenol compounds, hydroxybiphenyl compounds, bisarene compounds having an amino group (bisarylalkane compounds having an amino group, bisarylsulfone compounds having an amino group, biphenyl compounds having an amino group, etc.), and the like. Hydroxyarene compounds (hydroxynaphthalene compounds, phenol compounds, etc.), aminoarene compounds (aminonaphthalene compounds, aniline compounds (aminobenzenesulfonic acid, alkylaminobenzenesulfonic acid, etc.), etc.), etc.] are preferable.
  • the aromatic compound may further have a substituent.
  • the organic shrinkage proofing agent may contain one kind of residues of these compounds, or may contain a plurality of kinds.
  • bisphenol compound bisphenol A, bisphenol S, bisphenol F and the like are preferable.
  • the negative electrode material contains a condensate of a bis-alene compound (such as a condensate of an aldehyde compound)
  • the amount of overcharge electricity tends to increase, but the direct or indirect mutual of the first component and the first additive.
  • the amount of overcharged electricity can be suppressed to a low level.
  • charge acceptability and PSOC life performance can be improved as compared with the case of using a lignin compound.
  • the organic shrinkage proofing agent for example, a condensation containing at least one selected from the group consisting of a unit of the above-mentioned bisarene compound and a unit of a monocyclic aromatic compound (hydroxyarene compound and / or aminoarene compound, etc.). At least one may be used.
  • the organic shrinkage proofing agent may contain at least a condensate containing a unit of a bisarene compound and a unit of a monocyclic aromatic compound (particularly, a hydroxyarene compound). Examples of such a condensate include a condensate of a bis-alene compound and a monocyclic aromatic compound made of an aldehyde compound.
  • hydroxyarene compound a phenol sulfonic acid compound (such as phenol sulfonic acid or a substitute thereof) is preferable.
  • aminoarene compound aminobenzenesulfonic acid, alkylaminobenzenesulfonic acid and the like are preferable.
  • monocyclic aromatic compound a hydroxyarene compound is preferable.
  • the sulfur element content of the first organic shrinkage proofing agent may be 2000 ⁇ mol / g or more, preferably 3000 ⁇ mol / g or more.
  • the upper limit of the sulfur element content of the first organic shrinkage proofing agent is not particularly limited. From the viewpoint of further enhancing the effect of reducing the amount of overcharged electricity, the sulfur element content of the organic shrinkage proofing agent is preferably 9000 ⁇ mol / g or less, and more preferably 8000 ⁇ mol / g or less.
  • the sulfur element content of the first organic shrinkage proofing agent is, for example, 2000 ⁇ mol / g or more (or 3000 ⁇ mol / g or more) 9000 ⁇ mol / g or less, or 2000 ⁇ mol / g or more (or 3000 ⁇ mol / g or more) 8000 ⁇ mol / g or less. good.
  • the first organic shrinkage proofing agent contains a condensate containing a unit of an aromatic compound having a sulfur-containing group, and the condensate may contain at least a unit of a bisarene compound (such as a bisphenol compound) as a unit of the aromatic compound.
  • a bisarene compound such as a bisphenol compound
  • the weight average molecular weight (Mw) of the first organic shrinkage proofing agent is preferably 7,000 or more.
  • the Mw of the first organic shrinkage proofing agent is, for example, 100,000 or less, and may be 20,000 or less.
  • the Mw of the second organic shrinkage proofing agent is, for example, less than 7,000.
  • the Mw of the second organic shrinkage proofing agent is, for example, 3000 or more.
  • the negative electrode material may contain a second organic shrinkage proofing agent in addition to the first organic shrinkage proofing agent.
  • a second organic shrinkage proofing agent in addition to the first organic shrinkage proofing agent.
  • the content of the organic shrinkage proofing agent contained in the negative electrode electrode material is, for example, 0.005% by mass or more, and may be 0.01% by mass or more. When the content of the organic shrink proofing agent is in such a range, a high discharge capacity can be ensured.
  • the content of the organic shrinkage proofing agent is, for example, 1.0% by mass or less, and may be 0.5% by mass or less. From the viewpoint of further enhancing the effect of suppressing the decrease in charge acceptability, the content of the organic shrinkage proofing agent is preferably 0.3% by mass or less, more preferably 0.25% by mass or less, and 0.2% by mass or less. There may be.
  • the content of the organic shrinkage barrier contained in the negative electrode electrode material is 0.005% by mass or more (or 0.01% by mass) 1.0% by mass or less, 0.005% by mass or more (or 0.01% by mass). (More than) 0.5% by mass or less, 0.005% by mass or more (or 0.01% by mass or more) 0.3% by mass or less, 0.005% by mass or more (or 0.01% by mass or more) 0.25% by mass % Or less, or 0.005% by mass or more (or 0.01% by mass or more) and 0.2% by mass or less.
  • Carbonate material As the carbonaceous material contained in the negative electrode electrode material, carbon black, graphite, hard carbon, soft carbon and the like can be used. Examples of carbon black include acetylene black, furnace black, and lamp black. Furness Black also includes Ketjen Black (trade name).
  • a carbonaceous material having an I D / IG strength ratio of 0 or more and 0.9 or less is referred to as graphite.
  • the graphite may be either artificial graphite or natural graphite.
  • the negative electrode material may contain one kind of carbonaceous material, or may contain two or more kinds.
  • the content of the carbonaceous material in the negative electrode electrode material is, for example, 0.05% by mass or more, and may be 0.10% by mass or more.
  • the content of the carbonaceous material is, for example, 5% by mass or less, and may be 3% by mass or less.
  • the content of the carbonaceous material in the negative electrode material is 0.05% by mass or more and 5% by mass or less, 0.05% by mass or more and 3% by mass or less, 0.10% by mass or more and 5% by mass or less, or 0.10. It may be mass% or more and 3 mass% or less.
  • barium sulfate The content of barium sulfate in the negative electrode electrode material is, for example, 0.05% by mass or more, and may be 0.10% by mass or more. The content of barium sulfate in the negative electrode electrode material is, for example, 3% by mass or less, and may be 2% by mass or less.
  • the content of barium sulfate in the negative electrode material is 0.05% by mass or more and 3% by mass or less, 0.05% by mass or more and 2% by mass or less, 0.10% by mass or more and 3% by mass or less, or 0.10% by mass. It may be% or more and 2% by mass or less.
  • a fully charged lead-acid battery is disassembled to obtain a negative electrode plate to be analyzed.
  • the obtained negative electrode plate is washed with water to remove sulfuric acid from the negative electrode plate. Wash with water by pressing the pH test paper against the surface of the negative electrode plate washed with water until it is confirmed that the color of the test paper does not change. However, the time for washing with water shall be within 2 hours.
  • the negative electrode plate washed with water is dried at 60 ⁇ 5 ° C. for about 6 hours in a reduced pressure environment. If the negative electrode plate contains a sticking member after drying, the sticking member is removed by peeling.
  • sample A a sample (hereinafter referred to as sample A) is obtained by separating the negative electrode material from the negative electrode plate. Sample A is pulverized as needed and subjected to analysis.
  • Chloroform-soluble components are recovered from the chloroform solution in which the first additive obtained by extraction is dissolved by distilling off chloroform under reduced pressure.
  • the chloroform-soluble component is dissolved in deuterated chloroform, and the 1 H-NMR spectrum is measured under the following conditions. From this 1 H-NMR spectrum, a peak with a chemical shift in the range of 3.2 ppm or more and 3.8 ppm or less is confirmed. Further, the type of oxyC 2-4 alkylene unit is specified from the peak in this range.
  • the obtained mixture is analyzed by thermal decomposition GC-MS under the following conditions to identify the hydrophobic group contained in the esterified product.
  • Analyzer High-performance general-purpose gas chromatogram GC-2014 manufactured by Shimadzu Corporation Column: DEGS (diethylene glycol succinate) 2.1m Oven temperature: 180-120 ° C Injection port temperature: 240 ° C Detector temperature: 240 ° C Carrier gas: He (flow rate: 50 mL / min) Injection volume: 1 ⁇ L to 2 ⁇ L
  • 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.
  • LC / MS device LC unit (manufactured by Agilent Technologies, 1200 Series), MS unit (manufactured by Agilent Technologies 6140) Column: United UK-C18 UP made by Imtakat (inner diameter 2 mm, length 10 cm) Column temperature: 50 ° C ⁇ 1 ° C
  • Mobile phase Using a mixture of the first solution and the second solution, gradually change the mixing ratio of the first solution and the second solution from 20:80 (volume ratio) to 0: 100 (volume ratio) over 3 minutes. Change and use only the second solution after 3 to 10 minutes.
  • First solution aqueous solution containing 10 mmol / L concentration ammonium formate and 10 mmol / L concentration formic acid
  • Second solution methanol solution containing 10 mmol / L concentration ammonium formate and 10 mmol / L formic acid
  • Measurement mode: SCAN (mass measurement range: m / z 100 to 1000)
  • the infrared spectroscopic spectrum measured using the sample C of the organic shrinkage proofing agent thus obtained the ultraviolet visible absorption spectrum measured by diluting the sample C with distilled water or the like, and the sample C being used as heavy water or the like.
  • the first organic shrinkage proofing agent and the second organic shrinkage proofing agent are separated from the above extract as follows. First, the extract is measured by infrared spectroscopy, NMR, and / or GC / MS to determine whether or not it contains a plurality of organic shrink proofing agents. Next, the molecular weight distribution is measured by GPC analysis of the extract, and if a plurality of organic shrink-proofing agents can be separated by molecular weight, the organic shrinkage-proofing agents are separated by column chromatography based on the difference in molecular weight.
  • one of the organic shrinkage proofing agents is separated by a precipitation separation method by utilizing the difference in solubility which differs depending on the type of functional group and / or the amount of functional groups of the organic shrinkage proofing agent.
  • one of the organic shrink-proofing agents is aggregated and separated by adding a sulfuric acid aqueous solution to a mixture in which the above extract is dissolved in a NaOH aqueous solution and adjusting the pH of the mixture.
  • the insoluble component is removed by filtration from the mixture obtained by dissolving the separated product in the aqueous NaOH solution again as described above.
  • the remaining solution after separating one of the organic shrink proofing agents is concentrated.
  • the obtained concentrate contains the other organic shrink-proofing agent, and the insoluble component is removed from the concentrate by filtration as described above.
  • GPC device Build-up GPC system SD-8022 / DP-8020 / AS-8020 / CO-8020 / UV-8020 (manufactured by Tosoh Corporation)
  • Standard substance: Na polystyrene sulfonate (Mw 275,000, 35,000, 12,500, 7,500, 5,200, 1,680)
  • a carbonaceous material and components other than barium sulfate are removed from the dispersion liquid using a sieve.
  • the dispersion liquid is suction-filtered using a membrane filter whose mass has been measured in advance, and the membrane filter is dried together with the filtered sample in a dryer at 110 ° C. ⁇ 5 ° C.
  • the filtered sample is a mixed sample of a carbonaceous material and barium sulfate.
  • the mass of the sample D (M m ) is measured by subtracting the mass of the membrane filter from the total mass of the dried mixed sample (hereinafter referred to as sample D) and the membrane filter.
  • the sample D is put into a crucible together with a membrane filter and incinerated at 1300 ° C. or higher.
  • the remaining residue is barium oxide.
  • the mass of barium oxide is converted into the mass of barium sulfate to obtain the mass of barium sulfate ( MB ).
  • the mass of the carbonaceous material is calculated by subtracting the mass MB from the mass M m .
  • the negative electrode plate can be formed by applying or filling a negative electrode paste to a negative electrode current collector, aging and drying to produce an unchemical negative electrode plate, and then forming an unchemical negative electrode plate.
  • the negative electrode paste contains, for example, lead powder, an organic shrink proofing agent, a first additive, and if necessary, at least one selected from the group consisting of a carbonaceous material and other additives, and water and sulfuric acid ( Alternatively, it is prepared by adding (or aqueous sulfuric acid) and kneading. At the time of aging, it is preferable to ripen the unchemical negative electrode plate at a temperature higher than room temperature and high humidity.
  • Chemical formation can be performed by charging the electrode plate group in a state where the electrode plate group including the unchemical negative electrode plate is immersed in the electrolytic solution containing sulfuric acid in the electric tank of the lead storage battery. However, the chemical formation may be performed before assembling the lead-acid battery or the electrode plate group. The formation produces spongy lead.
  • the positive electrode plate of a lead storage battery can be classified into a paste type, a clad type and the like. Either a paste type or a clad type positive electrode plate may be used.
  • the paste type positive electrode plate includes a positive electrode current collector and a positive electrode material. The configuration of the clad type positive electrode plate is as described above.
  • the positive electrode current collector may be formed by casting lead (Pb) or a lead alloy, or may be formed by processing a lead sheet or a lead alloy sheet. Examples of the processing method include expanding processing and punching processing. It is preferable to use a grid-shaped current collector as the positive electrode current collector because it is easy to support the positive electrode material.
  • the positive electrode current collector may include a surface layer.
  • the composition of the surface layer and the inner layer of the positive electrode current collector may be different.
  • the surface layer may be formed on a part of the positive electrode current collector.
  • the surface layer may be formed only on the lattice portion, the ear portion, or the frame bone portion of the positive electrode current collector.
  • the positive electrode material contained in the positive electrode plate contains a positive electrode active material (lead dioxide or lead sulfate) that develops a capacity by a redox reaction.
  • the positive electrode material may contain other additives, if necessary.
  • the unchemical paste type positive electrode plate is obtained by filling a positive electrode current collector with a positive electrode paste, aging and drying.
  • the positive electrode paste is prepared by kneading lead powder, additives, water, and sulfuric acid.
  • lead powder or slurry-like lead powder is filled in a porous tube into which a core metal (spine) connected by a current collector is inserted, and a plurality of tubes are connected to each other (spine projector). ) Is formed. Then, a positive electrode plate is obtained by forming these unchemical positive electrode plates.
  • Chemical formation can be performed by charging the electrode plate group in a state where the electrode plate group including the unchemical positive electrode plate is immersed in the electrolytic solution containing sulfuric acid in the electric tank of the lead storage battery. However, the chemical formation may be performed before assembling the lead-acid battery or the electrode plate group.
  • a separator can be arranged between the negative electrode plate and the positive electrode plate.
  • As the separator at least one selected from a non-woven fabric and a microporous membrane is used.
  • Nonwoven fabric is a mat that is entwined without weaving fibers, and is mainly composed of fibers.
  • the non-woven fabric for example, 60% by mass or more of the non-woven fabric is formed of fibers.
  • the fiber glass fiber, polymer fiber (polyolefin fiber, acrylic fiber, polyester fiber (polyethylene terephthalate fiber, etc.), etc.), pulp fiber, and the like can be used. Of these, glass fiber is preferable.
  • the non-woven fabric may contain components other than fibers (for example, acid-resistant inorganic powder, polymer as a binder).
  • the microporous film is a porous sheet mainly composed of components other than fiber components.
  • a composition containing a pore-forming agent is extruded into a sheet and then the pore-forming agent is removed to form pores. It is obtained by.
  • the microporous membrane is preferably composed of a material having acid resistance, and a microporous membrane mainly composed of a polymer component is preferable.
  • the polymer component polyolefin (polyethylene, polypropylene, etc.) is preferable.
  • the pore-forming agent include at least one selected from the group consisting of polymer powders and oils.
  • the separator may be composed of, for example, only a non-woven fabric or only a microporous membrane. Further, the separator may be a laminate of a non-woven fabric and a microporous film, a material obtained by laminating different or similar materials, or a material in which irregularities are engaged with different or similar materials, as required.
  • the separator may be in the shape of a sheet or in the shape of a bag.
  • a sheet-shaped separator may be sandwiched between the positive electrode plate and the negative electrode plate.
  • the electrode plate may be arranged so as to sandwich the electrode plate with one sheet-shaped separator in a bent state.
  • the positive electrode plate sandwiched between the bent sheet-shaped separators and the negative electrode plate sandwiched between the bent sheet-shaped separators may be overlapped, and one of the positive electrode plate and the negative electrode plate may be sandwiched between the bent sheet-shaped separators. , May be overlapped with the other electrode plate.
  • the sheet-shaped separator may be bent in a bellows shape, and the positive electrode plate and the negative electrode plate may be sandwiched between the bellows-shaped separators so that the separator is interposed between them.
  • the separator may be arranged so that the bent portion is along the horizontal direction of the lead storage battery (for example, the bent portion is parallel to the horizontal direction), or along the vertical direction. (For example, the separator may be arranged so that the bent portion is parallel to the vertical direction).
  • recesses are alternately formed on both main surface sides of the separator.
  • the positive electrode plate is formed only in the concave portion on one main surface side of the separator.
  • a negative electrode plate is arranged (that is, a double separator is interposed between the adjacent positive electrode plate and the negative electrode plate).
  • the separator is arranged so that the bent portion is along the vertical direction of the lead storage battery, the positive electrode plate can be accommodated in the recess on one main surface side and the negative electrode plate can be accommodated in the recess on the other main surface side (that is,).
  • the separator can be in a single interposition between the adjacent positive electrode plate and the negative electrode plate).
  • the bag-shaped separator may accommodate a positive electrode plate or a negative electrode plate.
  • the electrolytic solution is an aqueous solution containing sulfuric acid, and may be gelled if necessary.
  • the electrolytic solution contains metal ions.
  • the metal ion contains at least one first component selected from the group consisting of lithium ion, sodium ion, and aluminum ion.
  • the effect of reducing the amount of overcharged electricity and the effect of improving charge acceptability are further achieved by the direct or indirect interaction with the first additive contained in the negative electrode electrode material. Can obtain the effect of improving the PSOC life performance.
  • the electrolytic solution may contain at least one of lithium ion and sodium ion and aluminum ion. In this case, the amount of overcharged electricity can be further reduced. Above all, when the first component contains at least lithium ions and aluminum ions, it is preferable because the charge acceptability can be further improved.
  • the concentration of each of the first components in the electrolytic solution may be 0.35 mol / L or less. From the viewpoint of easily ensuring higher charge acceptability and PSOC life performance, the concentration of each of the first components is preferably 0.3 mol / L or less or 0.25 mol / L or less, preferably 0.2 mol / L. It may be as follows. The concentration of each of the first components is determined, for example, so that the total concentration of the first components is 0.02 mol / L or more. The concentration of each of the first components is, for example, 0.01 mol / L or more, and may be 0.02 mol / L or more.
  • the concentration of each of the first components in the electrolytic solution is 0.01 mol / L or more (or 0.02 mol / L or more) 0.35 mol / L or less, 0.01 mol / L or more (or 0.02 mol / L or more). 0.3 mol / L or less, 0.01 mol / L or more (or 0.02 mol / L or more) 0.25 mol / L or less, or 0.01 mol / L or more (or 0.02 mol / L or more) 0.2 mol / L It may be as follows.
  • the total concentration of the first component in the electrolytic solution is 0.02 mol / L or more.
  • the upper limit of the total concentration of the first component can be determined according to the concentration of each first component. From the viewpoint of easily ensuring higher charge acceptability and PSOC life performance, the total concentration of the first component is preferably 0.7 mol / L or less, and is preferably 0.5 mol / L or less or 0.4 mol / L or less. May be good.
  • the metal component in the component may be contained.
  • the content is low, and the effect on the concentration of the first component in the electrolytic solution is small.
  • the constituent elements other than the electrolytic solution contain the same metal component as the type of the first component (for example, sodium lignin sulfonate in the negative electrode electrode material, sodium salt as a surfactant), the first component is the same.
  • the total concentration of the first component in the electrolytic solution is less than 0.02 mol / L (usually less than 0.01 mol / L). ).
  • the electrolytic solution contains at least one selected from the group consisting of cations other than the first component (for example, metal cations) and anions (for example, anions other than sulfate anions (such as phosphate ions)), if necessary. You may be.
  • Metal cations other than the first component may be referred to as the second component. Examples of the second component include magnesium ion and potassium ion.
  • the total concentration of the second component in the electrolytic solution may be, for example, 0.01 mol / L or less. It is also preferable that the electrolytic solution does not contain the second component. When the electrolytic solution does not contain the second component, the case where the second component in the electrolytic solution is below the detection limit is included.
  • the electrolytic solution may contain the above-mentioned first additive.
  • the specific gravity of the electrolytic solution in a fully charged lead storage battery at 20 ° C. is, for example, 1.20 or more, and may be 1.25 or more.
  • the specific gravity of the electrolytic solution at 20 ° C. is 1.35 or less, preferably 1.32 or less.
  • the specific gravity of the electrolytic solution at 20 ° C. may be 1.20 or more and 1.35 or less, 1.20 or more and 1.32 or less, 1.25 or more and 1.35 or less, or 1.25 or more and 1.32 or less. ..
  • the concentrations of the first component and the second component in the electrolytic solution are determined by high-frequency inductively coupled plasma (ICP) emission spectroscopy of the electrolytic solution taken out from a fully charged lead-acid battery. More specifically, for the electrolytic solution, the type of metal ion in the electrolytic solution is identified by using an ICP emission spectroscopic measuring device, and the emission intensity of the metal ion is measured. From the measured value of the emission luminous intensity and the calibration curve prepared in advance, the concentration of the metal ion contained in the electrolytic solution is obtained. As the ICP emission spectroscopic measuring device, ICPS-8000 manufactured by Shimadzu Corporation is used.
  • the lead-acid battery can be obtained by a manufacturing method including a step of accommodating a group of plates and an electrolytic solution in a cell chamber of an electric tank.
  • Each cell of the lead-acid battery includes a group of plates and an electrolytic solution housed in each cell chamber.
  • the electrode plate group is assembled by laminating the positive electrode plate, the negative electrode plate, and the separator so that the separator is interposed between the positive electrode plate and the negative electrode plate prior to the accommodation in the cell chamber.
  • the positive electrode plate, the negative electrode plate, the electrolytic solution, and the separator are each prepared prior to assembling the electrode plate group.
  • the method for manufacturing a lead-acid battery may include, if necessary, a step of forming at least one of a positive electrode plate and a negative electrode plate after a step of accommodating a group of electrode plates and an electrolytic solution in a cell chamber.
  • Each electrode plate in the electrode plate group may be one plate or two or more plates.
  • the electrode plate group includes two or more negative electrode plates, if the condition that the negative electrode electrode material contains the first additive is satisfied in at least one negative electrode plate, the charge acceptability of this negative electrode plate is improved.
  • the ratio of the negative electrode plates satisfying the above conditions is 100% or less. All of the negative electrode plates included in the electrode plate group may be negative electrode plates satisfying the above conditions.
  • the lead-acid battery has two or more cells
  • at least a group of electrode plates of some cells may be provided with a negative electrode plate that satisfies the above conditions.
  • 50% or more (more preferably 80% or more or 90% or more) of the number of cells contained in the lead storage battery 50% or more (more preferably 80% or more or 90% or more) of the number of cells contained in the lead storage battery.
  • the ratio of the cells including the electrode plate group including the negative electrode plate satisfying the above conditions is 100% or less. It is preferable that all of the electrode plates included in the lead storage battery are provided with a negative electrode plate that satisfies the above conditions.
  • FIG. 1 shows the appearance of an example of a lead storage battery according to an embodiment of the present invention.
  • the lead-acid battery 1 includes an electric tank 12 for accommodating a plate group 11 and an electrolytic solution (not shown).
  • the inside of the electric tank 12 is partitioned into a plurality of cell chambers 14 by a partition wall 13.
  • One electrode plate group 11 is housed in each cell chamber 14.
  • the opening of the battery case 12 is closed by a lid 15 including a negative electrode terminal 16 and a positive electrode terminal 17.
  • the lid 15 is provided with a liquid spout 18 for each cell chamber. At the time of refilling water, the liquid spout 18 is removed and the refilling liquid is replenished.
  • the liquid spout 18 may have a function of discharging the gas generated in the cell chamber 14 to the outside of the battery.
  • the electrode plate group 11 is configured by laminating a plurality of negative electrode plates 2 and positive electrode plates 3 via a separator 4, respectively.
  • the bag-shaped separator 4 accommodating the negative electrode plate 2 is shown, but the form of the separator is not particularly limited.
  • the negative electrode shelf portion 6 for connecting the plurality of negative electrode plates 2 in parallel is connected to the through connection body 8, and the positive electrode shelf portion for connecting the plurality of positive electrode plates 3 in parallel is connected.
  • 5 is connected to the positive electrode column 7.
  • the positive electrode column 7 is connected to the positive electrode terminal 17 outside the lid 15.
  • the negative electrode column 9 is connected to the negative electrode shelf portion 6, and the penetration connecting body 8 is connected to the positive electrode shelf portion 5.
  • the negative electrode column 9 is connected to the negative electrode terminal 16 outside the lid 15.
  • Each through-connecting body 8 passes through a through-hole provided in the partition wall 13 and connects the electrode plates 11 of the adjacent cell chambers 14 in series.
  • the positive electrode shelf 5 is formed by welding the ears provided on the upper part of each positive electrode plate 3 by a cast-on-strap method or a burning method.
  • the negative electrode shelf portion 6 is also formed by welding the selvage portions provided on the upper portions of the negative electrode plates 2 as in the case of the positive electrode shelf portion 5.
  • the lid 15 of the lead storage battery has a single structure (single lid), but is not limited to the case shown in the illustrated example.
  • the lid 15 may have, for example, a double structure including an inner lid and an outer lid (or upper lid).
  • the lid having a double structure may be provided with a reflux structure between the inner lid and the outer lid for returning the electrolytic solution to the inside of the battery (inside the inner lid) from the reflux port provided on the inner lid.
  • each of the overcharged electricity amount, PSOC life performance, and charge acceptability is evaluated by the following procedure.
  • the rated voltage of the test battery used for the evaluation is 2V / cell, and the rated 5-hour rate capacity is 32Ah.
  • Amount of overcharged electricity Using the above test battery, the amount of overcharged electricity is evaluated under the following conditions. A 1-minute discharge-10-minute charge test (1-10-minute test) at 75 ° C ⁇ 3 ° C to overcharge the normal 4-minute-10-minute test specified in JIS D5301: 2019. Perform (high temperature and light load test). In the high temperature light load test, charging and discharging are repeated for 1220 cycles. The amount of overcharged electricity (Ah) per cycle is obtained by summing and averaging the amount of overcharged electricity (charged electricity amount-discharged electricity amount) in each cycle up to 1220 cycles. Discharge: 25A, 1 minute Charge: 2.47V / cell, 25A, 10 minutes Water tank temperature: 75 ° C ⁇ 3 ° C
  • the lead-acid batteries according to one aspect of the present invention are summarized below.
  • the lead-acid battery comprises at least one cell comprising a group of plates and an electrolyte.
  • the electrode plate group includes a positive electrode plate, a negative electrode plate, and a separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate comprises a negative electrode material and is provided with a negative electrode material.
  • the negative electrode material contains at least one additive (first additive) selected from the group consisting of a surfactant and a polymer compound having a repeating structure of an oxyC 2-4 alkylene unit, and an organic shrinkage proofing agent.
  • the electrolytic solution contains metal ions and contains metal ions.
  • the metal ion contains at least one component (first component) selected from the group consisting of lithium ion, sodium ion, and aluminum ion.
  • the total concentration of the components in the electrolytic solution is 0.02 mol / L or more.
  • a lead-acid battery in which the concentration of each of the components in the electrolytic solution is 0.35 mol / L or less.
  • the concentration of each of the first components may be 0.3 mol / L or less, 0.25 mol / L or less, or 0.2 mol / L or less.
  • the concentration of each of the first components may be 0.01 mol / L or more, or 0.02 mol / L or more.
  • the total concentration of the first component is 0.7 mol / L or less, 0.5 mol / L or less, or 0.4 mol / L or less. You may.
  • the first component may contain at least one of lithium ion and sodium ion and aluminum ion.
  • the first component may contain at least lithium ions and aluminum ions.
  • the first additive contains the polymer compound (including a nonionic surfactant having a repeating structure of an oxyC 2-4 alkylene unit).
  • the polymer compound may contain a compound having Mn of 5 million or less, 1 million or less, 100,000 or less, 50,000 or less, 20000 or less, 10000 or less, 9000 or less, or 8000 or less.
  • the Mn of the compound may be 300 or more, 400 or more, 500 or more, 1000 or more, or 1500 or more.
  • the first additive is a hydroxy compound having a repeating structure of an oxyC 2-4 alkylene unit, an etherified product of the hydroxy compound, and the hydroxy. Containing at least one selected from the group consisting of esterified compounds of the compound.
  • the hydroxy compound is at least one selected from the group consisting of a poly C 2-4 alkylene glycol, a copolymer containing a repeating structure of oxy C 2-4 alkylene, and a poly C 2-4 alkylene oxide adduct of a polyol. There may be.
  • the first additive may contain a compound (polymer compound) having a repeating structure of an oxypropylene unit.
  • the number average molecular weight of the compound (polymer compound) may be 1000 or more and 10000 or less, and 1500 or more and 10000 or less.
  • the polymer compound is polypropylene glycol, polyoxypropylene-polyoxyethylene copolymer (polyoxypropylene-polyoxyethylene block copolymer, etc.), polypropylene glycol alkyl ether.
  • R 2 is an alkyl having 10 or less carbon atoms (or 8 or less or 6 or less), such as an alkyl ether (methyl ether, ethyl ether, butyl ether, etc.)), polyoxyethylene-polyoxypropylene alkyl ether (the above R 2 is Alkyl ether (butyl ether, hydroxyhexyl ether, etc.) which is an alkyl having 10 or less carbon atoms (or 8 or less or 6 or less), polypropylene glycol carboxylate (R 3 above has 10 or less carbon atoms (or 8 or less or 6 or less)).
  • It may contain at least one selected from the group consisting of polypropylene glycol carboxylate (such as polypropylene glycol acetate) which is an alkyl of the above, and polypropylene oxide adduct of a polyol of triol or higher (such as polypropylene oxide adduct of glycerin).
  • polypropylene glycol carboxylate such as polypropylene glycol acetate
  • polypropylene oxide adduct of a polyol of triol or higher such as polypropylene oxide adduct of glycerin
  • the proportion of the oxypropylene unit in the polymer compound may be 5 mol% or more, 10 mol% or more, or 20 mol% or more.
  • the proportion of the oxypropylene unit in the polymer compound may be 100 mol% or less.
  • the compound (polymer compound) does not have to contain the repeating structure of the oxyethylene unit.
  • the first additive (among others, the surfactant) does not contain a sulfur element.
  • the surfactant may contain a cationic surfactant.
  • the cationic surfactant may contain a quaternary ammonium salt.
  • the negative electrode material contains a carbonaceous material, and the negative electrode material contains a carbonaceous material.
  • the first additive has at least one hydrophobic group and a hydrophilic group. At least one of the hydrophobic groups may be a long-chain aliphatic hydrocarbon group having 8 or more carbon atoms.
  • the carbon number of the long-chain aliphatic hydrocarbon group may be 30 or less, 26 or less, 24 or less, or 22 or less.
  • the negative electrode material may further contain a carbonaceous material.
  • the content of the carbonaceous material in the negative electrode electrode material is 0.05% by mass or more, or 0.10% by mass or more. May be good.
  • the content of the carbonaceous material in the negative electrode electrode material may be 5% by mass or less, or 3% by mass or less.
  • the content of the first additive in the negative electrode electrode material is 8 ppm or more, 10 ppm or more, 50 ppm or more, 100 ppm or more on a mass basis. It may be 300 ppm or more, or 400 ppm or more.
  • the content of the first additive in the negative electrode electrode material is 10,000 ppm or less, 6000 ppm or less, 5000 ppm or less, 1000 ppm or less on a mass basis. Alternatively, it may be 700 ppm or less.
  • the content of the organic shrinkage-proofing agent in the negative electrode electrode material is 0.005% by mass or more, or 0.01% by mass or more. May be good.
  • the content of the organic shrinkage-proofing agent in the negative electrode electrode material is 1.0% by mass or less, 0.5% by mass or less, 0.3. It may be 0% by mass or less, 0.25% by mass or less, or 0.2% by mass or less.
  • the organic shrinkage proofing agent (or the negative electrode electrode material) is the first organic shrinkage proofing agent having a sulfur element content of 2000 ⁇ mol / g or more or 3000 ⁇ mol / g or more. It may contain an agent.
  • the sulfur element content of the first organic shrinkage proofing agent may be 9000 ⁇ mol / g or less, or 8000 ⁇ mol / g or less.
  • the Mw of the first organic shrinkage proofing agent may be 7,000 or more.
  • the Mw of the first organic shrinkage proofing agent may be 100,000 or less, or 20,000 or less.
  • the organic shrinkage proofing agent (or the first organic shrinkage proofing agent) may contain a condensate of a bisarene compound.
  • the negative electrode material may further contain barium sulfate.
  • the content of the barium sulfate in the negative electrode electrode material may be 0.05% by mass or more, or 0.10% by mass or more.
  • the content of the barium sulfate in the negative electrode electrode material may be 3% by mass or less, or 2% by mass or less.
  • the specific gravity of the electrolytic solution in the fully charged lead-acid battery at 20 ° C. may be 1.20 or more or 1.25 or more.
  • the specific gravity of the electrolytic solution in the fully charged lead-acid battery at 20 ° C. may be 1.35 or less or 1.32 or less.
  • Lead-acid batteries E1 to E40, C1 to C4, and R1 to R4 >> (1) Preparation of lead-acid battery (a) Preparation of negative electrode plate Lead powder as raw material, barium sulfate, carbon black, the first additive shown in Tables 2 to 4, and the organic shrinkage shrinkage shown in Tables 2 to 4 The agent is mixed with an appropriate amount of aqueous sulfuric acid solution to obtain a negative electrode paste. At this time, the contents of the first additive and the organic shrink-proofing agent in the negative electrode electrode material, which are obtained by the above-mentioned procedure, are the values shown in Tables 2 to 4, and the content of barium sulfate is 0.
  • the negative electrode paste is filled in the mesh portion of the expanded lattice made of Pb—Ca—Sn alloy and aged and dried to obtain an unchemicald negative electrode plate.
  • E1 Lignin: Sodium lignin sulfonate (sulfur element content 600 ⁇ mol / g, Mw5500)
  • E2 Bisphenol condensate: A formaldehyde-based condensate of a bisphenol compound having a sulfonic acid group introduced (sulfur element content 4000 ⁇ mol / g, Mw8000).
  • the lead-acid battery has a rated voltage of 2 V / cell and a rated 5-hour rate capacity of 32 Ah.
  • the electrode plate group of the test battery is composed of seven positive electrode plates and seven negative electrode plates.
  • the negative electrode plate is housed in a bag-shaped separator formed of a microporous polyethylene film, and is alternately laminated with the positive electrode plate to form a group of electrode plates.
  • a group of electrode plates is housed in a polypropylene electric tank together with an electrolytic solution, and chemical formation is performed in the electric tank to produce a liquid-type lead-acid battery.
  • the specific gravity of the electrolytic solution in a fully charged lead-acid battery at 20 ° C. is 1.28.
  • a sulfuric acid aqueous solution containing a metal sulfate corresponding to the first component shown in Tables 2 to 4 is used as the electrolytic solution.
  • the amount of the metal sulfate added is adjusted so that the concentration of each of the first components obtained in the above-mentioned procedure becomes the value shown in Tables 2 to 4.
  • the concentration of Na ion in the table is ⁇ 0.01 mol / L
  • the Na ion is derived from the sodium lignin sulfonate used for the negative electrode electrode material, and when it is ⁇ 0.002 mol / L, the Na ion is , Derived from the first additive.
  • the electrolyte is prepared without the addition of sodium sulfate.
  • the PSOC life performance of each lead-acid battery is expressed as a ratio (%) when the result of the lead-acid battery C1 is 100.
  • (C) Charge acceptability Using the lead-acid battery after full charge, charge acceptability is evaluated by the procedure described above. The charge acceptability of each lead storage battery is evaluated by the ratio (%) when the integrated electric energy of the lead storage battery C1 is 100.
  • the results are shown in Tables 2 to 4.
  • the Mn of polypropylene glycol and polyethylene glycol is Mn obtained by the above-mentioned procedure.
  • the Mn of the esterified product is the Mn of the esterified product used for preparing the negative electrode material.
  • Lead-acid batteries E1 to E40 are examples.
  • Lead-acid batteries C1 to C4 are comparative examples.
  • Lead-acid batteries R1 to R4 are reference examples.
  • the negative electrode is provided with a negative electrode material containing an organic shrinkage proofing agent but not containing the first additive.
  • the lead-acid battery includes a negative electrode material containing an organic shrinkage proofing agent and a first additive, if the electrolytic solution does not contain the first component at a total concentration of 0.02 mol / L or more, the amount of overcharged electricity is increased. It can be reduced, but the charge acceptability is reduced (comparison between C1 and R1).
  • the electrolytic solution contains the first component at a total concentration of 0.02 mol / L or more, so that the charge acceptability is improved by 12%, the amount of overcharge electricity does not change, and the PSOC life performance is 54. % Has improved. Further, since the negative electrode material contains the first additive in addition to the organic shrinkage proofing agent, the charge acceptability is reduced by 35%, the amount of overcharged electricity is reduced by 25%, and the PSOC life performance is improved by 10%. From these results, when an electrolytic solution containing the first component at a total concentration of 0.02 mol / L or more and a negative electrode plate provided with a negative electrode material containing an organic shrinkage proofing agent and the first additive are combined, charge acceptability is obtained.
  • E1 the charge acceptability is 121%, the overcharge electricity amount is 65%, and the PSOC life performance is 184%.
  • the result of such E1 is much better than expected from C1, C2 and R1, and it can be seen that the synergistic effect is obtained by the combination of the electrolytic solution and the negative electrode plate.
  • C3, C4 and R2 and E2 are the same as above, and in the case of synthetic organic shrinkage proofing agents, both in improving charge acceptability and PSOC life performance, and reducing the amount of overcharged electricity. A synergistic effect can be obtained.
  • the first additive preferably does not contain a sulfur element, and it is preferable to use a cationic surfactant (a cationic surfactant is used).
  • a cationic surfactant a cationic surfactant is used.
  • At least one of the hydrophobic groups of the surfactant is a long-chain aliphatic hydrocarbon group having 8 or more carbon atoms (1). Comparison between E6 and E7).
  • the content of the first additive is preferably 10 ppm or more (or 50 ppm or more) of 10000 ppm or less, and may be 100 ppm or more and 8000 ppm or less.
  • the concentration of each of the first components in the electrolytic solution is 0.35 mol / L or less, preferably 0.3 mol / L or less, and 0.25 mol / L or less. Or 0.2 mol / L or less is more preferable.
  • the first component preferably contains at least one of Li ion and Na ion and Al ion (E15 to E18 and E2 and E20 to E34). Comparison, comparison between E36 to E38 and E39 and E40). In this case, the amount of overcharged electricity can be further suppressed.
  • the first component preferably contains at least Li ion and Al ion (comparison between E15, E17, E18, E20 and E2 and E36 to E40).
  • the lead-acid battery according to one aspect of the present invention is suitable for use in an idling stop vehicle as, for example, a lead-acid battery for IS that is charged and discharged under PSOC conditions.
  • the lead-acid battery can be suitably used, for example, as a power source for starting a vehicle (automobile, motorcycle, etc.) and an industrial power storage device (for example, a power source for an electric vehicle (forklift, etc.)). It should be noted that these are merely examples, and the use of the lead storage battery is not limited to these.
  • Negative electrode plate 3 Positive electrode plate 4: Separator 5: Positive electrode shelf part 6: Negative electrode shelf part 7: Positive electrode pillar 8: Through connection body 9: Negative electrode pillar 11: Electrode plate group 12: Electric tank 13: Bulk partition 14: Cell chamber 15: Lid 16: Negative electrode terminal 17: Positive electrode terminal 18: Liquid spout

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