WO2021070738A1 - 二次電池電極用バインダー、二次電池電極合剤層用組成物、二次電池電極及び二次電池 - Google Patents

二次電池電極用バインダー、二次電池電極合剤層用組成物、二次電池電極及び二次電池 Download PDF

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WO2021070738A1
WO2021070738A1 PCT/JP2020/037497 JP2020037497W WO2021070738A1 WO 2021070738 A1 WO2021070738 A1 WO 2021070738A1 JP 2020037497 W JP2020037497 W JP 2020037497W WO 2021070738 A1 WO2021070738 A1 WO 2021070738A1
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secondary battery
mass
binder
polymer
monomer
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English (en)
French (fr)
Japanese (ja)
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直彦 斎藤
朋子 仲野
綾乃 日笠山
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Toagosei Co Ltd
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Toagosei Co Ltd
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Priority to CN202080071240.4A priority Critical patent/CN114514639B/zh
Priority to KR1020227012852A priority patent/KR20220078615A/ko
Priority to JP2021551469A priority patent/JP7530052B2/ja
Priority to US17/767,988 priority patent/US12482822B2/en
Priority to EP20874102.5A priority patent/EP4043503A4/en
Publication of WO2021070738A1 publication Critical patent/WO2021070738A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • 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 binder for a secondary battery electrode, a composition for a mixture layer of a secondary battery electrode, a secondary battery electrode, and a secondary battery.
  • a secondary battery various power storage devices such as a nickel hydrogen secondary battery, a lithium ion secondary battery, and an electric double layer capacitor have been put into practical use.
  • the electrodes used in these secondary batteries are produced by applying, drying, or the like on a current collector a composition for forming an electrode mixture layer containing an active material, a binder, and the like.
  • a composition for forming an electrode mixture layer containing an active material, a binder, and the like for example, in a lithium ion secondary battery, an aqueous binder containing styrene-butadiene rubber (SBR) latex and carboxymethyl cellulose (CMC) is used as the binder used in the composition for the negative electrode mixture layer.
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • a binder used for the positive electrode mixture layer a solution of polyvinylidene fluoride (PVDF) in N-methyl-2-pyrrolidone (NMP) is
  • Patent Document 1 discloses an acrylic acid polymer cross-linked with a specific cross-linking agent as a binder for forming a negative electrode coating film of a lithium ion secondary battery.
  • Patent Document 2 discloses an aqueous electrode binder for a secondary battery containing a water-soluble polymer containing a structural unit derived from an ethylenically unsaturated carboxylate monomer and a structural unit derived from a vinyl alcohol monomer. There is.
  • Patent Document 3 contains a water-soluble polymer containing a structural unit derived from an ethylenically unsaturated carboxylate monomer and a structural unit derived from a highly hydrophilic ethylenically unsaturated monomer containing no carboxylic acid.
  • Water-based electrode binders for secondary batteries are disclosed.
  • Patent Document 4 discloses a crosslinked acrylic acid polymer having a specific particle size in a 1% NaCl aqueous solution.
  • the secondary battery electrode is generally obtained by applying and drying a composition for an electrode mixture layer containing an active material and a binder (hereinafter, also referred to as “electrode slurry”) on the surface of an electrode current collector.
  • electrode slurry a binder
  • the concentration of the active material increases, the viscosity of the electrode slurry also increases, so that it becomes difficult to ensure good coatability.
  • the binders described in Patent Documents 1 and 4 are microcrosslinked to enhance the binding property of the acrylic acid-based polymer, but the microcrosslinking increases the spread in water. Therefore, it was difficult to increase the concentration of the active material because the viscosity greatly increased even in a small amount.
  • the present invention has been made in view of such circumstances, and an object of the present invention is that it can exhibit better binding properties than before and that the concentration of the active material in the composition for the electrode mixture layer is high. It is an object of the present invention to provide a binder for a secondary battery electrode capable of reducing the viscosity of an electrode slurry even when the viscosity is high. In addition, the present invention also provides a composition for a secondary battery electrode mixture layer, a secondary battery electrode, and a secondary battery obtained by using the above binder.
  • the present inventors can exhibit better binding properties than before by including a specific amount of a specific structural unit in the carboxyl group-containing polymer.
  • the present invention has been completed by finding that the viscosity of the electrode slurry can be reduced even when the concentration of the active material in the composition for the electrode mixture layer is high.
  • a binder for a secondary battery electrode containing a carboxyl group-containing polymer or a salt thereof, and the carboxyl group-containing polymer or a salt thereof is derived from a monomer represented by the general formula (1).
  • the general formula (1) includes a structural unit and a structural unit derived from an ethylenically unsaturated carboxylic acid monomer different from the general formula (1), and is used for all structural units of the carboxyl group-containing polymer or a salt thereof.
  • the carboxyl group-containing polymer or a salt thereof contains 50% by mass or more of structural units derived from an ethylenically unsaturated carboxylic acid monomer different from the general formula (1) with respect to all structural units thereof.
  • the carboxyl group-containing polymer is a crosslinked polymer obtained by polymerizing a monomer composition containing a non-crosslinkable monomer and a crosslinkable monomer. The above-mentioned binder for a secondary battery electrode.
  • a secondary battery electrode comprising an electrode mixture layer containing the binder for the secondary battery electrode according to any one of [1] to [7] on the surface of the current collector.
  • a secondary battery comprising the secondary battery electrode according to [9].
  • the binder for a secondary battery electrode of the present invention excellent binding properties can be exhibited, and the viscosity of the electrode slurry is reduced even when the concentration of the active material in the composition for the electrode mixture layer is high. it can.
  • the binder for a secondary battery electrode of the present invention contains a carboxyl group-containing polymer or a salt thereof, and can be mixed with an active material and water to prepare a composition for a secondary battery electrode mixture layer. .. It is preferable that the above composition is an electrode slurry in a slurry state that can be applied to the current collector from the viewpoint of achieving the effect of the present invention, but it is prepared in a wet powder state and applied to the surface of the current collector. It may be possible to cope with press working.
  • the secondary battery electrode of the present invention can be obtained by forming an electrode mixture layer formed from the above composition on the surface of a current collector such as copper foil or aluminum foil.
  • (meth) acrylic means acrylic and / or methacrylic
  • (meth) acrylate means acrylate and / or methacrylate
  • (meth) acryloyl group means an acryloyl group and / or a methacryloyl group.
  • the binder of the present invention contains a carboxyl group-containing polymer or a salt thereof, and the carboxyl group-containing polymer is a structural unit derived from the monomer represented by the above general formula (1), and the above general formula ( It has a structural unit derived from an ethylenically unsaturated carboxylic acid monomer different from 1).
  • the carboxyl group-containing polymer (hereinafter, also referred to as “the present polymer”) is a structural unit derived from the monomer represented by the above general formula (1) (hereinafter, also referred to as “component (a)”).
  • the component (a) is contained in an amount of 0.1% by mass or more and 20% by mass or less with respect to all the structural units of the carboxyl group-containing polymer or a salt thereof.
  • the present polymer By containing the component (a) in such a range, the present polymer reduces the viscosity of the electrode slurry even when the concentration of the active material in the composition for the electrode mixture layer is high, and provides good coatability.
  • the binder containing the present polymer exhibits excellent binding properties, and excellent adhesiveness to the current collector can be easily secured.
  • the lower limit is, for example, 0.15% by mass or more, for example 0.2% by mass or more, for example 0.25% by mass or more, and for example 0.3% by mass or more. When the lower limit is 0.1% by mass or more, it is preferable in that the coatability of the electrode slurry, the binding property, and the durability as a battery are improved.
  • the upper limit is, for example, 19% by mass or less, for example, 18% by mass or less, for example, 17% by mass or less, and for example, 16% by mass or less.
  • the range may be a range in which such a lower limit and an upper limit are appropriately combined.
  • the present polymer has a structural unit (hereinafter, also referred to as “component (b)”) derived from an ethylenically unsaturated carboxylic acid monomer different from the above general formula (1). .. Since this polymer has the component (b), the adhesiveness to the current collector is improved, and the lithium ion desolvation effect and ionic conductivity are excellent, so that the electrode has low resistance and excellent high rate characteristics. Is obtained. Further, since water swelling property is imparted, the dispersion stability of the active material or the like in the composition for the electrode mixture layer can be enhanced.
  • the component (b) can be introduced into the present polymer, for example, by polymerizing a monomer containing an ethylenically unsaturated carboxylic acid monomer different from the general formula (1). Alternatively, it can also be obtained by (co) polymerizing a (meth) acrylic acid ester monomer and then hydrolyzing it. Further, after polymerizing (meth) acrylamide, (meth) acrylonitrile or the like, it may be treated with a strong alkali, or it may be a method of reacting an acid anhydride with a polymer having a hydroxyl group.
  • Examples of the ethylenically unsaturated carboxylic acid monomer different from the above general formula (1) include (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, and fumaric acid; (meth) acrylamide hexane acid and (meth) acrylamide. (Meta) acrylamide alkylcarboxylic acids such as dodecanoic acid; ethylenically unsaturated monomers having carboxyl groups such as monohydroxyethyl (meth) acrylates and ⁇ -carboxy-caprolactone mono (meth) acrylates or their (partial) ) Alkaline neutralized products may be mentioned, and one of these may be used alone, or two or more thereof may be used in combination.
  • a compound having an acryloyl group as a polymerizable functional group is preferable, and acrylic acid is particularly preferable, in that a polymer having a long primary chain length can be obtained because the polymerization rate is high and the binding force of the binder is good. is there.
  • acrylic acid is used as the ethylenically unsaturated carboxylic acid monomer, a polymer having a high carboxyl group content can be obtained.
  • the content of the component (b) in the present polymer is not particularly limited, but can be, for example, 10% by mass or more and 99.9% by mass or less with respect to all the structural units of the present polymer.
  • the lower limit is, for example, 20% by mass or more, for example, 30% by mass or more, and for example, 40% by mass or more.
  • the lower limit is 10% by mass or more, it is preferable in that the coatability of the electrode slurry, the binding property, and the durability as a battery are improved.
  • the lower limit may be 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more.
  • the upper limit is, for example, 99% by mass or less, for example 98% by mass or less, for example 95% by mass or less, and for example 90% by mass or less.
  • the range may be a range in which such a lower limit and an upper limit are appropriately combined.
  • This polymer is a structural unit derived from other ethylenically unsaturated monomers copolymerizable with the component (a) and the component (b) (hereinafter, also referred to as “component (c)”). Can be included.
  • the component (c) is a structural unit derived from a monomer having an ethylenically unsaturated group other than the components (a) and (b), and is, for example, other than a carboxyl group such as a sulfonic acid group and a phosphoric acid group.
  • Examples thereof include a structural unit derived from an ethylenically unsaturated monomer compound having an anionic group of the above, a nonionic ethylenically unsaturated monomer, and the like.
  • These structural units are ethylenically unsaturated monomer compounds having anionic groups other than carboxyl groups such as sulfonic acid groups and phosphoric acid groups, or monomers containing nonionic ethylenically unsaturated monomers. Can be introduced by copolymerizing.
  • the ratio of the component (c) can be 0% by mass or more and 89.9% by mass or less with respect to all the structural units of the present polymer.
  • the ratio of the component (c) may be 0.5% by mass or more and 70% by mass or less, 1% by mass or more and 60% by mass or less, and 2% by mass or more and 50% by mass or less. It may be 5% by mass or more and 40% by mass or less, or 10% by mass or more and 30% by mass or less.
  • the range may be a range in which such a lower limit and an upper limit are appropriately combined.
  • the affinity for the electrolytic solution is improved, so that the effect of improving the lithium ion conductivity can be expected.
  • a structural unit derived from a nonionic ethylenically unsaturated monomer is preferable from the viewpoint of obtaining an electrode having good bending resistance, and a nonionic ethylenically unsaturated monomer is preferable.
  • the monomer include (meth) acrylamide and its derivatives, an alicyclic structure-containing ethylenically unsaturated monomer, a hydroxyl group-containing ethylenically unsaturated monomer, and the like.
  • Examples of the (meth) acrylamide derivative include N-alkyl (meth) acrylamide compounds such as isopropyl (meth) acrylamide and t-butyl (meth) acrylamide; Nn-butoxymethyl (meth) acrylamide and N-isobutoxymethyl.
  • N-alkoxyalkyl (meth) acrylamide compounds such as (meth) acrylamide; N, N-dialkyl (meth) acrylamide compounds such as dimethyl (meth) acrylamide and diethyl (meth) acrylamide include one of them. It may be used alone or in combination of two or more.
  • Examples of the alicyclic structure-containing ethylenically unsaturated monomer include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, and (meth).
  • Cyclodecyl acrylate and cyclododecyl (meth) acrylate and other aliphatic substituents may have (meth) cycloalkyl acrylate; isobornyl (meth) acrylate, adamantyl (meth) acrylate, (meth).
  • Cycloalkyl polyalcohol mono (meth) acrylate and the like can be mentioned, and one of these may be used alone, or two or more thereof may be used in combination.
  • hydroxyl group-containing ethylenically unsaturated monomer examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate, and one of these is used alone. It may be used in combination, or two or more kinds may be used in combination.
  • (meth) acrylic acid ester examples include (meth) methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.
  • Acrylic acid alkyl ester compound (Meta) Acrylic acid aralkyl ester compounds such as (meth) phenyl acrylate, (meth) phenylmethyl acrylate, (meth) phenylethyl acrylate; Examples thereof include (meth) acrylic acid alkoxyalkyl ester compounds such as 2-methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate, and one of these may be used alone or 2 You may use a combination of seeds or more.
  • the present polymer or a salt thereof preferably contains a structural unit derived from (meth) acrylamide, a derivative thereof, an alicyclic structure-containing ethylenically unsaturated monomer, or the like, because the binder has excellent binding properties.
  • a structural unit derived from a hydrophobic ethylenically unsaturated monomer having a solubility in water of 1 g / 100 ml or less is introduced as the component (c)
  • a strong interaction with the electrode material can be achieved.
  • a solid and well-integrated electrode mixture layer can be obtained.
  • hydrophobic ethylenically unsaturated monomer having a solubility in water of 1 g / 100 ml or less is particularly selected.
  • An alicyclic structure-containing ethylenically unsaturated monomer is preferable.
  • the present polymer or a salt thereof preferably contains a structural unit derived from a hydroxyl group-containing ethylenically unsaturated monomer in that the cycle characteristics of the obtained secondary battery are improved, and the structural unit is 0.5% by mass. % Or more and 70% by mass or less, more preferably 2.0% by mass or more and 50% by mass or less, and even more preferably 10.0% by mass or more and 50% by mass or less.
  • a compound having an acryloyl group is preferable in that a polymer having a long primary chain length can be obtained due to its high polymerization rate and the binding force of the binder is improved.
  • the present polymer may be a salt.
  • the type of salt is not particularly limited, but alkali metal salts such as lithium salt, sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt, calcium salt and barium salt; other metal salts such as aluminum salt; ammonium. Examples thereof include salts and organic amine salts. Among these, alkali metal salts and magnesium salts are preferable, and alkali metal salts are more preferable, from the viewpoint that adverse effects on battery characteristics are unlikely to occur. Further, a lithium salt is particularly preferable from the viewpoint of obtaining a battery having low resistance.
  • the carboxyl group-containing polymer of the present invention is crosslinked because the binder containing the polymer can ensure good coatability of the electrode slurry even at a high concentration of active material and can further exhibit good binding performance. It is preferably a coalescence (hereinafter, simply referred to as “crosslinked polymer”).
  • the cross-linking method in the cross-linked polymer is not particularly limited, and examples thereof include the following methods. 1) Copolymerization of crosslinkable monomers 2) Utilizing chain transfer to polymer chains during radical polymerization 3) After synthesizing a polymer having a reactive functional group, post-crosslinking is performed by adding a crosslinking agent as necessary.
  • the binder containing the polymer or a salt thereof can have an excellent binding force.
  • the method by copolymerization of crosslinkable monomers is preferable because the operation is simple and the degree of crosslinking can be easily controlled.
  • crosslinkable monomer examples include a polyfunctional polymerizable monomer having two or more polymerizable unsaturated groups, a monomer having a self-crosslinkable crosslinkable functional group such as a hydrolyzable silyl group, and the like. Can be mentioned.
  • the polyfunctional polymerizable monomer is a compound having two or more polymerizable functional groups such as a (meth) acryloyl group and an alkenyl group in the molecule, and is a polyfunctional (meth) acrylate compound, a polyfunctional alkenyl compound, ( Meta) Examples thereof include compounds having both an acryloyl group and an alkenyl group. These compounds may be used alone or in combination of two or more. Among these, a polyfunctional alkenyl compound is preferable because a uniform crosslinked structure can be easily obtained, and a polyfunctional allyl ether compound having two or more allyl ether groups in the molecule is particularly preferable.
  • polyfunctional (meth) acrylate compound examples include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate.
  • Di (meth) acrylates of dihydric alcohols such as meta) acrylate; trimethylol propantri (meth) acrylate, tri (meth) acrylate of trimethyl propanethylene oxide modified product, glycerin tri (meth) acrylate, pentaerythritol tri (meth) Tri (meth) acrylates of trivalent or higher polyhydric alcohols such as meta) acrylates and pentaerythritol tetra (meth) acrylates, poly (meth) acrylates such as tetra (meth) acrylates; Bisamides and the like can be mentioned.
  • polyfunctional alkenyl compound examples include polyfunctional allyl ether compounds such as trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, tetraallyloxyethane, and polyallyl saccharose; diallyl phthalate and the like.
  • Polyfunctional allyl compound; Polyfunctional vinyl compounds such as divinylbenzene and the like can be mentioned.
  • Compounds having both (meth) acryloyl group and alkenyl group include allyl (meth) acrylate, isopropenyl (meth) acrylate, butenyl (meth) acrylate, pentenyl (meth) acrylate, and (meth) acrylate. 2- (2-Vinyloxyethoxy) ethyl and the like can be mentioned.
  • the above-mentioned monomer having a crosslinkable functional group include a hydrolyzable silyl group-containing vinyl monomer, N-methylol (meth) acrylamide, N-methoxyalkyl (meth) acrylamide and the like. Can be mentioned. These compounds can be used alone or in combination of two or more.
  • the hydrolyzable silyl group-containing vinyl monomer is not particularly limited as long as it is a vinyl monomer having at least one hydrolyzable silyl group.
  • vinyl silanes such as vinyl trimethoxysilane, vinyl triethoxysilane, vinyl methyl dimethoxysilane, vinyl dimethyl methoxysilanen; silyl such as trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, methyldimethoxysilylpropyl acrylate and the like.
  • Group-containing acrylic acid esters silyl group-containing methacrylate esters such as trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, methyldimethoxysilylpropyl methacrylate, dimethylmethoxysilylpropyl methacrylate; trimethoxysilylpropyl vinyl ether and the like.
  • Cyril group-containing vinyl ethers; silyl group-containing vinyl esters such as trimethoxysilyl undecanoate vinyl and the like can be mentioned.
  • the amount of the crosslinkable monomer used is the total amount of the monomers other than the crosslinkable monomer (non-crosslinkable monomer). On the other hand, it is preferably 0.010 to 3.0 mol%, more preferably 0.050 to 2.0 mol%, further preferably 0.10 to 1.5 mol%, and 0. It is more preferably .20 to 1.0 mol%.
  • the amount of the crosslinkable monomer used is 0.010 mol% or more, the binding property and the stability of the electrode slurry are more preferable. When it is 3.0 mol% or less, it is preferable in that the binding property is good.
  • the amount of the crosslinkable monomer used is preferably 0.05 to 5.0% by mass, more preferably 0.10 to 3.0% by mass, based on the total constituent monomers of the crosslinked polymer. Yes, more preferably 0.20 to 2.5% by mass, and even more preferably 0.30 to 2.0% by mass.
  • the sol fraction of the crosslinked polymer or a salt thereof is preferably less than 40% by mass.
  • the lower limit of the sol fraction may be 0.1% by mass or more, 0.2% by mass or more, 0.5% by mass or more, or 1.0% by mass or more. It may be.
  • the upper limit of the sol fraction may be 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, or 15% by mass. It may be less than or equal to%.
  • the sol content in the present specification is mainly composed of a polymer having no three-dimensional crosslinked structure, and the sol content contained in the crosslinked polymer or a salt thereof can be adjusted by a known method. it can. That is, the sol fraction can be set in a desired range by adjusting the type of the cross-linking agent, the amount used thereof, the primary chain length of the polymer, and the like. For example, the sol fraction generally decreases by increasing the amount of the cross-linking agent used or increasing the primary chain length.
  • the weight average molecular weight of the sol content of the crosslinked polymer or a salt thereof is preferably 300,000 or less in terms of polyethylene oxide / polyethylene glycol. It is more preferably 200,000 or less, further preferably 150,000 or less, and even more preferably 100,000 or less.
  • the lower limit of the weight average molecular weight of the sol content may be 1,000 or more, 2,000 or more, 3,000 or more, or 5,000 or more. It may be 10,000 or more.
  • the weight average molecular weight of the sol of the crosslinked polymer is a value in terms of polyethylene oxide / polyethylene glycol.
  • the crosslinked polymer when the crosslinked polymer does not exist as a mass (secondary agglomerate) having a large particle size and is well dispersed as water-swelled particles having an appropriate particle size, the crosslinked polymer is concerned.
  • a binder containing a polymer is preferable because it can exhibit good binding performance.
  • the crosslinked polymer of the present invention or a salt thereof has a particle size (water-swelling particle size) when a crosslinked polymer having a degree of neutralization based on a carboxyl group of 80 to 100 mol% is dispersed in water.
  • the volume-based median diameter is preferably in the range of 0.1 ⁇ m or more and 10.0 ⁇ m or less.
  • the particle size is in the range of 0.1 ⁇ m or more and 10.0 ⁇ m or less, the composition for the electrode mixture layer is uniformly present in a suitable size in the composition for the electrode mixture layer, so that the composition for the electrode mixture layer is highly stable. , It is possible to exhibit excellent binding properties. If the particle size exceeds 10.0 ⁇ m, the binding property may be insufficient as described above.
  • the lower limit of the particle size may be 0.2 ⁇ m or more, 0.3 ⁇ m or more, or 0.5 ⁇ m or more.
  • the upper limit of the particle size may be 9.0 ⁇ m or less, 8.0 ⁇ m or less, 7.0 ⁇ m or less, 5.0 ⁇ m or less, 3.0 ⁇ m or less. There may be.
  • the range of the particle size can be set by appropriately combining the above lower limit value and upper limit value, and may be, for example, 0.1 ⁇ m or more and 9.0 ⁇ m or less, and 0.2 ⁇ m or more and 8.0 ⁇ m or less. It may be 0.3 ⁇ m or more and 5.0 ⁇ m or less.
  • the water-swelled particle size can be measured by the method described in the examples of the present specification.
  • the crosslinked polymer is unneutralized or has a neutralization degree of less than 80 mol%, neutralize it to a neutralization degree of 80 to 100 mol% with an alkali metal hydroxide or the like, and measure the particle size when dispersed in water. do it.
  • the crosslinked polymer or a salt thereof often exists as agglomerated particles in which primary particles are associated and aggregated in the state of powder or solution (dispersion liquid).
  • the crosslinked polymer or a salt thereof has extremely excellent dispersibility, and is neutralized to a degree of neutralization of 80 to 100 mol% to be water.
  • the agglomerated particles are disintegrated, and even if it is a dispersion of almost primary particles or a secondary agglomerate, a stable dispersed state in which the particle size is in the range of 0.1 to 10.0 ⁇ m is formed. It is a thing.
  • the particle size distribution which is the value obtained by dividing the volume average particle size of the water-swelled particle size by the number average particle size, is preferably 10 or less, more preferably 5.0 or less, from the viewpoint of bondability and coatability. Yes, more preferably 3.0 or less, still more preferably 1.5 or less.
  • the lower limit of the particle size distribution is usually 1.0.
  • the particle size (dry particle size) of the crosslinked polymer of the present invention or a salt thereof at the time of drying is preferably in the range of 0.03 ⁇ m or more and 3 ⁇ m or less in terms of volume-based median size.
  • a more preferable range of the particle size is 0.1 ⁇ m or more and 1 ⁇ m or less, and a more preferable range is 0.3 ⁇ m or more and 0.8 ⁇ m or less.
  • the crosslinked polymer or a salt thereof contains an acid group such as a carboxyl group derived from an ethylenically unsaturated carboxylic acid monomer so that the neutralization degree is 20 to 100 mol% in the composition for the electrode mixture layer. It is preferably neutralized and used as a salt embodiment.
  • the degree of neutralization is more preferably 50 to 100 mol%, further preferably 60 to 95 mol%. When the degree of neutralization is 20 mol% or more, the water swelling property is good and the dispersion stabilizing effect is easily obtained, which is preferable.
  • the degree of neutralization can be calculated by calculation from the charged values of a monomer having an acid group such as a carboxyl group and a neutralizing agent used for neutralization.
  • the crosslinked polymer has a three-dimensional crosslinked structure and exists as a microgel in a medium such as water.
  • a three-dimensional crosslinked polymer is insoluble in a solvent, so its molecular weight cannot be measured. Similarly, it is usually difficult to measure and quantify the primary chain length of crosslinked polymers.
  • the crosslinked polymer or a salt thereof preferably has a water swelling degree of 4.0 or more and 60 or less at pH 8.
  • the degree of water swelling may be, for example, 5.0 or more, 6.0 or more, 7.0 or more, 10 or more, or 15 or more. May be good.
  • the degree of water swelling When the degree of water swelling is 4.0 or more, the crosslinked polymer or a salt thereof spreads on the surface of the active material or the current collector, and a sufficient adhesive area can be secured, so that good binding property can be obtained.
  • the upper limit of the degree of water swelling at pH 8 may be 55 or less, 50 or less, 45 or less, 40 or less, or 35 or less.
  • the degree of water swelling exceeds 60, the viscosity of the composition for the electrode mixture layer (electrode slurry) containing the crosslinked polymer or a salt thereof tends to increase, resulting in insufficient uniformity of the mixture layer, which is sufficient. Cohesiveness may not be obtained. In addition, the coatability of the electrode slurry may decrease.
  • the range of the degree of water swelling at pH 8 can be set by appropriately combining the above upper limit value and lower limit value, and is, for example, 5.0 or more and 60 or less, and for example, 6.0 or more and 60 or less. Further, for example, it is 5.0 or more and 55 or less.
  • the degree of water swelling at pH 8 can be obtained by measuring the degree of swelling of the crosslinked polymer or a salt thereof in water at pH 8.
  • the water having a pH of 8 for example, ion-exchanged water can be used, and the pH value may be adjusted by using an appropriate acid or alkali, a buffer solution or the like, if necessary.
  • the pH at the time of measurement is, for example, in the range of 8.0 ⁇ 0.5, preferably in the range of 8.0 ⁇ 0.3, more preferably in the range of 8.0 ⁇ 0.2, and further. It is preferably in the range of 8.0 ⁇ 0.1.
  • the measurement is performed at 25 ⁇ 5 ° C.
  • a person skilled in the art can adjust the degree of water swelling by controlling the composition and structure of the crosslinked polymer or a salt thereof.
  • the degree of water swelling can be increased by introducing an acidic functional group or a highly hydrophilic structural unit into the crosslinked polymer. Further, by lowering the degree of cross-linking of the cross-linked polymer, the degree of water swelling is usually increased.
  • ⁇ Method for producing this polymer or its salt> Known polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, and emulsion polymerization can be used for this polymer, but precipitation polymerization and suspension polymerization (reverse phase suspension polymerization) can be used in terms of productivity. ) Is preferable. Non-uniform polymerization methods such as precipitation polymerization, suspension polymerization, and emulsion polymerization are preferable, and the precipitation polymerization method is more preferable, because better performance can be obtained in terms of binding property and the like.
  • Precipitation polymerization is a method for producing a polymer by carrying out a polymerization reaction in a solvent that dissolves an unsaturated monomer as a raw material but does not substantially dissolve the polymer to be produced.
  • the polymer particles become larger due to aggregation and growth, and a dispersion liquid of the polymer particles in which the primary particles of several tens of nm to several hundreds nm are secondarily aggregated to several ⁇ m to several tens of ⁇ m can be obtained.
  • Dispersion stabilizers can also be used to control the particle size of the polymer.
  • the dispersion stabilizer examples include a dispersion stabilizer produced by a living radical polymerization method, a macromonomer type dispersion stabilizer, and a nonionic surfactant.
  • the secondary aggregation can also be suppressed by selecting a dispersion stabilizer, a polymerization solvent, or the like. In general, precipitation polymerization in which secondary aggregation is suppressed is also called dispersion polymerization.
  • a solvent selected from water, various organic solvents, etc. can be used as the polymerization solvent in consideration of the type of monomer used. In order to obtain a polymer having a longer primary chain length, it is preferable to use a solvent having a small chain transfer constant.
  • the polymerization solvent examples include water-soluble solvents such as methanol, t-butyl alcohol, acetone, methyl ethyl ketone, acetonitrile and tetrahydrofuran, as well as benzene, ethyl acetate, dichloroethane, n-hexane, cyclohexane and n-heptane. , One of these can be used alone or in combination of two or more. Alternatively, it may be used as a mixed solvent of these and water.
  • the water-soluble solvent refers to a solvent having a solubility in water at 20 ° C. of more than 10 g / 100 ml.
  • the formation of coarse particles and adhesion to the reactor are small and the polymerization stability is good, and the precipitated polymer fine particles are difficult to secondary agglomerate (or even if secondary agglomeration occurs, they dissolve in the aqueous medium.
  • Methyl ethyl ketone and acetonitrile are preferable because they are easy to use), a polymer having a small chain transfer constant and a large degree of polymerization (primary chain length) can be obtained, and the operation is easy during the step neutralization described later. ..
  • a highly polar solvent preferably include water and methanol.
  • the amount of the highly polar solvent used is preferably 0.05 to 20.0% by mass, more preferably 0.1 to 10.0% by mass, still more preferably 0.1 to 5% by mass, based on the total mass of the medium. It is 0.0% by mass, more preferably 0.1 to 1.0% by mass.
  • the polymerization rate is improved when a highly polar solvent is added, and it becomes easy to obtain a polymer having a long primary chain length.
  • a highly polar solvent water is particularly preferable because it has a large effect of improving the polymerization rate.
  • a monomer component containing a monomer represented by the general formula (1) and an ethylenically unsaturated carboxylic acid monomer different from the general formula (1) is used. It is preferable to include a polymerization step of polymerizing.
  • the ethylenically unsaturated carboxylic acid monomer from which the component (a) is derived is 0.1% by mass or more and 20% by mass or less, and other ethylenically unsaturated monomers from which the component (b) is derived. It is preferable to include a polymerization step of polymerizing a monomer component containing 10% by mass or more and 99.9% by mass or less.
  • the structural unit (component (a)) derived from the monomer represented by the general formula (1) is introduced into the crosslinked polymer.
  • a structural unit (component (b)) derived from an ethylenically unsaturated carboxylic acid monomer different from the general formula (1) is introduced in an amount of 10% by mass or more and 99.9% by mass or less.
  • the amount of the monomer represented by the general formula (1) is, for example, 0.1% by mass or more and 19% by mass or less, and for example, 0.1% by mass or more and 18% by mass or less.
  • the amount of the monomer used is, for example, 20% by mass or more and 99.9% by mass or less, and for example, 50% by mass or more and 99.9% by mass or less, and for example, 60% by mass or more. It is 99.9% by mass or less, and is, for example, 70% by mass or more and 99.9% by mass or less, and for example, 80% by mass or more and 99.9% by mass or less.
  • Examples of the other ethylenically unsaturated monomer include an ethylenically unsaturated monomer compound having an anionic group other than a carboxyl group such as a sulfonic acid group and a phosphoric acid group, and a nonionic ethylenically.
  • Examples include unsaturated monomers.
  • Specific examples of the compound include a monomer compound into which the above-mentioned component (c) can be introduced.
  • the other ethylenically unsaturated monomer may contain 0% by mass or more and 89.9% by mass or less, and 0.5% by mass or more and 70% by mass or less with respect to the total amount of the monomer components.
  • crosslinkable monomer may be used in the same manner.
  • the monomer component polymerized in the polymerization step may contain a crosslinkable monomer.
  • a crosslinkable monomer as described above, it has a polyfunctional polymerizable monomer having two or more polymerizable unsaturated groups and a self-crosslinkable crosslinkable functional group such as a hydrolyzable silyl group. Examples thereof include monomers, and the amount of the crosslinkable monomer used is as described above.
  • the monomer concentration at the time of polymerization is preferably high from the viewpoint of obtaining a polymer having a longer primary chain length.
  • the monomer concentration at the start of polymerization is generally in the range of about 2 to 40% by mass, preferably in the range of 5 to 40% by mass.
  • the "monomer concentration" indicates the monomer concentration in the reaction solution at the time when the polymerization is started.
  • the present polymer may be produced by carrying out a polymerization reaction in the presence of a basic compound.
  • the monomer concentration may be 13.0% by mass or more, preferably 15.0% by mass or more, more preferably 17.0% by mass or more, and further preferably 19.0% by mass or more. It is more preferably 20.0% by mass or more.
  • the monomer concentration is still preferably 22.0% by mass or more, and even more preferably 25.0% by mass or more.
  • the higher the monomer concentration at the time of polymerization the higher the molecular weight can be, and a polymer having a long primary chain length can be produced. Further, a polymer having a long primary chain length tends to be incorporated into a three-dimensional crosslinked structure, so that the sol fraction tends to be reduced.
  • the upper limit of the monomer concentration differs depending on the type of monomer and solvent used, the polymerization method, various polymerization conditions, etc., but if the heat of the polymerization reaction can be removed, the precipitation polymerization is as described above. It is about 40%, about 50% for suspension polymerization, and about 70% for emulsion polymerization.
  • the above-mentioned base compound is a so-called alkaline compound, and either an inorganic base compound or an organic base compound may be used.
  • an inorganic base compound By carrying out the polymerization reaction in the presence of a basic compound, the polymerization reaction can be stably carried out even under high monomer concentration conditions such as exceeding 13.0% by mass. Further, the polymer obtained by polymerizing at such a high monomer concentration has a high molecular weight (because the primary chain length is long), and therefore has excellent binding properties.
  • the inorganic base compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, and alkalis such as sodium carbonate and potassium carbonate.
  • Examples thereof include metal carbonates, and one or more of these can be used.
  • Examples of the organic base compound include ammonia and organic amine compounds, and one or more of these can be used. Of these, an organic amine compound is preferable from the viewpoint of polymerization stability and binding property of a binder containing the obtained crosslinked polymer or a salt thereof.
  • organic amine compound examples include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monobutylamine, dibutylamine, tributylamine, monohexylamine, dihexylamine, trihexylamine, trioctylamine and tridodecylamine.
  • N-alkyl substituted amines such as: monoethanolamine, diethanolamine, triethanolamine, propanolamine, dimethylethanolamine and (alkyl) alkanolamines such as N, N-dimethylethanolamine; pyridine, piperidine, piperazine, 1,8- Cyclic amines such as bis (dimethylamino) naphthalene, morpholin and diazabicycloundecene (DBU); diethylenetriamine, N, N-dimethylbenzylamine, and one or more of these can be used. ..
  • the C / N value is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more, and even more preferably 20 or more.
  • the amount of the base compound used is preferably in the range of 0.001 mol% or more and 4.0 mol% or less with respect to the ethylenically unsaturated carboxylic acid monomer. When the amount of the basic compound used is within this range, the polymerization reaction can be smoothly carried out.
  • the amount used may be 0.05 mol% or more and 4.0 mol% or less, 0.1 mol% or more and 4.0 mol% or less, and 0.1 mol% or more and 3.0 mol. It may be 0.1 mol% or more and 2.0 mol% or less.
  • the amount of the base compound used represents the molar concentration of the base compound used with respect to the ethylenically unsaturated carboxylic acid monomer, and does not mean the degree of neutralization. That is, the valence of the base compound used is not considered.
  • polymerization initiator known polymerization initiators such as azo compounds, organic peroxides, and inorganic peroxides can be used, but the polymerization initiator is not particularly limited.
  • the conditions of use can be adjusted by known methods such as heat initiation, redox initiation with a reducing agent, and UV initiation so that the amount of radicals generated is appropriate.
  • heat initiation heat initiation
  • redox initiation with a reducing agent
  • UV initiation UV initiation
  • Examples of the azo compound include 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (N-butyl-2-methylpropionamide), and 2- (tert-butylazo) -2.
  • -Cyanopropane, 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane) and the like, and one or more of these are used. be able to.
  • organic peroxide examples include 2,2-bis (4,5-di-t-butylperoxycyclohexyl) propane (manufactured by Nichiyu Co., Ltd., trade name "Pertetra A”) and 1,1-di (t-).
  • inorganic peroxide examples include potassium persulfate, sodium persulfate, ammonium persulfate and the like.
  • potassium persulfate sodium persulfate
  • sodium persulfate sodium persulfate
  • ammonium persulfate and the like.
  • sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, sulfurous acid gas (SO 2 ), ferrous sulfate and the like can be used as the reducing agent.
  • the preferable amount of the polymerization initiator used is, for example, 0.001 to 2 parts by mass and, for example, 0.005 to 1 part by mass, when the total amount of the monomer components used is 100 parts by mass. Further, for example, it is 0.01 to 0.1 parts by mass.
  • the amount of the polymerization initiator used is 0.001 part by mass or more, the polymerization reaction can be stably carried out, and when it is 2 parts by mass or less, a polymer having a long primary chain length can be easily obtained.
  • the polymerization temperature depends on conditions such as the type and concentration of the monomer used, but is preferably 0 to 100 ° C., more preferably 20 to 80 ° C., the polymerization temperature may be constant, or the polymerization reaction. It may change over time.
  • the present polymer dispersion obtained through the polymerization step can be obtained in a powder state by subjecting the polymer dispersion to a reduced pressure and / or heat treatment in the drying step and distilling off the solvent.
  • a solid-liquid separation step such as centrifugation and filtration, and water.
  • a monomer composition containing a monomer represented by the general formula (1) and an ethylenically unsaturated carboxylic acid monomer different from the general formula (1) in the presence of a basic compound After neutralizing the polymer by adding an alkaline compound to the polymer dispersion obtained in the polymerization step (hereinafter, also referred to as “step neutralization”), the solvent is removed in the drying step. You may. Further, after obtaining the powder of the present polymer without performing the above-mentioned step neutralization treatment, an alkaline compound is added when preparing the electrode slurry to neutralize the polymer (hereinafter, also referred to as "post-neutralization”). You may say). Of the above, process neutralization is preferable because the secondary aggregates tend to be easily disintegrated.
  • composition for the secondary battery electrode mixture layer of the present invention contains the binder, active material and water containing the present polymer or a salt thereof.
  • the amount of the present polymer or a salt thereof used in the composition for the electrode mixture layer of the present invention is, for example, 0.1% by mass or more and 20% by mass or less with respect to the total amount of the active material.
  • the amount used is, for example, 0.2% by mass or more and 10% by mass or less, for example, 0.3% by mass or more and 8% by mass or less, and for example, 0.4% by mass or more and 5% by mass or less. .. If the amount of the polymer and its salt used is less than 0.1% by mass, sufficient binding properties may not be obtained.
  • the dispersion stability of the active material or the like may become insufficient, and the uniformity of the formed mixture layer may decrease.
  • the amount of the present polymer and its salt used exceeds 20% by mass, the composition for the electrode mixture layer becomes highly viscous and the coatability to the current collector may be deteriorated. As a result, the obtained mixture layer may have lumps or irregularities, which may adversely affect the electrode characteristics.
  • the amount of the present polymer and its salt used is within the above range, a composition having excellent dispersion stability can be obtained, and a mixture layer having extremely high adhesion to the current collector can be obtained. As a result, the durability of the battery is improved. Further, the present polymer and its salt show sufficiently high binding property to the active material even in a small amount (for example, 5% by mass or less) and have a carboxy anion, so that the interfacial resistance is small and the high rate characteristic is obtained. An excellent electrode can be obtained.
  • a lithium salt of a transition metal oxide can be used as the positive electrode active material, and for example, layered rock salt type and spinel type lithium-containing metal oxides can be used.
  • ⁇ Li (Ni 1-ab Co a Al b ) ⁇ and the like can be mentioned.
  • a spinel type positive electrode active material lithium manganate and the like can be mentioned.
  • phosphates include olivine-type lithium iron phosphate and the like.
  • the positive electrode active material one of the above may be used alone, or two or more thereof may be combined and used as a mixture or a composite.
  • the amount of the unneutralized or partially neutralized present polymer used should be equal to or greater than the amount of alkali eluted from the active material so that the amount of unneutralized carboxyl groups in the present polymer is equal to or greater than the amount of alkali eluted from the active material. Is preferable.
  • the conductive auxiliary agent include carbon-based materials such as carbon black, carbon nanotubes, carbon fibers, graphite fine powder, and carbon fibers. Among these, carbon black, carbon nanotubes, and carbon are easy to obtain excellent conductivity. Fiber is preferred. Further, as the carbon black, Ketjen black and acetylene black are preferable. As the conductive auxiliary agent, one of the above types may be used alone, or two or more types may be used in combination.
  • the amount of the conductive auxiliary agent used can be, for example, 0.2 to 20% by mass with respect to the total amount of the active material from the viewpoint of achieving both conductivity and energy density, and for example, 0.2 to 10%. It can be mass%.
  • the positive electrode active material a material whose surface is coated with a conductive carbon-based material may be used.
  • examples of the negative electrode active material include carbon-based materials, lithium metals, lithium alloys, metal oxides, and the like, and one or a combination of two or more of these can be used.
  • active materials made of carbon-based materials such as natural graphite, artificial graphite, hard carbon and soft carbon (hereinafter, also referred to as "carbon-based active material") are preferable, and graphite such as natural graphite and artificial graphite, and graphite such as artificial graphite, and Hard carbon is more preferred.
  • spherical graphite is preferably used from the viewpoint of battery performance, and the preferable range of the particle size thereof is, for example, 1 to 20 ⁇ m, and for example, 5 to 15 ⁇ m.
  • a metal or a metal oxide capable of occluding lithium such as silicon or tin can be used as the negative electrode active material.
  • silicon has a higher capacity than graphite, and is an active material made of a silicon-based material such as silicon, a silicon alloy, and a silicon oxide such as silicon monoxide (SiO) (hereinafter, also referred to as "silicon-based active material"). ) Can be used.
  • the silicon-based active material has a high capacity, the volume change due to charging and discharging is large. Therefore, it is preferable to use it in combination with the above carbon-based active material.
  • the amount of the silicon active material used is preferably 2 to 80% by mass with respect to the total amount of the carbon-based active material and the silicon-based active material.
  • the amount of the silicon-based active material used may be 5 to 70% by mass, 8 to 60% by mass, or 10 to 50% by mass.
  • This polymer is derived from a structural unit (component (a)) derived from the monomer represented by the general formula (1) and an ethylenically unsaturated carboxylic acid monomer different from the general formula (1). It has a structural unit (component (b)), and the components (a) and (b) have high affinity for silicon-based active materials and show good binding properties. Therefore, since the binder of the present invention exhibits excellent binding properties even when a high-capacity type active material containing a silicon-based active material is used, it is also effective for improving the durability of the obtained electrode. It is considered to be.
  • the present polymer is a crosslinked polymer having a structural unit (component (c)) derived from a specific monomer having a hydroxyl group in that an increase in the viscosity of the electrode slurry can be suppressed or reduced. Is preferable. The reason why such an effect can be obtained is not clear, but since the present polymer has a relatively flexible hydroxyl group in the side chain of the polymer, it interacts with the carboxyl group in the present polymer, and as a result, the crosslinked polymer in water. It is presumed that this is due to the suppression of the swelling of the polymer. However, the above inference does not limit the scope of the present invention.
  • the carbon-based active material itself has good electrical conductivity, it is not always necessary to add a conductive additive.
  • a conductive additive is added for the purpose of improving cycle characteristics, the amount used is, for example, 10% by mass or less, and for example, 5% by mass or less, based on the total amount of active material, from the viewpoint of energy density. Is.
  • the amount of the active material used is, for example, in the range of 10 to 75% by mass with respect to the total amount of the composition. If the amount of the active material used is 10% by mass or more, migration of the binder or the like can be suppressed. Further, since it is advantageous in terms of the drying cost of the medium, the amount of the active material used is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. .. On the other hand, if it is 75% by mass or less, the fluidity and coatability of the composition can be ensured, and a uniform mixture layer can be formed.
  • Water is used as a medium in the composition for the secondary battery electrode mixture layer. Further, for the purpose of adjusting the properties and dryness of the composition, lower alcohols such as methanol and ethanol, carbonates such as ethylene carbonate, ketones such as acetone, and water-soluble organic solvents such as tetrahydrofuran and N-methylpyrrolidone. It may be used as a mixed solvent with.
  • the proportion of water in the mixing medium is, for example, 50% by mass or more, and for example, 70% by mass or more.
  • the solid content concentration is not limited to about 50% by mass, and the content of the medium containing water in the entire composition is the electrode.
  • the energy cost required for drying, and the productivity it can be, for example, in the range of 25 to 90% by mass, and can be, for example, 35 to 70% by mass. For example, it can be 45 to 70% by mass.
  • the binder of the present invention may consist only of the above polymer or a salt thereof, but other binders such as styrene / butadiene latex (SBR), acrylic latex and polyvinylidene fluoride latex. Binder components may be used in combination. When other binder components are used in combination, the amount used may be, for example, 0.1 to 5% by mass or less, and for example, 0.1 to 2% by mass or less, based on the active material. And, for example, it can be 0.1 to 1% by mass or less. If the amount of the other binder component used exceeds 5% by mass, the resistance increases and the high rate characteristics may become insufficient. Among the above, styrene / butadiene latex is preferable because it has an excellent balance between binding property and bending resistance.
  • SBR styrene / butadiene latex
  • acrylic latex acrylic latex
  • polyvinylidene fluoride latex polyvinylidene fluoride late
  • the styrene / butadiene latex is a copolymer having a structural unit derived from an aromatic vinyl monomer such as styrene and a structural unit derived from an aliphatic conjugated diene monomer such as 1,3-butadiene. Shows an aqueous dispersion.
  • aromatic vinyl monomer include ⁇ -methylstyrene, vinyltoluene, divinylbenzene and the like in addition to styrene, and one or more of these can be used.
  • the structural unit derived from the aromatic vinyl monomer in the copolymer can be, for example, in the range of 20 to 60% by mass, and for example, 30 to 50, mainly from the viewpoint of binding property. It can be in the range of% by mass.
  • Examples of the aliphatic conjugated diene-based monomer include 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 2-chloro-1,3-in addition to 1,3-butadiene. Butadiene and the like can be mentioned, and one or more of these can be used.
  • the structural unit derived from the aliphatic conjugated diene-based monomer in the copolymer is, for example, 30 to 70% by mass in that the binding property of the binder and the flexibility of the obtained electrode are good. It can be in the range of 40 to 60% by mass, for example.
  • styrene / butadiene-based latex includes nitrile group-containing monomers such as (meth) acrylonitrile and (meth) as other monomers in order to further improve performance such as binding properties.
  • a carboxyl group-containing monomer such as acrylic acid, itaconic acid, and maleic acid may be used as the copolymerization monomer.
  • the structural unit derived from the other monomer in the copolymer can be, for example, in the range of 0 to 30% by mass, or can be, for example, in the range of 0 to 20% by mass.
  • the composition for the secondary battery electrode mixture layer of the present invention contains the above-mentioned active material, water and a binder as essential constituents, and can be obtained by mixing the respective components using known means.
  • the mixing method of each component is not particularly limited, and a known method can be adopted. However, after dry blending the powder components such as the active material, the conductive auxiliary agent and the present polymer particles which are binders, water is used. A method of mixing with a dispersion medium such as the above and dispersing and kneading is preferable.
  • a dispersion medium such as the above and dispersing and kneading is preferable.
  • a known mixer such as a planetary mixer, a thin film swirl mixer, or a self-revolving mixer can be used, but a thin film swirl mixer is used because a good dispersion state can be obtained in a short time. It is preferable to do this.
  • a thin film swirl mixer it is preferable to pre-disperse in advance with a stirrer such as a disper.
  • the viscosity of the slurry can be, for example, in the range of 500 to 10,000 mPa ⁇ s.
  • the upper limit of the viscosity is preferably 7,000 mPa ⁇ s or less, more preferably 6,000 mPa ⁇ s or less, and further preferably 5,000 mPa ⁇ s or less. It is more preferably 4,000 mPa ⁇ s or less, and even more preferably 3,000 mPa ⁇ s or less.
  • the slurry viscosity can be measured by the method described in Examples under the condition of a liquid temperature of 25 ° C.
  • composition for the electrode mixture layer when obtained in a wet powder state, it is preferable to knead the composition to a uniform state without uneven concentration using a Henschel mixer, a blender, a planetary mixer, a twin-screw kneader or the like.
  • the electrode for a secondary battery of the present invention is provided with a mixture layer formed from the above-mentioned electrode mixture layer composition on the surface of a current collector such as copper or aluminum.
  • the mixture layer is formed by applying the composition for an electrode mixture layer of the present invention to the surface of a current collector and then drying and removing a medium such as water.
  • the method for applying the composition for the electrode mixture layer is not particularly limited, and known methods such as a doctor blade method, a dip method, a roll coating method, a comma coating method, a curtain coating method, a gravure coating method and an extrusion method can be used. Can be adopted.
  • the drying can be performed by a known method such as blowing warm air, reducing the pressure, (far) infrared rays, and irradiating microwaves.
  • the mixture layer obtained after drying is subjected to a compression treatment by a mold press, a roll press or the like. By compressing, the active material and the binder can be brought into close contact with each other, and the strength of the mixture layer and the adhesion to the current collector can be improved.
  • the thickness of the mixture layer can be adjusted to, for example, about 30 to 80% before compression by compression, and the thickness of the mixture layer after compression is generally about 4 to 200 ⁇ m.
  • a secondary battery can be manufactured by providing the electrode for the secondary battery of the present invention with a separator and an electrolytic solution.
  • the electrolytic solution may be in the form of a liquid or in the form of a gel.
  • the separator is arranged between the positive electrode and the negative electrode of the battery, and plays a role of preventing a short circuit due to contact between the two electrodes and holding an electrolytic solution to ensure ionic conductivity.
  • the separator is preferably a film-like insulating microporous membrane having good ion permeability and mechanical strength.
  • polyolefins such as polyethylene and polypropylene, polytetrafluoroethylene and the like can be used.
  • the electrolytic solution a known one that is generally used depending on the type of active material can be used.
  • specific solvents include cyclic carbonates having a high dielectric constant and high solubility of electrolytes such as propylene carbonate and ethylene carbonate, and low-viscosity chains such as ethylmethyl carbonate, dimethyl carbonate and diethyl carbonate. Examples thereof include a state carbonate, and these can be used alone or as a mixed solvent.
  • the electrolytic solution is used by dissolving lithium salts such as LiPF 6 , LiSbF 6 , LiBF 4 , LiClO 4 , and LiAlO 4 in these solvents.
  • an aqueous potassium hydroxide solution can be used as the electrolytic solution.
  • the secondary battery is obtained by forming a positive electrode plate and a negative electrode plate partitioned by a separator into a spiral or laminated structure and storing them in a case or the like.
  • the binder for the secondary battery electrode disclosed in the present specification exhibits excellent adhesion to the electrode material and excellent adhesion to the current collector in the mixture layer. Therefore, the secondary battery provided with the electrodes obtained by using the above binder is expected to ensure good integrity and exhibit good durability (cycle characteristics) even after repeated charging and discharging, and is in-vehicle. Suitable for secondary batteries and the like.
  • the degree of water swelling at pH 8 was measured by the following method.
  • the measuring device is shown in FIG.
  • the measuring device is composed of ⁇ 1> to ⁇ 3> in FIG. ⁇ 1> It is composed of a burette 1, a pinch cock 2, a silicon tube 3 and a polytetrafluoroethylene tube 4 having a branch tube for venting air.
  • a support cylinder 8 having a large number of holes on the bottom surface is installed on the funnel 5, and a filter paper 10 for a device is installed on the support cylinder 8.
  • a sample 6 (measurement sample) of a carboxyl group-containing polymer or a salt thereof is sandwiched between two sample fixing filter papers 7, and the sample fixing filter paper is fixed by an adhesive tape 9.
  • All the filter papers used are ADVANTEC No. 2.
  • the inner diameter is 55 mm.
  • ⁇ 1> and ⁇ 2> are connected by a silicon tube 3.
  • the heights of the funnel 5 and the support cylinder 8 are fixed with respect to the burette 1, and the lower end of the polytetrafluoroethylene tube 4 installed inside the burette branch pipe and the bottom surface of the support cylinder 8 are at the same height. (Dotted line in FIG. 1).
  • the measuring method will be described below. The following operations were carried out at 25 ° C. unless otherwise specified.
  • the pinch cock 2 in ⁇ 1> is removed, ion-exchanged water adjusted to pH 8.0 is put through the silicon tube 3 from the upper part of the burette 1, and the burette 1 to the filter paper 10 for the device are filled with the ion-exchanged water 12. And.
  • the pinch cock 2 is closed, and air is removed from the polytetrafluoroethylene tube 4 connected to the burette branch pipe with a rubber stopper. In this way, the ion-exchanged water 12 is continuously supplied from the burette 1 to the filter paper 10 for the apparatus.
  • the reading (a) of the scale of the burette 1 is recorded. Weigh 0.1 to 0.2 g of the dry powder of the measurement sample, and place it evenly on the center of the sample fixing filter paper 7 as shown in ⁇ 3>. The sample is sandwiched between another filter paper, and the two filter papers are fastened with the adhesive tape 9 to fix the sample. The filter paper on which the sample is fixed is placed on the filter paper 10 for equipment shown in ⁇ 2>. Next, the reading (b) of the scale of the burette 1 is recorded 30 minutes after the lid 11 is placed on the filter paper 10 for the device.
  • the total (c) of the water absorption of the measurement sample and the water absorption of the two sample fixing filter papers 7 is obtained by (ab).
  • the water absorption amount (d) of only the two filter papers 7 containing no sample of the carboxyl group-containing polymer or a salt thereof is measured.
  • the above operation was performed, and the degree of water swelling was calculated from the following formula.
  • the value measured by the method described later was used.
  • Water swelling degree ⁇ dry mass of measurement sample (g) + (cd) ⁇ / ⁇ dry mass of measurement sample (g) ⁇
  • the dry mass (g) of the measurement sample the mass (g) of the measurement sample ⁇ (solid content (%) ⁇ 100)
  • the obtained polymerization reaction solution was centrifuged to settle the polymer particles, and then the supernatant was removed. Then, after redispersing the precipitate in acetonitrile having the same mass as the polymerization reaction solution, the washing operation of precipitating the polymer particles by centrifugation to remove the supernatant was repeated twice.
  • the precipitate was recovered and dried under reduced pressure at 80 ° C. for 3 hours to remove volatile components to obtain a powder of the carboxyl group-containing polymer salt R-1. Since the carboxyl group-containing polymer salt R-1 has hygroscopicity, it was stored in a container having a water vapor barrier property.
  • the degree of water swelling was 63.4, and the sol fraction was 30% by mass.
  • -AA Acrylic acid (purity: 99.9% by mass or more, content of monomer represented by the general formula (1): less than 0.1% by mass)
  • -CEAA ⁇ -carboxyethyl acrylate (manufactured by SIGMA-ALDRICH, trade name "2-carboxyethyl acrylate")
  • -HEA 2-Hydroxyethyl acrylate-T-20: Trimethylolpropane diallyl ether (manufactured by Daiso, trade name "Neoallyl T-20")
  • -P-30 Pentaerythritol triallyl ether (manufactured by Daiso, trade name "Neoallyl P-30”)
  • -TEA 2-Hydroxy
  • Example 1 An electrode using the carboxyl group-containing polymer salt R-1 was prepared and evaluated. The specific procedure and evaluation method are shown below.
  • composition for electrode mixture layer (electrode slurry))
  • Si-based active material a SiOx (0.8 ⁇ x ⁇ 1.2) surface coated with carbon by the CVD method
  • graphite manufactured by Nippon Graphite Co., Ltd., trade name "CGB”.
  • a mixture of -10 ” and a Si-based active material was used as the active material.
  • the mass of graphite: Si-based active material: R-1 90: 10: 2.8 (solid content) using water as a diluting solvent so that the solid content concentration of the composition for the electrode mixture layer is 45% by mass.
  • the electrode slurry obtained above has a viscosity of a shear rate of 60s -1 at 25 ° C. on a CP25-5 cone plate (diameter 25 mm, cone angle 5 °) using a rheometer (Physica MCR301) manufactured by Anton Pearl Co., Ltd. Was measured and found to be 9,700 mPa ⁇ s.
  • the electrode slurry was applied onto a copper foil having a thickness of 12 ⁇ m using a variable applicator, and dried in a ventilation dryer at 100 ° C. for 15 minutes to form a mixture layer. Then, the mixture layer was rolled so that the thickness was 50 ⁇ 5 ⁇ m and the packing density was 1.60 ⁇ 0.10 g / cm 3 , to obtain a negative electrode plate.
  • a sample for a peeling test was prepared by pasting the mixture layer surface of the negative electrode electrode plate having a size of 100 mm ⁇ 25 mm on a 120 mm ⁇ 30 mm acrylic plate via a double-sided tape (Nichiban Co., Ltd. Nystack NW-20). After drying at 60 ° C. overnight under reduced pressure conditions, 90 ° peeling was performed at a measurement temperature of 25 ° C. and a tensile speed of 50 mm / min using a tensile tester (Tencilon universal test material machine RTE-1210 manufactured by ORIENTEC). , The binding property was evaluated by measuring the peel strength between the mixture layer and the copper foil. The peel strength was as high as 11.4 N / m, which was good.
  • composition for the negative electrode mixture layer was prepared by performing the same operation as in Example 1 except that the carboxyl group-containing polymer salt used as the binder was used as shown in Table 2.
  • the slurry viscosity and 90 ° peel strength of each composition for the negative electrode mixture layer were evaluated. The results are shown in Table 2.
  • the electrode slurry containing the binder for the secondary battery electrode of the present invention has a low viscosity, and the peel strength between the mixture layer of the obtained electrode and the current collector is all high. A high value was obtained, indicating excellent binding properties.
  • the binder for a secondary battery electrode of the present invention can exhibit better binding properties than before, and has an electrode slurry viscosity even when the concentration of the active material in the composition for the electrode mixture layer is high. It can be reduced. Therefore, the secondary battery provided with the electrodes obtained by using the above binder is expected to exhibit good durability (cycle characteristics), and is expected to be applied to an in-vehicle secondary battery. It is also useful for the use of active materials containing silicon, and is expected to contribute to increasing the capacity of batteries.
  • the binder for a secondary battery electrode of the present invention can be particularly preferably used for a non-aqueous electrolyte secondary battery electrode, and is particularly useful for a non-aqueous electrolyte lithium ion secondary battery having a high energy density.

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PCT/JP2020/037497 2019-10-11 2020-10-02 二次電池電極用バインダー、二次電池電極合剤層用組成物、二次電池電極及び二次電池 Ceased WO2021070738A1 (ja)

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KR1020227012852A KR20220078615A (ko) 2019-10-11 2020-10-02 이차전지 전극용 바인더, 이차전지 전극 합제층용 조성물, 이차전지 전극 및 이차전지
JP2021551469A JP7530052B2 (ja) 2019-10-11 2020-10-02 二次電池電極用バインダー、二次電池電極合剤層用組成物、二次電池電極及び二次電池
US17/767,988 US12482822B2 (en) 2019-10-11 2020-10-02 Secondary battery electrode binder, secondary battery electrode mixture layer composition, secondary battery electrode and secondary battery
EP20874102.5A EP4043503A4 (en) 2019-10-11 2020-10-02 BINDING AGENT FOR SECONDARY BATTERY ELECTRODES, LAYER COMPOSITION FOR SECONDARY BATTERY ELECTRODE MIXTURE, SECONDARY BATTERY ELECTRODE AND SECONDARY BATTERY

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