WO2020129802A1 - Composition d'électrolyte solide, feuille contenant l'électrolyte solide, batterie secondaire entièrement solide, procédé de production de feuille contenant l'électrolyte solide, et procédé de production de batterie secondaire entièrement solide - Google Patents

Composition d'électrolyte solide, feuille contenant l'électrolyte solide, batterie secondaire entièrement solide, procédé de production de feuille contenant l'électrolyte solide, et procédé de production de batterie secondaire entièrement solide Download PDF

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WO2020129802A1
WO2020129802A1 PCT/JP2019/048675 JP2019048675W WO2020129802A1 WO 2020129802 A1 WO2020129802 A1 WO 2020129802A1 JP 2019048675 W JP2019048675 W JP 2019048675W WO 2020129802 A1 WO2020129802 A1 WO 2020129802A1
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solid electrolyte
polymer
solid
electrolyte composition
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Japanese (ja)
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智則 三村
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富士フイルム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of 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
    • H01M4/36—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solid electrolyte composition, a solid electrolyte-containing sheet and an all-solid secondary battery, and a method for manufacturing a solid electrolyte-containing sheet and an all-solid secondary battery.
  • a lithium-ion secondary battery is a storage battery that has a negative electrode, a positive electrode, and an electrolyte sandwiched between the negative electrode and the positive electrode, and can charge and discharge by moving lithium ions back and forth between both electrodes.
  • an organic electrolytic solution has been used as an electrolyte in a lithium ion secondary battery.
  • the organic electrolytic solution is liable to leak, and there is a risk of short circuit inside the battery due to overcharging or overdischarging, which may cause ignition. Therefore, further improvement in safety and reliability is required. Under these circumstances, an all-solid secondary battery using an inorganic solid electrolyte instead of the organic electrolyte has been receiving attention.
  • the all-solid-state secondary battery has a solid negative electrode, electrolyte, and positive electrode, and can greatly improve the safety and reliability of a battery using an organic electrolytic solution.
  • Patent Document 1 discloses a solid electrolyte composition having an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table and a polymer binder, wherein the polymer binder is , A solid electrolyte composition composed of a polymer having a hard segment and a soft segment is described.
  • Patent Document 2 includes an inorganic solid electrolyte, binder particles composed of a polymer having a reactive group, and a dispersion medium, and at least one component selected from a crosslinking agent and a crosslinking accelerator.
  • Solid electrolyte compositions are described. When forming a constituent layer, this solid electrolyte composition is prepared by polymerizing a binder particle (a polymer having a reactive group) fixed to an electrolyte particle or an active material particle by a polymerization reaction (chain polymerization reaction, polyaddition reaction, ring-opening polymerization reaction). And the like) to cure.
  • Patent Document 3 discloses a binder aqueous solution used for manufacturing a non-aqueous electrolyte battery, which contains a neutral salt of an ⁇ -olefin-maleic acid copolymer obtained by copolymerizing an ⁇ -olefin and a maleic acid and a polyamine. There is described a binder aqueous solution for a non-aqueous electrolyte battery, which comprises a binder composition for a water electrolyte battery and water.
  • Patent Document 1 JP-A-2005-088480 International Publication No. 2016/129427 International Publication No. 2017/026475
  • the constituent layers of an all-solid secondary battery are usually formed of solid particles such as an inorganic solid electrolyte, a binder, and an active material, the interfacial contact between the solid particles is not sufficient and the interfacial resistance increases (ion The conductivity will decrease.).
  • the constituent layers formed on the surface of the current collector are easily peeled off from the current collector, and the charge and discharge (release and absorption of lithium ions) of the all-solid-state secondary battery are involved.
  • Contact failure between solid particles occurs due to contraction and expansion of the constituent layers, especially the active material layer, leading to an increase in electrical resistance and a decrease in battery performance.
  • the material for forming the constituent layer is preferably a material containing solid particles and exhibiting excellent dispersibility.
  • a material having good dispersibility it may not be possible to suppress the above-mentioned increase in interfacial resistance and decrease in battery performance.
  • the present invention is a solid electrolyte composition exhibiting excellent dispersibility, and by using it as a material forming a constituent layer of an all-solid secondary battery, the obtained all-solid secondary battery has an interfacial resistance between solid particles. It is an object of the present invention to provide a solid electrolyte composition that suppresses the rise of the solid particles and firmly binds the solid particles to realize excellent battery performance. Another object of the present invention is to provide a solid electrolyte-containing sheet and an all-solid secondary battery having a layer composed of this solid electrolyte composition. Further, it is an object of the present invention to provide a solid electrolyte containing sheet using the above solid electrolyte composition and a method for manufacturing an all solid state secondary battery.
  • the present inventor as a result of various studies, the inorganic solid electrolyte and the non-aqueous dispersion medium, by using a binder containing a polymer and a cross-linking agent having a physically cross-linkable group in the side chain, the polymer It has been found that a solid electrolyte composition having excellent dispersibility is created by forming a physical crosslinked structure in the side chain via a crosslinking agent. Further, by using this solid electrolyte composition as a material for forming a constituent layer of an all-solid-state secondary battery, while suppressing an increase in interfacial resistance between solid particles, a constituent layer in which solid particles are firmly bound is formed. It was found that an all-solid secondary battery that can be formed and has excellent battery performance can be manufactured. The present invention has been completed through further studies based on these findings.
  • a solid electrolyte composition containing an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, a binder, and a non-aqueous dispersion medium A solid electrolyte composition in which the binder comprises a polymer having a physical crosslinkable group in its side chain and a crosslinking agent having two or more physical crosslinkable functional groups that crosslink with this physical crosslinkable group.
  • the binder comprises a polymer having a physical crosslinkable group in its side chain and a crosslinking agent having two or more physical crosslinkable functional groups that crosslink with this physical crosslinkable group.
  • the polymer forming physical crosslinks has a physical crosslink structure formed by ionic bond with a cation represented by the following formula (H-1A) or formula (H-1B).
  • the solid electrolyte composition according to any one of claims.
  • L 11A and L 11B are an alkylene group having 1 to 24 carbon atoms, an arylene group having 6 to 60 carbon atoms, an alkenylene group having 2 to 24 carbon atoms, an oxygen atom, —N(R NL )—, a carbonyl group.
  • R NL represents a hydrogen atom or a substituent.
  • R 11 to R 18 represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alkylsilyl group.
  • L 21 is an alkylene group having 5 to 12 carbon atoms, an arylene group having 6 to 18 carbon atoms, an alkenylene group having 5 to 12 carbon atoms, an oxygen atom, —N(R NL )—, or an imine linking group or these A group combining is shown.
  • R NL represents a hydrogen atom or a substituent.
  • R 21 to R 26 represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
  • ⁇ 8> The solid electrolyte composition according to any one of ⁇ 3> to ⁇ 7>, in which the polymer contains 0.15 to 1 mmol/g of a group selected from the group group (a).
  • ⁇ 9> The solid electrolyte composition according to any one of ⁇ 1> to ⁇ 8>, in which the polymer is polyurethane or a (meth)acrylic polymer.
  • the binder is particles having an average particle size of 5 nm to 10 ⁇ m.
  • M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al and Ge.
  • A represents an element selected from I, Br, Cl and F.
  • a1 to e1 represent composition ratios of the respective elements, and a1:b1:c1:d1:e1 satisfies 1 to 12:0 to 5:1:2 to 12:0 to 10.
  • the non-aqueous dispersion medium contains at least one organic solvent selected from a ketone compound, an ester compound, an aromatic compound and an aliphatic compound.
  • a solid electrolyte-containing sheet having a layer composed of the solid electrolyte composition according to any one of ⁇ 1> to ⁇ 16> above.
  • An all-solid secondary battery comprising a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order, At least one layer of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer is a layer formed of the solid electrolyte composition according to any one of ⁇ 1> to ⁇ 16>. .. ⁇ 19>
  • a method for producing a solid electrolyte-containing sheet comprising forming a film of the solid electrolyte composition according to any one of ⁇ 1> to ⁇ 16> above.
  • a method for manufacturing an all-solid secondary battery including the method according to ⁇ 19>.
  • the present invention is a solid electrolyte composition exhibiting excellent dispersibility, and by using it as a material forming a constituent layer of an all-solid secondary battery, in an all-solid secondary battery obtained, interfacial resistance between solid particles It is possible to provide a solid electrolyte composition in which solid particles are firmly bound to each other while suppressing an increase in temperature, and excellent battery performance can be realized. It is possible to provide a solid electrolyte-containing sheet and an all-solid secondary battery having a layer composed of this solid electrolyte composition. Furthermore, the present invention can provide a method for producing a solid electrolyte-containing sheet and an all-solid secondary battery using the above solid electrolyte composition.
  • FIG. 1 is a vertical cross-sectional view schematically showing an all-solid secondary battery according to a preferred embodiment of the present invention.
  • FIG. 2 is a vertical cross-sectional view schematically showing the all-solid-state secondary battery (coin battery) produced in the example.
  • the numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.
  • acrylic or “(meth)acrylic
  • it means acrylic and/or methacrylic.
  • the expression of a compound (for example, when it is referred to as a compound at the end) is used to include the compound itself, a salt thereof, and an ion thereof.
  • it is meant to include a derivative in which a part of the derivative is changed, such as by introducing a substituent, within a range in which a desired effect is exhibited.
  • a substituent a linking group, etc.
  • substituent (hereinafter referred to as a substituent, etc.) which is not specified as substituted or unsubstituted in the present specification, it means that the group may have an appropriate substituent. Therefore, in the present specification, even when the YYY group is simply described, the YYY group includes not only a mode having no substituent but also a mode having a substituent. This is also synonymous with compounds that do not specify substituted or unsubstituted.
  • the following substituent T is mentioned as a preferable substituent.
  • each substituent may be the same or different from each other. It means good. Further, even when not otherwise specified, when a plurality of substituents and the like are adjacent to each other, they may be linked to each other or condensed to form a ring.
  • the solid electrolyte composition of the present invention (also referred to as an inorganic solid electrolyte-containing composition) contains an inorganic solid electrolyte, a binder, and a non-aqueous dispersion medium.
  • This binder comprises a polymer having a physical crosslinkable group in its side chain and a crosslinking agent (physical crosslinkable compound) having two or more physical crosslinkable functional groups that physically crosslink the physical crosslinkable group in the polymer. Contains.
  • the binder present in the solid electrolyte composition contains a polymer and a cross-linking agent
  • their existing state formation state of physical cross-linking
  • dispersion of the solid electrolyte composition From the viewpoint of properties, it is preferable to include a state in which the polymer and the cross-linking agent are physically cross-linked (a mode in which a polymer having a side cross-linking structure with the cross-linking agent is formed).
  • the presence state of the polymer and the cross-linking agent is, in addition to the above-described aspect, a state in which the cross-linking agent is bonded to the side chain of the polymer with one of the physically cross-linking functional groups in a graft or pendant form, May exist independently of each other, and may further include a state in which two or more of the above states are mixed.
  • the degree of cross-linking in this case is not particularly limited, and for example, with respect to the total number of moles of the physical cross-linkable group in the polymer, the physical cross-linkable group forming a physical cross-link with the physical cross-linkable functional group of the cross-linking agent.
  • the physical cross-linking rate (mol %) showing the ratio can be 10 to 100%.
  • the physical cross-linking group and the physical cross-linking functional group of the polymer and the cross-linking agent may remain in the state of the group (before the physical cross-linking).
  • the polymer and the crosslinking agent are usually contained in the binder (constituting the binder), but may be present outside the binder (for example, dispersed in a non-aqueous dispersion medium, Alternatively, it may be bound to solid particles).
  • the polymer is different from the polymer forming a conventional binder in that the side chain physically crosslinks through a crosslinking agent, and the mechanical properties such as strength are improved.
  • the physical crosslinks may be formed in one molecule of polymer (intramolecular crosslink), may be formed between different polymers (intermolecular crosslink), or may be mixed.
  • the physical crosslinks are formed between the side chains of the polymer, but when the binder is in the form of particles, the physical crosslinks may be formed within the particles or between the particles.
  • the physical crosslink is a crosslink other than the chemical crosslink formed by the physical crosslinkable group in the polymer and the physical crosslinkable functional group of the crosslinker being bonded by a covalent bond, that is, a chemical bond other than the covalent bond.
  • a crosslink formed by the bonding of The bond other than the covalent bond that forms the physical crosslink is not particularly limited, and examples thereof include an ionic bond, a hydrogen bond, an intermolecular interaction, and the like. Of these, physical crosslinking by ionic bonding is preferable from the viewpoint of bond strength.
  • the plurality of physically crosslinkable groups and the physically crosslinkable functional groups that the polymer and the crosslinking agent have in the molecule may be groups that crosslink with any of the bonds other than the above covalent bond, and groups that crosslink with different types of bonds. However, groups that crosslink with the same type of bond are preferred. Details of the physical crosslinkable group and the physical crosslinkable functional group will be described later.
  • the inorganic solid electrolyte when the inorganic solid electrolyte and the specific binder defined in the present invention coexist in the non-aqueous dispersion medium, the inorganic solid electrolyte can be highly and stably dispersed, The dispersibility of the solid electrolyte composition can be improved.
  • solid particles are bound to each other, and further, solid particles and a current collector are firmly bound while suppressing the interfacial resistance between the solid particles to be low. You can The details of the reason are not yet clear, but it is considered as follows.
  • the polymer forming the binder is likely to form physical cross-linking with the cross-linking agent, especially in the non-aqueous dispersion medium.
  • the polymer physically cross-linked with a side chain through a cross-linking agent forms a network structure and exhibits high mechanical strength.
  • the binder containing such a polymer expresses high mechanical strength and imparts high strength to the constituent layer made of the solid electrolyte composition.
  • this binder is considered to interact with solid particles such as an inorganic solid electrolyte via a physical cross-linking structure. When the binder interacts with the solid particles, the solid particles can be highly and stably dispersed in the non-aqueous dispersion medium.
  • the constituent layer can be formed while interacting with the solid particles, the resulting constituent layer can firmly bind the solid particles to each other, and when the constituent layer is formed on the current collector. Can also firmly bond the current collector and the solid particles.
  • the binder is a physically cross-linked polymer and does not spread on the solid particles, an ionic conduction path can be constructed without impairing the contact between the solid particles. Therefore, the interface resistance between solid particles can be suppressed low.
  • a polymer having a physically crosslinked structure in its side chain is superior in interaction with solid particles and the like to a polymer having a chemically crosslinked structure in its side chain formed by a covalent bond.
  • the constituent layer constituted by the solid electrolyte composition of the present invention the contact state between solid particles (building amount of ion conduction paths etc.) and the binding force between solid particles etc. are improved in a well-balanced manner, and ion conduction paths etc. It is considered that the solid particles are bound to each other with a strong binding property while being constructed, and the interfacial resistance between the solid particles is reduced. In addition, this constituent layer exhibits high strength.
  • Each sheet or all-solid-state secondary battery provided with a constitutional layer exhibiting such excellent characteristics shows a high ionic conductivity by suppressing an increase in electric resistance, and further, this excellent battery performance, repeated charge and discharge. Even if it does, it can be maintained.
  • the excellent dispersibility of the solid electrolyte composition means a state in which the solid particles are highly and stably dispersed in the non-aqueous dispersion medium, for example, in the “dispersibility test” in Examples described later. , Showing dispersibility of evaluation rank “4” or more.
  • the binder is preferably dispersed as particles (in the solid state) in the non-aqueous dispersion medium, and the inorganic solid electrolyte and the binder are dispersed in the non-aqueous dispersion medium in the solid state. It is more preferable that the solid electrolyte composition is in a dispersed state (suspension).
  • the binder is a constituent layer or a coating and drying layer of the solid electrolyte composition described below, solid particles such as an inorganic solid electrolyte are bound to each other, and further adjacent layers (for example, a current collector) and solid particles are bound to each other. It is sufficient that the solid particles are not necessarily bound to each other in the dispersed state of the solid electrolyte composition.
  • the solid electrolyte composition of the present invention also includes a mode in which, in addition to the inorganic solid electrolyte, as the dispersoid, an active material, a conductive additive, and the like are contained (the composition of this mode is referred to as an electrode layer composition). ).
  • the solid electrolyte composition of the present invention is a non-aqueous composition.
  • the non-aqueous composition includes not only a form containing no water but also a form having a water content (also referred to as water content) of 200 ppm or less.
  • the water content is preferably 150 ppm or less, more preferably 100 ppm or less, and further preferably 50 ppm or less.
  • the water content indicates the amount of water (mass ratio to the solid electrolyte composition) contained in the solid electrolyte composition.
  • the water content can be determined by Karl Fischer titration by filtering the solid electrolyte composition with a 0.45 ⁇ m membrane filter.
  • the inorganic solid electrolyte is an inorganic solid electrolyte
  • the solid electrolyte is a solid electrolyte in which ions can move. Since it does not contain an organic substance as a main ion conductive material, it is an organic solid electrolyte (a polymer electrolyte typified by polyethylene oxide (PEO) or the like, an organic typified by lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or the like. Electrolyte salt) is clearly distinguished. Further, since the inorganic solid electrolyte is solid in the steady state, it is not usually dissociated or released into cations and anions.
  • PEO polyethylene oxide
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide
  • the electrolytic solution or the inorganic electrolyte salt LiPF 6 , LiBF 4 , LiFSI, LiCl, etc.
  • the inorganic solid electrolyte is not particularly limited as long as it has ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and generally has no electron conductivity.
  • the inorganic solid electrolyte has ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table.
  • a solid electrolyte material applicable to this type of product can be appropriately selected and used.
  • the inorganic solid electrolyte include (i) sulfide-based inorganic solid electrolyte, (ii) oxide-based inorganic solid electrolyte, (iii) halide-based inorganic solid electrolyte, and (iV) hydride-based solid electrolyte.
  • the sulfide-based inorganic solid electrolyte is preferable because of its high ionic conductivity and ease of interparticle interfacial bonding.
  • the inorganic solid electrolyte preferably has lithium-ion ionic conductivity.
  • the sulfide-based inorganic solid electrolyte contains a sulfur atom, has ion conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation. Compounds having properties are preferred.
  • the sulfide-based inorganic solid electrolyte preferably contains at least Li, S and P as elements and has lithium ion conductivity, but other than Li, S and P depending on the purpose or case. It may contain an element.
  • Examples of the sulfide-based inorganic solid electrolyte include a lithium ion conductive sulfide-based inorganic solid electrolyte satisfying the composition represented by the following formula (1).
  • L represents an element selected from Li, Na and K, and Li is preferable.
  • M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al and Ge.
  • A represents an element selected from I, Br, Cl and F.
  • a1 to e1 represent composition ratios of the respective elements, and a1:b1:c1:d1:e1 satisfies 1 to 12:0 to 5:1:2 to 12:0 to 10.
  • a1 is preferably 1 to 9, and more preferably 1.5 to 7.5.
  • b1 is preferably 0 to 3, and more preferably 0 to 1.
  • d1 is preferably 2.5 to 10, and more preferably 3.0 to 8.5.
  • e1 is preferably 0 to 5, and more preferably 0 to 3.
  • composition ratio of each element can be controlled by adjusting the compounding ratio of the raw material compounds when producing the sulfide-based inorganic solid electrolyte as described below.
  • the sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass-ceramic), or only a part thereof may be crystallized.
  • glass glass
  • glass-ceramic glass-ceramic
  • Li—P—S based glass containing Li, P and S, or Li—P—S based glass ceramics containing Li, P and S can be used.
  • the sulfide-based inorganic solid electrolyte is, for example, lithium sulfide (Li 2 S), phosphorus sulfide (eg, phosphorus pentasulfide (P 2 S 5 )), elemental phosphorus, elemental sulfur, sodium sulfide, hydrogen sulfide, lithium halide (eg, LiI, LiBr, LiCl) and a sulfide of the element represented by M (for example, SiS 2 , SnS, GeS 2 ) can be produced by a reaction of at least two raw materials.
  • Li 2 S lithium sulfide
  • phosphorus sulfide eg, phosphorus pentasulfide (P 2 S 5 )
  • elemental phosphorus elemental sulfur
  • sodium sulfide sodium sulfide
  • hydrogen sulfide lithium halide
  • a sulfide of the element represented by M for example, SiS 2 , S
  • the ratio of Li 2 S and P 2 S 5 is, Li 2 S: at a molar ratio of P 2 S 5, preferably 60: 40 ⁇ 90:10, more preferably 68:32 to 78:22.
  • the lithium ion conductivity can be increased.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 ⁇ 4 S/cm or more, more preferably 1 ⁇ 10 ⁇ 3 S/cm or more. There is no particular upper limit, but it is practically 1 ⁇ 10 ⁇ 1 S/cm or less.
  • Li 2 S-P 2 S 5 Li 2 S-P 2 S 5 -LiCl, Li 2 S-P 2 S 5 -H 2 S, Li 2 S-P 2 S 5 -H 2 S-LiCl, Li 2 S-LiI-P 2 S 5 , Li 2 S-LiI-Li 2 O-P 2 S 5 , Li 2 S-LiBr-P 2 S 5 , Li 2 S-Li 2 O-P 2 S 5 , Li 2 S-Li 3 PO 4 -P 2 S 5 , Li 2 S-P 2 S 5 -P 2 O 5 , Li 2 S-P 2 S 5 -SiS 2 , Li 2 S-P 2 S 5 -SiS 2- LiCl, Li 2 S-P 2 S 5 -SnS, Li 2 S-P 2 S 5 -Al 2 S 3 , Li 2 S-
  • amorphization method examples include a mechanical milling method, a solution method and a melt quenching method. This is because processing at room temperature is possible and the manufacturing process can be simplified.
  • the oxide-based inorganic solid electrolyte contains an oxygen atom, has ion conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation. Compounds having properties are preferred.
  • the ionic conductivity of the oxide-based inorganic solid electrolyte is preferably 1 ⁇ 10 ⁇ 6 S/cm or more, more preferably 5 ⁇ 10 ⁇ 6 S/cm or more, and 1 ⁇ 10 ⁇ 5 S. /Cm or more is particularly preferable.
  • the upper limit is not particularly limited, but it is practically 1 ⁇ 10 ⁇ 1 S/cm or less.
  • nb (M bb is at least one element of Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, Sn, xb satisfies 5 ⁇ xb ⁇ 10, and yb satisfies 1 ⁇ yb ⁇ 4, zb satisfies 1 ⁇ zb ⁇ 4, mb satisfies 0 ⁇ mb ⁇ 2, and nb satisfies 5 ⁇ nb ⁇ 20.), Li xc Byc M cc zc O nc (M cc is At least one element of C, S, Al, Si, Ga, Ge, In, and Sn, xc satisfies 0 ⁇ xc ⁇ 5, yc satisfies 0 ⁇ yc ⁇ 1, and zc satisfies 0 ⁇ zc ⁇ 1 and nc satisfies 0 ⁇ nc ⁇ 6), Li xd (Al, Ga) yd (Ti, Ge) zd Si ad P
  • Li 1+xh+yh (Al, Ga) xh (Ti, Ge) 2-xh Si yh P 3-yh O 12 (where 0 ⁇ xh ⁇ 1, 0 ⁇ yh ⁇ 1), Li having a garnet type crystal structure 7 La 3 Zr 2 O 12 (LLZ) and the like can be mentioned.
  • a phosphorus compound containing Li, P and O is also desirable.
  • lithium phosphate (Li 3 PO 4 ), LiPON and LiPOD 1 (D 1 is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr) in which a part of oxygen of lithium phosphate is replaced with nitrogen. , Nb, Mo, Ru, Ag, Ta, W, Pt, Au, etc.).
  • LiA 1 ON (A 1 is at least one selected from Si, B, Ge, Al, C, Ga, etc.) and the like can also be preferably used.
  • the halide-based inorganic solid electrolyte is generally used, and has a ionic conductivity of a metal containing a halogen atom and belonging to Group 1 or 2 of the periodic table. A compound having and having an electronic insulating property is preferable.
  • the halide-based inorganic solid electrolyte is not particularly limited, and examples thereof include compounds such as LiCl, LiBr, LiI, and Li 3 YBr 6 and Li 3 YCl 6 described in ADVANCED MATERIALS, 2018, 30, 1803075. Of these, Li 3 YBr 6 and Li 3 YCl 6 are preferable.
  • the hydride-based inorganic solid electrolyte is generally used, and it shows the ionic conductivity of a metal containing a hydrogen atom and belonging to Group 1 or 2 of the periodic table. A compound having and having an electronic insulating property is preferable.
  • the hydride-based inorganic solid electrolyte is not particularly limited, but examples thereof include LiBH 4 , Li 4 (BH 4 ) 3 I, 3LiBH 4 —LiCl, and the like.
  • the inorganic solid electrolyte is preferably particles.
  • the average particle size (volume average particle size) of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more.
  • the upper limit is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • the average particle size of the inorganic solid electrolyte is measured by the following procedure.
  • the inorganic solid electrolyte particles are prepared by diluting a 1% by mass dispersion liquid in a 20 mL sample bottle with water (heptane in the case of a substance which is unstable to water).
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes, and immediately thereafter, used for the test.
  • a laser diffraction/scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA) was used, and data was captured 50 times at a temperature of 25° C. using a quartz cell for measurement. Obtain the volume average particle size.
  • JIS Z 8828:2013 “Particle size analysis-Dynamic light scattering method” if necessary. Five samples are prepared for each level, and the average value is adopted.
  • the inorganic solid electrolyte may be used alone or in combination of two or more.
  • the content of the inorganic solid electrolyte in the solid electrolyte composition is not particularly limited, but in terms of dispersibility, reduction of interfacial resistance and binding property, it is 50% by mass or more at 100% by mass of solid content. It is preferably 70% by mass or more, more preferably 90% by mass or more. From the same viewpoint, the upper limit is preferably 99.99% by mass or less, more preferably 99.95% by mass or less, and particularly preferably 99.9% by mass or less.
  • the content of the inorganic solid electrolyte in the solid electrolyte composition is the total content of the inorganic solid electrolyte and the active material.
  • the solid content means a component that does not disappear by volatilization or evaporation when the solid electrolyte composition is dried for 6 hours at 150° C. under a nitrogen atmosphere under a pressure of 1 mmHg. .. Typically, it refers to components other than the non-aqueous dispersion medium described later.
  • the solid electrolyte composition of the present invention contains a binder that binds solid particles.
  • This binder contains a polymer having a physical crosslinkable group in its side chain, and a crosslinker having two or more physical crosslinkable functional groups capable of crosslinking with the physical crosslinkable group of this polymer (capable of forming a physical crosslink). Therefore, the state of existence of the polymer and the crosslinking agent in the solid electrolyte composition is as described above.
  • the binder may be soluble in the non-aqueous dispersion medium, but is particularly insoluble or hardly soluble in the non-aqueous dispersion medium in terms of ion conductivity. (Particles of) are preferred.
  • the phrase “insoluble or hardly soluble in a non-aqueous dispersion medium” means that a binder is added to a non-aqueous dispersion medium at 30° C. (the amount used is 10 times the mass of the binder), and the mixture is allowed to stand for 24 hours.
  • the amount dissolved in the non-aqueous dispersion medium is 30 mass% or less, preferably 20 mass% or less, and more preferably 10 mass% or less. This dissolved amount is the ratio of the binder mass dissolved in the non-aqueous dispersion medium after 24 hours to the binder mass added to the non-aqueous dispersion medium.
  • the binder may be present in the solid electrolyte composition by being dissolved in, for example, a non-aqueous dispersion medium, and may be present in a solid state (as the insoluble or hardly soluble particles) in the non-aqueous dispersion medium (preferably It may be dispersed) (a binder that exists in a solid state is referred to as a particulate binder).
  • the binder is preferably a particulate binder in the solid electrolyte composition from the viewpoint of battery resistance and cycle characteristics. It is one of the preferable embodiments that the particulate binder maintains the particulate state even in the solid electrolyte layer (coating dry layer).
  • the binder is a particulate binder
  • its shape is not particularly limited and may be flat, amorphous or the like, but spherical or granular is preferable.
  • the average particle size of the particulate binder is not particularly limited, but is preferably 5 nm or more and 10 ⁇ m or less. This can improve the dispersibility of the solid electrolyte composition, the binding property between solid particles, and the ionic conductivity.
  • the average particle size is preferably 10 nm or more and 5 ⁇ m or less, more preferably 15 nm or more and 1 ⁇ m or less, and further preferably 20 nm or more and 0.5 ⁇ m or less, from the viewpoint that dispersibility, binding property and ionic conductivity can be further improved.
  • the average particle size of the binder can be measured in the same manner as for the inorganic solid electrolyte.
  • the average particle size of the particulate binder in the constituent layer of the all-solid secondary battery is, for example, measured in advance after disassembling the battery and peeling the constituent layer containing the particulate binder, and then measuring the constituent layer. The measurement can be performed by excluding the measured value of the average particle diameter of the particles other than the particulate binder that has been used.
  • the average particle size of the particulate binder is, for example, depending on the type of the non-aqueous dispersion medium used when preparing the binder dispersion, the content of the constituent components in the polymer constituting the binder, the type and content of the cross-linking agent, etc. Can be adjusted.
  • Binder the content in the solid electrolyte composition, dispersibility, further inorganic solid electrolyte particles, in terms of compatibility with the binding properties with solid particles such as the active material and the conductive auxiliary agent and ion conductivity, solid.
  • 100 mass% of the component 0.001 mass% or more is preferable, 0.05 mass% or more is more preferable, 0.1 mass% or more is further preferable, and 0.2 mass% or more is particularly preferable.
  • the upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.
  • the content of the binder is the total content of a polymer having a physical crosslinkable group in its side chain and a crosslinking agent, which will be described later.
  • the mass ratio [(mass of inorganic solid electrolyte+mass of active material)/(mass of binder)] of the total mass (total mass) of the inorganic solid electrolyte and the active material to the mass of the binder is , 1,000 to 1 is preferable. This ratio is more preferably 1000 to 2, and even more preferably 500 to 10.
  • a polymer having physical crosslinkable group in side chain A polymer having a side chain having a physical crosslinkable group used in the solid electrolyte composition of the present invention (also referred to as a polymer that does not form a physical crosslink with the crosslinking agent or a polymer that does not have a physical crosslink structure with the crosslinking agent). ) Is a polymer that is physically crosslinkable with a crosslinking agent as described above, and is not particularly limited except that it has a physically crosslinkable group in its side chain, and is a solid electrolyte composition for all solid state secondary batteries. Polymers usually used for can be used.
  • the main chain of the polymer means a linear molecular chain in which all the other molecular chains constituting the polymer can be regarded as branched chains or pendant chains with respect to the main chain. Although it depends on the mass average molecular weight of a molecular chain regarded as a branched chain or a pendant chain, the longest chain is typically the main chain among the molecular chains constituting the polymer. However, the functional group at the polymer end is not included in the main chain.
  • the side chain of the polymer means a molecular chain other than the main chain, and includes a short molecular chain and a long molecular chain.
  • having a physically crosslinkable group in the side chain means that the side chain itself has the physically crosslinkable group (an aspect in which the physically crosslinkable group is directly bonded to the atom constituting the main molecular chain).
  • a mode having a physical crosslinkable group as a substituent of a side chain a mode in which a physical crosslinkable group is bonded to an atom constituting a main chain molecular chain through another atom, and a mode in which these are mixed Includes.
  • Examples of the polymer that is not physically crosslinked with the crosslinking agent include, for example, sequential polymerization (polycondensation, polyaddition or addition of polyurethane, polyurea, polyamide, polyimide, polyester, polyether, polycarbonate, etc. Condensation type polymers, and further chain polymerization type polymers such as fluorine-containing polymers, hydrocarbon-based polymers, vinyl polymers, and (meth)acrylic polymers.
  • the non-crosslinked polymer is preferably a sequential polymerization polymer, a fluoropolymer, a hydrocarbon polymer or a (meth)acrylic polymer, and is preferably a polyurethane, polyurea, polyamide, polyimide, a fluoropolymer, a hydrocarbon polymer or (meth).
  • Acrylic polymers are more preferred, and polyurethane or (meth)acrylic polymers are even more preferred.
  • Each of the above polymers may be a polymer composed of one segment or a polymer composed of two or more segments.
  • a sequential polymerization type polymer suitable as an uncrosslinked polymer is a combination of two or more (preferably two or three) constituent components represented by any of the following formulas (I-1) to (I-4). Or a main chain formed by sequentially polymerizing a carboxylic acid dianhydride represented by the following formula (I-5) and a diamine compound leading to a constituent component represented by the following formula (I-6) Polymers are preferred.
  • the combination of each constituent component is appropriately selected according to the polymer species.
  • the main chain made of polycarbonate, a configuration component formula (I-3) as a constituent or R P1 is represented by the following formula was introduced oxygen atoms at both ends of R P1 (I-2)
  • Examples thereof include a main chain having a constituent component represented by the following formula (I-2) and a constituent component represented by the following formula (I-3).
  • One kind of constituent in the combination of constituents means the number of kinds of constituents represented by any one of the following formulas, and has two kinds of constituents represented by the following formula. Is not to be construed as two constituents.
  • R P1 and R P2 each represent a molecular chain having a (mass average) molecular weight of 14 or more and 200,000 or less.
  • the molecular weight of this molecular chain cannot be unambiguously determined because it depends on its type, but is preferably 30 or more, more preferably 50 or more, further preferably 100 or more, and particularly preferably 150 or more.
  • the upper limit is preferably 100,000 or less, more preferably 10,000 or less.
  • the molecular weight of the molecular chain is measured with respect to the raw material compound before being incorporated into the main chain of the polymer.
  • the molecular chain that can be taken as R P1 and R P2 is not particularly limited, but is preferably a hydrocarbon chain, a polyalkylene oxide chain, a polycarbonate chain or a polyester chain, more preferably a hydrocarbon chain or a polyalkylene oxide chain, and a hydrocarbon chain. , Polyethylene oxide chains or polypropylene oxide chains are more preferred.
  • the hydrocarbon chain which can be taken as R P1 and R P2 means a hydrocarbon chain composed of a carbon atom and a hydrogen atom, and more specifically, at least two compounds of a compound composed of a carbon atom and a hydrogen atom. It means a structure in which an atom (for example, a hydrogen atom) or a group (for example, a methyl group) is eliminated.
  • the hydrocarbon chain also includes a chain having a group containing an oxygen atom, a sulfur atom or a nitrogen atom, such as a hydrocarbon group represented by the following formula (M2).
  • M2 hydrocarbon group represented by the following formula
  • This hydrocarbon chain may have a carbon-carbon unsaturated bond and may have a ring structure of an aliphatic ring and/or an aromatic ring. That is, the hydrocarbon chain may be a hydrocarbon chain composed of a hydrocarbon selected from an aliphatic hydrocarbon and an aromatic hydrocarbon.
  • Such a hydrocarbon chain may be one that satisfies the above-mentioned molecular weight, and both a hydrocarbon chain having a low molecular weight and a hydrocarbon chain having a hydrocarbon polymer (also referred to as a hydrocarbon polymer chain).
  • the low molecular weight hydrocarbon chain is a chain composed of a normal (non-polymerizable) hydrocarbon group, and examples of this hydrocarbon group include an aliphatic or aromatic hydrocarbon group.
  • Is an alkylene group (which preferably has 1 to 12 carbon atoms, more preferably 1 to 6 and still more preferably 1 to 3) and an arylene group (which preferably has 6 to 22 carbon atoms, preferably 6 to 14 and 6 to 10 carbon atoms). Is more preferable), or a group consisting of a combination thereof is preferable.
  • an alkylene group is more preferable.
  • This hydrocarbon chain may have a polymer chain (for example, a (meth)acrylic polymer) as a substituent.
  • Examples of the aliphatic hydrocarbon group include a hydrogen-reduced product of an aromatic hydrocarbon group represented by the following formula (M2), a partial structure of a known aliphatic diisosonate compound (for example, a group consisting of isophorone), and the like. Can be mentioned. Moreover, the hydrocarbon group which each of the constituent components shown below has is also mentioned. Examples of the aromatic hydrocarbon group include a hydrocarbon group contained in each of the constituent components shown below, and a phenylene group or a hydrocarbon group represented by the following formula (M2) is preferable.
  • M2 aromatic hydrocarbon group represented by the following formula
  • X represents a single bond, —CH 2 —, —C(CH 3 ) 2 —, —SO 2 —, —S—, —CO— or —O—, and is a binding point of view.
  • —CH 2 — or —O— is preferable, and —CH 2 — is more preferable.
  • the alkyl group exemplified here may be substituted with a substituent T, preferably a halogen atom (more preferably a fluorine atom).
  • R M2 to R M5 each represent a hydrogen atom or a substituent, and a hydrogen atom is preferable.
  • the substituent which can be taken as R M2 to R M5 is not particularly limited, and examples thereof include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, —OR M6 , —N(R M6 ) 2 , —SR M6 (R M6 represents a substituent, preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms), halogen atom (eg, fluorine atom, chlorine atom, bromine atom) Is mentioned.
  • R M6 represents a substituent, preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms
  • halogen atom eg, fluorine atom, chlorine atom, bromine atom
  • —N(R M6 ) 2 is an alkylamino group (having preferably 1 to 20 carbon atoms, more preferably 1 to 6) or an arylamino group (having 6 to 40 carbon atoms, preferably 6 to 20 carbon atoms). More preferred).
  • the hydrocarbon polymer chain may be a polymer chain formed by polymerizing (at least two) polymerizable hydrocarbons, and a chain composed of a hydrocarbon polymer having a larger number of carbon atoms than the above-mentioned low molecular weight hydrocarbon chain.
  • a chain composed of a hydrocarbon polymer composed of 30 or more, more preferably 50 or more carbon atoms is preferably a chain composed of a hydrocarbon polymer composed of 30 or more, more preferably 50 or more carbon atoms.
  • the upper limit of the number of carbon atoms constituting the hydrocarbon polymer is not particularly limited and may be, for example, 3,000.
  • This hydrocarbon polymer chain is preferably a chain composed of a hydrocarbon polymer whose main chain satisfies the above-mentioned number of carbon atoms and which is composed of an aliphatic hydrocarbon, and is composed of an aliphatic saturated hydrocarbon or an aliphatic unsaturated hydrocarbon. It is more preferable that the chain is a polymer (preferably elastomer) chain. Specific examples of the polymer include a diene polymer having a double bond in the main chain and a non-diene polymer having no double bond in the main chain.
  • diene-based polymer examples include styrene-butadiene copolymer, styrene-ethylene-butadiene copolymer, copolymer of isobutylene and isoprene (preferably butyl rubber (IIR)), butadiene polymer, isoprene polymer and ethylene.
  • IIR butyl rubber
  • non-diene polymer examples include olefin polymers such as ethylene-propylene copolymer and styrene-ethylene-butylene copolymer, and hydrogen reduction products of the above diene polymers.
  • the hydrocarbon that becomes the hydrocarbon chain preferably has a reactive group at its terminal, and more preferably has a polycondensable terminal reactive group.
  • the end-reactive group capable of polycondensation or polyaddition forms a group bonded to R P1 or R P2 in each of the above formulas by polycondensation or polyaddition.
  • Examples of such a terminal reactive group include an isocyanate group, a hydroxy group, a carboxy group and an amino group, and among them, a hydroxy group is preferable.
  • hydrocarbon polymer having a terminal reactive group examples are, under the trade names, NISSO-PB series (manufactured by Nippon Soda Co., Ltd.), Claysol series (manufactured by Tomoe Kogyo Co., Ltd.), PolyVEST-HT series (manufactured by Evonik). , Poly-bd series (manufactured by Idemitsu Kosan Co., Ltd.), poly-ip series (manufactured by Idemitsu Kosan Co., Ltd.), EPOL (manufactured by Idemitsu Kosan Co., Ltd.) and Polytail series (manufactured by Mitsubishi Chemical Co., Ltd.) are preferably used.
  • polyalkylene oxide chain examples include known polyalkylene oxide chains.
  • the alkyleneoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 2 or 3 (polyethylene oxide chain or polypropylene oxide chain).
  • the polyalkylene oxide chain may be a chain composed of one kind of alkylene oxide or a chain composed of two or more kinds of alkylene oxide (for example, a chain composed of ethylene oxide and propylene oxide).
  • polycarbonate chain or polyester chain examples include known chains of polycarbonate or polyester.
  • Each of the polyalkylene oxide chain, the polycarbonate chain and the polyester chain preferably has an alkyl group (having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms) at the terminal.
  • Polyalkylene oxide chain which can be taken as R P1 and R P2, end of the polycarbonate chain and a polyester chain, appropriately changing the constituents as R P1 and R P2 are represented by the formulas above the embeddable ordinary chemical structure be able to.
  • the terminal oxygen atom of the polyalkylene oxide chain is removed and incorporated as R P1 or R P2 of the above component.
  • R N is a hydrogen atom, It may have an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms) or the like.
  • R P1 and R P2 are divalent molecular chains, but at least one hydrogen atom is replaced by —NH—CO—, —CO—, —O—, —NH— or —N ⁇ Therefore, it may have a trivalent or higher molecular chain.
  • R P1 is preferably a hydrocarbon chain, more preferably a low molecular weight hydrocarbon chain, and further preferably a hydrocarbon chain composed of an aliphatic or aromatic hydrocarbon group, Hydrocarbon chains consisting of aromatic hydrocarbon groups are particularly preferred.
  • R P2 is preferably a low molecular weight hydrocarbon chain (more preferably an aliphatic hydrocarbon group) or a molecular chain other than the low molecular weight hydrocarbon chain, and the low molecular weight hydrocarbon chain and the low molecular weight hydrocarbon chain are preferable. More preferable is an embodiment in which each molecular chain other than the hydrocarbon chain having a molecular weight is contained.
  • the constituent represented by any of the formula (I-3), the formula (I-4) and the formula (I-6) is a constituent in which R P2 is a low molecular weight hydrocarbon group. And R P2 contains at least two kinds of constituent components which are molecular chains other than low molecular weight hydrocarbon chains.
  • constituent components represented by the above formula (I-1) are shown below.
  • the raw material compound (diisocyanate compound) for deriving the constituent component represented by the formula (I-1) include diisocyanate compounds represented by the formula (M1) described in WO2018/020827 and Specific examples thereof include, further, polymeric 4,4′-diphenylmethane diisocyanate and the like.
  • the constituent component represented by the formula (I-1) and the raw material compound leading to the constituent component are not limited to those described in the following specific examples and the above-mentioned documents.
  • the raw material compound (carboxylic acid or acid chloride thereof, etc.) leading to the constituent component represented by the above formula (I-2) is not particularly limited and is described in, for example, paragraph [0074] of International Publication No. 2018/020827. , Carboxylic acid or acid chloride compounds and specific examples thereof.
  • the constituent components represented by the above formula (I-3) or formula (I-4) are shown below.
  • the starting compounds (diol compounds or diamine compounds) for deriving the constituents represented by the above formula (I-3) or formula (I-4) are described in, for example, International Publication No. 2018/020827. Each compound and specific examples thereof are mentioned, and further dihydroxyoxamide is also mentioned.
  • the constituent components represented by formula (I-3) or formula (I-4) and the raw material compounds leading to them are not limited to those described in the following specific examples and the above-mentioned documents.
  • the repeating number is an integer of 1 or more and is appropriately set within a range satisfying the molecular weight or the number of carbon atoms of the molecular chain.
  • R P3 represents an aromatic or aliphatic linking group (tetravalent), and a linking group represented by any of the following formulas (i) to (ix) is preferable.
  • X 1 represents a single bond or a divalent linking group.
  • the divalent linking group is preferably an alkylene group having 1 to 6 carbon atoms (eg methylene, ethylene, propylene). As propylene, 1,3-hexafluoro-2,2-propanediyl is preferable.
  • L represents —CH 2 ⁇ CH 2 — or —CH 2 —.
  • R X and R Y each represent a hydrogen atom or a substituent. In each formula, the substituent that can be used as R X and R Y is not particularly limited, and examples thereof include the substituent T described below.
  • alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, 1 to 3 is more preferable
  • an aryl group having 6 to 22 carbon atoms is preferable, 6 to 14 is more preferable, and 6 to 10 is further preferable.
  • * Indicates a binding site to the carbonyl group in formula (1-5).
  • the carboxylic acid dianhydride represented by the above formula (I-5) and the raw material compound (diamine compound) leading to the constituent component represented by the above formula (I-6) are not particularly limited, and include, for example, Each compound described in WO2018/020827 and WO2015/046313 and specific examples thereof can be mentioned.
  • R P1 , R P2, and R P3 may each have a substituent.
  • the substituent is not particularly limited, and examples thereof include the substituent T described later, and the above-mentioned substituent that can be adopted as R M2 is preferably exemplified.
  • the constituent component represented by any one of the above formulas (I-1) to (I-6) does not have a physical crosslinkable group to be described later as a substituent in the partial structure part which is a side chain of the polymer, That is, the constituent components represented by the above formulas are not constituent components that form physical crosslinks with side chains.
  • the polymer of the sequential polymerization system contains a constituent having a physical crosslinkable group in the partial structure part which is a side chain of the polymer (sometimes referred to as a crosslinkable constituent).
  • the physical crosslinkable group refers to a group capable of forming a physical crosslink with a physical crosslinkable functional group of a crosslinker, a chemical bond such as an ionic bond or a hydrogen bond, or an intermolecular interaction, to bond to each other or A group capable of forming an interaction.
  • the physical crosslinkable group contained in the uncrosslinked polymer (crosslinkable constituent) can be selected as appropriate depending on the type (reaction (bond) or interaction) of the physical crosslink with the physical crosslinkable group contained in the crosslinker. ..
  • Examples of such a physically crosslinkable group include a group which can become a cation or an anion when physically crosslinked by an ionic bond.
  • Examples of the group capable of becoming a cation include a group having a property of forming a cation by receiving a hydrogen cation, an alkali metal cation, an alkaline earth metal cation, a transition metal cation, and the like.
  • a basic group Specific examples include each group included in the following group (b) of groups.
  • the group capable of becoming an anion includes a group having a property of forming an anion by donating (eliminating) a hydrogen cation, an alkali metal cation, an alkaline earth metal cation, a transition metal cation, and the like.
  • a hydrogen cation an alkali metal cation
  • an alkaline earth metal cation an alkaline earth metal cation
  • a transition metal cation and the like.
  • Is an acidic group more specifically, each group included in the following group (a).
  • a group capable of donating a hydrogen atom or a group capable of accepting a hydrogen atom may be mentioned.
  • Examples of the group capable of donating a hydrogen atom include a group having a hydrogen atom covalently bonded to an atom having a high electronegativity (for example, each atom of oxygen, nitrogen, sulfur, etc.).
  • a group, an amino group, each group included in the following group (a), and the like can be mentioned.
  • examples of the physical cross-linkable group include an aryl group having 6 to 100 carbon atoms.
  • group (a) a carboxy group is preferable, and among the group (b), an amino group is preferable.
  • ⁇ Base group (a)> Carboxy group, sulfo group (-SO 3 H), phosphoric acid group (phospho group, -OPO 3 H 2 ) and phosphonic acid group (-P( O)(OH) 2 )
  • Each of the phosphoric acid group and the phosphonic acid group may be substituted with one of two hydrogen atoms to form an ester.
  • the substituent is not particularly limited, but examples thereof include the substituent T described later, and an alkyl group, an aryl group and the like are preferable.
  • the substituted amino group include an amino group in which at least one hydrogen atom is substituted with an alkyl group, an aryl group, an alkylsilyl group or the like.
  • alkyl group and the alkylsilyl group examples include an alkyl group and an alkylsilyl group that can be used as R 11 of the formula (H-1A) described later, and the aryl group includes the aryl group of the above-described substituent T. Specific examples of the crosslinkable constituents will be described later.
  • the physical crosslinkable groups may be the same or different groups in which the bonds or interactions forming the physical crosslinks are the same.
  • the same kind of group is preferable.
  • the same type of groups the same group is more preferable.
  • the number of physical crosslinkable groups contained in one crosslinkable constituent component may be 1 or more, preferably 1 to 6, and more preferably 1 or 2.
  • the constituent having a physically crosslinkable group may be any constituent capable of forming an uncrosslinked polymer, and is represented by any one of the above formulas (I-1) to (I-4) and (I-6).
  • the above-mentioned physical crosslinkable group is introduced as a substituent into R P1 and R P2 of the constituent component.
  • those in which the above-mentioned physical crosslinkable group is introduced as a substituent to R P2 of the constituent component represented by the above formula (I-3) or formula (I-4) are preferable.
  • the non-crosslinked polymer of the sequential polymerization system is a formula (I-3) or a formula (I-4), preferably a formula (I- As the constituent component represented by 3), a constituent component in which R P2 is a polycarbonate chain, a polyester chain or a polyalkylene oxide chain as a molecular chain (a constituent component represented by the following formula (I-3B)), and R P2 Preferably has, as a molecular chain, a constituent component that is the above-mentioned hydrocarbon polymer chain (a constituent component represented by the following formula (I-3C)), and further, a constituent component in which R P2 is a hydrocarbon group. (Constituent component represented by the following formula (I-3A)) may be included.
  • the uncrosslinked polymer is a component represented by the following formula (I-1), a component represented by the formula (I-3B), a component represented by the formula (I-3C), And a constituent component represented by the following formula (II) as a constituent component having a physical crosslinkable group, and further a constituent component represented by the formula (I-3A) in addition to these constituent components. May be.
  • R P1 is as described above.
  • R P2A represents a low molecular weight hydrocarbon chain.
  • R P2B represents a polycarbonate chain, a polyester chain or a polyalkylene oxide chain.
  • R P2C represents a hydrocarbon polymer chain.
  • the low molecular weight hydrocarbon chain that can be taken as R P2A , the polycarbonate chain that can be taken as R P2B , the polyester chain or the polyalkylene oxide chain, and the hydrocarbon polymer chain that can be taken as R P2C are each represented by the above formula (I-3).
  • R P2 It has the same meaning as a low molecular weight hydrocarbon chain, polycarbonate chain, polyester chain or polyalkylene oxide chain and hydrocarbon polymer chain that can be taken as R P2 , and the preferred ones are also the same.
  • two Z's each represent -O- or -NH- (the two Z's are not different from each other), and both are preferably -O-.
  • R P4 is a molecular chain having a physical crosslinkable group, and is physically crosslinked to the side chain of the non-crosslinked polymer of the sequential polymerization system (atoms other than the atoms forming the molecular chain having two Z ends).
  • the molecular chain having Z at the end is preferably a hydrocarbon chain, more preferably a chain composed of a low molecular weight hydrocarbon group, and even more preferably an aliphatic hydrocarbon group.
  • An alkylene group (having 1 to 12 carbon atoms, preferably 2 to 6 carbon atoms, and more preferably 2 to 5 carbon atoms) is particularly preferable.
  • Such a constituent component is a compound having a physically crosslinkable group capable of being sequentially polymerized with the compound leading to the constituent component represented by any one of the above formulas (I-1) to (I-4) and (I-6). Can be incorporated into the uncrosslinked polymer.
  • the compound forming the crosslinkable constituent component the compound capable of introducing the physical crosslinkable group
  • a compound having a physical crosslinkable group and capable of polymer-reacting with the side chain of the polymer can also be mentioned.
  • the number of physically crosslinkable groups possessed by this compound is the same as that of the above-mentioned crosslinkable constituent components.
  • the non-crosslinked polymer of the sequential polymerization system may have constituent components other than the constituent components represented by the above formulas. Such constituents are not particularly limited as long as they can be successively polymerized with the constituents represented by the above formulas.
  • the (total) content of the constituent components represented by any one of the above formulas (1-1) to (I-6) and (II) in the unpolymerized polymer of the sequential polymerization system is not particularly limited. It is preferably 5 to 100% by mass, more preferably 10 to 100% by mass, and further preferably 50 to 100% by mass. The upper limit of this content may be, for example, 90% by mass or less, regardless of the above 100% by mass.
  • the content of the constituents other than the constituents represented by the above formulas in the unpolymerized polymer of the sequential polymerization system is not particularly limited, but is preferably 80% by mass or less.
  • the content of the crosslinkable constituent component, preferably the constituent component represented by the above formula (II), in the uncrosslinked polymer of the sequential polymerization system is not particularly limited as long as it is within the above (total) content range, From the viewpoint that the dispersibility of the solid electrolyte composition, the binding property between solid particles and the like and the ion conductivity can be exhibited at a high level, for example, it is preferably more than 0 mass% and less than 50 mass %.
  • the content is more preferably the mass%, further preferably 2.5 to 15 mass%.
  • the content thereof is not particularly limited and is set within the following range. it can. That is, the content of the constituent component represented by the formula (I-1) or the formula (I-2) or the constituent component derived from the carboxylic acid dianhydride represented by the formula (I-5) in the uncrosslinked polymer.
  • the amount is not particularly limited and is preferably 0 to 70% by mass, more preferably 0.01 to 50% by mass, and further preferably 0.1 to 40% by mass.
  • the content of each of the constituent components represented by is not particularly limited and is preferably 0 to 80% by mass, more preferably 5 to 70% by mass, and 15 to 30% by mass. More preferable.
  • constituents represented by formula (I-3) or (I-4) constituents in which R P2 is a low molecular weight hydrocarbon chain (for example, the constituent represented by the above formula (I-3A))
  • the content of () in the uncrosslinked polymer of the sequential polymerization system is not particularly limited, but is, for example, preferably 0 to 50% by mass, more preferably 0 to 30% by mass, and 0 to 20% by mass. % Is more preferable.
  • constituents represented by the formula (I-3) or the formula (I-4) constituents in which R P2 is the above polycarbonate chain, polyester chain or polyalkylene oxide chain as a molecular chain (for example, the above formula (I-).
  • the content of the constituent component 3B)) in the unpolymerized polymer of the sequential polymerization system is not particularly limited, but is preferably 0 to 70% by mass, and 0.1 to 60% by mass, for example. It is more preferable that the amount is 10 to 50% by mass, further preferably 10 to 30% by mass, and particularly preferably 10 to 30% by mass.
  • the constituent component in which R P2 is the above hydrocarbon polymer chain as a molecular chain (for example, represented by the above formula (I-3C))
  • the content of the constituent component) in the uncrosslinked polymer of the sequential polymerization system is not particularly limited, but is, for example, preferably 0 to 80% by mass, more preferably 5 to 60% by mass, and 10 to 10% by mass. It is more preferably 50% by mass.
  • the above content of each constituent component shall be the total content.
  • polyurethane, polyurea, polyamide, and polyimide which can be taken as the uncrosslinked polymer of the sequential polymerization system, in addition to those synthesized in the examples, for example, International Publication No. 2018/020827 and International Publication No. 2015/046313. Further, there may be mentioned those obtained by introducing a crosslinkable constituent into each of the polymers described in JP-A-2015-088480.
  • a chain-polymerization type polymer suitable as an uncrosslinked polymer is a polymer obtained by chain-polymerizing one or more monomers having a non-aromatic carbon-carbon double bond, and a side chain having physical crosslinkability. Has a group.
  • the above-mentioned fluorine-containing polymer, hydrocarbon-based polymer or (meth)acrylic polymer is preferable, and (meth)acrylic polymer is more preferable.
  • the fluorine-containing polymer is not particularly limited, and examples thereof include polytetrafluoroethylene (PTFE), polyvinylene difluoride (PVdF), a copolymer of polyvinylene difluoride and hexafluoropropylene (PVdF-HFP), A copolymer (PVdF-HFP-TFE) of polyvinylidene fluoride, hexafluoropropylene and tetrafluoroethylene can be mentioned.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylene difluoride
  • PVdF-HFP a copolymer of polyvinylene difluoride and hexafluoropropylene
  • PVdF-HFP-TFE A copolymer of polyvinylidene fluoride, hexafluoropropylene and tetrafluoroethylene can be mentioned.
  • the hydrocarbon-based polymer is not particularly limited, and examples thereof include polyethylene, polypropylene, natural rubber, polybutadiene, polyisoprene, polystyrene butadiene copolymer, polybutylene, acrylonitrile butadiene copolymer, and hydrogenated (hydrogenated) polymers thereof.
  • the hydrocarbon-based polymer is preferably one that does not have an unsaturated group (for example, 1,2-butadiene constituent component) bonded to the main chain because the formation of chemical crosslinks can be suppressed.
  • the (meth)acrylic polymer is not particularly limited, but at least one (meth)acrylic compound (M1) selected from a (meth)acrylic acid ester compound, a (meth)acrylamide compound and a (meth)acrylonitrile compound is used. Polymers obtained by (co)polymerization are preferred. A (meth)acrylic polymer made of a copolymer of the (meth)acrylic compound (M1) and another polymerizable compound (M2) is also preferable.
  • the other polymerizable compound (M2) is not particularly limited, and examples thereof include vinyl compounds such as styrene compounds, vinylnaphthalene compounds, vinylcarbazole compounds, allyl compounds, vinyl ether compounds, vinyl ester compounds, and dialkyl itaconate compounds.
  • vinyl compound include “vinyl-based monomers” described in JP-A-2015-88486.
  • (meth)acrylic compound (M1) and the vinyl compound (M2) which lead the constituent components of the (meth)acrylic polymer compounds represented by the following formula (b-1) are preferable.
  • This compound does not have the above-mentioned physical crosslinkable group as a substituent in the partial structure part which becomes the side chain of the polymer.
  • R 1 is a hydrogen atom, a hydroxy group, a cyano group, a halogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms), and an alkenyl group (having 2 carbon atoms).
  • an alkyl group preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms
  • an alkenyl group having 2 carbon atoms.
  • 2 to 12 are more preferable
  • 2 to 6 are particularly preferable
  • an alkynyl group having 2 to 24 carbon atoms is preferable
  • 2 to 12 is more preferable
  • 2 to 6 is particularly preferable
  • an aryl group It preferably has 6 to 22 carbon atoms, and more preferably 6 to 14 carbon atoms.
  • a hydrogen atom or an alkyl group is preferable, and a hydrogen atom or a methyl group
  • R 2 represents a hydrogen atom or a substituent.
  • the substituent that can be used as R 2 is not particularly limited, but is an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms, particularly preferably 1 to 12 carbon atoms, and may be a branched chain but preferably a straight chain), An alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14), an aralkyl group (preferably having 7 to 23 carbon atoms, 7 And a cyano group, a hydroxy group, a sulfanyl group, and an oxygen-containing aliphatic heterocyclic group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms).
  • the aliphatic heterocyclic group containing an oxygen atom is preferably an epoxy group-containing group, an oxetane group-containing group,
  • L 1 is a linking group and is not particularly limited, and examples thereof include an alkylene group having 1 to 6 carbon atoms (preferably 1 to 3), an alkenylene group having 2 to 6 carbon atoms (preferably 2 to 3), and a carbon atom number. 6 to 24 (preferably 6 to 10) arylene group, oxygen atom, sulfur atom, imino group (—NR N —), carbonyl group, phosphoric acid linking group (—OP(OH)(O)—O— ), a phosphonic acid linking group (—P(OH)(O)—O—), or a group related to a combination thereof, and the like.
  • —CO—O— group, —CO—N(R N )— group ( R N is as described above.) is preferable.
  • the linking group may have any substituent.
  • the number of atoms constituting the linking group and the number of linking atoms are as described later.
  • Examples of the optional substituent include the substituent T described later, and examples thereof include an alkyl group and a halogen atom.
  • n is 0 or 1, and 1 is preferable.
  • -(L 1 ) n -R 2 represents one kind of substituent (for example, an alkyl group)
  • n is 0 and R 2 is a substituent (alkyl group).
  • R 1 and n have the same meaning as in the above formula (b-1).
  • R 3 has the same meaning as R 2 .
  • L 2 is a linking group and has the same meaning as L 1 .
  • L 3 is a linking group and has the same meaning as L 1 above, but an alkylene group having 1 to 6 carbon atoms (preferably 1 to 3) is preferable.
  • m is an integer of 1 to 200, preferably an integer of 1 to 100, and more preferably an integer of 1 to 50.
  • the substituent is not particularly limited, and examples thereof include the above-mentioned groups that can be taken as R 1 .
  • a group which may take a substituent such as an alkyl group, an aryl group, an alkylene group and an arylene group is a substituent within a range not impairing the effects of the present invention. May have.
  • substituents examples include the substituent T described later, and specifically, a halogen atom, a hydroxy group, a sulfanyl group, an acyl group, an acyloxy group, an alkoxy group, an aryloxy group, an aryloyl group, an aryloyloxy group and the like. Are listed.
  • the polymer constituting the binder is a chain polymerization type polymer, preferably an addition polymerization type polymer, it is preferable to have a constituent component (MM) derived from a macromonomer having a mass average molecular weight of 1,000 or more.
  • MM constituent component
  • the mass average molecular weight of the macromonomer is preferably 2,000 or more, more preferably 3,000 or more.
  • the upper limit is preferably 500,000 or less, more preferably 100,000 or less, and particularly preferably 30,000 or less.
  • the mass average molecular weight of the constituent component (MM) can be identified by measuring the mass average molecular weight of the macromonomer incorporated when the polymer constituting the binder is synthesized.
  • the macromonomer is not particularly limited as long as it has a mass average molecular weight of 1,000 or more, but a macromonomer having a polymer chain bonded to a polymerizable group such as a group having an ethylenically unsaturated bond is preferable.
  • the polymer chain of the macromonomer constitutes a side chain (graft chain) with respect to the polymer main chain.
  • the above polymer chain has the function of further improving the dispersibility in a non-aqueous dispersion medium. As a result, both suppression of interfacial resistance between solid particles and improvement of binding property are further achieved.
  • the molecular weight of a polymer, a polymer chain and a macromonomer refers to a mass average molecular weight or a number average molecular weight in terms of standard polystyrene by gel permeation chromatography (GPC) unless otherwise specified.
  • the measurement method is basically a value measured by the method of the following condition 1 or condition 2 (priority). However, an appropriate eluent may be selected and used depending on the type of polymer or macromonomer. (Condition 1) Column: Two TOSOH TSKgel Super AWM-H (trade name, manufactured by Tosoh Corporation) are connected.
  • Carrier 10 mM LiBr/N-methylpyrrolidone Measurement temperature: 40°C Carrier flow rate: 1.0 ml/min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector (condition 2) Column: A column in which TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 (both are trade names, manufactured by Tosoh Corporation) is used.
  • Carrier Tetrahydrofuran Measurement temperature: 40°C Carrier flow rate: 1.0 ml/min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector
  • the polymerizable group contained in the macromonomer is not particularly limited and will be described in detail later, but examples thereof include various vinyl groups and (meth)acryloyl groups, and (meth)acryloyl groups are preferable.
  • the polymer chain of the macromonomer is not particularly limited, and ordinary polymer components can be applied. Examples thereof include a (meth)acrylic resin chain, a polyvinyl resin chain, a polysiloxane chain, a polyalkylene ether chain, and a hydrocarbon chain, and a (meth)acrylic resin chain or a polysiloxane chain is preferable.
  • the chain of the (meth)acrylic resin preferably contains a constituent component derived from a (meth)acrylic compound selected from a (meth)acrylic acid ester compound, a (meth)acrylonitrile compound, and the like, and two or more kinds of (meth)acryl It may be a polymer of a compound.
  • the (meth)acrylic compound has the same meaning as the (meth)acrylic compound (M1).
  • the polysiloxane chain is not particularly limited, and examples thereof include polymers of siloxane having an alkyl group or an aryl group.
  • Examples of the hydrocarbon chain include chains made of the above-mentioned hydrocarbon-based polymer.
  • the macromonomer preferably has a polymerizable group represented by the following formula (b-11).
  • R 11 has the same meaning as R 1 . * Is a binding position.
  • the macromonomer preferably has a linking group that links the polymerizable group and the polymer chain.
  • This linking group is usually incorporated into the side chain of the macromonomer.
  • the linking group is not particularly limited, and examples thereof include the groups described for the linking group L 1 in the above formula (b-1).
  • the number of atoms constituting the linking group is preferably 1 to 36, more preferably 1 to 24, further preferably 1 to 12, and more preferably 1 to 6. Particularly preferred.
  • the number of connecting atoms in the connecting group is preferably 10 or less, more preferably 8 or less.
  • the lower limit is 1 or more.
  • the above-mentioned number of connecting atoms means the minimum number of atoms connecting predetermined structural parts. For example, in the case of —CH 2 —C( ⁇ O)—O—, the number of atoms constituting the linking group is 6, but the number of linking atoms is 3.
  • the macromonomer preferably has a polymerizable moiety represented by any of the following formulas (b-12a) to (b-12c).
  • R b2 has the same meaning as R 1 .
  • R N2 has the same meaning as R N1 described later.
  • the benzene ring of formula (b-12c) may be substituted with any substituent T.
  • the structural portion existing before the bonding position of * is not particularly limited as long as the molecular weight as a macromonomer is satisfied, but the polymer chain (which may be bonded via a linking group) is preferable. At this time, the linking group and the polymer chain may each have a substituent T, for example, a halogen atom (fluorine atom) or the like.
  • the carbon atom to which R 11 or R b2 is not bonded is represented as an unsubstituted carbon atom, but may have a substituent as described above.
  • the substituent is not particularly limited, and examples thereof include the above-mentioned groups that can be taken as R 1 .
  • the above macromonomer is preferably a compound represented by the following formula (b-13a).
  • R b2 has the same meaning as R 1 .
  • na is not particularly limited, it is preferably an integer of 1 to 6, more preferably 1 or 2, and further preferably 1.
  • Ra represents a substituent when na is 1 and a linking group when na is 2 or more.
  • the substituent which can be taken as Ra is not particularly limited, but the above-mentioned polymer chain is preferable, and a (meth)acrylic resin chain or a polysiloxane chain is more preferable.
  • Ra may be directly bonded to the oxygen atom (—O—) in the formula (b-13a) or may be bonded via a linking group.
  • the linking group is not particularly limited, and examples thereof include the above-mentioned linking group that links the polymerizable group and the polymer chain.
  • the linking group is not particularly limited, and examples thereof include an alkane linking group having 1 to 30 carbon atoms, a cycloalkane linking group having 3 to 12 carbon atoms, and an aryl linking group having 6 to 24 carbon atoms.
  • R is a hydrogen atom or alkyl group having 1 to 6 carbon atoms
  • silylene group is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R Si is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • a carbonyl group an imino group
  • R N1 is a hydrogen atom or a substituent, preferably a hydrogen atom, It is preferably an alkyl group having 6 or an aryl group having 6 to 10 carbon atoms), or a combination thereof.
  • macromonomers other than the above-mentioned macromonomers examples include “macromonomer (X)” described in JP-A-2015-88486.
  • the chain-polymerized polymer contains a constituent (crosslinkable constituent) having a physical crosslinkable group in a partial structure part which is a side chain of the polymer.
  • the physical crosslinkable group is as described above, and an appropriate group can be selected according to the type of physical crosslink with the physical crosslinkable group contained in the crosslinker.
  • the crosslinkable constituent component may be a constituent component capable of forming an uncrosslinked polymer, and for example, a compound having a physical crosslinkable group in a partial structure part which is a side chain of the uncrosslinked polymer (hereinafter, simply referred to as a copolymerizable compound.
  • Such a copolymerizable compound is not particularly limited as long as it is a compound that can be copolymerized with a compound that guides the constituent components of the chain-polymerization polymer, and has, for example, the above-mentioned physical crosslinkable group, a vinyl compound. Or a (meth)acrylic compound etc. are mentioned. Specifically, for example, a (meth)acrylic acid compound, a compound in which the above-mentioned physical crosslinkable group is introduced as a substituent to at least one of L 1 and R 2 of the compound represented by the above formula (b-1), Furthermore, the above-mentioned macromonomer into which a physical crosslinkable group is introduced as a substituent can be mentioned.
  • a (meth)acrylic acid compound and further, a (meth)acrylic acid ester compound of an alkyl group in which at least one hydrogen atom is substituted with a carboxy group, a sulfonyl group, a phosphoric acid group or a phosphonic acid (for example, , (Meth)acrylic acid (carboxyalkyl) ester compound), and an alkyl group (meth)acrylic acid ester compound in which at least one hydrogen atom is substituted with a group contained in the above group (b) (for example, ( (Meth)acrylic acid aminoalkyl ester compounds) and the like.
  • the carbon number of the alkyl group is not particularly limited, preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 4. Further, the substitution position of the physical crosslinkable group with respect to the alkyl group is not particularly limited, and in consideration of the molecular structure of the crosslinking agent, a position satisfying the number of connecting atoms of the crosslinked structure including the physical crosslinked structure described later is preferable.
  • a compound forming a crosslinkable constituent (a compound capable of introducing a physical crosslinkable group), it has a physical crosslinkable group in addition to the above-mentioned copolymerizable compound, and causes a polymer reaction with a side chain of the polymer Compounds are also included.
  • the number of physical crosslinkable groups that each of the copolymerizable compound and the polymer-reactive compound has may be 1 or more, preferably 1 to 6, and more preferably 1 or 2. preferable.
  • the chain-polymerization uncrosslinked polymer contains a crosslinkable constituent component, and further, a constituent component derived from the (meth)acrylic compound (M1), a constituent component derived from the vinyl compound (M2), and a constituent component derived from a macromonomer. (MM), other components that can be copolymerized with the compounds leading to these components may be contained.
  • the (meth)acrylic polymer preferably contains a constituent component derived from the (meth)acrylic compound (M1) and a crosslinkable constituent component, and more preferably a constituent component (MM) derived from a macromonomer. ..
  • the (meth)acrylic polymer may contain the constituent component derived from the vinyl compound (M2) and further other constituent components.
  • the content of the crosslinkable constituent in the uncrosslinked polymer is not particularly limited, but in that the dispersibility of the solid electrolyte composition and the binding property between solid particles and the ion conductivity can be exhibited at a high level, For example, it is preferably more than 0% by mass and less than 50% by mass, more preferably 1 to 30% by mass, and further preferably 2.5 to 15% by mass.
  • the content of the constituent component derived from the (meth)acrylic compound (M1) in the polymer is not particularly limited, but is 1 to 99% by mass. Is more preferable, 5 to 97% by mass is more preferable, 10 to 95% by mass is particularly preferable, and 30 to 80% by mass is particularly preferable.
  • the content of the constituent component derived from the vinyl compound (M2) in the polymer is not particularly limited, but is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and 0 to 10% by mass. It is particularly preferable that the content is mass %.
  • the content of the constituent component (MM) in the polymer is not particularly limited, but is preferably 1 to 60% by mass. Thereby, the dispersibility of the solid electrolyte composition, the binding property between solid particles, and the ionic conductivity can be exhibited at a high level.
  • the content of the constituent component (MM) in the polymer is more preferably 3 to 50% by mass, further preferably 5 to 40% by mass.
  • the uncrosslinked polymer (each component) may have a substituent.
  • substituents include groups selected from the following substituents T, and a group that does not function as a physical crosslinkable group when introduced into an uncrosslinked polymer is preferable.
  • the substituent T is shown below, but the substituent T is not limited thereto.
  • Alkyl group preferably alkyl group having 1 to 20 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • alkenyl group Preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl etc.
  • an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl etc.
  • a cycloalkyl group preferably an alkynyl group having 1 to 20 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpenty
  • a cycloalkyl group having 3 to 20 carbon atoms for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.
  • an aryl group preferably an aryl group having 6 to 26 carbon atoms, for example, phenyl, 1-naphthyl) , 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.
  • a heterocyclic group preferably a heterocyclic group having 2 to 20 carbon atoms, and preferably having at least one oxygen atom, sulfur atom, nitrogen atom
  • a 5- or 6-membered heterocyclic group which includes an aromatic heterocyclic group and an aliphatic heterocyclic group, for example, a tetrahydropyran ring group, a tetrahydrofuran ring group, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazoly
  • An alkylthio group preferably an alkylthio group having 1 to 20 carbon atoms, for example, methylthio, ethylthio, isopropylthio, benzylthio, etc.
  • R P is a hydrogen atom or a substituent (preferably a group selected from the substituent T). Further, each of the groups listed as the substituent T may be further substituted with the above substituent T.
  • the compound, the substituent, the linking group and the like include an alkyl group, an alkylene group, an alkenyl group, an alkenylene group, an alkynyl group and/or an alkynylene group, these may be cyclic or linear, or linear or branched. Good.
  • the mass average molecular weight of the uncrosslinked polymer contained in the binder is not particularly limited, but is preferably 5,000 or more, more preferably 10,000 or more, and particularly preferably 30,000 or more.
  • the upper limit is preferably 1,000,000 or less, more preferably 200,000 or less.
  • the number of physically crosslinkable groups in one molecule of the uncrosslinked polymer is determined by the number of physically crosslinkable groups in the crosslinkable constituent and the content of the crosslinkable constituent in the uncrosslinked polymer, and is 1 or more. The number is not particularly limited as long as it is 2 to 100,000.
  • the content of the group selected from the group (a) in the uncrosslinked polymer is not particularly limited, but dispersibility, and further In terms of strength and the like, it is preferably 0.15 to 1 mmol/g, more preferably 0.2 to 0.7 mmol/g, and further preferably 0.2 to 0.5 mmol/g. ..
  • the above content is from the above-mentioned respective group groups, particularly the above group group (a), which the physically crosslinked polymer has. It is the total amount with the content of the selected group (derived cation or anion).
  • the above content can be measured by measuring the polymer by infrared spectroscopy and calculating from the peak area of the functional group.
  • the polymer contained in the solid electrolyte composition is measured using a binder or polymer separated (isolated) from other components by a conventional method.
  • the content of the uncrosslinked polymer in the solid electrolyte composition is not particularly limited as long as it satisfies the content of the binder described above, and is set appropriately.
  • the content with respect to the binder (total mass of the polymer having a side chain having a physical crosslinkable group and the crosslinking agent) is, for example, preferably 1 to 99.9% by mass, and 30 to 99.0% by mass. Is more preferable and 50 to 98.0% by mass is further preferable.
  • the polymer having a physically crosslinkable group in its side chain is physically crosslinked with the crosslinking agent, the above both contents of the uncrosslinked polymer are the total amount including the physically crosslinked polymer.
  • the uncrosslinked polymer is obtained by arbitrarily combining raw material compounds that lead to predetermined constituents according to the type of the main chain, and optionally polymerizing (sequentially in the presence of a catalyst (including a polymerization initiator, a chain transfer agent, etc.)). It can be synthesized by polymerizing or chain polymerizing such as addition polymerizing.
  • a catalyst including a polymerization initiator, a chain transfer agent, etc.
  • the method and conditions for carrying out sequential polymerization or chain polymerization are not particularly limited, and known methods and conditions can be appropriately selected.
  • the properties and physical properties of the uncrosslinked polymer can be adjusted by the type of the uncrosslinked polymer, the type or content of the constituent component (raw material compound), the molecular weight of the polymer, and the like.
  • a known compound is appropriately selected according to the type of uncrosslinked polymer.
  • Each raw material compound that forms In addition, it can also be synthesized by polymerizing a side chain of a usual sequential polymerization type or chain polymerization type polymer and a compound having a physical crosslinkable group.
  • the solvent for synthesizing the non-crosslinked polymer is not particularly limited, and those listed as the non-aqueous dispersion medium described later can be preferably used.
  • the dispersion liquid of the uncrosslinked polymer is prepared by the phase inversion emulsification method described later (when the binder is prepared)
  • the uncrosslinked polymer is synthesized (when the uncrosslinked polymer solution is prepared)
  • a method is preferred in which the solvent is replaced with a dispersion medium capable of emulsifying and dispersing the uncrosslinked polymer, and the solvent used when synthesizing the uncrosslinked polymer is removed.
  • the boiling point of the solvent used when synthesizing the uncrosslinked polymer is preferably lower than the boiling point of the dispersion medium in which the uncrosslinked polymer can be emulsified and dispersed.
  • the dispersion medium capable of emulsifying and dispersing the uncrosslinked polymer a dispersion medium capable of emulsifying and dispersing the uncrosslinked polymer described below can be preferably used.
  • the method for preparing the dispersion liquid of the non-crosslinked polymer is not particularly limited, and it can be prepared by the synthesis of the above-mentioned non-crosslinked polymer (for example, emulsion polymerization method).
  • the synthesized non-crosslinked polymer is dispersed in an appropriate dispersion medium. It can also be prepared.
  • Examples of the method of dispersing the uncrosslinked polymer in the dispersion medium include a method of using a flow reactor (a method of colliding primary particles of the uncrosslinked polymer), a method of stirring using a homogenizer, and a phase inversion emulsification method. ..
  • the method of phase inversion emulsification of the synthesized non-crosslinked polymer is preferable from the viewpoint of productivity, and further the characteristics and physical properties of the obtained non-crosslinked polymer.
  • the phase inversion emulsification method includes a step of dispersing the uncrosslinked polymer and a step of removing the solvent used during the synthesis of the uncrosslinked polymer.
  • a solution of the uncrosslinked polymer is added dropwise to the dispersion medium for emulsification capable of emulsifying and dispersing the uncrosslinked polymer (for example, at -20 to 150° C. for 0.5 to 8 hours) to emulsify.
  • the method includes a method in which the dispersion medium for emulsification is slowly dropped while emulsifying the solution of the uncrosslinked polymer while stirring strongly.
  • Examples of the step of removing the solvent include a method in which the dispersion liquid of the uncrosslinked polymer thus obtained is concentrated under reduced pressure or heated under an inert gas stream.
  • the solvent used during the synthesis of the uncrosslinked polymer can be selectively removed, and the concentration of the emulsifying dispersion medium can be increased.
  • the “strong stirring” is not particularly limited as long as mechanical energy such as impact, shear, shear stress, friction, vibration is applied to the polymer solution.
  • a homogenizer, a homodisper, a Shinto machine, a dissolver, a Titec mixer, a stirring blade in a stirring tank, a high-pressure jet disperser, an ultrasonic disperser, a ball mill, a bead mill, etc. are used, for example, at 300 to 1000 rpm.
  • a mode in which stirring is performed under conditions such as the number of rotations can be mentioned.
  • the term “slowly dropping” is not particularly limited as long as it is not added all at once, but examples thereof include a condition in which the emulsifying dispersion medium to be dropped is added dropwise to the uncrosslinked polymer solution for 10 minutes or more.
  • the dispersion medium for emulsification is appropriately determined depending on the type of constituent components of the uncrosslinked polymer.
  • a solvent which can easily dissolve this constituent component and hardly dissolve other components such as the constituent component represented by the formula (I-1) can be mentioned.
  • the emulsifying solvent is not particularly limited, but aliphatic compounds and aromatic compounds are preferable among the non-aqueous dispersion media.
  • Examples of the aliphatic compound include hexane, heptane, normal octane, isooctane, nonane, decane, dodecane, cyclohexane, cycloheptane, cyclooctane, methylcyclohexane, ethylcyclohexane, decalin, light oil, kerosene, gasoline and the like.
  • Examples of the aromatic compound include benzene, toluene, ethylbenzene, xylene, mesitylene, tetralin and the like.
  • the dispersion medium for emulsification may be used alone or in combination of two or more.
  • a polar solvent (ether solvent, ketone solvent, ester solvent, etc.) may be added as long as it does not hinder the emulsion dispersion of the polymer.
  • the mass ratio [mass for emulsification/mass of polar solvent] of the dispersion medium for emulsification and the polar solvent is preferably 100/0 to 70/30, more preferably 100/0 to 90/10, and 100/0 to 99/. 1 is most preferred.
  • the boiling point of the dispersion medium for emulsification capable of emulsifying and dispersing the uncrosslinked polymer at normal pressure is preferably 60°C or higher, preferably 70°C or higher, and more preferably 80°C or higher.
  • the average particle size depending on the solid content concentration or dropping rate of the uncrosslinked polymer solution used, the type of the uncrosslinked polymer, further, the type or content of the constituent components, etc. Can be prepared.
  • the cross-linking agent used in the present invention is a compound (cross-linking compound) having at least two physical cross-linking functional groups that physically cross-link with the physical cross-linking group of the uncrosslinked polymer. This cross-linking agent reacts or interacts with the above-mentioned physical cross-linking group of the uncross-linked polymer to form a physical cross-linking structure.
  • the physical crosslinkable functional group refers to a functional group capable of forming a physical crosslink with the physical crosslinkable group of the uncrosslinked polymer, by ionic bond or hydrogen bond chemical bond, or by intermolecular interaction, A functional group capable of forming a bond or an interaction.
  • the physical crosslinkable functional group contained in the crosslinking agent include the above-mentioned physical crosslinkable groups without particular limitation, and the type of physical crosslink with the physical crosslinkable group of the uncrosslinked polymer (reaction (bond) or Interaction).
  • reaction (bond) or Interaction the type of physical crosslink with the physical crosslinkable group of the uncrosslinked polymer
  • the physical crosslinkable functional group may be 2 or more, preferably 2 to 20, more preferably 2 to 6, and particularly preferably 2 or 3.
  • the physical crosslinkable functional group may have the same kind of functional group or different kinds of functional groups as the bond or interaction forming the physical crosslink, but the same kind of functional group is preferable. Among the functional groups of the same type, the same functional group is more preferable.
  • the basic structure constituting the cross-linking agent other than the physical cross-linkable functional group is not particularly limited, and may be an aliphatic or aromatic structure or a polymer structure.
  • a molecular chain which can be taken as R P1 and R P2 described above and a group which can be taken as L 11A in the formula (H-1A) described later.
  • a hydrocarbon group (aliphatic or aromatic) that can be taken as a low molecular weight hydrocarbon chain is preferable from the viewpoint of improving dispersibility in a non-aqueous dispersion medium.
  • Examples of such a cross-linking agent include a carboxylic acid compound having a plurality of carboxy groups (polycarboxylic acid compound), a sulfonic acid compound having a plurality of sulfo groups (polysulfonic acid compound), and a phosphoric acid compound having a plurality of phosphoric acid groups (polyphosphoric acid compound).
  • Acid compounds phosphonic acid compounds having a plurality of phosphonic acid groups (polyphosphonic acid compounds), amine compounds having a plurality of amino groups (polyamine compounds), pyridine rings, and other nitrogen-containing aromatic rings contained in group (b)
  • Examples thereof include a compound having a plurality (for example, a pyridine compound having a plurality of pyridinyl groups).
  • polyamine compound and the pyridine compound include respective compounds capable of forming a cation represented by the formula (H-1A) or the formula (H-1B) described below, and more specifically, the below-mentioned compounds.
  • the compound which can form the specific example of the physically crosslinked structure is mentioned.
  • the cross-linking agent is preferably a non-polymer compound, for example, a low molecular weight compound.
  • the molecular weight of the crosslinking agent is not particularly limited, but is preferably less than 1000, more preferably 100 to 700, for example.
  • As the cross-linking agent a commercially available product or one synthesized by a conventional method may be used.
  • the content of the cross-linking agent with respect to the binder (the total mass of the polymer having a physical cross-linking group in the side chain and the cross-linking agent) is appropriately determined according to the number of the physical cross-linking functional groups, and is, for example, 0.
  • both contents of the cross-linking agent are the total amount including the cross-linking agent that is physically cross-linked.
  • the polymer having a physical crosslinked structure in the side chain is a polymer in which the physical crosslinkable group of the uncrosslinked polymer and the physical crosslinkable functional group of the crosslinking agent react or interact with each other to form physical crosslinks, It has a physical cross-linking structure with a cross-linking agent.
  • the fact that the polymer has a physical cross-linking structure can be confirmed by, for example, the appearance of absorption of a functional group capable of having a physical cross-linking structure by infrared spectroscopy, the presence or absence of behavior derived from the cross-linking structure by viscoelasticity measurement, etc. You can
  • the physical cross-linking structure is a basic bond other than the above-mentioned physical cross-linking functional group of the cross-linking agent and the bonding portion that bonds or interacts with each other, depending on the types of the physical cross-linking group of the uncrosslinked polymer and the physical cross-linking functional group of the cross-linking agent. Consists of structure and. For example, when the physical crosslink is formed by an ionic bond, examples of the binding part include a salt composed of a cation and an anion (ionic bond by acid and base).
  • the polymer that forms physical crosslinks by ionic bond has a cation and an anion, and the cation and anion are derived from the physical crosslinkable group of the uncrosslinked polymer and the physical crosslinkable functional group of the crosslinker.
  • the bonding part include a hydrogen bond between a (functional) group capable of donating a hydrogen atom and a (functional) group capable of accepting a hydrogen atom via a hydrogen atom.
  • examples of the bonding portion include a stacking structure with an aryl group.
  • the number (and the content) of the bonding parts that the polymer forming the physical crosslink has is the same as the number (and the content) of the physical crosslinkable group that the uncrosslinked polymer has, and may be at least one. ..
  • the anion constituting the binding part (salt) in this embodiment an anion of a group (origin) selected from the above group (a) is preferable, and a carboxy group anion (—COO ⁇ ) is more preferable.
  • a cation of a group (origin) selected from the above group (b) is preferable, and an cation of an amino group (—N + R 3 ) is more preferable.
  • R represents the hydrogen atom, the alkyl group, the aryl group, or the alkylsilyl group described above in ⁇ Group (b)>.
  • the physical crosslinked structure is preferably formed by an anion or cation derived from a physical crosslinkable group which the polymer has and a polyfunctional cation or polyfunctional anion derived from a crosslinking agent. That is, it is preferable that the polymer forming the physical crosslink has a physical crosslink structure formed by ionic bond with a polyfunctional cation or a polyfunctional anion.
  • the physical crosslinked structure is more preferably formed by an anion derived from the physical crosslinkable group of the polymer and a polyfunctional cation derived from the crosslinking agent.
  • the polyfunctional cation is preferably a cation derived from a diamino compound represented by the following formula (H-1A) or a cation derived from a bipyridine compound represented by the following formula (H-1B).
  • H-1A diamino compound represented by the following formula
  • H-1B bipyridine compound represented by the following formula
  • L 11A and L 11B are an alkylene group having 1 to 24 carbon atoms, an arylene group having 6 to 60 carbon atoms, an alkenylene group having 2 to 24 carbon atoms, an oxygen atom, —N(R NL )—, a carbonyl group. , A silane linking group or an imine linking group, or a group combining these.
  • the alkylene group and alkenylene group that can be used as L 11A and L 11B may be linear, branched or cyclic, and are preferably linear from the viewpoint of affinity with the non-aqueous dispersion medium.
  • the alkylene group and the alkenylene group each have preferably 2 or more carbon atoms, more preferably 4 or more, further preferably 5 or more, particularly preferably 5 or more in terms of affinity with the non-aqueous dispersion medium. It is 6 or more.
  • the upper limit of the number of carbon atoms is preferably 24 or less, more preferably 18 or less, further preferably 12 or less, and particularly preferably 10 or less.
  • Specific examples of the alkylene group include groups in which one hydrogen atom is further removed from the groups mentioned as the alkyl group or cycloalkyl group in the substituent T described later.
  • the arylene group that can be used as L 11A and L 11B has preferably 6 to 60 carbon atoms, more preferably 6 to 24 carbon atoms, further preferably 6 to 18 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
  • the silane linking group that can be used as L 11A and L 11B is not particularly limited and includes, for example, —[Si(R S1 )(R S2 )]n— or —[Si(R S1 )(R S2 )O]n.
  • R S1 and R S2 are not particularly limited and may have a substituent T described later, and an alkoxy group, an aryloxy group or an amino group is preferable.
  • n is an integer of 1 or more, preferably an integer of 1 to 6.
  • R NL represents a hydrogen atom or a substituent, and the substituent can be the substituent T described later.
  • an alkyl group preferably having 1 to 24 carbon atoms, more preferably 1 to 12 and further preferably 1 to 6 and particularly preferably 1 to 3 and an alkenyl group (preferably having 2 to 24 carbon atoms, 2 To 12 are more preferable, 2 to 6 are further preferable, 2 to 3 are particularly preferable, and an alkynyl group (having 2 to 24 carbon atoms is preferable, 2 to 12 is more preferable, 2 to 6 is further preferable, and 2 to 3 is Particularly preferred), aralkyl group (preferably having 7 to 22 carbon atoms, more preferably 7 to 14 and particularly preferably 7 to 10), aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 and 6 to 10 is particularly preferable).
  • the number of groups, atoms or linking groups to be combined is not particularly limited, but is, for example, 2 to 100, preferably 2 to 20.
  • the combined group include a group combining an alkyl group and an aryl group, a group combining an alkyl group and -N(R NL )-, a group combining an alkyl group and an oxygen atom, an alkyl group and an ester.
  • Examples thereof include a group combining a group (oxygen atom and carbonyl group).
  • L 11A and L 11B those having a hydrophobicity close to that of the non-aqueous dispersion medium are preferable in terms of affinity for the non-aqueous dispersion, and examples thereof include an alkyl group, an alkyl group and -N(R NL )-.
  • R 11 to R 18 each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alkylsilyl group, preferably a hydrogen atom or an alkyl group.
  • the alkyl group that can be used as R 11 to R 18 may be linear, branched or cyclic, but is preferably linear.
  • the alkyl group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. Specific examples of the alkyl group include an alkyl group or a cycloalkyl group in the substituent T described later.
  • the alkylsilyl group that can be used as R 11 to R 18 is not particularly limited, and examples thereof include a group represented by —Si(R S3 ) 3 .
  • R S3 represents a hydrogen atom or an alkyl group.
  • the alkyl group that can be taken as R S3 has the same meaning as the alkyl group that can be taken as R 11 above, and the preferred ones are also the same
  • R 11 to R 13 and R 14 to R 16 may be the same or different, but at least one of R 11 to R 13 and R 14 to R 16 At least one is preferably a hydrogen atom, and the remaining two are more preferably alkyl groups. This hydrogen atom is usually derived from the physically crosslinkable group of the uncrosslinked polymer.
  • the two amino cations in formula (H-1A) may be the same or different, but are preferably the same.
  • R 17 and R 18 may be the same or different, but each is preferably a hydrogen atom (generally derived from the physically crosslinkable group of the uncrosslinked polymer). ..
  • the above polyfunctional cation is more preferably a cation (partial structure) derived from a diamino compound represented by the following formula (H-2).
  • L 21 is an alkylene group having 5 to 12 carbon atoms, an arylene group having 6 to 18 carbon atoms, an alkenylene group having 5 to 12 carbon atoms, an oxygen atom, —N(R NL )— or an imine linking group, or The group which combined these is shown.
  • the alkylene group, arylene group, and alkenylene group that can be adopted as L 21 are the same as the alkylene group, arylene group, and alkenylene group that can be adopted as L 11A , respectively, except for the number of carbon atoms.
  • the alkylene group and the alkenylene group that can be used as L 21 each have preferably 5 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms.
  • the arylene group preferably has 6 to 12 carbon atoms, and more preferably 6 to 8 carbon atoms.
  • the combined group which can be taken as L 21 has the same meaning as the combined group which can be taken as L 11A .
  • R 21 to R 26 represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and the alkyl group has the same meaning as the alkyl group which can be adopted as R 11 .
  • the two amino cation moieties (-N + (R 21 )(R 22 )(R 23 ), and -N + (R 24 )(R 25 )(R 26 )) in the formula (H-2) are represented by the above formula. It has the same meaning as the two amino cation moieties in (H-1A).
  • the polyfunctional anion is preferably a polyfunctional cation represented by the formula (H-1A) or the formula (H-1B), and more preferably a cation of the polyfunctional cation represented by the formula (H-2).
  • Examples include polyfunctional anions in which a part is changed to the anion of the above-mentioned physically crosslinkable functional group.
  • polyfunctional cation or polyfunctional anion derived from the crosslinking agent are shown below, but the present invention is not limited thereto.
  • a polymer having a physical crosslinked structure in its side chain has a crosslinked structure including a physical crosslinked structure.
  • This crosslinked structure is a structural portion that bonds the main chains of the polymer, and includes a physically crosslinked structure and a part of the side chain of the polymer or a part of the physically crosslinkable functional group.
  • the number of connecting atoms of the crosslinked structure including the physical crosslinked structure can be appropriately set depending on the combination of the side chain of the polymer and the crosslinking agent, but when the physical crosslinked structure is formed by an ionic bond or a hydrogen bond, dispersibility, further strength In view of the above, 8 to 30 is preferable, 9 to 25 is more preferable, and 10 to 22 is further preferable.
  • the number of connecting atoms in the crosslinked structure refers to the minimum number of atoms connecting main chains, and includes atoms serving as ions forming ionic bonds and hydrogen atoms forming hydrogen bonds. However, hydrogen atoms or groups for forming cations are not included in the number of atoms.
  • the binder may contain the above-mentioned uncrosslinked polymer, crosslinking agent, and polymer having a physically crosslinked structure in the side chain, each alone or in combination of two or more.
  • the binder is preferably prepared by mixing (physically crosslinking) an uncrosslinked polymer (preferably a dispersion of the uncrosslinked polymer) and a crosslinking agent before being mixed with the solid electrolyte or the like.
  • the mixing conditions at this time are not particularly limited, and are appropriately determined depending on the reaction or interaction of physical crosslinking.
  • the uncrosslinked polymer and the cross-linking agent can be physically cross-linked by mixing without heating or under heating.
  • the solid electrolyte composition of the present invention contains a non-aqueous dispersion medium.
  • the non-aqueous dispersion medium may be one that disperses each component contained in the solid electrolyte composition of the present invention, and is preferably one in which the above binder is dispersed in particles.
  • the non-aqueous dispersion medium means a dispersion medium containing no water, and is usually a dispersion medium selected from organic solvents.
  • the phrase "the dispersion medium does not contain water” includes not only the embodiment in which the water content is 0 mass% but also the embodiment in which the water content is 0.1 mass% or less. However, the water content in the solid electrolyte composition of the present invention is preferably within the above range (non-aqueous composition).
  • the organic solvent is not particularly limited, and examples thereof include alcohol compounds, ether compounds, amide compounds, amine compounds, ketone compounds, aromatic compounds, aliphatic compounds, nitrile compounds, ester compounds and the like.
  • the non-aqueous dispersion medium preferably contains an organic solvent having 6 or more carbon atoms, more preferably an organic solvent having 6 to 12 carbon atoms, from the viewpoint of dispersibility and strength. It is preferable to include an organic solvent having 6 to 9 carbon atoms.
  • Examples of the alcohol compound include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, and 2 -Methyl-2,4-pentanediol, 1,3-butanediol and 1,4-butanediol may be mentioned.
  • alkylene glycol diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.
  • alkylene glycol alkyl ether ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether
  • Ether dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.
  • dialkyl ether dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, etc.
  • cyclic ether tetrahydrofuran, dioxane (1,2) -, 1,3- and 1,4-isomers are included)
  • amide compound examples include N,N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, ⁇ -caprolactam, formamide, N-methylformamide, acetamide. , N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.
  • Examples of the amine compound include triethylamine, diisopropylethylamine, tributylamine and the like.
  • Examples of the ketone compound include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, diisobutyl ketone (DIBK) and the like.
  • Examples of the aromatic compound include aromatic hydrocarbon compounds such as benzene, toluene and xylene.
  • Examples of the aliphatic compound include aliphatic hydrocarbon compounds such as hexane, heptane, octane and decane.
  • Examples of the nitrile compound include acetonitrile, propionitrile, isobutyronitrile and the like.
  • Examples of the ester compound include ethyl acetate, butyl acetate, propyl acetate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, butyl pentanoate, ethyl isobutyrate, propyl isobutyrate, isopropyl isobutyrate, isobutyl isobutyrate, and pivalic acid.
  • Examples thereof include carboxylic acid esters such as propyl, isopropyl pivalate, butyl pivalate, and isobutyl pivalate.
  • the non-aqueous dispersion medium is preferably a ketone compound, an ester compound, an aromatic compound or an aliphatic compound, and at least one organic solvent selected from a ketone compound, an ester compound, an aromatic compound and an aliphatic compound. It is more preferable to include.
  • the non-aqueous dispersion medium contained in the solid electrolyte composition may be one type or two or more types.
  • the content of the non-aqueous dispersion medium in the solid electrolyte composition is not particularly limited and is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass.
  • the content of the organic solvent having 6 or more carbon atoms in the non-aqueous dispersion medium is not particularly limited, and can be, for example, 50 to 100 mass% with respect to the total amount of the non-aqueous dispersion medium.
  • the solid electrolyte composition of the present invention can also contain an active material.
  • This active material is a material capable of inserting and releasing ions of a metal element belonging to Group 1 or 2 of the periodic table.
  • Examples of such an active material include a positive electrode active material and a negative electrode active material.
  • a metal oxide (preferably a transition metal oxide) is preferable as the positive electrode active material, and a carbonaceous material, a metal oxide, a silicon-based material, a simple substance of lithium, a lithium alloy, and an alloy with lithium can be formed as the negative electrode active material.
  • a negative electrode active material is preferred.
  • a solid electrolyte composition containing a positive electrode active material (a composition for an electrode layer) may be referred to as a positive electrode composition
  • a solid electrolyte composition containing a negative electrode active material may be referred to as a negative electrode composition.
  • the positive electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table, and is preferably one capable of reversibly inserting and releasing lithium ions.
  • the material is not particularly limited as long as it has the above-mentioned characteristics, and may be a transition metal oxide, an organic material, an element such as sulfur that can be composited with Li, a composite of sulfur and a metal, or the like.
  • the element M b (elements of Group 1 (Ia), elements of Group 2 (IIa), Al, Ga, In, Ge, Sn, Pb of the metal periodic table other than lithium, Elements such as Sb, Bi, Si, P or B) may be mixed.
  • the mixing amount is preferably 0 ⁇ 30 mol% relative to the amount of the transition metal element M a (100mol%). That the molar ratio of li / M a was synthesized were mixed so that 0.3 to 2.2, more preferably.
  • transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt type structure, (MB) a transition metal oxide having a spinel type structure, (MC) a lithium-containing transition metal phosphate compound, (MD) ) Lithium-containing transition metal halogenated phosphoric acid compounds and (ME) lithium-containing transition metal silicic acid compounds.
  • MA a transition metal oxide having a layered rock salt type structure
  • MB transition metal oxide having a spinel type structure
  • MC lithium-containing transition metal phosphate compound
  • MD Lithium-containing transition metal halogenated phosphoric acid compounds
  • ME lithium-containing transition metal silicic acid compounds.
  • transition metal oxide having a (MA) layered rock salt structure examples include LiCoO 2 (lithium cobalt oxide [LCO]), LiNi 2 O 2 (lithium nickelate), LiNi 0.85 Co 0.10 Al 0. 05 O 2 (lithium nickel cobalt aluminum oxide [NCA]), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (lithium nickel manganese cobalt oxide [NMC]) and LiNi 0.5 Mn 0.5 O 2 ( Lithium manganese nickelate).
  • transition metal oxide having a (MB) spinel structure examples include LiMn 2 O 4 (LMO), LiCoMnO 4 , Li 2 FeMn 3 O 8 , Li 2 CuMn 3 O 8 , Li 2 CrMn 3 O 8 and Li.
  • Examples of the (MC) lithium-containing transition metal phosphate compound include olivine-type iron phosphate salts such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , LiCoPO 4, and the like. And the monoclinic naconic vanadium phosphate salts such as Li 3 V 2 (PO 4 ) 3 (lithium vanadium phosphate).
  • (MD) as the lithium-containing transition metal halogenated phosphate compound for example, Li 2 FePO 4 F such fluorinated phosphorus iron salt, Li 2 MnPO 4 hexafluorophosphate manganese salts such as F and Li 2 CoPO 4 F And the like, such as cobalt fluorophosphates.
  • the (ME) lithium-containing transition metal silicic acid compound include Li 2 FeSiO 4 , Li 2 MnSiO 4, and Li 2 CoSiO 4 .
  • a transition metal oxide having a (MA) layered rock salt structure is preferable, and LCO or NMC is more preferable.
  • the shape of the positive electrode active material is not particularly limited, but a particulate shape is preferable.
  • the average particle size of the positive electrode active material is not particularly limited. For example, it can be 0.1 to 50 ⁇ m. In order to make the positive electrode active material have a predetermined particle size, an ordinary pulverizer or classifier may be used.
  • the positive electrode active material obtained by the firing method may be used after washing with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
  • the average particle size of the positive electrode active material particles can be measured in the same manner as the average particle size of the inorganic solid electrolyte.
  • the positive electrode active material may be used alone or in combination of two or more.
  • the mass (mg) (unit weight) of the positive electrode active material per unit area (cm 2 ) of the positive electrode active material layer is not particularly limited. It can be appropriately determined according to the designed battery capacity.
  • the content of the positive electrode active material in the electrode layer composition is not particularly limited and is preferably 10 to 95% by mass, more preferably 30 to 90% by mass, and further preferably 50 to 85% by mass, based on 100% by mass of the solid content. Is more preferable, and 55 to 80% by mass is particularly preferable.
  • the negative electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table, and is preferably one capable of reversibly inserting and releasing lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, and it is a carbonaceous material, a metal oxide, a metal composite oxide, a simple substance of lithium, a lithium alloy, or an anode active that can form an alloy with lithium (can be alloyed). Examples include substances. Above all, a carbonaceous material, a metal composite oxide, or a simple substance of lithium is preferably used from the viewpoint of reliability.
  • An active material capable of alloying with lithium is preferable from the viewpoint that the capacity of the all-solid secondary battery can be increased. Since the solid particles are firmly bound to each other in the constituent layer formed of the solid electrolyte composition of the present invention, a negative electrode active material capable of forming an alloy with lithium can be used as the negative electrode active material. As a result, it is possible to increase the capacity of the all-solid-state secondary battery and extend the life of the battery.
  • the carbonaceous material used as the negative electrode active material is a material consisting essentially of carbon.
  • carbon black such as acetylene black (AB)
  • graphite natural graphite, artificial graphite such as vapor-grown graphite
  • PAN polyacrylonitrile
  • various carbon fibers such as PAN-based carbon fibers, cellulose-based carbon fibers, pitch-based carbon fibers, vapor-grown carbon fibers, dehydrated PVA (polyvinyl alcohol)-based carbon fibers, lignin carbon fibers, glassy carbon fibers and activated carbon fibers.
  • Examples thereof include mesophase microspheres, graphite whiskers, and flat graphite.
  • These carbonaceous materials can be divided into non-graphitizable carbonaceous materials (also called hard carbon) and graphite-based carbonaceous materials depending on the degree of graphitization.
  • the carbonaceous material preferably has the interplanar spacing or density and crystallite size described in JP-A-62-22066, JP-A-2-6856 and JP-A-3-45473.
  • the carbonaceous material does not have to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, etc. may be used.
  • Can also Hard carbon or graphite is preferably used as the carbonaceous material, and graphite is more preferably used.
  • the metal or metalloid element oxide applied as the negative electrode active material is not particularly limited as long as it is an oxide capable of inserting and extracting lithium, and an oxide of a metal element (metal oxide), a composite of metal elements Examples thereof include oxides or composite oxides of metal elements and metalloid elements (collectively referred to as metal composite oxides) and oxides of metalloid elements (metalloid oxides).
  • metal oxide metal oxide
  • metal composite oxides oxides or composite oxides of metal elements and metalloid elements
  • metalloid elements metalloid elements
  • amorphous oxides are preferable, and chalcogenide, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferable.
  • the metalloid element refers to an element exhibiting intermediate properties between a metal element and a non-metalloid element, and usually contains 6 elements of boron, silicon, germanium, arsenic, antimony and tellurium, and further selenium. , Polonium and astatine.
  • Amorphous means an X-ray diffraction method using CuK ⁇ rays and having a broad scattering band having an apex in a region of 20° to 40° at a 2 ⁇ value. You may have.
  • the highest intensity of the crystalline diffraction lines observed at 2 ⁇ values of 40° to 70° is 100 times or less than the diffraction line intensity of the apex of the broad scattering band observed at 20° to 40° of 2 ⁇ values. Is preferable, and is more preferably 5 times or less, and particularly preferably not having a crystalline diffraction line.
  • the amorphous oxide of a metalloid element or the above chalcogenide is more preferable, and an element of Group 13 (IIIB) to 15 (VB) of the periodic table (for example, , Al, Ga, Si, Sn, Ge, Pb, Sb and Bi) are preferably used alone or as a (composite) oxide composed of a combination of two or more thereof, or a chalcogenide.
  • an element of Group 13 (IIIB) to 15 (VB) of the periodic table for example, Al, Ga, Si, Sn, Ge, Pb, Sb and Bi
  • preferable amorphous oxides and chalcogenides are, for example, Ga 2 O 3 , GeO, PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , and Sb 2.
  • O 4, Sb 2 O 8 Bi 2 O 3, Sb 2 O 8 Si 2 O 3, Sb 2 O 5, Bi 2 O 3, Bi 2 O 4, GeS, PbS, PbS 2, Sb 2 S 3 and Sb 2 S 5 is preferably mentioned.
  • the negative electrode active material that can be used in combination with the amorphous oxide centered on Sn, Si, and Ge include carbonaceous materials that can store and/or release lithium ions or lithium metal, lithium simple substance, lithium alloy, lithium. An active material that can be alloyed with is preferably used.
  • the oxide of a metal or metalloid element particularly the metal composite oxide and the chalcogenide, contain at least one of titanium and lithium as a constituent component.
  • the metal composite oxide containing lithium include, for example, a composite oxide of lithium oxide and the above metal composite oxide or the above chalcogenide, and more specifically, Li 2 SnO 2. ..
  • the negative electrode active material for example, the metal oxide contains a titanium atom (titanium oxide).
  • the metal oxide contains a titanium atom (titanium oxide).
  • Li 4 Ti 5 O 12 lithium titanate [LTO]
  • LTO lithium titanate
  • the lithium alloy as the negative electrode active material is not particularly limited as long as it is an alloy usually used as the negative electrode active material of a secondary battery, and examples thereof include a lithium aluminum alloy.
  • the negative electrode active material capable of forming an alloy with lithium is not particularly limited as long as it is one that is usually used as the negative electrode active material of a secondary battery. Such an active material has large expansion and contraction due to charge and discharge, and the binding property of the solid particles is lowered as described above, but in the present invention, the binder can achieve high binding property.
  • examples of such an active material include a negative electrode active material having a silicon atom or a tin atom, each metal such as Al and In, and a negative electrode active material having a silicon atom that enables higher battery capacity (silicon atom-containing active material).
  • a silicon atom-containing active material in which the content of silicon atoms is 50 mol% or more of all the constituent atoms is more preferable.
  • a negative electrode containing such a negative electrode active material for example, a Si negative electrode containing a silicon atom-containing active material, a Sn negative electrode containing a tin atom-containing active material
  • a carbon negative electrode graphite, acetylene black, etc.
  • silicon atom-containing active material examples include silicon materials such as Si and SiOx (0 ⁇ x ⁇ 1), and further silicon-containing alloys including titanium, vanadium, chromium, manganese, nickel, copper, lanthanum (for example, LaSi 2 , VSi 2 , La-Si, Gd-Si, Ni-Si), or an organized active material (for example, LaSi 2 /Si), as well as silicon atoms and tin atoms such as SnSiO 3 and SnSiS 3.
  • silicon materials such as Si and SiOx (0 ⁇ x ⁇ 1)
  • silicon-containing alloys including titanium, vanadium, chromium, manganese, nickel, copper, lanthanum (for example, LaSi 2 , VSi 2 , La-Si, Gd-Si, Ni-Si), or an organized active material (for example, LaSi 2 /Si), as well as silicon atoms and tin atoms such as SnSiO 3 and
  • Examples include active materials containing SiOx can be used as a negative electrode active material (semi-metal oxide) itself, and since Si is generated by the operation of an all-solid secondary battery, an active material (precursor thereof) that can be alloyed with lithium. It can be used as a body substance).
  • Examples of the negative electrode active material having a tin atom include Sn, SnO, SnO 2 , SnS, SnS 2 , and the active material containing the above silicon atom and tin atom.
  • a complex oxide with lithium oxide for example, Li 2 SnO 2 is also included.
  • the above-mentioned negative electrode active material can be used without particular limitation, but in terms of battery capacity, a negative electrode active material that can be alloyed with lithium is a preferred embodiment, among them,
  • a negative electrode active material that can be alloyed with lithium is a preferred embodiment, among them,
  • the above silicon material or silicon-containing alloy (alloy containing silicon element) is more preferable, and silicon (Si) or silicon-containing alloy is further preferable.
  • the shape of the negative electrode active material is not particularly limited, but a particulate shape is preferable.
  • the average particle size of the negative electrode active material is preferably 0.1 to 60 ⁇ m.
  • An ordinary crusher or classifier is used to obtain a predetermined particle size.
  • a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling airflow type jet mill or a sieve is preferably used.
  • wet crushing can also be performed in the presence of water or an organic solvent such as methanol. In order to obtain the desired particle size, it is preferable to carry out classification.
  • the classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as desired. Classification can be performed both dry and wet.
  • the average particle size of the negative electrode active material can be measured in the same manner as the average particle size of the inorganic solid electrolyte.
  • the negative electrode active material may be used alone or in combination of two or more.
  • the mass (mg) (unit weight) of the negative electrode active material per unit area (cm 2 ) of the negative electrode active material layer is not particularly limited. It can be appropriately determined according to the designed battery capacity.
  • the content of the negative electrode active material in the electrode layer composition is not particularly limited, and is preferably 10 to 80% by mass, and more preferably 20 to 80% by mass based on 100% by mass of the solid content.
  • the chemical formula of the compound obtained by the above calcination method can be calculated from the mass difference of the powder before and after calcination as a simple method, and as a simple method.
  • the negative electrode active material layer when the negative electrode active material layer is formed by charging the battery, in place of the negative electrode active material, ions of a metal belonging to Group 1 or Group 2 of the periodic table generated in the all-solid secondary battery are used. Can be used. A negative electrode active material layer can be formed by combining these ions with an electron and depositing as a metal.
  • the surfaces of the positive electrode active material and the negative electrode active material may be surface-coated with another metal oxide.
  • the surface coating agent include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si or Li. Specific examples thereof include spinel titanate, tantalum-based oxides, niobium-based oxides, lithium niobate-based compounds, and the like, and specifically, Li 4 Ti 5 O 12 , Li 2 Ti 2 O 5 , and LiTaO 3.
  • the surface of the electrode containing the positive electrode active material or the negative electrode active material may be surface-treated with sulfur or phosphorus. Furthermore, the surface of the particles of the positive electrode active material or the negative electrode active material may be surface-treated with active rays or active gas (plasma etc.) before and after the surface coating.
  • the solid electrolyte composition of the present invention may contain a conductive auxiliary agent, and it is particularly preferable that the silicon atom-containing active material as the negative electrode active material is used in combination with the conductive auxiliary agent.
  • the conductive aid is not particularly limited, and those known as general conductive aids can be used.
  • electronic conductive materials such as graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, Ketjen black and furnace black, amorphous carbon such as needle coke, vapor grown carbon fiber or carbon nanotube.
  • ions of a metal belonging to Group 1 or Group 2 of the periodic table preferably Li Ions are not inserted and released, and those that do not function as an active material are used as the conduction aid.
  • the conductive assistants those that can function as the active material in the active material layer when the battery is charged/discharged are classified as the active material, not the conductive assistant. Whether or not the battery functions as an active material when charged and discharged is not unique and is determined by a combination with the active material.
  • the conductive additive one type may be used, or two or more types may be used.
  • the content of the conductive additive in the electrode layer composition is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass based on 100 parts by mass of the solid content.
  • the shape of the conductive additive is not particularly limited, but a particulate form is preferable.
  • the median diameter D50 of the conductive additive is not particularly limited and is, for example, preferably 0.01 to 1 ⁇ m, and more preferably 0.02 to 0.1 ⁇ m.
  • the solid electrolyte composition of the present invention contains a lithium salt, an ionic liquid, a thickener, a defoaming agent, a leveling agent, a dehydrating agent, an antioxidant, etc., as a component other than the above components.
  • a cross-linking agent such as one that causes a cross-linking reaction by radical polymerization, condensation polymerization or ring-opening polymerization
  • a polymerization initiator such as one that generates an acid or radical by heat or light
  • the solid electrolyte composition of the present invention is suitable for forming a solid electrolyte layer and an active material layer of an all-solid secondary battery, more preferable as a composition for forming a solid electrolyte layer or a negative electrode active material layer, a negative electrode active material layer Is particularly preferable as the composition for forming.
  • the solid electrolyte composition of the present invention can be prepared, preferably as a slurry, by mixing an inorganic solid electrolyte, a binder, a non-aqueous dispersion medium, and further other components with, for example, various commonly used mixers. ..
  • the mixing method is not particularly limited, and the respective components may be mixed together or sequentially.
  • it is preferable that the polymer and the cross-linking agent are physically cross-linked in advance and then mixed with the solid electrolyte or the like to form the solid electrolyte composition.
  • the particulate binder When the particulate binder is used, it is preferably used as a dispersion liquid of the particulate binder in which the particulate non-crosslinked polymer is synthesized and then physically crosslinked with the crosslinking agent, but the present invention is not limited thereto.
  • the environment for mixing is not particularly limited, and examples thereof include a dry air atmosphere or an inert gas atmosphere.
  • the solid electrolyte-containing sheet of the present invention is a sheet-shaped molded product that can form a constituent layer of an all-solid secondary battery, and includes various modes depending on its use.
  • a sheet preferably used for a solid electrolyte layer also referred to as a solid electrolyte sheet for all solid state secondary batteries
  • an electrode or a sheet preferably used for a laminate of an electrode and a solid electrolyte layer (electrode for all solid state secondary battery) Sheet) and the like.
  • the solid electrolyte sheet for an all-solid secondary battery may be a sheet having a solid electrolyte layer, even a sheet having a solid electrolyte layer formed on a substrate does not have a substrate and is formed from a solid electrolyte layer. It may be a sheet.
  • the solid electrolyte sheet for all solid state secondary batteries may have other layers in addition to the solid electrolyte layer. Examples of the other layer include a protective layer (release sheet), a current collector, and a coat layer.
  • Examples of the solid electrolyte sheet for all solid state secondary batteries include, for example, a sheet having a layer composed of the solid electrolyte composition of the present invention on a substrate, a normal solid electrolyte layer, and optionally a protective layer in this order.
  • the solid electrolyte layer formed from the solid electrolyte composition of the present invention contains an inorganic solid electrolyte and a binder containing a polymer whose side chain is physically crosslinked with the above-mentioned crosslinking agent, and exhibits high strength.
  • the content of each component in this solid electrolyte layer is not particularly limited, but is preferably synonymous with the content of each component in the solid content of the solid electrolyte composition of the present invention.
  • the solid electrolyte layer is the same as the solid electrolyte layer in the all-solid-state secondary battery described later, and usually contains no active material.
  • the solid electrolyte sheet for all-solid secondary batteries can be used suitably as a material which comprises the solid electrolyte layer of all-solid secondary batteries.
  • the base material is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include a sheet (plate-like body) made of a material, an organic material, an inorganic material, and the like, which will be described later with reference to a current collector.
  • the organic material include various polymers and the like, and specific examples include polyethylene terephthalate, polypropylene, polyethylene, cellulose and the like.
  • the inorganic material include glass and ceramics.
  • the electrode sheet for an all-solid secondary battery may be any electrode sheet having an active material layer, and the active material layer is formed on a base material (current collector). However, it may be a sheet having no base material and formed of an active material layer.
  • This electrode sheet is usually a sheet having a current collector and an active material layer, but an embodiment having a current collector, an active material layer and a solid electrolyte layer in this order, and a current collector, an active material layer and a solid electrolyte. A mode having a layer and an active material layer in this order is also included.
  • the electrode sheet may have other layers as described above.
  • the layer thickness of each layer constituting the electrode sheet is the same as the layer thickness of each layer described in the all-solid secondary battery described later.
  • the active material layer of the electrode sheet is preferably formed of the solid electrolyte composition (electrode layer composition) of the present invention.
  • the content of each component in the active material layer of the electrode sheet is not particularly limited, but is preferably synonymous with the content of each component in the solid content of the solid electrolyte composition (electrode composition) of the present invention. ..
  • This electrode sheet can be suitably used as a material forming the (negative electrode or positive electrode) active material layer of the all-solid secondary battery.
  • the method for producing the solid electrolyte-containing sheet is not particularly limited.
  • the solid electrolyte-containing sheet can be manufactured using the solid electrolyte composition of the present invention.
  • the solid electrolyte composition of the present invention is prepared as described above, and the obtained solid electrolyte composition is formed into a film (coating and drying) on a substrate (may have other layers interposed).
  • a method of forming a solid electrolyte layer (coating dry layer) on a substrate can be mentioned. Thereby, a solid electrolyte-containing sheet having a base material (current collector) and a coating and drying layer can be produced as desired.
  • the coating dry layer is a layer formed by applying the solid electrolyte composition of the present invention and drying the non-aqueous dispersion medium (that is, using the solid electrolyte composition of the present invention, Layer of the composition obtained by removing the non-aqueous dispersion medium from the solid electrolyte composition of.
  • the nonaqueous dispersion medium may remain in the active material layer and the coating dried layer as long as the effects of the present invention are not impaired.
  • the remaining amount is, for example, 3% by mass or less in each layer. it can.
  • the solid electrolyte composition of the present invention is preferably used as a slurry, and if desired, the solid electrolyte composition of the present invention can be slurried by a known method.
  • Each process such as application and drying of the solid electrolyte composition of the present invention will be described in the following method for manufacturing an all-solid secondary battery.
  • the coating dried layer obtained as described above can be pressed.
  • the pressurizing condition and the like will be described later in the method of manufacturing an all-solid-state secondary battery.
  • the base material, the protective layer (particularly the release sheet) and the like can be peeled off.
  • the all-solid secondary battery of the present invention includes a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer disposed between the positive electrode active material layer and the negative electrode active material layer.
  • the positive electrode active material layer is formed on the positive electrode current collector, if desired, and constitutes a positive electrode.
  • the negative electrode active material layer is optionally formed on the negative electrode current collector to form a negative electrode.
  • At least one layer of the solid electrolyte layer, the positive electrode active material layer, and the negative electrode active material layer of the all-solid secondary battery is preferably formed of the solid electrolyte composition of the present invention, and all layers are the solid of the present invention.
  • the active material layer contains an inorganic solid electrolyte, an active material, and preferably a conductive additive.
  • the negative electrode active material layer when not formed by the solid electrolyte composition of the present invention, a layer containing an inorganic solid electrolyte, an active material, preferably a conductive additive and optionally the above components, the metal described as the negative electrode active material or A layer made of an alloy (such as a lithium metal layer), and a layer (sheet) made of the carbonaceous material or the silicon atom-containing active material described as the negative electrode active material are adopted.
  • the layer made of metal or alloy includes, for example, a layer formed by depositing or molding powder of metal or alloy such as lithium, metal foil or alloy foil, and vapor deposition film.
  • the thickness of the layer made of a metal or alloy and the layer made of a carbonaceous material are not particularly limited, and may be, for example, 0.01 to 100 ⁇ m.
  • the solid electrolyte layer contains a solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table and, if desired, each of the above components.
  • the solid electrolyte composition or the active material layer can be formed by the solid electrolyte composition of the present invention or the solid electrolyte-containing sheet.
  • the solid electrolyte layer and the active material layer to be formed are preferably the same as those in the solid content of the solid electrolyte composition or the solid electrolyte-containing sheet, unless otherwise specified, for each component and the content thereof. ..
  • the thicknesses of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer are not particularly limited.
  • each layer is preferably 10 to 1,000 ⁇ m, and more preferably 20 ⁇ m or more and less than 500 ⁇ m, in consideration of the dimensions of a general all-solid secondary battery.
  • the thickness of at least one of the positive electrode active material layer, the solid electrolyte layer and the negative electrode active material layer is more preferably 50 ⁇ m or more and less than 500 ⁇ m.
  • the positive electrode active material layer and the negative electrode active material layer may each be provided with a current collector on the side opposite to the solid electrolyte layer.
  • the all-solid-state secondary battery of the present invention may be used as an all-solid-state secondary battery with the above structure depending on the application, but in order to obtain the form of a dry battery, it should be further enclosed in a suitable casing before use.
  • the housing may be made of metal or resin (plastic).
  • metallic casing is preferably divided into a casing on the positive electrode side and a casing on the negative electrode side and electrically connected to the positive electrode current collector and the negative electrode current collector, respectively. It is preferable that the housing on the positive electrode side and the housing on the negative electrode side are joined and integrated via a gasket for preventing a short circuit.
  • FIG. 1 is a sectional view schematically showing an all-solid-state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention.
  • the all-solid secondary battery 10 of the present embodiment has a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 in this order when viewed from the negative electrode side. ..
  • the layers are in contact with each other and have a laminated structure. By adopting such a structure, during charging, electrons (e ⁇ ) are supplied to the negative electrode side, and lithium ions (Li + ) are accumulated there.
  • the solid electrolyte composition of the present invention can be preferably used as a molding material for a solid electrolyte layer, a negative electrode active material layer or a positive electrode active material layer. Further, the solid electrolyte-containing sheet of the present invention is suitable as a solid electrolyte layer, a negative electrode active material layer or a positive electrode active material layer.
  • the positive electrode active material layer and the negative electrode active material layer may be collectively referred to as an electrode layer or an active material layer.
  • this all-solid secondary battery When the all-solid secondary battery having the layer structure shown in FIG. 1 is put into a 2032 type coin case, this all-solid secondary battery is referred to as an all-solid secondary battery laminate, and this all-solid secondary battery laminate is A battery produced by putting it in a 2032 type coin case may be referred to as an all-solid secondary battery.
  • any one of the solid electrolyte layer and the active material layer is formed using the solid electrolyte composition of the present invention or the solid electrolyte containing sheet.
  • all layers are formed by using the solid electrolyte composition of the present invention or the solid electrolyte-containing sheet, and in another preferred embodiment, the solid electrolyte layer and the negative electrode active material layer are the solid electrolyte composition of the present invention or the above. It is formed using a solid electrolyte containing sheet.
  • the negative electrode active material layer is a layer formed of a metal or an alloy as a negative electrode active material, a carbonaceous material or a silicon atom-containing as a negative electrode active material, in addition to the solid electrolyte composition of the present invention or the electrode sheet. It can also be formed by using a layer or the like made of an active material and further by depositing a metal belonging to Group 1 or 2 of the periodic table on the negative electrode current collector or the like during charging.
  • the components contained in the positive electrode active material layer 4, the solid electrolyte layer 3 and the negative electrode active material layer 2 may be the same or different from each other.
  • the positive electrode current collector 5 and the negative electrode current collector 1 are preferably electron conductors.
  • either or both of the positive electrode current collector and the negative electrode current collector may be simply referred to as a current collector.
  • Materials for forming the positive electrode current collector include aluminum, aluminum alloy, stainless steel, nickel and titanium, as well as aluminum or stainless steel whose surface is treated with carbon, nickel, titanium or silver (a thin film is formed). The above) are preferable, and among them, aluminum and aluminum alloys are more preferable.
  • As a material for forming the negative electrode current collector in addition to aluminum, copper, copper alloy, stainless steel, nickel and titanium, etc., carbon, nickel, titanium or silver is treated on the surface of aluminum, copper, copper alloy or stainless steel. Preferred are aluminum, copper, copper alloy and stainless steel.
  • the shape of the current collector is usually a film sheet, but a net, a punch, a lath, a porous body, a foam, a molded body of fibers, and the like can also be used.
  • the thickness of the current collector is not particularly limited, but is preferably 1 to 500 ⁇ m. Further, it is also preferable that the surface of the current collector is made uneven by surface treatment.
  • a functional layer, a member or the like is appropriately interposed or arranged between or outside each layer of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer and the positive electrode current collector. You may. Each layer may be composed of a single layer or multiple layers.
  • the all-solid secondary battery of the present invention is not particularly limited, and can be manufactured by (via) the method for manufacturing a solid electrolyte-containing sheet of the present invention. Focusing on the raw material used, the solid electrolyte composition of the present invention can also be used for production. Specifically, the all-solid secondary battery, the solid electrolyte composition of the present invention is prepared as described above, using the obtained solid electrolyte composition and the like, a solid electrolyte layer of the all-solid secondary battery and It can be manufactured by forming an active material layer. This makes it possible to manufacture an all-solid secondary battery having excellent battery performance such as battery capacity. Since the method for preparing the solid electrolyte composition of the present invention is as described above, it is omitted.
  • the all-solid secondary battery of the present invention has a step of applying the solid electrolyte composition of the present invention onto a substrate (for example, a metal foil serving as a current collector) to form a coating film (form a film). It can be manufactured via a method.
  • a solid electrolyte secondary battery a solid electrolyte composition (electrode layer composition) of the present invention is applied as a positive electrode composition onto a metal foil that is a positive electrode current collector to form a positive electrode active material layer.
  • a positive electrode sheet is prepared.
  • the solid electrolyte composition of the present invention for forming a solid electrolyte layer is applied onto the positive electrode active material layer to form a solid electrolyte layer.
  • the solid electrolyte composition of the present invention (composition for electrode layer) is applied on the solid electrolyte layer as a composition for negative electrode to form a negative electrode active material layer.
  • a composition for negative electrode to form a negative electrode active material layer.
  • each layer is reversed, and the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collector is stacked to manufacture an all-solid secondary battery. You can also do it.
  • the positive electrode sheet for all solid state secondary batteries is produced as described above.
  • the solid electrolyte composition of the present invention is applied as a negative electrode composition onto a metal foil that is a negative electrode current collector to form a negative electrode active material layer, and a negative electrode sheet for an all-solid secondary battery is produced.
  • the solid electrolyte layer-forming composition of the present invention is applied onto any one of the active material layers of these sheets to form a solid electrolyte layer, as described above.
  • the other of the positive electrode sheet for all-solid secondary battery and the negative electrode sheet for all-solid secondary battery is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other.
  • the all solid state secondary battery can be manufactured.
  • the following method can be given as another method. That is, the positive electrode sheet for all-solid secondary batteries and the negative electrode sheet for all-solid secondary batteries are produced as described above. Separately from this, a solid electrolyte composition is applied onto a substrate to prepare a solid electrolyte sheet for an all-solid secondary battery including a solid electrolyte layer. Further, the positive electrode sheet for all-solid secondary battery and the negative electrode sheet for all-solid secondary battery are laminated so as to sandwich the solid electrolyte layer peeled from the base material. In this way, the all solid state secondary battery can be manufactured.
  • the positive electrode sheet for all-solid secondary battery or the negative electrode sheet for all-solid secondary battery, and the solid electrolyte sheet for all-solid secondary battery are produced. Then, the positive electrode sheet for all solid state secondary batteries or the negative electrode sheet for all solid state secondary batteries and the solid electrolyte sheet for all solid state secondary batteries were brought into contact with the positive electrode active material layer or the negative electrode active material layer and the solid electrolyte layer. Overlap and pressurize. In this way, the solid electrolyte layer is transferred to the positive electrode sheet for all-solid secondary batteries or the negative electrode sheet for all-solid secondary batteries.
  • the solid electrolyte layer and the all-solid secondary battery negative electrode sheet or all-solid secondary battery positive electrode sheet for which the base material of the solid electrolyte sheet for all-solid secondary battery is peeled off (a solid electrolyte layer with a negative electrode active material layer or The positive electrode active material layers are stacked and pressed together. In this way, an all-solid-state secondary battery can be manufactured.
  • the pressurizing method, pressurizing condition, and the like in this method are not particularly limited, and the method, pressurizing condition, and the like described below for pressurizing the applied composition can be applied.
  • Each of the above manufacturing methods is a method of forming a solid electrolyte layer, a negative electrode active material layer and a positive electrode active material layer with the solid electrolyte composition of the present invention, in the manufacturing method of the all solid state secondary battery of the present invention. At least one of the solid electrolyte layer, the negative electrode active material layer and the positive electrode active material layer, preferably the solid electrolyte layer and the negative electrode active material layer, is formed from the solid electrolyte composition of the present invention.
  • a solid electrolyte layer with a composition other than the solid electrolyte composition of the present invention, as a material thereof, a commonly used solid electrolyte composition or the like, when forming a negative electrode active material layer, a known negative electrode active material composition Examples thereof include a metal or alloy (metal layer) as a negative electrode active material, a carbonaceous material (carbonaceous material layer) as a negative electrode active material, a silicon atom-containing active material, and the like. Further, the negative electrode active material layer was not formed during the production of the all-solid-state secondary battery, and the negative electrode current collector accumulated in the negative electrode current collector during initialization or charging during use described later belongs to Group 1 or 2 of the periodic table.
  • a negative electrode active material layer can also be formed by combining a metal ion with an electron and precipitating it as a metal on a negative electrode current collector or the like.
  • the solid electrolyte layer or the like can be formed, for example, on the substrate or the active material layer by pressure-molding the solid electrolyte composition or the like under the pressure condition described below, or by forming a sheet molded body of the solid electrolyte or the active material. It can also be used.
  • the method of applying the composition used for manufacturing the all-solid secondary battery is not particularly limited and can be appropriately selected. Examples thereof include coating (preferably wet coating), spray coating, spin coating, dip coating, slit coating, stripe coating and bar coating. At this time, the composition may be subjected to a drying treatment after each coating, or may be subjected to a multilayer treatment and then a drying treatment.
  • the drying temperature is not particularly limited. The lower limit is preferably 30° C. or higher, more preferably 60° C. or higher, even more preferably 80° C. or higher.
  • the upper limit is preferably 300°C or lower, more preferably 250°C or lower, and further preferably 200°C or lower.
  • the non-aqueous dispersion medium can be removed and a solid state (coating dried layer) can be obtained. It is also preferable because the temperature is not raised too high and each member of the all solid state secondary battery is not damaged. As a result, in the all-solid secondary battery, excellent overall performance can be obtained and good binding property can be obtained.
  • a reaction or interaction for forming a physical crosslink can be further caused depending on its type, etc., and a polymer having a physical crosslink structure with a crosslinking agent.
  • a coating dry layer having a small interfacial resistance between solid particles can be formed.
  • the pressurizing method include a hydraulic cylinder press machine.
  • the applied pressure is not particularly limited, and generally, it is preferably in the range of 0.1 to 1500 MPa.
  • the applied composition may be heated simultaneously with the pressurization.
  • the heating temperature is not particularly limited and is generally in the range of 30 to 300°C. It is also possible to press at a temperature higher than the glass transition temperature of the inorganic solid electrolyte.
  • the pressurization may be performed in a state in which the coating solvent or the non-aqueous dispersion medium has been dried in advance, or in a state in which the coating solvent or the non-aqueous dispersion medium remains.
  • each composition may be applied at the same time, or the application and drying press may be applied simultaneously and/or sequentially.
  • the atmosphere during pressurization is not particularly limited, and may be air, dry air (dew point ⁇ 20° C. or lower), inert gas (eg, argon gas, helium gas, nitrogen gas). Since the inorganic solid electrolyte reacts with water, the atmosphere during pressurization is preferably under dry air or in an inert gas.
  • the pressing time may be a short time (for example, within several hours) and high pressure may be applied, or a long time (one day or more) and medium pressure may be applied.
  • a restraint (screw tightening pressure or the like) of the all solid state secondary battery can be used in order to continue applying a medium pressure.
  • the pressing pressure may be uniform or different with respect to the pressed portion such as the sheet surface.
  • the pressing pressure can be changed according to the area and film thickness of the pressed portion. It is also possible to change the same site stepwise with different pressures.
  • the pressed surface may be smooth or roughened.
  • the all-solid-state secondary battery manufactured as described above is preferably initialized after manufacturing or before use.
  • the initialization is not particularly limited, and can be performed, for example, by performing initial charge/discharge in a state where the press pressure is increased, and then releasing the pressure until it becomes a general working pressure of the all solid state secondary battery.
  • the all-solid secondary battery of the present invention can be applied to various uses.
  • the application mode is not particularly limited, but for example, when it is mounted on an electronic device, it is a notebook computer, a pen input computer, a mobile computer, an electronic book player, a mobile phone, a cordless phone handset, a pager, a handy terminal, a mobile fax, a mobile phone. Examples include copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, mini disk, electric shaver, transceiver, electronic organizer, calculator, portable tape recorder, radio, backup power supply, memory card.
  • consumer products include automobiles (electric vehicles, etc.), electric vehicles, motors, lighting equipment, toys, game devices, road conditioners, clocks, strobes, cameras, medical devices (pacemakers, hearing aids, shoulder scuffers, etc.), etc. .. Further, it can be used for various military purposes and for space. It can also be combined with a solar cell.
  • binders used in Examples and Comparative Examples are shown below.
  • the structure of the polymer constituting the binder and the crosslinked structure are also shown.
  • the binder and the inorganic solid electrolyte used in Examples and Comparative Examples were synthesized as follows.
  • Neostan U-600 trade name, bismuth tris(2-ethylhexanoate), manufactured by Nitto Kasei Co., Ltd.
  • Binder Dispersion Liquid B-1 0.76 g of N,N,N′,N′-tetramethylethylenediamine (NEDA) as a cross-linking agent was added to the obtained heptane dispersion liquid B-1, and the mixture was stirred at a temperature of 25° C. for 30 minutes to give a polymer B- A binder dispersion B-1 (10% by mass heptane dispersion) containing 1 and a crosslinking agent NEDA was obtained.
  • NEDA N,N,N′,N′-tetramethylethylenediamine
  • binder dispersion liquid B-1 the binder dispersion liquid B-1 was prepared, except that the compounds shown in Table 1 below were used as the cross-linking agent in the amounts used in the contents shown in the same table.
  • Binder dispersions B-2 to B-10 were prepared in the same manner as in.
  • a solution prepared in a separate container (103.8 g of ethyl acrylate (manufactured by Wako Pure Chemical Industries), 20 g of acrylic acid (manufactured by Wako Pure Chemical Industries), 60 g of macromonomer AB-6 (manufactured by Toagosei Co., Ltd.) (Amount of solid content) and 2.0 g of a polymerization initiator V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) were added dropwise over 2 hours and then stirred at 80° C. for 2 hours. Further 1.0 g of V-601 was added to the obtained mixture, and the mixture was stirred at 90° C. for 2 hours.
  • a (meth)acrylic polymer B-11 was synthesized as an uncrosslinked polymer to prepare a polymer dispersion liquid B-11.
  • 16.2 g of N,N,N′,N′-tetramethylethylenediamine as a cross-linking agent was added to the obtained polymer dispersion B-11, and the mixture was stirred at a temperature of 25° C. for 30 minutes to give a polymer B-11.
  • a binder dispersion liquid B-11 containing a crosslinking agent NEDA was obtained.
  • the macromonomer AB-6 used is polybutyl acrylate (number average molecular weight 6000) whose terminal functional group is a methacryloyl group.
  • binder dispersion B-11 the above-mentioned binder dispersion B-11 was prepared, except that the compounds shown in Table 1 below were used as the cross-linking agent in the amounts used shown in the table.
  • Binder dispersions B-12 and B-13 were prepared in the same manner as in.
  • ⁇ Synthesis Example 14 Synthesis of polymer B-14 and preparation of binder solution B-14>
  • the above polymer B- was prepared except that the compounds leading to the constituents shown in Table 1 below were used as the compounds leading to the respective constituents in the amounts used shown in the same table.
  • a urethane polymer B-14 was synthesized in the same manner as in the synthesis of 1, to prepare a polymer solution B-14.
  • the binder solution was prepared in the same manner as in the preparation of the binder dispersion B-1 except that the obtained polymer solution B-14 was used (without phase inversion emulsification). B-14 was prepared.
  • ⁇ Synthesis Example 15 Synthesis of polymer BC-1 and preparation of binder solution BC-1> 2.5 g of 4,4′-diphenylmethane diisocyanate (manufactured by Wako Pure Chemical Industries, Ltd.), 17.6 g of Jeffamine D-2000 (trade name, polyoxypropylene diamine, number average molecular weight of 2,000, manufactured by Huntsman) of 200 mL. And was dissolved in 52 g of methyl ethyl ketone. The resulting solution was heated to 60° C. and heated and stirred for 30 minutes, then 51 mg of neostan U-600) was added, and the mixture was further heated and stirred at 60° C. for 5 hours.
  • 4,4′-diphenylmethane diisocyanate manufactured by Wako Pure Chemical Industries, Ltd.
  • Jeffamine D-2000 trade name, polyoxypropylene diamine, number average molecular weight of 2,000, manufactured by Huntsman
  • the urea polymer BC-1 was synthesized to prepare the polymer solution BC-1 (content: 30% by mass).
  • the polymer solution BC-1 thus obtained was used as a binder solution BC-1.
  • the binder solution BC-1 contains the urea polymer BC-1 that has not been crosslinked with a crosslinking agent as a binder.
  • Binder solution BC-2 The heptane dispersion B-1 of the polyurethane polymer B-1 prepared in Synthesis Example 1 above was used as a binder solution BC-2.
  • This binder solution BC-2 contains, as a binder, a urethane polymer B-1 which has not been crosslinked with a crosslinking agent.
  • ⁇ Preparation Example 1 Preparation of binder aqueous solution BC-3>
  • an aqueous binder solution BC-3 containing a copolymer resin of isobutene and maleic anhydride and polyethyleneimine was prepared.
  • Preparation Example 2 Preparation of Binder Dispersion Liquid BC-3> Using the binder aqueous solution BC-3 prepared in Preparation Example 1 above, an attempt was made to prepare a polymer dispersion liquid BC in the same manner as the polymer dispersion liquid B-1. However, the copolymer resin (binder) was not dispersed in the non-aqueous dispersion medium (butyl acetate), and the dispersion could not be prepared.
  • the non-aqueous dispersion medium butyl acetate
  • ⁇ Synthesis Example 16 Synthesis of polymer BC-4 and preparation of binder dispersion liquid BC-4>
  • the above polymer B- was prepared except that the compounds leading to the constituents shown in Table 1 below were used as the compounds leading to the respective constituents in the amounts used shown in the same table.
  • urethane polymer BC-4 was synthesized to prepare a polymer solution BC-4.
  • a polymer dispersion liquid BC-4 was prepared in the same manner as the polymer dispersion liquid B-1.
  • the polymer dispersion liquid BC-4 thus obtained was used as a binder dispersion liquid BC-4.
  • a liquid prepared in a separate container (93 parts by mass of a 43% by mass butyl butyrate solution of the macromonomer M-1, butyl acrylate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), 90 parts by mass of methyl methacrylate (Fuji 26 parts by weight of film Wako Pure Chemical Industries, Ltd., 20 parts by weight of 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (trade name: Karenz MOI-BP, Showa Denko KK), V-601 (Product name, dimethyl-2,2'-azobis (2-methylpropinate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 1.1 parts by mass) is added dropwise over 2 hours, and then at 80° C.
  • AD-1 Polymer synthesized by the following method 190 parts by mass of toluene was added to a 1 L three-necked flask equipped with a reflux condenser and a gas introduction cock, and nitrogen gas was introduced for 10 minutes at a flow rate of 200 mL/min, and then the temperature was raised to 80°C. Warmed. Solution prepared in another container (150 parts by mass of butyl acrylate, 50 parts by mass of hydroxybutyl acrylate, 1.9 parts by mass of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed for 2 hours. Was added dropwise, and then the mixture was stirred at 80° C. for 2 hours.
  • the obtained solid was dissolved in 300 parts by mass of heptane to obtain a solution of macromonomer M-1.
  • the solid content concentration was 43.4%, and the mass average molecular weight was 16,000.
  • Dodecyl methacrylate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • 150 parts by mass Methyl methacrylate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • 59 parts by mass 3-mercaptoisobutyric acid manufactured by Tokyo Chemical Industry Co., Ltd.
  • binder dispersions B-1 to B-14 it was confirmed by the above-mentioned method that the polymer constituting each binder was physically crosslinked. As a result, as shown in the above formulas, it was confirmed that all the polymers formed a salt (bonding part) composed of a carboxylate anion derived from a carboxy group and an ammonium cation derived from an amino group, and a crosslinked structure. Table 1 shows the number of connecting atoms in the formed crosslinked structure.
  • the (meth)acrylic polymer BC-5 has a structure in which its side chain is chemically crosslinked by a covalent bond.
  • the average particle diameter of the binder was measured by the method described above. The results are shown in Table 1.
  • the mass average molecular weight of the (uncrosslinked) polymer having a physically crosslinkable group in its side chain was measured by the above-mentioned method. The results are shown in Table 1. Further, the results of measuring the content of the group selected from the group group (a) (referred to as "functional group amount" in Table 1) by the above-mentioned method for the polymer having a physically crosslinkable group in the side chain are shown in Table 1. Show. With respect to each of the obtained binder dispersions, the dispersion state of the binder was visually evaluated and shown in the "shape" column of Table 1.
  • the state in which the binder is dispersed in the non-aqueous dispersion medium to form a particulate binder is referred to as “particle”.
  • the binder solution a state in which the binder is dissolved in the non-aqueous dispersion medium to form a particulate binder and is in a solution is referred to as a “solution”.
  • the constituent components M1 to M4 are as follows.
  • Urethane polymer Component M1 Component represented by Formula (I-1)
  • Component M2 Component represented by Formula (I-3B)
  • Component M3 Component represented by Formula (I-3C)
  • Constituent M4 Constituent Component
  • Constituent M1 Constituent Component Represented by Formula (I-1)
  • Constituent M2 Both Constituent Represented by Formula (I-3B) Constituent component in which terminal oxygen atom is changed to NH
  • Constituent component M3 Constituent component (meth)acrylic polymer represented by formula (I-3C)
  • Constituent component M1 (Meth)acrylic compound (M1)-derived constituent component M3: Constituent component derived from macromonomer
  • Constituent component M4 Constituent component having a physical crosslinkable group
  • Each constituent component of the polymer BC-5 is described in order in each constituent component column.
  • Li 2 S lithium sulfide
  • P 2 S 5 diphosphorus pentasulfide
  • Example 1 A solid electrolyte composition and a solid electrolyte-containing sheet were produced, and the following characteristics were evaluated for the solid electrolyte composition and the solid electrolyte-containing sheet. The results are shown in Table 2.
  • ⁇ Preparation of solid electrolyte composition 180 zirconia beads having a diameter of 5 mm were placed in a zirconia 45 mL container (manufactured by Fritsch), 4.85 g of LPS synthesized in Synthesis Example A above, and a binder dispersion or solution shown in Table 2 (0.15 g as solid content mass). ), and 16.0 g of the non-aqueous dispersion medium shown in Table 2. After that, this container was set in a planetary ball mill P-7 (trade name) manufactured by Fritsch Co., and mixing was continued for 10 minutes at a temperature of 25° C. and a rotation speed of 150 rpm to obtain solid electrolyte composition C-1 to C C-15 and CC-1 to CC-4 were prepared respectively.
  • a planetary ball mill P-7 trade name
  • the total amount refers to the total amount (10 cm) of the solid electrolyte composition charged in the glass test tube, and the height of the supernatant refers to the solid component of the solid electrolyte composition settling (solid-liquid separation).
  • the amount of the supernatant (cm). In this test, the smaller the ratio is, the better the dispersibility is, and the evaluation rank "4" or higher is the pass level.
  • ⁇ Evaluation 2 Evaluation of binding property>
  • the solid electrolyte-containing sheet was wrapped around rods having different diameters, and the presence or absence of cracks, cracks or cracks in the solid electrolyte layer and the presence or absence of peeling of the solid electrolyte layer from the aluminum foil (current collector) were confirmed.
  • the binding property was evaluated according to which of the following evaluation ranks included the minimum diameter of the rod wound without causing defects such as these defects. In the present invention, the smaller the minimum diameter of the bar is, the stronger the binding property is, and the evaluation rank “4” or more is passed.
  • the ionic conductivity was measured using the obtained all-solid-state secondary battery 13 for measuring ionic conductivity. Specifically, in a 25° C. constant temperature bath, AC impedance was measured up to a voltage amplitude of 5 mV and a frequency of 1 MHz to 1 Hz using a 1255B FREQUENCY RESPONSE ANALYZER (trade name) manufactured by SOLARTRON. Thus, the resistance in the film thickness direction of the sample was obtained and calculated by the following formula (1).
  • Ionic conductivity (mS/cm) 1000 ⁇ sample film thickness (cm)/ ⁇ resistance ( ⁇ ) ⁇ sample area (cm 2 ) ⁇ ...Equation (1)
  • the sample film thickness and the sample area are measured before putting the all-solid-state secondary battery laminate 12 into the 2032 type coin case 16, and the value obtained by subtracting the thickness of the aluminum foil (that is, the solid electrolyte layer). Film thickness and area).
  • the results shown in Table 2 show the following.
  • the solid electrolyte composition CC-1 using a binder composed of a urea polymer (uncrosslinked urea polymer) which can be hydrogen-bonded in the main chain but is not physically crosslinked in the side chain had no problem in dispersibility, but contained solid electrolyte.
  • Sheet BS-1 does not show sufficient binding property and ionic conductivity.
  • solid electrolyte compositions CC-2 and CS-3 using a binder composed of a urethane polymer (uncrosslinked urethane polymer) that can hydrogen bond in the main chain but is not physically crosslinked in the side chain have insufficient dispersibility.
  • the solid electrolyte-containing sheets BS-2 and BS-3 produced from these solid electrolyte compositions are also inferior in binding property and ionic conductivity.
  • the solid electrolyte composition CC-4 using a binder composed of a (meth)acrylic polymer having a side chain having a chemical cross-linking structure by covalent bonds is a solid having poor dispersibility and having sufficient binding property and ionic conductivity. An electrolyte containing sheet cannot be obtained.
  • the solid electrolyte compositions C-1 to C-15 of the present invention using a binder composed of a urethane polymer or a (meth)acrylic polymer having a physical crosslinked structure show excellent dispersibility.
  • the solid electrolyte-containing sheets S-1 to S-15 of the present invention produced by using these solid electrolyte compositions have both excellent binding properties and ionic conductivity.
  • L 11 in the formula (H-1A) defined in the present invention is an alkyl group and the alkyl group has 5 or more carbon atoms
  • the solid electrolyte composition exhibits higher dispersibility, It is possible to achieve both high adhesion and high ionic conductivity.
  • a non-aqueous dispersion medium having 6 or more carbon atoms is used in combination with the binder specified in the present invention, the dispersibility can be further improved, and excellent binding properties and ionic conductivity can be achieved.
  • Example 2 An all-solid secondary battery was manufactured and the following characteristics were evaluated. The results are shown in Tables 3 and 4.
  • the composition for a negative electrode obtained above was applied onto a stainless steel foil (negative electrode current collector) having a thickness of 10 ⁇ m by a baker type applicator (trade name: SA-201, manufactured by Tester Sangyo Co., Ltd.) and at 100° C. for 2 hours. It heated and dried the composition for negative electrodes (the non-aqueous dispersion medium was removed). Then, the dried negative electrode composition was pressed (10 MPa, 1 minute) at 25° C. using a heat press machine, and a negative electrode sheet PU- for an all-solid secondary battery having a negative electrode active material layer with a film thickness of 50 ⁇ m was formed. 1 to PU-17 and PV-1 to V-6 were prepared respectively.
  • Si Silicon LPS: Sulfide-based inorganic solid electrolyte AB synthesized in Synthesis Example A: Acetylene black (manufactured by Denka)
  • THF Tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd.)
  • composition for positive electrode 180 pieces of zirconia beads having a diameter of 5 mm were placed in a zirconia 45 mL container (manufactured by Fritsch), 2.7 g of LPS synthesized in Synthesis Example A, KYNAR FLEX 2500-20 (trade name, PVdF-HFP: polyfluoride). 0.3 g of vinylidene hexafluoropropylene copolymer, manufactured by Arkema Inc.) was added as solid mass, and 22 g of butyl butyrate was added. This container was set in a planetary ball mill P-7 (trade name) manufactured by Fritsch Co., and stirred at 25° C. at a rotation speed of 300 rpm for 60 minutes.
  • the composition for positive electrode obtained above was applied onto a 20 ⁇ m thick aluminum foil (positive electrode current collector) with a Baker applicator (trade name: SA-201, manufactured by Tester Sangyo Co., Ltd.) and heated at 100° C. for 2 hours. Then, the positive electrode composition was dried (non-aqueous dispersion medium was removed). Then, the dried positive electrode composition was pressed (10 MPa, 1 minute) at 25° C. using a heat press machine to prepare a positive electrode sheet for an all-solid secondary battery having a positive electrode active material layer with a film thickness of 80 ⁇ m. did. A disc-shaped positive electrode sheet was obtained by punching out a disc-shaped positive electrode sheet having a diameter of 14.0 mm from this positive electrode sheet for all-solid secondary batteries.
  • the prepared negative electrode sheet for all solid-state secondary batteries (the aluminum foil of the solid electrolyte-containing sheet has been peeled off) was cut into a disk shape having a diameter of 14.5 mm, and as shown in FIG. 2, a spacer and a washer (see FIG. 2). (Not shown) was put in a stainless steel 2032 type coin case 11 and a disk-shaped positive electrode sheet was overlaid on the solid electrolyte layer.
  • a laminate 12 for an all-solid secondary battery (a laminate comprising an aluminum foil-a positive electrode active material layer-a solid electrolyte layer-a negative electrode active material layer-a stainless steel foil) was formed. After that, the 2032 type coin case 11 was caulked to manufacture the all solid state secondary batteries 201 to 219 and c21 to c26 shown in FIG. 2, respectively.
  • the all-solid-state secondary battery 13 manufactured in this way has the layer structure shown in FIG.
  • One cycle of charging and discharging was performed by using this charging once and discharging once, and the charging and discharging was performed for one cycle to initialize the all solid state secondary battery.
  • the discharge capacity (initial discharge capacity) in the first charge/discharge cycle after initialization is 100%
  • the charge when the discharge capacity maintenance ratio (discharge capacity relative to the initial discharge capacity) reaches (decreases) 80%.
  • the cycle characteristics were evaluated depending on which of the following evaluation ranks the discharge cycle number was included in. In this test, the discharge capacity retention rate is evaluated as "4" or higher.
  • the initial discharge capacities of the all-solid-state secondary batteries 201 to 219 all showed values sufficient to function as all-solid-state secondary batteries.
  • the results shown in Table 4 show the following.
  • No. The all-solid-state secondary batteries c21 to c23, c25 and c26 are prepared by using a binder made of an uncrosslinked polymer, and are negative electrode compositions PV-1 to PV-3, PV-5, PV-6 and a solid electrolyte. It is an all-solid-state secondary battery in which a negative electrode active material layer and a solid electrolyte layer are produced from the containing sheets BS-1 to BS-3. None of these all-solid-state secondary batteries have high resistance and show battery performance compatible with discharge capacity.
  • a positive electrode active material layer and a solid electrolyte layer prepared by a negative electrode composition PV-4 containing a binder made of a polymer having a chemical cross-linking structure by a covalent bond in a side chain and a solid electrolyte containing sheet BS-4 were provided.
  • the negative electrode compositions PU-1 to PU-17 and the solid electrolyte-containing sheet S-1 produced by using the solid electrolyte compositions C-1 to C-15 of the present invention prepared in Example 1 To S-15, all-solid-state secondary battery No. 1 in which the negative electrode active material layer and the solid electrolyte layer were produced.
  • All of 201 to 219 have a high discharge capacity retention rate, suppress an increase in resistance (high battery voltage), and show excellent battery performance.
  • L 11 in the formula (H-1A) specified in the present invention is an alkyl group and the alkyl group has 5 or more carbon atoms, further excellent battery performance is exhibited.
  • a non-aqueous dispersion medium having 6 or more carbon atoms is used in combination with the binder specified in the present invention, high battery performance is exhibited. High energy density is exhibited when silicon is used as the negative electrode active material.
  • Example 3 Preparation of Solid Electrolyte Composition of Example 1
  • Solid electrolyte composition of Example 1 except that Li 0.33 La 0.55 TiO 3 (LLT) was used in place of LPS in C-1 to C-15.
  • solid electrolyte compositions containing LLT as a solid electrolyte were prepared.
  • a solid electrolyte-containing sheet and a negative electrode sheet for an all-solid secondary battery were produced in the same manner as in Examples 1 and 2, to produce all-solid secondary batteries, and The test was conducted.
  • the solid electrolyte composition containing LLT, the solid electrolyte-containing sheet, and the all-solid secondary battery were all solid electrolyte compositions containing LPS, and the solid electrolyte-containing sheet and all-solid secondary battery using the same. Like a battery, it exhibits excellent characteristics or performance.

Abstract

La présente invention concerne une composition d'électrolyte solide contenant un électrolyte solide inorganique, un liant et un milieu de dispersion non aqueux, et qui est configuré de telle sorte que le liant contient un polymère qui a un groupe physiquement réticulable dans une chaîne latérale et un agent de réticulation qui a deux groupes fonctionnels physiquement réticulables ou plus qui sont réticulables avec le groupe physiquement réticulable ; une feuille contenant un électrolyte solide qui a une couche qui est formée à partir de cette composition ; une batterie secondaire entièrement solide ; un procédé de production d'une feuille contenant un électrolyte solide ; et un procédé de production d'une batterie secondaire entièrement solide.
PCT/JP2019/048675 2018-12-21 2019-12-12 Composition d'électrolyte solide, feuille contenant l'électrolyte solide, batterie secondaire entièrement solide, procédé de production de feuille contenant l'électrolyte solide, et procédé de production de batterie secondaire entièrement solide WO2020129802A1 (fr)

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