WO2023249014A1 - 二次電池用バインダー組成物、二次電池用固体電解質含有組成物、全固体二次電池用シート及び全固体二次電池 - Google Patents

二次電池用バインダー組成物、二次電池用固体電解質含有組成物、全固体二次電池用シート及び全固体二次電池 Download PDF

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WO2023249014A1
WO2023249014A1 PCT/JP2023/022773 JP2023022773W WO2023249014A1 WO 2023249014 A1 WO2023249014 A1 WO 2023249014A1 JP 2023022773 W JP2023022773 W JP 2023022773W WO 2023249014 A1 WO2023249014 A1 WO 2023249014A1
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Prior art keywords
secondary battery
group
solid
solid electrolyte
binder
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PCT/JP2023/022773
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English (en)
French (fr)
Japanese (ja)
Inventor
裕三 永田
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2024529028A priority Critical patent/JPWO2023249014A1/ja
Priority to EP23827197.7A priority patent/EP4546467A4/en
Priority to CN202380044898.XA priority patent/CN119318035A/zh
Priority to KR1020247038747A priority patent/KR20250004313A/ko
Publication of WO2023249014A1 publication Critical patent/WO2023249014A1/ja
Priority to US18/954,459 priority patent/US20250079500A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • C08K3/10—Metal compounds
    • 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
    • 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
    • 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
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C08L101/08—Carboxyl groups
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • 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
    • H01M4/139—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a binder composition for secondary batteries, a solid electrolyte-containing composition for secondary batteries, a sheet for all-solid-state secondary batteries, and an all-solid-state secondary battery.
  • a non-aqueous electrolyte secondary battery (also referred to as a non-aqueous secondary battery) has a negative electrode, a positive electrode, a non-aqueous electrolyte between the negative electrode and the positive electrode, and a specific metal ion such as lithium ion between the two electrodes.
  • This is a storage battery that can be charged and discharged by moving it back and forth.
  • nonaqueous secondary batteries nonaqueous electrolyte secondary batteries using organic electrolytes and all-solid secondary batteries using solid electrolytes are used in a wide range of applications.
  • all-solid-state secondary batteries have a negative electrode, an electrolyte, and a positive electrode all made of solid materials, and can greatly improve safety and reliability, which are issues of non-aqueous electrolyte secondary batteries. It is also said that it will be possible to extend the lifespan.
  • the all-solid-state secondary battery can have a structure in which electrodes and solid electrolytes are directly arranged in series. Therefore, all-solid-state secondary batteries can have higher energy density than nonaqueous electrolyte secondary batteries, and are expected to be applied to electric vehicles, large storage batteries, and the like.
  • Electrode layers (negative electrode active material layer, positive electrode active material layer), solid electrolyte layers, etc. (collectively referred to as constituent layers) in non-aqueous electrolyte secondary batteries and all-solid-state secondary batteries are used to improve productivity, etc.
  • a composition constituting each layer such as an active material and an inorganic solid electrolyte.
  • the binder plays an important role in firmly binding the solid particles together and developing the desired battery characteristics. fulfill. Therefore, various studies have been made on the binder itself or the binder composition. For example, binders and binder compositions are being studied that have a reduced amount or content of metal impurities that cause deterioration of battery characteristics, occurrence of short circuits, and the like.
  • Patent Document 1 states that "the content of particulate metal components with a particle size of 20 ⁇ m or more is 10 ppm or less" obtained by a specific manufacturing method including a particulate metal removal step of removing particulate metal components.
  • "A certain binder composition for secondary batteries” is described.
  • Patent Document 2 describes a binder for a secondary battery electrode containing a crosslinked polymer having a carboxyl group or a salt thereof, wherein the crosslinked polymer or salt thereof is an ethylenically unsaturated carboxylic acid monomer.
  • the binder contains structural units derived from 30% by mass or more and 100% by mass or less, and the polyvalent metal ion content of the crosslinked polymer or its salt is 100 ppm or less.
  • Patent Document 3 describes a "binder composition for a non-aqueous secondary battery positive electrode containing a first binder, which contains iron and at least one of ruthenium and rhodium, and rhodium, the total content of which is 5 ⁇ 10 ⁇ 3 parts by mass or less per 100 parts by mass of the first binder,” is described.
  • Patent Document 4 states, “A binder composition for producing a positive electrode for a secondary battery, including a hydrogenated polymer obtained by hydrogenating a polymer containing a conjugated diene monomer unit and a nitrile group-containing monomer unit.
  • the amount of the platinum group element in the binder composition is 8 x 10 -4 parts by weight or less based on 100 parts by weight of the hydrogenated polymer contained in the binder composition, and A binder composition in which the Wallace plasticity of the polymer at 25° C. is 30 to 97 is described.
  • An object of the present invention is to provide a binder composition for a secondary battery that can further reduce the battery resistance of the secondary battery.
  • the present invention also provides a solid electrolyte-containing composition for a secondary battery containing a binder composition for a secondary battery, and an all-solid battery having a constituent layer formed using the solid electrolyte-containing composition for a secondary battery.
  • An object of the present invention is to provide a sheet for a secondary battery and an all-solid-state secondary battery.
  • binder compositions that contain binders that bind solid particles constituting the constituent layers of secondary batteries
  • the present inventors discovered that , composed of a polymer having a constituent derived from ethylenically unsaturated carboxylic acid in a content of less than 30% by mass in the total constituents, and a metallic element having a particle size of 10 ⁇ m or less for this binder.
  • the binder can be appropriately aggregated to ensure direct interfacial contact of the solid particles. It has been discovered that solid particles can be bound together, and as a result, a constituent layer can be formed in which an increase in resistance is highly suppressed.
  • the present invention was completed after further studies based on these findings.
  • ⁇ 5> The secondary according to any one of ⁇ 1> to ⁇ 4>, wherein the polymer forming the polymer binder has 0.1 to 10% by mass of a component having a carboxyl group in the total components of the polymer.
  • ⁇ 6> The binder composition for a secondary battery according to any one of ⁇ 1> to ⁇ 5>, wherein the polymer binder has a weight average molecular weight of 1.0 ⁇ 10 4 to 1.0 ⁇ 10 6 .
  • ⁇ 7> The binder composition for a secondary battery according to any one of ⁇ 1> to ⁇ 6> above, and an inorganic solid having ion conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table.
  • a solid electrolyte-containing composition for a secondary battery comprising an electrolyte, A solid electrolyte-containing composition for a secondary battery, wherein the content of a component containing a metal element in the solid electrolyte-containing composition for a secondary battery is 1.0 ⁇ 10 ⁇ 3 to 1.0 ⁇ 10 4 ppm.
  • the solid electrolyte-containing composition for a secondary battery according to ⁇ 7> which contains an active material.
  • An all-solid-state secondary battery sheet having a layer composed of the solid electrolyte-containing composition for secondary batteries according to any one of ⁇ 7> to ⁇ 9> 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 solid electrolyte layer, and the negative electrode active material layer is a layer composed of the solid electrolyte-containing composition for secondary batteries according to any one of ⁇ 7> to ⁇ 9>. , all-solid-state secondary battery.
  • An all-solid-state secondary battery comprising a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order, An all-solid-state secondary battery, wherein at least one of the positive electrode active material layer and the negative electrode active material layer is an active material layer composed of the solid electrolyte-containing composition for secondary batteries according to ⁇ 8> or ⁇ 9>.
  • the binder composition for secondary batteries and the solid electrolyte-containing composition for secondary batteries of the present invention as a material for forming a constituent layer, it is possible to form a constituent layer that highly suppresses an increase in resistance, and has a low resistance. It is possible to realize a secondary battery that exhibits high ionic conductivity (high ionic conductivity). Further, by incorporating the all-solid-state secondary battery sheet as a constituent layer of a secondary battery, a secondary battery exhibiting low resistance can be realized. Furthermore, the secondary battery of the present invention exhibits low resistance.
  • FIG. 1 is a vertical cross-sectional view schematically showing an all-solid-state secondary battery according to a preferred embodiment of the present invention.
  • FIG. 2 is a vertical cross-sectional view schematically showing a coin-type all-solid-state secondary battery produced in an example.
  • the expression of a compound is used to include the compound itself, its salt, and its ion.
  • the term also includes derivatives that have been partially changed, such as by introducing a substituent, within a range that does not impair the effects of the present invention.
  • (meth)acrylic means one or both of acrylic and methacrylic.
  • substituents, linking groups, etc. hereinafter referred to as substituents, etc.
  • substituents, etc. that do not specify whether they are substituted or unsubstituted mean that they may have an appropriate substituent.
  • this YYY group includes not only an embodiment having no substituent but also an embodiment having a substituent. This also applies to compounds that do not specify whether they are substituted or unsubstituted.
  • Preferred substituents include, for example, substituent Z described below.
  • polymer refers to a polymer, and has the same meaning as a so-called high molecular compound.
  • a polymer binder also simply referred to as a binder refers to a binder made of a polymer, and includes the polymer itself and a binder made up (formed) of a polymer.
  • the main chain of a polymer or polymer chain refers to a linear molecular chain in which all other molecular chains constituting the polymer or polymer chain can be considered as branched chains or pendant groups with respect to the main chain. means.
  • the longest chain among the molecular chains constituting the polymer or polymer chain is the main chain.
  • the main chain does not include terminal groups at the ends of the polymer or polymer chain.
  • the side chain of a polymer refers to a branched chain other than the main chain, and includes short chains and long chains.
  • the binder composition for a secondary battery of the present invention contains a specific content of a metal element-containing component having a particle size of 10 ⁇ m or less, and a specific polymer binder.
  • a binder for forming a constituent layer in a constituent layer forming material for example, a solid electrolyte-containing composition for secondary batteries, it is possible to form a constituent layer that highly suppresses an increase in resistance.
  • All-solid-state secondary battery sheets having constituent layers with resistance (high ionic conductivity), secondary batteries exhibiting low resistance (high ionic conductivity), etc. can be manufactured.
  • the binder composition of the present invention was discovered as a result of various studies on binder compositions, and although the details of the reason are not yet clear, it is thought to be as follows. That is, in the binder composition, the polymer binder interacts with the metal element-containing component (e.g., electrostatic attraction, intermolecular force, coordination force, etc.) and increase cohesiveness.
  • the metal element-containing component e.g., electrostatic attraction, intermolecular force, coordination force, etc.
  • the polymer binder is thought to form moderately agglomerated and moderately sized aggregates, without forming too large agglomerates that cause precipitation, and when these aggregates bind solid particles, Without interfering with the state of direct contact between particles, a direct contact area can be ensured, and solid particles can be bound together while suppressing an increase in interfacial resistance.
  • the binder composition of the present invention is preferably a non-aqueous composition.
  • the non-aqueous composition includes not only a form containing no water but also a form in which the water content (also referred to as water content) is preferably 500 ppm or less.
  • the water content is more preferably 200 ppm or less, even more preferably 100 ppm or less, and particularly preferably 50 ppm or less.
  • the water content indicates the amount of water contained in the binder composition (mass ratio to the binder composition), and specifically, it is measured by filtering with a 0.02 ⁇ m membrane filter and using Karl Fischer titration. value.
  • the binder composition of the present invention only needs to contain a polymer binder and a component containing a metal element, and may contain raw material compounds forming constituent layers such as an inorganic solid electrolyte and an active material.
  • the binder composition of the present invention since the binder composition of the present invention is used as a preparation material for the solid electrolyte-containing composition for secondary batteries of the present invention, which is a constituent layer forming material, it may contain the raw material compound forming the above constituent layer. It is preferable that you do not.
  • "not containing raw material compounds” does not mean excluding raw material compounds that are unavoidably contained, but within a range that does not impair the effects of the present invention, for example, 5% by mass or less in the binder composition. This means that it may be contained if the content is .
  • the binder composition of the present invention can be used as a material for forming constituent layers of a secondary battery, particularly as a material for preparing a solid electrolyte-containing composition for a secondary battery, and also as a material for forming a sheet for an all-solid-state secondary battery and a composition of an all-solid-state secondary battery. It is preferably used as a material for forming layers.
  • the binder composition of the present invention contains a component containing a metal element with a particle size of 10 ⁇ m or less.
  • the metal element-containing component may be any component as long as it has the property of interacting with (the polar portion of) the polymer binder, which will be described later. Examples include compounds that have On the other hand, this metal element-containing component is used as a constituent layer forming material of a secondary battery, but does not include an active material, an inorganic solid electrolyte, a conductive aid, a lithium salt, etc.
  • metal elements examples include simple metal elements (single metals), compounds containing one or more metal elements, and the like.
  • the metal elements include so-called metalloid elements, specifically, each metal element belonging to Groups 1 to 14 of the periodic table (excluding hydrogen element), and periodic elements. Includes metalloid elements belonging to any of Groups 13 to 17 of the Table of Contents.
  • semimetal elements include boron, silicon, germanium, antimony, bismuth, selenium, tellurium, and the like.
  • the metal element contained in the metal element-containing component is not particularly limited, but metal elements and metalloid elements belonging to any of Groups 2 to 14 are preferred, and metals belonging to Group 13 or Group 14 are preferred.
  • Elements and metalloid elements are more preferable, and one or two selected from each element of aluminum (Al), boron, (B), gallium (Ga), indium (In), silicon (Si), and germanium (Ge). It is more preferable that the number of species is greater than or equal to one.
  • the number of types of metal elements contained in the metal element-containing component may be one or more, and the upper limit may be 30, but preferably 1 to 4.
  • the metal element-containing component may be a component (compound) formed only with a metal element, or a component (compound) formed with a metal element and another element.
  • components formed from metal elements and other elements include inorganic compounds or organic compounds containing metal elements, and specifically, oxides of metal elements, halides of metal elements, and halides of metal elements. Examples include hydroxides, inorganic or organic acid salts of metal elements, metal element salts or esters of boric acid, and organometallic compounds such as alkylated or arylated metals, metal alkoxides, or metal aryloxides. Can be mentioned.
  • the inorganic acid is not particularly limited, and examples thereof include hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, and silicic acid (including aluminosilicic acid).
  • the organic acid is not particularly limited, and includes, for example, organic carboxylic acids such as formic acid and acetic acid, organic sulfonic acids such as para-toluenesulfonic acid, organic phosphonic acids such as alkylphosphonic acids, and phosphinic acids.
  • the above oxides are also referred to as composite oxides when they contain two or more metal elements.
  • the component containing a metal element is preferably a non-metal component such as a single metal element or an alloy, more preferably a component (compound) formed of a metal element and another element, and a (composite) oxide of a metal element.
  • a non-metal component such as a single metal element or an alloy
  • a component (compound) formed of a metal element and another element preferably a component (compound) formed of a metal element and another element
  • a (composite) oxide of a metal element preferably a non-metal component such as a single metal element or an alloy, more preferably a component (compound) formed of a metal element and another element, and a (composite) oxide of a metal element.
  • inorganic or organic acid salts of metal elements, metal element salts of boric acid, organometallic compounds, etc. are more preferred
  • examples of compounds containing the Al element include aluminum metal, aluminum oxide (alumina), aluminum hydroxide, trialkoxyaluminum, aluminosilicate, aluminum halide, and the like.
  • examples of the compound containing element B include boron oxide, boron halide, alkylated boron, and trialkyl borate.
  • examples of the compound containing the Ga element include gallium metal, gallium oxide, trialkoxygallium, and gallium halide.
  • examples of compounds containing In element include indium metal, indium oxide, alkoxyindium, and indium halide.
  • Examples of the compound containing the Si element include silicon oxide (silica), alkoxy silicon, silicon halide, and siloxane compounds.
  • the siloxane compound may be a chain compound or a cyclic compound (cyclic siloxane compound).
  • a siloxane compound generally refers to a compound having one or more siloxane units: -Si(R 2 )O- units, and the number of siloxane units is appropriately determined.
  • the number can be 3 to 10, and 3 to 6 is preferable.
  • R in the siloxane unit can be an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, etc., but an alkyl group is preferable, and an alkyl group having 1 to 3 carbon atoms is preferable. More preferred.
  • Two R's in one siloxane unit may be different, but are preferably the same. Note that each group that can be used as R is not particularly limited, and includes, for example, a group corresponding to the substituent Z described below.
  • the metal element-containing component includes the compounds used in the examples described later, but the present invention is not limited thereto. Among these, alumina, silica, and aluminosilicates of one or more metal elements are preferred.
  • the metal element-containing component may be present as an elemental metal or a compound itself in the binder composition, the solid electrolyte-containing composition for secondary batteries described below, and the constituent layers in coexistence with the polymer binder.
  • the element-containing components may be decomposed, dissociated, etc., and exist as metal ions or the like.
  • the metal element-containing component may exist in the form of particles in coexistence with the polymer binder, or may exist in a state dissolved in a dispersion medium or the like.
  • the metallic element-containing component when the metallic element-containing component is present in a dissolved state, its particle size cannot be specified, but is set to "0 ⁇ m" for convenience. That is, the metal element-containing component with a particle size of 10 ⁇ m or less includes a particulate metal element-containing component with a particle size of more than 0 ⁇ m and 10 ⁇ m or less, and a dissolved metal element-containing component with a particle size of 0 ⁇ m. do.
  • the metal element-containing component is preferably present in a dissolved state. The existence of the metal element-containing component in a dissolved state can be confirmed by measuring using a light scattering particle size distribution analyzer and by not observing a particle size distribution (the presence of particles cannot be confirmed).
  • the particle size of the metal element-containing component is 10 ⁇ m or less.
  • the particle size of the metal element-containing component is preferably 6 ⁇ m or less, more preferably 3 ⁇ m or less, and even more preferably 1 ⁇ m or less.
  • the lower limit of the particle size is preferably greater than 0 ⁇ m.
  • the particle size of the metal element-containing component is the value of the particle size obtained by measuring particles obtained by filtering the binder composition using a magnetic filter or the like with an optical microscope.
  • the particle size of the metal element-containing component in the binder composition can be adjusted by an appropriate method. For example, the particle size of the metal element-containing component used when preparing the binder composition, the preparation conditions of the binder composition (mixing conditions etc.), and further by adjusting (changing) the content of the metal element-containing component.
  • the binder composition may contain one or two types of metal element-containing components.
  • the content C MB of the metal element-containing component in the binder composition is 1.0 ⁇ 10 ⁇ 3 to 1.0 ⁇ 10 4 ppm. In the present invention, ppm is based on mass. When the content CMB of the metal element-containing component is within this range, it is possible to form a constituent layer that suppresses an increase in resistance without excessively covering the solid particles while appropriately increasing the cohesiveness of the polymer binder. Further, it is possible to suppress deterioration and loss of battery function due to the presence of components containing metal elements.
  • the content C MB of the metal element-containing component is preferably 1.0 ⁇ 10 ⁇ 1 to 1.0 ⁇ 10 3 , in that the increase in resistance can be further suppressed while maintaining the battery function. It is more preferably from .0 to 1.0 ⁇ 10 3 , even more preferably from 5 to 5.0 ⁇ 10 2 ppm, particularly preferably from 10 to 1.0 ⁇ 10 2 ppm, and from 10 to 1.0 Most preferably it is 50 ppm.
  • the content CMB of the metal element-containing component can be calculated from the amount of the metal element-containing component used in preparing the binder composition, and can also be calculated from the amount of the metal element-containing component used in preparing the binder composition. It can be calculated from the analysis results. It goes without saying that the content CMB of metal element-containing components is the total content including the content of the components that are present after decomposition, etc., if the metal element-containing components exist as a result of decomposition, etc. Quantity.
  • the ratio [C MB /C PB ] of the metal element-containing component content C MB to the polymer binder content C PB described below is not particularly limited and is appropriately determined.
  • this ratio [C MB /C PB ] can be set to 1.0 ⁇ 10 ⁇ 8 to 1.0 ⁇ 10 ⁇ 1 in that the increase in resistance can be effectively suppressed; It is preferably 0 ⁇ 10 ⁇ 7 to 1.0 ⁇ 10 ⁇ 2 , more preferably 1.0 ⁇ 10 ⁇ 6 to 1.0 ⁇ 10 ⁇ 3 , and 5.0 ⁇ 10 ⁇ 5 to 1 It is more preferably .0 ⁇ 10 ⁇ 3 , particularly preferably 1.0 ⁇ 10 ⁇ 4 to 1.0 ⁇ 10 ⁇ 3 , and 1.0 ⁇ 10 ⁇ 4 to 5.0 ⁇ 10 ⁇ 4 Most preferably.
  • the metal element-containing component may contain a particle size exceeding 10 ⁇ m as long as it does not impair the effects of the present invention, but the binder composition may contain a metal element-containing component having a particle size exceeding 10 ⁇ m. It is preferable not to do so.
  • the range that does not impair the effects of the present invention is not particularly limited, but for example, the content of the metal element-containing component with a particle size exceeding 10 ⁇ m in the binder composition is 1.0 ⁇ 10 -1 ppm or less. Say something.
  • the polymer binder contained in the binder composition of the present invention is a polymer binder formed by containing a polymer, and this polymer (also referred to as a binder-forming polymer) contains a component derived from an ethylenically unsaturated carboxylic acid. It is a polymer having a content of less than 30% by mass in all the constituent components of the polymer.
  • a polymer binder formed of a polymer having the above-mentioned content of the component MA derived from ethylenically unsaturated carboxylic acid interacts with the coexisting metal element-containing component and exhibits appropriate cohesiveness.
  • the binder composition of the present invention can form a constituent layer while suppressing an increase in resistance.
  • the binder-forming polymer may have one or more constituent MAs.
  • ethylenic unsaturated carboxylic acids include (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, (meth)acrylamidoalkylcarboxylic acids, and ethylenic unsaturated carboxylic acids having a carboxy group. It refers to a saturated monomer or an alkali neutralized product thereof, and specifically includes the "ethylenic unsaturated carboxylic acid monomer” described in paragraph [0036] of Patent Document 2.
  • the content of the component MA in all the components of the binder-forming polymer may be less than 30% by mass, but is preferably from 0 to 20% by mass, from the viewpoint of further suppressing the increase in resistance.
  • the amount is more preferably 0.1 to 10% by weight, and even more preferably 0.1 to 5% by weight.
  • the binder-forming polymer preferably has one or more constituent components (also referred to as polar functional group-containing constituents) MC having at least one polar functional group among the functional group group (a) below.
  • polar functional group-containing constituents also referred to as polar functional group-containing constituents
  • the cohesiveness of the polymer binder can be further enhanced and the solid particles can be firmly bound together.
  • the polar functional group-containing component MC has at least one (one kind) of polar functional groups, and it is usually preferable that it has one to three kinds of polar functional groups.
  • the number of polar functional groups that the binder-forming polymer has is not particularly limited, and depends on the number of polar functional groups that the polar functional group-containing component MC itself has, the content of the polar functional group-containing component MC, the molecular weight of the binder-forming polymer, etc. It will be determined accordingly.
  • This polar functional group-containing component MC only needs to have a polar functional group, for example, a polycondensable compound having at least one (1 type) of polar functional groups from the following functional group group (a).
  • the polycondensable compound is preferably a compound having, for example, a polycondensable group, a polar functional group or a substituent having a polar functional group, and a linking group that appropriately connects the polycondensable group and the substituent. .
  • the polycondensable group is appropriately determined depending on the main chain structure of the binder-forming polymer. For example, in the case of a sequential polymerization polymer described below, a condensable functional group is selected, and in the case of a chain polymerization polymer, a polymerizable functional group is selected. groups (ethylenically unsaturated groups) are selected.
  • the substituent before being substituted with a polar functional group is not particularly limited, but includes, for example, a group selected from substituents Z described below, preferably an alkyl group, and more preferably an alkyl group having 1 to 6 carbon atoms. preferable.
  • the linking group is not particularly limited, but includes, for example, an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms), alkenylene group (preferably 2 to 6 carbon atoms).
  • arylene group (carbon number is preferably 6 to 24, more preferably 6 to 10), oxygen atom, sulfur atom, imino group (-NR N -: R N is a hydrogen atom, a carbon represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms), carbonyl group, phosphoric acid linking group (-O-P(OH)(O)-O-), phosphonic acid linking group (- Examples include groups such as P(OH)(O)-O-), or a combination thereof.
  • the linking group is preferably an alkylene group, an arylene group, a carbonyl group, an oxygen atom, a sulfur atom, an imino group, or a combination thereof; , or a combination thereof is more preferred, and a -CO-O- group is even more preferred.
  • the number of atoms constituting the linking group is preferably 1 to 36, more preferably 1 to 24, and even more preferably 1 to 12.
  • the number of linking atoms in the linking group is preferably 12 or less, more preferably 10 or less, and particularly preferably 8 or less.
  • the lower limit is 1 or more.
  • the above-mentioned number of connected atoms refers to the minimum number of atoms connecting predetermined structural parts. For example, in the case of a -CO-O- group, the number of atoms constituting the linking group is three, but the number of linking atoms is two.
  • the sulfonic acid group, phosphoric acid group, phosphonic acid group, etc. included in the functional group group (a) are each synonymous with the corresponding group of the substituent Z described later, although they are not particularly limited.
  • the dicarboxylic anhydride group is not particularly limited, but includes a group obtained by removing one or more hydrogen atoms from a dicarboxylic anhydride, and a component itself obtained by copolymerizing a polymerizable dicarboxylic anhydride. , further includes a group formed by reacting a dicarboxylic acid anhydride with an active hydrogen compound to cleave the anhydride group.
  • the group obtained by removing one or more hydrogen atoms from a dicarboxylic anhydride is preferably a group obtained by removing one or more hydrogen atoms from a cyclic dicarboxylic anhydride.
  • dicarboxylic anhydrides include acyclic dicarboxylic anhydrides such as acetic anhydride, propionic anhydride, and benzoic anhydride; cyclic dicarboxylic anhydrides such as maleic anhydride, phthalic anhydride, fumaric anhydride, succinic anhydride, and itaconic anhydride; Examples include dicarboxylic acid anhydrides.
  • polymerizable dicarboxylic anhydride examples include, but are not limited to, dicarboxylic anhydrides having an unsaturated bond in the molecule, preferably polymerizable cyclic dicarboxylic anhydrides. Specific examples include maleic anhydride and itaconic anhydride.
  • the active hydrogen compound is not particularly limited as long as it is a compound that reacts with a dicarboxylic anhydride group, and examples thereof include alcohol compounds, amine compounds, thiol compounds, and the like.
  • Ether group (-O-), thioether group (-S-), and thioester group (-CO-S-, -CS-O-, -CS-S-) each mean a bond shown in parentheses.
  • the terminal group bonded to this group is not particularly limited, and examples include groups selected from substituents Z described below, such as an alkyl group.
  • ether groups are included in carboxyl groups, hydroxy groups, oxetane groups, epoxy groups, dicarboxylic acid anhydride groups, etc., but -O- contained therein is not treated as an ether group. The same applies to thioether groups.
  • the fluoroalkyl group is a group in which at least one hydrogen atom of an alkyl group or a cycloalkyl group is substituted with a fluorine atom, and the number of carbon atoms thereof is preferably 1 to 20, more preferably 2 to 15, and still more preferably 3 to 10. preferable.
  • the number of fluorine atoms on carbon atoms may be such that some or all of the hydrogen atoms are replaced (perfluoroalkyl group).
  • Groups that can form salts, such as sulfonic acid groups (sulfo groups), phosphoric acid groups, phosphonic acid groups, and carboxy groups, may form salts. Examples of the salt include various metal salts, ammonium or amine salts, and the like.
  • the polar functional group contained in the polar functional group-containing constituent component MC is other than the carboxy group derived from ethylenically unsaturated carboxylic acid, in terms of improving the cohesiveness of the polymer binder and adsorbability (adhesion) with solid particles.
  • a carboxy group, hydroxy group, phosphoric acid group, epoxy group, dicarboxylic acid anhydride group or ether group is preferred.
  • the polar functional group-containing component MC has two or more types of polar functional groups, the combination is not particularly limited and can be determined as appropriate.
  • a combination of a carboxy group other than a carboxy group derived from an ethylenically unsaturated carboxylic acid, a sulfonic acid group, or a phosphonic acid group with either a hydroxy group, an oxetane group, an epoxy group, or an ether group is preferable; More preferred is a combination of a carboxy group other than a carboxy group derived from an unsaturated carboxylic acid and a hydroxy group or an ether group.
  • the polycondensable compound that leads to the polar functional group-containing component MC is not particularly limited as long as it has the above polar functional group, and examples thereof include compounds in which the above polar functional group is introduced into the raw material compound constituting the binder-forming polymer. Examples include a (meth)acrylic compound (M1) or a vinyl compound (M2), or a compound obtained by introducing the above-mentioned polar functional group into these compounds (M1) or (M2), which will be described later.
  • the binder-forming polymer may contain other components in addition to the above-mentioned components.
  • Other constituent components may be those that do not correspond to the above-mentioned constituent components, and include, for example, constituent components derived from the (meth)acrylic compound (M1) or vinyl compound (M2) described later.
  • constituent components derived from (meth)acrylic acid alkyl ester compounds are preferred, and components derived from acrylic ester compounds of long-chain alkyl groups are more preferred.
  • the number of carbon atoms in the long chain alkyl group can be, for example, 3 to 20, preferably 4 to 16, and more preferably 6 to 14.
  • the binder-forming polymer may contain one or more of the above components.
  • the binder-forming polymer has a carboxyl group, that is, it has a component having a carboxyl group, which can further improve the cohesiveness of the polymer binder and firmly bind the solid particles.
  • the component having a carboxyl group means a component having a carboxyl group in its structure among the components constituting the binder-forming polymer, and specifically includes the above-mentioned component MA, the above-mentioned component It refers to a component having a carboxyl group among the polar functional group-containing components MC.
  • the (total) content of the components having a carboxyl group in all the components of the binder-forming polymer is determined as appropriate, taking into account the content of the component MA and the polar functional group-containing component MC, cohesiveness, etc. However, it is preferably 0.01 to 10% by mass, and 0.1 to 10% by mass, since it can further improve the cohesiveness of the polymer binder and firmly bind solid particles.
  • the content is more preferably 0.1 to 5% by mass, even more preferably 0.2 to 3% by mass.
  • the content of each component in the binder-forming polymer is not particularly limited except for the content of the specific component described above, and is appropriately set in consideration of the physical properties of the entire polymer.
  • the content of the constituent components in the binder-forming polymer is set, for example, so that the total content of all constituent components is 100% by mass.
  • the content of each component is the total content of the plurality of components.
  • the content of the polar functional group-containing component MC is not particularly limited, and for example, the cohesiveness of the polymer binder and the adhesion (binding property) of the solid particles are taken into consideration with respect to the total content of all the components. and can be determined accordingly.
  • the polar functional group-containing constituent component MC has a carboxyl group, it is determined in consideration of the content of the above-mentioned constituent component having a carboxy group.
  • the content of the polar functional group-containing component MC is, for example, preferably 0 to 20% by mass, more preferably 0.1 to 10% by mass, and even more preferably 1 to 8% by mass. preferable.
  • the content of other constituent components is not particularly limited, but may be 1 to 100% by mass, preferably 20 to 100% by mass, and preferably 40 to 100% by mass, based on the total content of all constituent components. It is more preferably 60 to 100 mass %, particularly preferably 80 to 100 mass %.
  • the binder-forming polymer is not particularly limited as long as it contains the above component MA in the above content, and various known polymers can be used.
  • the primary structure (the bonding mode of the constituent components) of the binder-forming polymer is not particularly limited, and may have any bonding mode such as a random structure, block structure, alternating structure, or graft structure.
  • binder-forming polymers include polymers having a polymer chain of at least one type of bond selected from urethane bonds, urea bonds, amide bonds, imide bonds, ester bonds, and carbonate bonds, or carbon-carbon double bonds in the main chain. are preferred, and polymers having a polymer chain of carbon-carbon double bonds in the main chain are more preferred.
  • the above bond is not particularly limited as long as it is included in the main chain of the polymer, and may be included in the constituent components (repeat units) and/or may be included as a bond connecting different constituent components. .
  • the number of the above-mentioned bonds contained in the main chain is not limited to one type, but may be two or more types, preferably 1 to 6 types, and more preferably 1 to 4 types.
  • the bonding mode of the main chain is not particularly limited, and it may have two or more types of bonds randomly, and the main chain may have a segmented main chain with a segment having a specific bond and a segment having another bond. It can also be a chain.
  • polymers having a urethane bond, urea bond, amide bond, imide bond, ester bond, or carbonate bond in the main chain of the above bonds include sequential polymerization (polymerization) of polyurethane, polyurea, polyamide, polyimide, polyester, polycarbonate bond, etc. (condensation, polyaddition, or addition condensation) polymers, or copolymers thereof.
  • a polymer chain of carbon-carbon double bonds refers to a polymer chain formed by polymerization of carbon-carbon double bonds (ethylenic unsaturated groups), and specifically, A polymer chain formed by polymerizing (homopolymerizing or copolymerizing) monomers having saturated bonds.
  • Examples of polymers having a polymer chain of carbon-carbon double bonds in the main chain include chain polymers such as fluorine-containing polymers, hydrocarbon polymers, vinyl polymers, and (meth)acrylic polymers. Acrylic polymers are preferred.
  • Examples of (meth)acrylic polymers include polymers consisting of (co)polymers containing 50% by mass or more of constituent components derived from (meth)acrylic compounds.
  • the content of the component derived from the (meth)acrylic compound also includes the content of these components.
  • the content of the component derived from the (meth)acrylic compound is more preferably 60% by mass or more, and even more preferably 70% by mass or more. Although the upper limit content can be 100% by mass, it can also be 97% by mass or less.
  • the (meth)acrylic polymer a copolymer with a vinyl compound (M2) other than the (meth)acrylic compound (M1) is also preferable.
  • the content of the constituent components derived from the vinyl compound (M2) is 50% by mass or less, preferably 3 to 40% by mass, and more preferably 3 to 30% by mass.
  • the above constituent components MA and MC are derived from among (meth)acrylic acid compounds, (meth)acrylic acid ester compounds, (meth)acrylamide compounds, (meth)acrylonitrile compounds, etc. Examples include compounds other than compounds. Among these, (meth)acrylic acid ester compounds are preferred. Examples of the (meth)acrylic acid ester compound include (meth)acrylic acid alkyl ester compounds, (meth)acrylic acid aryl ester compounds, etc., and (meth)acrylic acid alkyl ester compounds are preferable.
  • the number of carbon atoms in the alkyl group constituting the (meth)acrylic acid alkyl ester compound is not particularly limited, but can be, for example, 1 to 24, and preferably 3 to 20 from the viewpoint of adhesion, etc. It is more preferably from 4 to 16, and even more preferably from 6 to 14.
  • the number of carbon atoms in the aryl group constituting the aryl ester is not particularly limited, but may be, for example, 6 to 24, preferably 6 to 10, and more preferably 6.
  • the nitrogen atom of the amide group may be substituted with an alkyl group or an aryl group.
  • the vinyl compound (M2) is not particularly limited, but among vinyl compounds copolymerizable with the (meth)acrylic compound (M1), vinyl compounds other than those that lead to the above-mentioned constituent components MA and MC are preferable, for example, Aromatic vinyl compounds such as styrene compounds, vinylnaphthalene compounds, vinylcarbazole compounds, vinylimidazole compounds, and vinylpyridine compounds, as well as allyl compounds, vinyl ether compounds, vinyl ester compounds (e.g. vinyl acetate compounds), dialkyl itaconate compounds, and the above. Examples include polymerizable cyclic dicarboxylic acid anhydrides. Examples of vinyl compounds include "vinyl monomers" described in JP-A No. 2015-88486.
  • the (meth)acrylic compound (M1) and the vinyl compound (M2) may have a substituent, but one preferred embodiment is that they are unsubstituted.
  • the substituent is not particularly limited, and includes groups selected from substituents Z described below, but groups other than the polar functional groups included in the above-mentioned functional group group (a) are preferable.
  • hydrocarbon polymer examples include polyethylene, polypropylene, natural rubber, polybutadiene, polyisoprene, polystyrene, polystyrene-butadiene copolymer, styrenic thermoplastic elastomer, polybutylene, acrylonitrile-butadiene copolymer, or hydrogenated (hydrogenated) ) polymers, and copolymers with copolymerizable compounds such as (meth)acrylic compounds (M1) and vinyl compounds (M2).
  • the styrene thermoplastic elastomer or its hydride is not particularly limited, but examples include styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), and hydrogenated SIS.
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • hydrogenated SIS hydrogenated SIS
  • SBS styrene-butadiene-styrene block copolymer
  • SEEPS styrene-ethylene-ethylene-propylene-styrene block copolymer
  • SEPS styrene-ethylene-propylene-styrene block copolymer
  • SBR styrene-butadiene rubber
  • HSBR hydrogenated styrene-butadiene rubber
  • random copolymers corresponding to each of the above block copolymers such as SEBS.
  • the binder-forming polymer may have a substituent.
  • the substituent is not particularly limited, but preferably includes a group selected from the following substituents Z, but groups other than the polar functional groups included in the above-mentioned functional group group (a) are preferable.
  • Substituent Z - Alkyl group preferably an alkyl group having 1 to 20 carbon atoms, such as 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.
  • cycloalkyl group Preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl
  • alkyl group usually includes a cycloalkyl group, but it is not specified separately here. ), aryl groups (preferably aryl groups having 6 to 26 carbon atoms, such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), aralkyl groups (preferably 7 to 26 carbon atoms), 23 aralkyl groups such as benzyl, phenethyl, etc.), heterocyclic groups (preferably heterocyclic groups having 2 to 20 carbon atoms, more preferably 5 or 6 carbon atoms having at least one oxygen atom, sulfur atom, or nitrogen atom) It is a membered heterocyclic group.
  • Heterocyclic groups include aromatic heterocyclic groups and aliphatic heterocyclic groups.For example, tetrahydropyran ring group, tetrahydrofuran ring group, 2-pyridyl, 4-pyridyl, 2-
  • alkoxy group preferably an alkoxy group having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy, etc.
  • aryloxy group Preferably, an aryloxy group having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.
  • a heterocyclic oxy group an -O- group is bonded to the above heterocyclic group) group
  • an alkoxycarbonyl group preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, dodecyloxycarbonyl, etc.
  • an aryloxycarbonyl group preferably an aryl group having 6 to 26 carbon atoms
  • alkoxycarbonyl group preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as eth
  • R P is a hydrogen atom or a substituent (preferably a group selected from substituents Z). Further, each of the groups listed as the substituent Z may be further substituted by the above substituent Z.
  • the above-mentioned alkyl group, alkylene group, alkenyl group, alkenylene group, alkynyl group and/or alkynylene group may be cyclic or chain-like, and may be linear or branched.
  • the binder-forming polymer can be synthesized by selecting a raw material compound and polymerizing the raw material compound by a known method.
  • the method of incorporating each polar functional group is not particularly limited, and includes, for example, a method of copolymerizing a compound having the above polar functional group, a method of using a polymerization initiator or chain transfer agent having (generates) the above polar functional group, Examples include a method using a polymer reaction, an ene reaction on a double bond, an ene-thiol reaction, and an ATRP (Atom Transfer Radical Polymerization) polymerization method using a copper catalyst.
  • ATRP Atom Transfer Radical Polymerization
  • polar functional groups can also be introduced using functional groups present in the main chain, side chains, or ends of the polymer as reaction sites.
  • a functional group can be introduced using a compound having a polar functional group through various reactions with a dicarboxylic acid anhydride group in a polymer chain.
  • binder-forming polymers include the polymers synthesized in Examples, but the present invention is not limited thereto.
  • the polymer binder or binder-forming polymer used in the present invention preferably has the following physical properties or characteristics.
  • the weight average molecular weight of the binder-forming polymer is preferably 1.0 ⁇ 10 3 to 1.0 ⁇ 10 7 from the viewpoint of cohesiveness of the polymer binder.
  • the weight average molecular weight of the binder-forming polymer is preferably 1.0 ⁇ 10 4 or more, more preferably 3.0 ⁇ 10 4 or more, and even more preferably 1.0 ⁇ 10 5 or more.
  • the upper limit is preferably 1.0 ⁇ 10 7 or less, more preferably 5.0 ⁇ 10 6 or less, even more preferably 1.0 ⁇ 10 6 or less, and particularly preferably 5.0 ⁇ 10 5 or less.
  • the weight average molecular weight of the binder-forming polymer can be adjusted as appropriate by changing the type and content of the polymerization initiator, polymerization time, polymerization temperature, and the like.
  • the molecular weight of a polymer chain such as a polymer refers to a weight average molecular weight or a number average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).
  • the measurement method basically includes a method set under Condition 1 or Condition 2 (priority) below. However, depending on the type of polymer etc., an appropriate eluent may be selected and used.
  • the polymer binder When the binder composition contains a dispersion medium, the polymer binder may be present in a dissolved state in the dispersion medium (binder composition) or may be dispersed in the dispersion medium in the form of particles.
  • the polymer binder dissolved in the dispersion medium means that the polymer binder is dissolved in the dispersion medium in the binder composition.
  • the solubility of the polymer binder in the following solubility measurement is 50%. This means the above.
  • the polymer binder is not limited to an embodiment in which all the polymer binder is dissolved in the dispersion medium in the binder composition, but also includes an embodiment in which a part of the polymer binder is present in an insoluble state.
  • the solubility of the polymer binder in the dispersion medium is determined by the type of polymer forming the polymer binder, the composition of this polymer (types and content of constituent components), the weight average molecular weight of this polymer, and the above-mentioned polar functional group. It can be applied as appropriate depending on the type of group, its content, combination with a dispersion medium, etc.
  • the water concentration of the binder is preferably 100 ppm (based on mass) or less.
  • the binder may be obtained by crystallizing the polymer and drying it, or by using the binder dispersion as it is.
  • the binder-forming polymer is amorphous.
  • a polymer being "amorphous" typically means that no endothermic peak due to crystal melting is observed when measured at the glass transition temperature.
  • the binder-forming polymer may be a non-crosslinked polymer or a crosslinked polymer. Further, when crosslinking of the polymer progresses by heating or application of voltage, the molecular weight may be larger than the above molecular weight. Preferably, the binder-forming polymer has a weight average molecular weight within the above-mentioned range at the beginning of use of the all-solid-state secondary battery.
  • the binder-forming polymer contained in the polymer binder may be one type or two or more types. Furthermore, the polymer binder may contain other polymers, etc., as long as they do not impair the effects of the binder-forming polymer described above. As other polymers, polymers commonly used as binders for all-solid-state secondary batteries can be used without particular limitation.
  • the binder composition may contain one or more kinds of polymer binders.
  • the content CPB of the polymer binder in the binder composition is not particularly limited, but from the viewpoint of binding properties and resistance, it is preferably 1 to 70% by mass, more preferably 5 to 50% by mass.
  • the content is preferably 8 to 40% by weight, more preferably 8 to 20% by weight.
  • the binder composition preferably contains a dispersion medium.
  • the dispersion medium may be any organic compound as long as it is liquid in the usage environment, such as various organic solvents, specifically alcohol compounds, ether compounds, amide compounds, amine compounds, ketone compounds, aromatic carbonized compounds, etc. Examples include hydrogen compounds, aliphatic hydrocarbon compounds, nitrile compounds, and ester compounds.
  • the dispersion medium may be either a nonpolar dispersion medium (hydrophobic dispersion medium) or a polar dispersion medium (hydrophilic dispersion medium), but a nonpolar dispersion medium is preferred since it can exhibit excellent dispersibility.
  • a non-polar dispersion medium generally refers to a property that has a low affinity for water, but in the present invention, examples thereof include ester compounds, ketone compounds, ether compounds, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, etc. .
  • alcohol compounds include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, -Methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-butanediol.
  • ether compounds include alkylene glycols (diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.), alkylene glycol monoalkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, etc.), alkylene glycol dialkyl ethers (ethylene glycol dimethyl ether, etc.), dialkyl ethers (dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, etc.), cyclic ethers (tetrahydrofuran, dioxane (including 1,2-, 1,3- and 1,4-isomers), etc.).
  • alkylene glycols diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol
  • amide compound examples include N,N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, ⁇ -caprolactam, formamide, N-methylformamide, and acetamide. , N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, and the like.
  • Examples of the amine compound include triethylamine, diisopropylethylamine, and tributylamine.
  • Examples of ketone compounds include acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, cycloheptanone, dipropyl ketone, dibutyl ketone, diisopropyl ketone, diisobutyl ketone (DIBK), isobutylpropyl ketone, sec- Examples include butylpropylketone, pentylpropylketone, butylpropylketone, and the like.
  • Examples of aromatic hydrocarbon compounds include benzene, toluene, xylene, perfluorotoluene, and the like.
  • Examples of aliphatic hydrocarbon compounds include hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, paraffin, gasoline, naphtha, kerosene, light oil, etc. It will be done.
  • Examples of the nitrile compound include acetonitrile, propionitrile, isobutyronitrile, and the like.
  • ester compounds include ethyl acetate, propyl acetate, butyl acetate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, butyl pentanoate, pentyl pentanoate, ethyl isobutyrate, propyl isobutyrate, isopropyl isobutyrate.
  • ether compounds, ketone compounds, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, and ester compounds are preferred, and ester compounds, ketone compounds, aromatic hydrocarbon compounds, and ether compounds are more preferred.
  • the number of carbon atoms in the compound constituting the dispersion medium is not particularly limited, and is preferably from 2 to 30, more preferably from 4 to 20, even more preferably from 6 to 15, and particularly preferably from 7 to 12.
  • the boiling point of the dispersion medium at normal pressure (1 atm: 101325 Pa) is preferably 50°C or higher, more preferably 70°C or higher.
  • the upper limit is preferably 250°C or less, more preferably 220°C or less.
  • the binder composition may contain one or more types of dispersion medium.
  • the content of the dispersion medium in the binder composition is not particularly limited and can be set as appropriate.
  • it is preferably 10 to 99% by weight, more preferably 30 to 95% by weight, particularly preferably 40 to 90% by weight.
  • the binder composition may also contain various additives and, as appropriate, various components contained in the material for forming the constituent layers of the secondary battery. good.
  • the content of other components in the binder composition is not particularly limited and is determined as appropriate.
  • the binder composition of the present invention can be prepared as a mixture by mixing the polymer binder and the metal element-containing component, preferably the dispersion medium, and further other components using, for example, various commonly used mixers.
  • a binder composition is usually prepared by actively mixing a metal element-containing component with a polymer binder.
  • the content of the metal element-containing component in the prepared binder composition is excessive, the content of the metal element-containing component can also be adjusted by a normal method, for example, a purification method.
  • the mixing method is not particularly limited, and it can be carried out using a known mixer such as a ball mill, bead mill, planetary mixer, blade mixer, roll mill, kneader, disc mill, revolution mixer, narrow gap disperser, etc. can.
  • Mixing conditions are also not particularly limited.
  • the above components may be mixed all at once or sequentially.
  • Mixing conditions are not particularly limited.
  • the mixing temperature can be 15 to 50°C.
  • the mixed atmosphere may be air, dry air (dew point -20° C. or less), inert gas (for example, argon gas, helium gas, nitrogen gas), or the like.
  • the constituent layer forming material of the present invention is a composition containing the binder composition of the present invention (or the above-mentioned constituent components thereof) as a polymer binder component.
  • the constituent layer forming material is used as a constituent layer forming material of an all-solid-state secondary battery, it is referred to as a solid electrolyte-containing composition for (all-solid) secondary batteries, and is a material forming the electrode layer of a non-aqueous electrolyte secondary battery.
  • a nonaqueous electrolyte secondary battery electrode composition it is sometimes referred to as an electrode composition for a non-aqueous electrolyte secondary battery.
  • the constituent layer forming material of the present invention contains appropriate components depending on the purpose and the like.
  • a non-aqueous electrolyte secondary battery electrode composition it contains the binder composition of the present invention, an active material, and other components, dispersion medium, etc., which will be described later as appropriate.
  • the binder composition of the present invention (or the above-mentioned constituent components thereof) has conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table. It contains an inorganic solid electrolyte, an active material, a conductive aid, a dispersion medium, and other components described later.
  • each component constituting the binder composition of the present invention does not need to exist integrally as a binder composition, and each component may exist independently (separately).
  • the polymer binder is insoluble in the dispersion medium in the composition (including the dispersion medium of the binder composition; hereinafter, the same meaning unless otherwise specified) and exists in a solid state. It may be dissolved or dissolved. Dissolving in a dispersion medium has the same meaning as dissolving in the above-mentioned dispersion medium.
  • the constituent layer forming material of the present invention contains a polymer binder and a predetermined amount of a metal element-containing component, it can form a low-resistance constituent layer, and has a low-resistance constituent layer in which solid particles are tightly adhered. It is possible to manufacture sheets for all-solid-state secondary batteries, and even low-resistance all-solid-state secondary batteries.
  • the constituent layer forming material of the present invention is preferably a slurry in which solid particles are dispersed in a dispersion medium.
  • the polymer binder functions as a binder that firmly binds the solid particles together while maintaining a direct contact state in the constituent layer formed from the constituent layer forming material. Furthermore, it functions as a binder that firmly binds a base material such as a current collector and solid particles.
  • the polymer binder may or may not have a function of binding solid particles together.
  • the solid electrolyte-containing composition for secondary batteries of the present invention is preferably a non-aqueous composition.
  • the non-aqueous composition has the same meaning as the description regarding the binder composition.
  • the solid electrolyte-containing composition for secondary batteries of the present invention exhibits the above-mentioned excellent properties, it can be used in sheets for secondary batteries (preferably all-solid secondary battery sheets) and electrode layers of secondary batteries (preferably It can be used as a material for forming a constituent layer of an all-solid-state secondary battery.
  • the solid electrolyte-containing composition for a secondary battery of the present invention includes an embodiment containing an active material and the like in addition to the inorganic solid electrolyte (the composition of this embodiment is referred to as an electrode composition).
  • the composition of this embodiment is referred to as an electrode composition.
  • the solid electrolyte-containing composition for secondary batteries of the present invention contains the above-mentioned binder composition.
  • the content of the binder composition in the solid electrolyte-containing composition for secondary batteries can be appropriately determined by taking into consideration the content of the polymer binder described below, but usually, the content of the polymer binder described below The ratio is set to the amount.
  • the solid electrolyte-containing composition for secondary batteries of the present invention contains one or more metal element-containing components.
  • the metal element-containing component including the particle size in the composition, is as described above.
  • the metal element-containing component contained in the solid electrolyte-containing composition for secondary batteries is usually derived from the above-mentioned binder composition.
  • the above-mentioned metal elements used in the binder composition are added to the binder composition. Ingredients can also be added and mixed as appropriate.
  • the metal element-containing component to be added and mixed may be the same or different from the metal element-containing component in the binder composition.
  • the content CMS of the metal element-containing component in the solid electrolyte-containing composition for secondary batteries is not particularly limited, and may be appropriately set depending on the content in the binder composition, the amount used of the binder composition, etc. Ru.
  • the content CMS of the metal element-containing component is the above-mentioned content CMB of the metal element-containing component in the binder composition, and the above usage amount of the binder composition in the solid electrolyte-containing composition for secondary batteries.
  • the range can be calculated by the product of .
  • the content C MS of the metal element-containing component is 1.0 ⁇ 10 -6 to 1 in the solid electrolyte-containing composition for secondary batteries, since it can further suppress the increase in resistance while maintaining the battery function. It is preferably .0 ⁇ 10 4 ppm, more preferably 1.0 ⁇ 10 ⁇ 3 to 1.0 ⁇ 10 4 ppm, and 1.0 ⁇ 10 ⁇ 3 to 1.0 ⁇ 10 2 ppm. It is more preferably 1.0 ⁇ 10 ⁇ 2 to 1.0 ⁇ 10 ppm, particularly preferably 1.0 ⁇ 10 ⁇ 2 to 1.0 ppm, and 1.0 ⁇ 10 -2 to 3.0 ⁇ 10 ⁇ 1 ppm is most preferred.
  • the content CMS can be measured or calculated in the same manner as the content CMB .
  • the ratio of the content C MS of the metal element-containing component to the content C PS of the polymer binder [C MS /C PS ] is not particularly limited and may be determined as appropriate, for example. , is preferably the same as the above-mentioned ratio [C MB /C PB ].
  • the solid electrolyte-containing composition for secondary batteries of the present invention contains one or more polymer binders derived from the above-mentioned binder compositions.
  • the polymer binder is as described above.
  • the above-mentioned polymer binder used in the binder composition can also be appropriately added and mixed.
  • the polymer binder to be added and mixed may be the same or different from the polymer binder in the binder composition.
  • the content C PS of the polymer binder in the solid electrolyte-containing composition for secondary batteries is not particularly limited, but is 0.1 to 8.0% by mass in terms of ionic conductivity and further binding properties.
  • the content is preferably from 0.2 to 4.0% by mass, and even more preferably from 0.3 to 2.5% by mass. Further, for the same reason, the content of the polymer binder in 100% by mass of the solid content of the solid electrolyte-containing composition for secondary batteries is preferably 0.1 to 10.0% by mass, and 0.3% by mass. It is more preferably 5.0% by mass, and even more preferably 0.4% to 3.0% by mass.
  • the mass ratio of the total mass (total amount) of the inorganic solid electrolyte and active material to the mass of the polymer binder is preferably in the range of 1,000 to 1. This ratio is more preferably 500-2, and even more preferably 100-10.
  • the solid electrolyte-containing composition for secondary batteries of the present invention contains an inorganic solid electrolyte.
  • the inorganic solid electrolyte refers to an inorganic solid electrolyte
  • the solid electrolyte refers to a solid electrolyte that can move ions within it. Because it does not contain organic substances as the main ion-conducting material, organic solid electrolytes (polymer electrolytes such as polyethylene oxide (PEO), organic materials such as lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)) It is clearly distinguished from electrolyte salts).
  • PEO polyethylene oxide
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide
  • the inorganic solid electrolyte is solid in a steady state, it is not normally dissociated or liberated into cations and anions. In this respect, it is clearly distinguishable from inorganic electrolyte salts (LiPF 6 , LiBF 4 , lithium bis(fluorosulfonyl)imide (LiFSI), LiCl, etc.) that are dissociated or liberated into cations and anions in electrolytes or polymers. be done.
  • the inorganic solid electrolyte is not particularly limited as long as it has conductivity for metal ions belonging to Group 1 or Group 2 of the periodic table, and generally does not have electron conductivity.
  • the inorganic solid electrolyte solid electrolyte materials commonly used in all-solid-state secondary batteries can be appropriately selected and used.
  • the inorganic solid electrolytes include (i) sulfide-based inorganic solid electrolytes, (ii) oxide-based inorganic solid electrolytes, (iii) halide-based inorganic solid electrolytes, and (iv) hydride-based inorganic solid electrolytes. Sulfide-based inorganic solid electrolytes are preferred from the viewpoint of being able to form a better interface between the active material and the inorganic solid electrolyte.
  • the all-solid-state secondary battery of the present invention is a lithium ion battery
  • the inorganic solid electrolyte preferably has ion conductivity for lithium ions.
  • Sulfide-based inorganic solid electrolyte contain sulfur atoms, have the ionic conductivity of metals belonging to Group 1 or 2 of the periodic table, and are electronically insulating. It is preferable that the material has a certain property.
  • the sulfide-based inorganic solid electrolyte preferably contains at least Li, S, and P as elements and has lithium ion conductivity, but may contain other elements other than Li, S, and P as appropriate. .
  • Examples of the sulfide-based inorganic solid electrolyte include a lithium ion conductive inorganic solid electrolyte that satisfies the composition represented by the following formula (S1).
  • L a1 M b1 P c1 S d1 A e1 (S1)
  • L represents an element selected from Li, Na, and K, with Li being preferred.
  • 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 indicate the composition ratio of each element, 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, more preferably 1.5 to 7.5.
  • b1 is preferably 0 to 3, more preferably 0 to 1.
  • d1 is preferably 2.5 to 10, more preferably 3.0 to 8.5.
  • e1 is preferably 0 to 5, more preferably 0 to 3.
  • composition ratio of each element can be controlled by adjusting the blending amount 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 partially crystallized.
  • Li-P-S glass containing Li, P, and S, or Li-P-S glass ceramic containing Li, P, and S can be used.
  • Sulfide-based inorganic solid electrolytes include, for example, lithium sulfide (Li 2 S), phosphorus sulfide (e.g. diphosphorus pentasulfide (P 2 S 5 )), elemental phosphorus, elemental sulfur, sodium sulfide, hydrogen sulfide, lithium halide (e.g. LiI, LiBr, LiCl) and sulfides of the elements represented by M (for example, SiS 2 , SnS, GeS 2 ) can be produced by reacting at least two raw materials.
  • Li 2 S lithium sulfide
  • phosphorus sulfide e.g
  • the ratio of Li 2 S to P 2 S 5 in Li-P-S glass and Li-P-S glass ceramics is a molar ratio of Li 2 S:P 2 S 5 , preferably 60:40 to 60:40.
  • the ratio is 90:10, more preferably 68:32 to 78:22.
  • the lithium ion conductivity can be made high.
  • the lithium ion conductivity can be preferably set to 1 ⁇ 10 ⁇ 4 S/cm or higher, more preferably 1 ⁇ 10 ⁇ 3 S/cm or higher. Although there is no particular upper limit, it is practical to set it to 1 ⁇ 10 ⁇ 1 S/cm or less.
  • Li 2 SP 2 S 5 Li 2 SP 2 S 5 , Li 2 SP 2 S 5 -LiCl, Li 2 SP 2 S 5 -H 2 S, Li 2 SP 2 S 5 -H 2 S-LiCl, Li 2 S-LiI-P 2 S 5 , Li 2 S-LiI-Li 2 OP 2 S 5 , Li 2 S-LiBr-P 2 S 5 , Li 2 S-Li 2 OP 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-GeS 2 , Li 2
  • amorphization method examples include a mechanical milling method, a solution method, and a melt quenching method. This is because processing at room temperature becomes possible and the manufacturing process can be simplified.
  • Oxide-based inorganic solid electrolyte contain oxygen atoms, have the ionic conductivity of metals belonging to Group 1 or 2 of the periodic table, and are electronically insulating. It is preferable that the material has a certain property.
  • 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 It is particularly preferable that it is at least /cm.
  • the upper limit is not particularly limited, but it is practical to be 1 ⁇ 10 ⁇ 1 S/cm or less.
  • Li xa La ya TiO 3 [xa satisfies 0.3 ⁇ xa ⁇ 0.7, and ya satisfies 0.3 ⁇ ya ⁇ 0.7. ]
  • LLT Li xb La yb Zr zb M bb mb Onb
  • M bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In and Sn Yes.
  • Li xc Byc M cc zc O nc (M cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In, and Sn.
  • xc is 0 ⁇ xc ⁇ 5 yc satisfies 0 ⁇ yc ⁇ 1, zc satisfies 0 ⁇ zc ⁇ 1, and nc satisfies 0 ⁇ nc ⁇ 6.); Li xd (Al, Ga) yd (Ti, Ge) zd Si ad P md O nd (xd satisfies 1 ⁇ xd ⁇ 3, yd satisfies 0 ⁇ yd ⁇ 1, zd satisfies 0 ⁇ zd ⁇ 2, ad satisfies 0 ⁇ ad ⁇ 1, md satisfies 1 ⁇ md ⁇ 7, nd satisfies 3 ⁇ nd ⁇ 13); Li (3-2xe) Mee xe D ee O (xe represents a number from 0 to 0.1, and M ee represents a divalent Represents a metal atom.Dee represents a halogen atom or a combination of two or more halogen atoms)
  • Li 7 La 3 Zr 2 O 12 (LLZ) having a garnet-type crystal structure.
  • phosphorus compounds containing Li, P and O include lithium phosphate (Li 3 PO 4 ); LiPON in which a part of the oxygen element of lithium phosphate is replaced with a nitrogen element; LiPOD 1 (D 1 is preferably Ti, V, Cr, Mn, Fe, Co, One or more elements selected from Ni, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt, and Au.
  • LiA 1 ON (A 1 is one or more elements selected from Si, B, Ge, Al, C, and Ga) can also be preferably used.
  • Halide-based inorganic solid electrolyte contains a halogen atom, has ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and has electron conductivity. Compounds having insulating properties are preferred.
  • the halide-based inorganic solid electrolyte include, but are not particularly limited to, compounds such as LiCl, LiBr, LiI, Li 3 YBr 6 and Li 3 YCl 6 described in ADVANCED MATERIALS, 2018, 30, 1803075. Among these, Li 3 YBr 6 and Li 3 YCl 6 are preferred.
  • Hydride-based inorganic solid electrolyte contains hydrogen atoms, has the ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is electronically insulating. Compounds having properties are preferred.
  • Examples of the hydride-based inorganic solid electrolyte include, but are not limited to, LiBH 4 , Li 4 (BH 4 ) 3 I, 3LiBH 4 -LiCl, and the like.
  • the inorganic solid electrolyte is preferably in the form of particles in the solid electrolyte-containing composition for secondary batteries.
  • the 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, more preferably 50 ⁇ m or less.
  • the particle size of the inorganic solid electrolyte is measured by the following procedure. A 1% by mass dispersion of inorganic solid electrolyte particles is prepared by diluting the inorganic solid electrolyte particles in a 20 mL sample bottle using water (or heptane in the case of a substance unstable in water).
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes, and immediately thereafter used for the test.
  • data was acquired 50 times using a laser diffraction/scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA) at a temperature of 25°C using a quartz cell for measurement. Obtain the volume average particle size.
  • JIS Japanese Industrial Standards
  • Z 8828:2013 Particle Size Analysis - Dynamic Light Scattering Method
  • the method for adjusting the particle size is not particularly limited, and any known method can be applied, such as a method using a normal pulverizer or classifier.
  • a normal pulverizer or classifier for example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling jet mill, a sieve, etc. are suitably used.
  • wet pulverization can be performed in the presence of a dispersion medium such as water or methanol.
  • classification is not particularly limited, and can be performed using a sieve, a wind classifier, or the like. Both dry and wet classification can be used.
  • the solid electrolyte-containing composition for secondary batteries may contain one or more types of inorganic solid electrolytes.
  • the content of the inorganic solid electrolyte in the solid electrolyte-containing composition for secondary batteries is not particularly limited, but from the viewpoint of binding properties and further dispersion properties, the content of the inorganic solid electrolyte is 50% by mass or more based on 100% by mass of solid content. It is preferably 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 90% by mass or more. From the same viewpoint, the upper limit is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less.
  • the content of the inorganic solid electrolyte in the solid electrolyte-containing composition for secondary batteries is the total content of the active material and the inorganic solid electrolyte. It is preferable that the amount is within the above range.
  • the solid content (solid component) refers to the solid content (solid component) that does not disappear by volatilization or evaporation when the solid electrolyte-containing composition for a secondary battery is dried at 150°C for 6 hours under an atmospheric pressure of 1 mmHg and a nitrogen atmosphere.
  • ingredients Typically, it refers to components other than the dispersion medium described below.
  • the solid electrolyte-containing composition for a secondary battery of the present invention preferably contains an active material capable of inserting and releasing ions of metals belonging to Group 1 or Group 2 of the periodic table.
  • the active material include a positive electrode active material and a negative electrode active material, which will be explained below.
  • a solid electrolyte-containing composition for a secondary battery containing an active material positive electrode active material or negative electrode active material
  • an electrode composition positive electrode composition or negative electrode composition
  • the positive electrode active material is an active material capable of inserting and extracting metal ions belonging to Group 1 or Group 2 of the periodic table, and is preferably one that can reversibly insert and release lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, and may be a transition metal oxide or an element such as sulfur that can be complexed with Li. Among these, it is preferable to use a transition metal oxide as the positive electrode active material, and a transition metal oxide containing a transition metal element M a (one or more elements selected from Co, Ni, Fe, Mn, Cu, and V) is preferable. more preferable.
  • this transition metal oxide contains elements M b (elements of group 1 (Ia) of the periodic table of metals other than lithium, elements of group 2 (IIa) of the periodic table of metals, Al, Ga, In, Ge, Sn, Pb, Elements such as Sb, Bi, Si, P, and B may be mixed.
  • the mixing amount is preferably 0 to 30 mol % based on the amount of transition metal element M a (100 mol %). More preferably, it is synthesized by mixing Li/M a in a molar ratio of 0.3 to 2.2.
  • transition metal oxides include (MA) transition metal oxides having a layered rock salt structure, (MB) transition metal oxides having a spinel structure, (MC) lithium-containing transition metal phosphate compounds, (MD ) Lithium-containing transition metal halide phosphoric acid compounds and (ME) lithium-containing transition metal silicate compounds.
  • transition metal oxides having a layered rock salt type structure include LiCoO 2 (lithium cobalt oxide [LCO]), LiNi 2 O 2 (lithium nickel oxide), LiNi 0.85 Co 0.10 Al 0. 05 O 2 (nickel cobalt lithium aluminate [NCA]), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (nickel manganese cobalt lithium [NMC]), and LiNi 0.5 Mn 0.5 O 2 ( lithium manganese nickelate).
  • LiCoO 2 lithium cobalt oxide [LCO]
  • LiNi 2 O 2 lithium nickel oxide
  • LiNi 0.85 Co 0.10 Al 0. 05 O 2 nickel cobalt lithium aluminate [NCA]
  • LiNi 1/3 Co 1/3 Mn 1/3 O 2 nickel manganese cobalt lithium [NMC]
  • LiNi 0.5 Mn 0.5 O 2 lithium manganese nickelate
  • transition metal oxides having a spinel structure 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 2NiMn3O8 is mentioned .
  • LMO LiMn 2 O 4
  • MC lithium-containing transition metal phosphate compounds
  • iron pyrophosphates such as LiFeP 2 O 7 , LiCoPO 4 , etc.
  • lithium-containing transition metal halide phosphate compounds include iron fluorophosphates such as Li 2 FePO 4 F, manganese fluorophosphates such as Li 2 MnPO 4 F, and Li 2 CoPO 4 F.
  • Examples include cobalt fluoride phosphates such as.
  • ME Examples of the lithium-containing transition metal silicate compound include Li 2 FeSiO 4 , Li 2 MnSiO 4 , Li 2 CoSiO 4 , and the like.
  • (MA) transition metal oxides having a layered rock salt type structure are preferred, and LCO or NMC is more preferred.
  • the shape of the positive electrode active material is not particularly limited, it is preferably particulate in the solid electrolyte-containing composition for secondary batteries.
  • the particle size (volume average particle size) of the positive electrode active material is not particularly limited. For example, it can be 0.1 to 50 ⁇ m.
  • the particle size of the positive electrode active material particles can be measured in the same manner as the particle size of the inorganic solid electrolyte.
  • the positive electrode active material obtained by the calcination method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
  • the solid electrolyte-containing composition for secondary batteries of the present invention may contain one or more types of positive electrode active materials.
  • the content of the positive electrode active material in the solid electrolyte-containing composition for secondary batteries is not particularly limited, and is preferably 10 to 97% by mass, more preferably 30 to 95% by mass, and 40 to 97% by mass, more preferably 30 to 95% by mass, based on 100% by mass of solid content. It is more preferably from 93% by weight, and particularly preferably from 50 to 90% by weight.
  • the negative electrode active material is an active material capable of inserting and extracting ions of metals belonging to Group 1 or Group 2 of the periodic table, and is preferably one that can reversibly insert and release lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, such as carbonaceous materials, metal oxides, metal composite oxides, lithium alone, lithium alloys, and negative electrode active materials that can be alloyed with lithium. Examples include substances. Among these, carbonaceous materials, metal composite oxides, or lithium alone are preferably used from the viewpoint of reliability.
  • An active material that can be alloyed with lithium is preferable in terms of increasing the capacity of an all-solid-state secondary 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, etc.
  • various synthetic materials such as PAN (polyacrylonitrile) resin or furfuryl alcohol resin.
  • PAN polyacrylonitrile
  • furfuryl alcohol resin examples include carbonaceous materials obtained by firing resin.
  • various carbon fibers such as PAN carbon fiber, cellulose carbon fiber, pitch carbon fiber, vapor grown carbon fiber, dehydrated PVA (polyvinyl alcohol) carbon fiber, lignin carbon fiber, glassy carbon fiber, and activated carbon fiber.
  • These carbonaceous materials can also be divided into non-graphitizable carbonaceous materials (also referred to as 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 need to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite with a coating layer as described in JP-A-6-4516, etc. may be used. You can also do it.
  • hard carbon or graphite is preferably used, and graphite is more preferably used.
  • the oxide of a metal or metalloid element used as a negative electrode active material is not particularly limited as long as it is an oxide that can absorb and release lithium, and metal element oxides (metal oxides) and composites of metal elements can be used. Examples 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). As these oxides, amorphous oxides are preferred, and chalcogenides, which are reaction products of metal elements and elements of group 16 of the periodic table, are also preferred.
  • a metalloid element refers to an element that exhibits intermediate properties between a metal element and a non-metallic element, and usually includes six elements: boron, silicon, germanium, arsenic, antimony, and tellurium, and further includes selenium. , polonium and astatine.
  • amorphous means that it has a broad scattering band with an apex in the 2 ⁇ value range of 20° to 40° when measured by X-ray diffraction using CuK ⁇ rays, and crystalline diffraction lines are not observed. May have.
  • the strongest intensity of the crystalline diffraction lines observed at 2 ⁇ values of 40° to 70° is 100 times or less than the diffraction line intensity at the top of the broad scattering band observed at 2 ⁇ values of 20° to 40°. , more preferably 5 times or less, and particularly preferably no crystalline diffraction lines.
  • amorphous oxides of metalloid elements or the above-mentioned chalcogenides are more preferable, and elements of groups 13 (IIIB) to 15 (VB) of the periodic table (e.g. , Al, Ga, Si, Sn, Ge, Pb, Sb and Bi) or a (composite) oxide or chalcogenide consisting of one selected from the group consisting of one or a combination of two or more thereof is particularly preferred.
  • preferable amorphous oxides and chalcogenides include, 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 , Sb 2 O4 , Sb2O8Bi2O3 , Sb2O8Si2O3 , Sb2O5 , Bi2O3 , Bi2O4 , GeS , PbS , PbS2 , Sb2S3 or Sb2 S5 is preferred.
  • negative electrode active materials that can be used in conjunction with amorphous oxides mainly containing Sn, Si, and Ge include carbonaceous materials that can absorb and/or desorb lithium ions or lithium metal, lithium alone, lithium alloys, and lithium.
  • Preferred examples include negative electrode active materials that can be alloyed with.
  • the oxide of a metal or metalloid element particularly the metal (composite) oxide and the chalcogenide described above, preferably contain at least one of titanium and lithium as a constituent from the viewpoint of high current density charge/discharge characteristics.
  • the metal composite oxide containing lithium (lithium composite metal oxide) is, for example, a composite oxide of lithium oxide and the above metal (composite) oxide or the above chalcogenide, more specifically, Li 2 SnO 2 Can be mentioned. It is also preferable that the negative electrode active material, such as a metal oxide, contains a titanium element (titanium oxide).
  • Li 4 Ti 5 O 12 lithium titanate [LTO]
  • Li 4 Ti 5 O 12 has excellent rapid charging and discharging characteristics due to its small volume fluctuation when intercalating and releasing lithium ions, suppresses electrode deterioration, and is used as a lithium ion secondary material. This is preferable in that the battery life can be improved.
  • the lithium alloy as the negative electrode active material is not particularly limited as long as it is an alloy commonly used as the negative electrode active material of secondary batteries. % added lithium aluminum alloy.
  • the negative electrode active material capable of forming an alloy with lithium is not particularly limited as long as it is commonly used as a negative electrode active material of secondary batteries.
  • active materials include (negative electrode) active materials (alloys, etc.) containing silicon element or tin element, and metals such as Al and In, and negative electrode active materials containing silicon element that enable higher battery capacity.
  • (Silicon element-containing active material) is preferable, and a silicon element-containing active material in which the content of silicon element is 50 mol% or more of all constituent elements is more preferable.
  • negative electrodes containing these negative electrode active materials are carbon negative electrodes (such as graphite and acetylene black).
  • carbon negative electrodes such as graphite and acetylene black
  • silicon-containing active materials include silicon materials such as Si and SiOx (0 ⁇ x ⁇ 1), and silicon-containing alloys containing titanium, vanadium, chromium, manganese, nickel, copper, lanthanum, etc.
  • SiOx itself can be used as a negative electrode active material (semi-metal oxide), and since SiOx generates Si when operating an all-solid-state secondary battery, it can be used as a negative electrode active material that can be alloyed with lithium (semi-metallic oxide). (precursor substances).
  • Examples of the negative electrode active material containing the tin element include Sn, SnO, SnO 2 , SnS, SnS 2 , and active materials containing the silicon element and tin element described above. Further, a composite oxide with lithium oxide, for example, Li 2 SnO 2 can also be used.
  • the above-mentioned negative electrode active materials can be used without particular limitation, but from the viewpoint of battery capacity, negative electrode active materials that can be alloyed with lithium are preferred as negative electrode active materials, and among them, negative electrode active materials that can be alloyed with lithium are preferred.
  • the silicon material or silicon-containing alloy alloy containing silicon element
  • the chemical formula of the compound obtained by the above firing method can be calculated using inductively coupled plasma (ICP) emission spectrometry as a measurement method, or from the difference in mass of the powder before and after firing as a simple method.
  • ICP inductively coupled plasma
  • the shape of the negative electrode active material is not particularly limited, it is preferably particulate in the solid electrolyte-containing composition for secondary batteries.
  • the particle size of the negative electrode active material is not particularly limited, but is preferably 0.1 to 60 ⁇ m.
  • the particle size of the negative electrode active material particles can be measured in the same manner as the particle size of the inorganic solid electrolyte.
  • the solid electrolyte-containing composition for secondary batteries of the present invention may contain one or more negative electrode active materials.
  • the content of the negative electrode active material in the solid electrolyte-containing composition for secondary batteries is not particularly limited, and is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, based on 100% by mass of solid content.
  • the content is preferably 30 to 80% by mass, more preferably 40 to 75% by mass.
  • the negative electrode active material layer when the negative electrode active material layer is formed by charging the secondary battery, a metal belonging to Group 1 or Group 2 of the periodic table, which is generated in the all-solid-state secondary battery, is used instead of the negative electrode active material. Ions can be used. A negative electrode active material layer can be formed by combining these ions with electrons and depositing them as metal.
  • the surfaces of the positive electrode active material and the negative electrode active material may be coated with another metal oxide.
  • the surface coating agent include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si, or Li. Specific examples include spinel titanate, tantalum oxides, niobium oxides, lithium niobate compounds, and specific examples include Li 4 Ti 5 O 12 , Li 2 Ti 2 O 5 , LiTaO 3 , LiNbO 3 , LiAlO 2 , Li 2 ZrO 3 , Li 2 WO 4 , Li 2 TiO 3 , Li 2 B 4 O 7 , Li 3 PO 4 , Li 2 MoO 4 , Li 3 BO 3 , LiBO 2 , Li 2 CO 3 , Li 2 SiO 3 , SiO 2 , TiO 2 , ZrO 2 , Al 2 O 3 , B 2 O 3 and the like.
  • the electrode surface containing the positive electrode active material or the negative electrode active material may be surface-treated with sulfur or phosphorus.
  • the particle surface of the positive electrode active material or the negative electrode active material may be surface-treated with active light or active gas (plasma, etc.) before or after the surface coating.
  • the solid electrolyte-containing composition for secondary batteries of the present invention may contain a conductive additive.
  • a conductive additive there are no particular limitations on the conductive aid, and those known as general conductive aids can be used.
  • electron 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 fibers, or carbon nanotubes.
  • a conductive additive is one that does not insert or release ions (ions) and does not function as an active material. Therefore, among conductive aids, those that can function as active materials in the active material layer when the battery is charged and discharged are classified as active materials rather than conductive aids. Whether or not it functions as an active material when charging and discharging a battery is not unique, but is determined by the combination with the active material.
  • the conductive aid is preferably in the form of particles in the solid electrolyte-containing composition for secondary batteries.
  • the particle diameter (volume average particle diameter) of the conductive aid is not particularly limited, but is preferably 0.02 to 1.0 ⁇ m, more preferably 0.03 to 0.5 ⁇ m. preferable.
  • the particle size of the conductive aid can be measured in the same manner as the particle size of the inorganic solid electrolyte.
  • the solid electrolyte-containing composition for secondary batteries may contain one or more types of conductive aids.
  • the content of the conductive aid in the solid electrolyte-containing composition for secondary batteries is 0 to 10% by mass based on 100% by mass of solid content. %, more preferably 1 to 5% by mass.
  • the solid electrolyte-containing composition for secondary batteries of the present invention may contain a dispersion medium.
  • the dispersion medium contained in the solid electrolyte-containing composition for a secondary battery include a dispersion medium derived from a binder composition, a dispersion medium used when preparing a solid electrolyte-containing composition for a secondary battery, and the like.
  • Such a dispersion medium may be any organic compound that disperses or dissolves each of the above-mentioned components and is liquid in the usage environment, such as the above-mentioned organic solvents explained in the binder composition. , preferred ones are also the same.
  • the dispersion medium used when preparing the solid electrolyte-containing composition for secondary batteries may be the same or different from the dispersion medium in the binder composition.
  • the solid electrolyte-containing composition for secondary batteries may contain one or more types of dispersion medium.
  • the content of the dispersion medium in the solid electrolyte-containing composition for secondary batteries is not particularly limited and can be set as appropriate.
  • the content of the dispersion medium in the solid electrolyte-containing composition for secondary batteries is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass.
  • the solid electrolyte-containing composition for a secondary battery of the present invention contains a lithium salt (supporting electrolyte).
  • the lithium salt is preferably a lithium salt that is normally used in this type of product, and is not particularly limited.
  • the lithium salts described in paragraphs 0082 to 0085 of JP-A No. 2015-088486 are preferable.
  • the content of the lithium salt is preferably 0.1 parts by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the solid electrolyte.
  • the upper limit is preferably 50 parts by mass or less, more preferably 20 parts by mass or less.
  • the solid electrolyte-containing composition for secondary batteries of the present invention does not need to contain any dispersant other than this polymer binder, but may contain a dispersant. Good too.
  • the dispersant those commonly used in all-solid-state secondary batteries can be appropriately selected and used. Generally, compounds intended for particle adsorption and steric repulsion and/or electrostatic repulsion are preferably used.
  • the solid electrolyte-containing composition for a secondary battery of the present invention contains an ionic liquid, a thickener, and a crosslinking agent (which undergoes a crosslinking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization) as appropriate components other than the above-mentioned components. etc.), a polymerization initiator (such as one that generates acid or radicals by heat or light), an antifoaming agent, a leveling agent, a dehydrating agent, an antioxidant, etc.
  • the ionic liquid is contained in order to further improve the ionic conductivity, and any known ionic liquid can be used without particular limitation. Furthermore, it may contain polymers other than the above-mentioned binder-forming polymers, commonly used binders, and the like.
  • the constituent layer forming material of the present invention can be prepared as a mixture, preferably as a slurry, by mixing the above-mentioned binder composition and each of the above-mentioned components depending on the use, for example, in the above-mentioned mixer. .
  • the above-mentioned polymer binder, the above-mentioned metal element-containing component, and each of the above-mentioned components depending on the application The constituent layer forming material can also be prepared by mixing them in a proportion that provides a predetermined content in the constituent layer forming material.
  • the mixing conditions are not particularly limited, and include, for example, the mixing conditions in preparing the binder composition described above. Note that since the inorganic solid electrolyte easily reacts with moisture, it is preferable to perform the mixing under dry air or in an inert gas.
  • a sheet for a nonaqueous secondary battery can be produced using the constituent layer forming material of the present invention.
  • This sheet for a non-aqueous secondary battery is a sheet-like molded product that can form an electrode layer of a non-aqueous secondary battery, and includes various embodiments depending on its use.
  • An all-solid-state secondary battery sheet which is a preferred form of a non-aqueous secondary battery sheet, will be explained below, but the following contents of this all-solid-state secondary battery sheet also apply to non-aqueous secondary battery sheets Applicable.
  • the all-solid-state secondary battery sheet of the present invention is a sheet-like molded product that can form a constituent layer of an all-solid-state secondary battery, and includes various embodiments 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
  • a sheet preferably used for an electrode or a laminate of an electrode and a solid electrolyte layer (all-solid-state secondary battery electrode) sheets
  • these various sheets are collectively referred to as sheets for all-solid-state secondary batteries.
  • each layer constituting the all-solid-state secondary battery sheet may have a single-layer structure or a multi-layer structure.
  • the solid electrolyte layer or the active material layer is formed from the solid electrolyte-containing composition for secondary batteries of the present invention.
  • the constituent layer formed of the solid electrolyte-containing composition for secondary batteries of the present invention is formed of components derived from the solid electrolyte-containing composition for secondary batteries, and is usually composed of solid particles (inorganic solid electrolytes and conductive aids). (active material) and polymer binder are mixed together and firmly adhered (bound). Moreover, it is preferable that the polymer binder interacts with the metal element-containing component and aggregates.
  • This sheet for an all-solid-state secondary battery can realize lower resistance of an all-solid-state secondary battery by appropriately peeling off the base material or by incorporating it into an all-solid-state secondary battery as it is.
  • the solid electrolyte sheet for an all-solid-state secondary battery of the present invention may be any sheet that has a solid electrolyte layer, and may be a sheet in which the solid electrolyte layer is formed on a base material or a sheet that does not have a base material and has a solid electrolyte layer. It may also be a sheet formed from a base material (a sheet from which the base material has been peeled off).
  • the solid electrolyte sheet for an all-solid-state secondary battery may have other layers in addition to the solid electrolyte layer. Examples of other layers include a protective layer (release sheet), a current collector, and a coat layer.
  • the solid electrolyte layer included in the solid electrolyte sheet for all-solid-state secondary batteries is preferably formed of the solid electrolyte-containing composition for secondary batteries of the present invention.
  • the content of each component in this solid electrolyte layer is not particularly limited, but preferably has the same meaning as the content of each component in the solid content of the solid electrolyte-containing composition for a secondary battery of the present invention.
  • the layer thickness of each layer constituting the solid electrolyte sheet for an all-solid-state secondary battery is the same as the layer thickness of each layer explained in the all-solid-state secondary battery described below.
  • the base material is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include sheets (plates) of materials such as materials described below for the current collector, organic materials, and inorganic materials.
  • the organic material include various polymers, and specific examples include polyethylene terephthalate, polypropylene, polyethylene, cellulose, and the like.
  • inorganic materials include glass and ceramics.
  • the electrode sheet for all-solid-state secondary batteries may be any electrode sheet having an active material layer, and the active material layer may be formed on a base material (current collector).
  • the active material layer may be a sheet formed from an active material layer without a base material (a sheet from which the base material has been peeled off).
  • This electrode sheet is usually a sheet having a current collector and an active material layer, but there are also embodiments in which the current collector, an active material layer, and a solid electrolyte layer are included in this order, and a current collector, an active material layer, and a solid electrolyte layer. Also included are embodiments having layers and active material layers in this order.
  • the active material layer and, if appropriate, the solid electrolyte layer of the electrode sheet are preferably formed from the solid electrolyte-containing composition for secondary batteries of the present invention.
  • the content of each component in this solid electrolyte layer or active material layer is not particularly limited, but preferably has the same meaning as the content of each component in the solid content of the solid electrolyte-containing composition for a secondary battery of the present invention. be.
  • the layer thickness of each layer constituting the electrode sheet of the present invention is the same as the layer thickness of each layer explained in the all-solid-state secondary battery described below.
  • the electrode sheet may have other layers mentioned above. Note that when the solid electrolyte layer or the active material layer is not formed from the solid electrolyte-containing composition for secondary batteries of the present invention, it is formed from a normal constituent layer forming material.
  • the all-solid-state secondary battery sheet of the present invention at least one of the constituent layers is formed from the solid electrolyte-containing composition for secondary batteries of the present invention. Therefore, the all-solid-state secondary battery sheet of the present invention includes a constituent layer in which the solid particles are firmly bound together while suppressing an increase in the interfacial resistance of the solid particles. Therefore, by incorporating this constituent layer into an all-solid-state secondary battery, lower resistance (higher conductivity) of the all-solid-state secondary battery can be realized.
  • the all-solid-state secondary battery sheet of the present invention is suitably used as a sheet-like member incorporated as a constituent layer of an all-solid-state secondary battery.
  • the method for producing the all-solid-state secondary battery sheet of the present invention is not particularly limited, and can be produced by forming the above-mentioned constituent layers using the solid electrolyte-containing composition for secondary batteries of the present invention. Form a layer (coated dry layer) of the solid electrolyte-containing composition for secondary batteries by forming a film (coating and drying) preferably on the base material or current collector (possibly with another layer interposed). One method is to do so. Thereby, an all-solid-state secondary battery sheet having a base material or a current collector and a coating drying layer can be produced.
  • the applied dry layer is a layer formed by applying the solid electrolyte-containing composition for secondary batteries of the present invention and drying the dispersion medium and organic solvent (i.e., the solid electrolyte-containing composition for secondary batteries of the present invention).
  • the dispersion medium and organic solvent may remain in the constituent layers and the coated dry layer as long as they do not impair the effects of the present invention, and the remaining amount may be, for example, 3% by mass or less in each layer. can.
  • each process such as coating and drying will be explained in the following method for manufacturing an all-solid-state secondary battery.
  • the coated dry layer obtained as described above can also be pressurized. Pressurization conditions and the like will be explained in the method for manufacturing an all-solid-state secondary battery, which will be described later.
  • the base material, the protective layer (particularly the release sheet), etc. can also be peeled off.
  • the nonaqueous 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 an electrolyte layer disposed between the positive electrode active material layer and the negative electrode active material layer. .
  • the nonaqueous secondary battery of the present invention is not particularly limited in other configurations as long as it has an electrolyte layer between the positive electrode active material layer and the negative electrode active material layer. configuration can be adopted.
  • the all-solid-state 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 all-solid-state secondary battery of the present invention is not particularly limited in other configurations as long as it has a solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer. configuration can be adopted.
  • the positive electrode active material layer is preferably formed on the positive electrode current collector and constitutes a positive electrode.
  • the negative electrode active material layer is preferably formed on the negative electrode current collector and constitutes a negative electrode.
  • each constituent layer (including a current collector, etc.) constituting the all-solid-state secondary battery may have a single-layer structure or a multi-layer structure.
  • the solid electrolyte layer, the negative electrode active material layer, and the positive electrode active material layer is formed from the solid electrolyte-containing composition for secondary batteries of the present invention. It is also a preferred embodiment that the solid electrolyte layer and either the negative electrode active material layer or the positive electrode active material layer are both formed of the solid electrolyte-containing composition for secondary batteries of the present invention. Another preferred embodiment is that both the negative electrode active material layer and the positive electrode active material layer are formed of the solid electrolyte-containing composition for secondary batteries of the present invention.
  • the electrode sheet be formed of the electrode sheet for use in an all-solid-state secondary battery of the present invention, and it is also one of the preferable embodiments that both of the electrode sheets be formed of the electrode sheet for an all-solid-state secondary battery of the present invention.
  • all the layers are formed from the solid electrolyte-containing composition for secondary batteries of the present invention.
  • forming the constituent layers of an all-solid-state secondary battery with the solid electrolyte-containing composition for a secondary battery of the present invention means an all-solid-state secondary battery sheet of the present invention (however, In the case where the sheet has a layer other than the layer formed from the solid electrolyte-containing composition, it includes an embodiment in which the constituent layer is formed from a sheet from which this layer is removed. Note that when the active material layer or the solid electrolyte layer is not formed from the solid electrolyte-containing composition for secondary batteries of the present invention, known materials can be used.
  • each constituent layer (including a current collector, etc.) constituting the all-solid-state secondary battery may have a single-layer structure or a multi-layer structure.
  • the solid electrolyte layer and the active material layer formed of the solid electrolyte-containing composition for secondary batteries of the present invention preferably have different types and contents of the components contained in the solid electrolyte-containing composition for secondary batteries of the present invention. It is the same as that in the solid content of
  • the thicknesses of the negative electrode active material layer, solid electrolyte layer, and positive electrode active material layer are not particularly limited. Considering the dimensions of a typical all-solid-state secondary battery, the thickness of each layer is preferably 10 to 1,000 ⁇ m, more preferably 20 ⁇ m or more and less than 500 ⁇ m. In the all-solid-state secondary battery of the present invention, the thickness of any one of the layers 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 include a current collector on the side opposite to the solid electrolyte layer.
  • An electron conductor is preferable as the positive electrode current collector and the negative electrode current collector.
  • 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 (to form a thin film). Among them, aluminum and aluminum alloys are more preferable.
  • Materials for forming the negative electrode current collector include aluminum, copper, copper alloy, stainless steel, nickel, and titanium, as well as carbon, nickel, titanium, or silver treated on the surface of aluminum, copper, copper alloy, or stainless steel.
  • aluminum, copper, copper alloys and stainless steel are more preferable.
  • the shape of the current collector is usually in the form of a film sheet, but nets, punched objects, lath bodies, porous bodies, foam bodies, molded bodies of fiber groups, etc. 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 or member, etc. is appropriately interposed or disposed between or outside each layer of the negative electrode current collector, negative electrode active material layer, solid electrolyte layer, positive electrode active material layer, and positive electrode current collector. You may.
  • the all-solid-state secondary battery of the present invention may be used as an all-solid-state secondary battery with the above structure, but in order to form a dry battery, it may be used by enclosing it in a suitable housing.
  • the housing may be made of metal or resin (plastic).
  • a metal material for example, one made of aluminum alloy or stainless steel can be used.
  • the metal casing is 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 positive electrode side casing and the negative electrode side casing be joined and integrated via a short-circuit prevention gasket.
  • FIG. 1 is a cross-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-state secondary battery 10 of the present embodiment includes, in this order, 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 when viewed from the negative electrode side. .
  • the layers are in contact with each other and have an adjacent structure. By adopting such a structure, during charging, electrons (e ⁇ ) are supplied to the negative electrode side, and lithium ions (Li + ) are accumulated there.
  • lithium ions (Li + ) accumulated in the negative electrode are returned to the positive electrode side, and electrons are supplied to the operating region 6 .
  • a light bulb is used as a model for the operating portion 6, and the light bulb is lit by discharge.
  • an all-solid-state secondary battery having the layer structure shown in FIG. A battery manufactured by placing the body 12 in a 2032-type coin case 11 is sometimes called a (coin-type) all-solid-state secondary battery 13.
  • all of the positive electrode active material layer, solid electrolyte layer, and negative electrode active material layer are formed from the solid electrolyte-containing composition for secondary batteries of the present invention.
  • the inorganic solid electrolyte, polymer binder, and metal element-containing component contained in the positive electrode active material layer 4, solid electrolyte layer 3, and negative electrode active material layer 2 may be the same or different.
  • the conductive additives contained in the positive electrode active material layer 4 and the negative electrode active material layer 2 may be of the same type or different types.
  • either or both of the positive electrode active material layer and the negative electrode active material layer may be simply referred to as an active material layer or an electrode active material layer. Further, either or both of the positive electrode active material and the negative electrode active material may be simply referred to as an active material or an electrode active material.
  • the solid electrolyte layer includes an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, the above-mentioned polymer binder, and the above-mentioned metal element-containing component, which impairs the effects of the present invention. It contains any of the above-mentioned components to the extent that it is not present, and usually does not contain a positive electrode active material and/or a negative electrode active material.
  • the positive electrode active material layer includes an inorganic solid electrolyte having conductivity for metal ions belonging to Group 1 or Group 2 of the periodic table, the above-mentioned polymer binder, the above-mentioned metal element-containing component, and the positive electrode active material.
  • the negative electrode active material layer preferably includes an inorganic solid electrolyte having conductivity for metal ions belonging to Group 1 or Group 2 of the periodic table, the above-mentioned polymer binder, the above-mentioned metal element-containing component, and the negative electrode active material. contains a conductive aid and any of the above-mentioned components within a range that does not impair the effects of the present invention.
  • the negative electrode active material layer can be a lithium metal layer.
  • the lithium metal layer examples include a layer formed by depositing or molding lithium metal powder, a lithium foil, and a lithium vapor-deposited film.
  • the thickness of the lithium metal layer can be, for example, 1 to 500 ⁇ m, regardless of the thickness of the negative electrode active material layer.
  • an all-solid-state secondary battery with low resistance can be realized. Moreover, since the all-solid-state secondary battery of the present invention has low resistance, it is also possible to extract a large current.
  • the positive electrode current collector 5 and the negative electrode current collector 1 are each as described above.
  • a layer formed from a known constituent layer forming material can also be applied.
  • each layer may be comprised of a single layer or may be comprised of multiple layers.
  • a non-aqueous secondary battery can be manufactured by a conventional method using the constituent layer forming material of the present invention.
  • an all-solid-state secondary battery can be manufactured by forming each of the above layers using the solid electrolyte-containing composition for secondary batteries of the present invention.
  • the all-solid-state secondary battery of the present invention is produced by applying the solid electrolyte-containing composition for a secondary battery of the present invention onto an appropriate base material (for example, a metal foil serving as a current collector). It can be manufactured by performing a method (method for manufacturing an all-solid-state secondary battery sheet of the present invention) including (through) a step of forming a film (forming a film).
  • a positive electrode composition containing a positive electrode active material is coated as a positive electrode material on a metal foil serving as a positive electrode current collector and dried to form a positive electrode active material layer, thereby forming a positive electrode for an all-solid-state secondary battery. Create a sheet.
  • a solid electrolyte-containing composition for forming a solid electrolyte layer is applied and dried to form a solid electrolyte layer.
  • a negative electrode composition containing a negative electrode active material is applied as a negative electrode material and dried to form a negative electrode active material layer.
  • an all-solid-state secondary battery By overlaying a negative electrode current collector (metal foil) on the negative electrode active material layer, an all-solid-state secondary battery with a structure in which a solid electrolyte layer is sandwiched between the positive electrode active material layer and the negative electrode active material layer can be obtained. Can be done. This can also be enclosed in a housing to form a desired all-solid-state secondary battery.
  • a negative electrode active material layer, a solid electrolyte layer, and a positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collector is stacked to produce an all-solid-state secondary battery. You can also.
  • a positive electrode sheet for an all-solid-state secondary battery is produced as described above.
  • a negative electrode composition containing a negative electrode active material is coated as a negative electrode material on a metal foil serving as a negative electrode current collector, and dried to form a negative electrode active material layer, thereby producing a negative electrode sheet for an all-solid-state secondary battery.
  • a solid electrolyte layer is formed on the active material layer of one of these sheets as described above.
  • the other of the positive electrode sheet for an all-solid-state secondary battery and the negative electrode sheet for an all-solid-state 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.
  • an all-solid-state secondary battery can be manufactured.
  • Another method is the following method. That is, as described above, a positive electrode sheet for an all-solid-state secondary battery and a negative electrode sheet for an all-solid-state secondary battery are produced. Separately, a solid electrolyte-containing composition is applied onto a base material to produce a solid electrolyte sheet for an all-solid-state secondary battery including a solid electrolyte layer. Further, a positive electrode sheet for an all-solid-state secondary battery and a negative electrode sheet for an all-solid-state secondary battery are laminated so as to sandwich the solid electrolyte layer peeled off from the base material. In this way, an all-solid-state secondary battery can be manufactured.
  • a positive electrode sheet for an all-solid-state secondary battery, a negative electrode sheet for an all-solid-state secondary battery, and a solid electrolyte sheet for an all-solid-state secondary battery are produced.
  • the positive electrode sheet for an all-solid-state secondary battery or the negative electrode sheet for an all-solid-state secondary battery and the solid electrolyte sheet for an all-solid-state secondary battery were brought into contact with the positive electrode active material layer or the negative electrode active material layer and the solid electrolyte layer. Stack and pressurize. In this way, the solid electrolyte layer is transferred to the positive electrode sheet for an all-solid-state secondary battery or the negative electrode sheet for an all-solid-state secondary battery.
  • the solid electrolyte layer has a negative electrode active material layer or (with the positive electrode active material layers in contact with each other) and pressurize.
  • an all-solid-state secondary battery can be manufactured.
  • the pressurizing method, pressurizing conditions, etc. in this method are not particularly limited, and the method, pressurizing conditions, etc. explained in the pressurizing step described later can be applied.
  • the solid electrolyte layer and the like can also be formed, for example, by pressure-molding a solid electrolyte-containing composition and the like on the substrate or the active material layer under pressure conditions described below.
  • the solid electrolyte-containing composition for secondary batteries of the present invention may be used in any of the solid electrolyte-containing composition, the positive electrode composition, and the negative electrode composition, and the solid electrolyte-containing composition of the present invention may be used in all the compositions.
  • a solid electrolyte-containing composition for secondary batteries can also be used.
  • examples of the material include commonly used compositions.
  • a negative electrode active material layer can also be formed by combining metal ions with electrons and depositing the metal on a negative electrode current collector or the like.
  • the method for applying the constituent layer forming material is not particularly limited and can be selected as appropriate. Examples include coating (preferably wet coating), spray coating, spin coating, dip coating, slit coating, stripe coating, and bar coating.
  • the coating temperature is not particularly limited, and includes, for example, a temperature range of about room temperature (eg, 15 to 30° C.) without heating.
  • the solid electrolyte-containing composition for a secondary battery may be subjected to a drying treatment after being applied respectively, or may be subjected to a drying treatment after being applied in multiple layers.
  • the drying temperature is not particularly limited. The lower limit is preferably 30°C or higher, more preferably 60°C or higher, and even more preferably 80°C or higher.
  • the upper limit is preferably 300°C or less, more preferably 250°C or less, and even more preferably 200°C or less.
  • the temperature does not become too high and each member of the non-aqueous secondary battery is not damaged. As a result, in a non-aqueous secondary battery, it is possible to exhibit excellent overall performance, and to obtain good binding properties and good ionic conductivity.
  • the pressurizing method include a hydraulic cylinder press machine.
  • the pressing force is not particularly limited, and is generally preferably in the range of 5 to 1,500 MPa.
  • the applied constituent layer forming material may be heated at the same time as being pressurized.
  • 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.
  • pressing can also be performed at a temperature higher than the glass transition temperature of the polymer contained in the polymer binder. However, the temperature generally does not exceed the melting point of this polymer. Pressurization may be carried out with the coating solvent or dispersion medium and organic solvent dried in advance, or may be carried out with the solvent or dispersion medium and organic solvent remaining. In addition, each composition may be applied at the same time, and the application
  • the atmosphere in the film forming method is not particularly limited, and may be in the atmosphere, in dry air (dew point -20°C or less), in an inert gas (for example, in argon gas, Helium gas, nitrogen gas), etc. may be used.
  • an inert gas for example, in argon gas, Helium gas, nitrogen gas
  • high pressure may be applied for a short time (for example, within several hours), or medium pressure may be applied for a long time (one day or more).
  • restraints screw tightening pressure, etc.
  • the all-solid-state secondary battery can also be used in order to continue applying moderate pressure.
  • the press pressure may be uniform or different for the pressurized portion such as the sheet surface.
  • the press pressure can be changed depending on the area or film thickness of the pressurized portion. It is also possible to apply different pressures to the same area in stages.
  • the press surface may be smooth or roughened.
  • the nonaqueous secondary battery manufactured as described above is preferably initialized after manufacturing or before use. Initialization is not particularly limited, and can be carried out, for example, by performing initial charging and discharging with increased press pressure, and then releasing the pressure until the pressure reaches the pressure generally used for non-aqueous secondary batteries.
  • the non-aqueous secondary battery of the present invention can be applied to various uses. There are no particular restrictions on how it can be applied, but for example, when installed in electronic devices, it can be used in notebook computers, pen input computers, mobile computers, e-book players, mobile phones, cordless phone handsets, pagers, handy terminals, mobile fax machines, mobile phones, etc. Examples include copiers, portable printers, headphone stereos, video movies, LCD televisions, handy cleaners, portable CDs, mini discs, electric shavers, walkie talkies, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, etc.
  • consumer products include automobiles (electric vehicles, etc.), electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (pacemakers, hearing aids, shoulder massagers, etc.), etc. . Furthermore, it can be used for various military purposes and space purposes. It can also be combined with solar cells.
  • Example 1 In Example 1, various compositions and sheets for all-solid-state secondary batteries were prepared or produced, all-solid-state secondary batteries were manufactured, and the battery characteristics of the all-solid-state secondary batteries were evaluated.
  • the obtained polymerization liquid was poured into 100 g of methanol, stirred for 10 minutes, and then left to stand for 10 minutes.
  • the precipitate obtained after removing the supernatant was dissolved in 15 g of butyl butyrate, and methanol was distilled off by heating at 30 hPa and 60° C. for 1 hour. In this way, polymer P1 was synthesized, and a solution P1 (concentration: 40% by mass) of this polymer was obtained.
  • Polymers P2 to P24, P28 to P32, and T1 to T5 were synthesized in the same manner as in Synthesis Example P1, and solutions P2 to P24, P28 to P32, and T1 to T5 (all at a concentration of 40% by mass) of each polymer were prepared. Obtained.
  • the polymer P11 was a monomethyl ester in which the acid anhydride group in the constituent components derived from maleic acid reacted with methanol and was cleaved.
  • Binder compositions S-1 to S-24, S-27 to S-32 and T-1 to Preparation of T-5 At room temperature, the metal element-containing components shown in Table 1 were added to the polymer solutions P1 to P24, P27 to P32, and T1 to T5 synthesized in the above synthesis examples P1 to P24, P27 to P32, and T1 to T5.
  • the dispersion shown in Table 1 is added so that the solid concentration of the polymer becomes the content shown in the "Content C PB " column of the "Polymer binder" column in Table 1.
  • Binder compositions S-1 to S-24, S-27 to S-32, and T-1 to T-5 were prepared by appropriately adjusting the content of the medium and mixing them.
  • the prepared binder composition T-1 does not contain any component containing a metal element with a particle size of 10 ⁇ m or less.
  • each binder composition Details of each binder composition are shown in Table 1.
  • the types, contents, and weight average molecular weights (values measured by the above method) of the constituent components constituting each synthesized polymer are shown in the "Polymer binder” column of Table 1.
  • “content CPB” in the "polymer binder” column of Table 1 indicates the content (solid content concentration) of the polymer binder in the binder composition. Note that the unit of "content” in Table 1 is mass % except for the content CMB , but is omitted in Table 1.
  • “HMCTS” in the "Metal element-containing component” column of Table 1 represents hexamethylcyclotrisiloxane.
  • the "Status” column in the same column indicates the state of the metal element-containing component in the binder composition (dissolved (denoted as “dissolved” in Table 1), or insoluble and dispersed in particulate form (Table 1). 1)) are shown as the results confirmed by the above method.
  • the particle size determined by the above method is also indicated.
  • binder compositions S-1 to S-15, S-18 to S-28, S-33, T-3 and T-4 each metal element containing component with a particle size of 0.1 ⁇ m was used, but the binder composition Compositions S-14 and S-15 did not dissolve because of their high content and existed in the form of particles with their particle sizes maintained.
  • binder compositions S-16, S-29, T-2, and T-5 alumina with the particle size shown in Table 1 was used (in binder composition T-2, the content was Even if the content was small, it did not dissolve and existed in the form of particles. On the other hand, in S-29 and T-5, the content was high, so it did not dissolve and existed in the form of particles with the particle size maintained.) .
  • binder compositions S-30 to S-32 the hexamethylcyclotrisiloxane used was dissolved in the compositions.
  • the ratio [ C MB /C PB ] of the content C MB of the metal element-containing component to the content C PB of the polymer binder in each binder composition is calculated, and the ratio [C MB /C PB ] in Table 1 is calculated. ” column. All of the binder compositions using polymer solutions were water-insoluble compositions, and the polymer binder was dissolved in the dispersion medium.
  • Constituent components A, MA and MC represent the above-mentioned other constituent components, component MA and polar functional group-containing component MC, respectively. However, for binder compositions S-25 to S-27 and S-33, each polymer is shown in the component A column for convenience.
  • Phosmer M is 2-(methacryloyloxy)ethyl phosphate (manufactured by Unichemical Co., Ltd.).
  • Li 2 S lithium sulfide
  • P 2 S 5 diphosphorus pentasulfide
  • each solid electrolyte-containing composition for secondary batteries shown in Tables 2-1 to 2-4 (collectively referred to as Table 2) was prepared.
  • the product was prepared as follows. ⁇ Preparation of inorganic solid electrolyte-containing composition> 60 g of zirconia beads with a diameter of 5 mm were placed in a zirconia 45 mL container (manufactured by Fritsch), 7.88 g of LPS synthesized in Synthesis Example A above, and 0.0 g of the binder composition shown in Table 2-1 or Table 2-4.
  • ⁇ Preparation of positive electrode composition 60 g of zirconia beads with a diameter of 5 mm were placed in a zirconia 45 mL container (manufactured by Fritsch), 4.58 g of LPS synthesized in Synthesis Example A, and the dispersion medium (binder) shown in Table 2-2 or Table 2-4. 12.00 g (total amount) (including organic solvent derived from the composition) was charged. Thereafter, this container was set in a planetary ball mill P-7 (trade name) and stirred at 25° C. and a rotation speed of 200 rpm for 30 minutes.
  • a planetary ball mill P-7 trade name
  • ⁇ Preparation of negative electrode composition 60 g of zirconia beads with a diameter of 5 mm were placed in a 45 mL zirconia container (manufactured by Fritsch), 3.6 g of LPS synthesized in Synthesis Example A, and 0.08 g of the binder composition shown in Table 2-3 or Table 2-4. (solid content mass) and 12 g (total amount) of the dispersion medium (including organic solvent derived from the binder composition) shown in Table 2-3 or Table 2-4 were added. Thereafter, this container was set in a planetary ball mill P-7 (trade name), and the mixture was mixed for 60 minutes at a temperature of 25° C. and a rotation speed of 300 rpm.
  • a planetary ball mill P-7 trade name
  • composition content is the content (mass%) relative to the total mass of each composition
  • solid content is the content (mass%) relative to 100 mass% solid content of each composition
  • Units are omitted in the table.
  • the "composition content" of the dispersion medium in Table 2 indicates the total amount including the content of the organic solvent derived from the binder composition.
  • content C MS of the metal element-containing component in each of the prepared compositions was calculated and shown in the "Content C MS " column of Table 2.
  • Each of the prepared compositions was a non-aqueous composition, and the polymer binder dissolved in the binder composition was also dissolved in the dispersion medium in each of the prepared compositions.
  • the metal element-containing components were dissolved in each composition using binder compositions S-1 to S-33 and T-3 to T-5, but each composition using binder composition T-2 In the material, the metal element-containing components existed as particles with the same particle size.
  • LPS LPS synthesized in Synthesis Example A
  • NMC LiNi 1/3 Co 1/3 Mn 1/3 O 2 Si: Silicon (APS 1-5 ⁇ m, manufactured by Alfa Aesar)
  • AB Acetylene black
  • VGCF Carbon nanofiber
  • a sheet for all-solid-state secondary battery was produced as follows. ⁇ Production of solid electrolyte sheet for all-solid-state secondary battery> Each inorganic solid electrolyte-containing composition shown in the "Solid electrolyte composition No.” column of Table 3-1 or Table 3-4 obtained above was applied onto a 20 ⁇ m thick aluminum foil using a Baker applicator (product name: SA -201, manufactured by Tester Sangyo Co., Ltd.) and heated at 80° C. for 2 hours to dry the inorganic solid electrolyte-containing composition (remove the dispersion medium).
  • the dried inorganic solid electrolyte-containing composition was heated and pressurized at a temperature of 120°C and a pressure of 40 MPa for 10 seconds to form a solid electrolyte sheet for an all-solid secondary battery (Table 3- 1 and Table 3-4. ) 101 to 133 and c11 to c15 were produced, respectively.
  • the thickness of the solid electrolyte layer was 40 ⁇ m.
  • all-solid-state secondary battery negative electrode sheets (negative electrode active material layer thickness 40 ⁇ m) 301 to 333 and c31 equipped with a solid electrolyte layer with a film thickness of 25 ⁇ m ⁇ c35 were produced respectively.
  • All-solid-state secondary battery No. 1 having the layer structure shown in FIG. 1 was prepared as follows. 401 was produced. All-solid-state secondary battery positive electrode sheet No. 1 including the solid electrolyte layer obtained above. 201 (the aluminum foil of the solid electrolyte-containing sheet has been peeled off) is cut into a disk shape with a diameter of 14.5 mm, and as shown in FIG. 2, a stainless steel 2032 is assembled with a spacer and a washer (not shown in FIG. 2). I put it in a coin case 11. Next, a lithium foil (thickness: 5 ⁇ m) cut out into a disk shape with a diameter of 15 mm was layered on the solid electrolyte layer.
  • the all-solid-state secondary battery manufactured in this way has the layer structure shown in FIG. 1 (however, the lithium foil corresponds to the negative electrode active material layer 2 and the negative electrode current collector 1).
  • All-solid-state secondary battery No. 401 all-solid-state secondary battery positive electrode sheet No. 401 including a solid electrolyte layer was manufactured.
  • All-solid-state secondary battery No. 1 was used except that the positive electrode sheet for all-solid-state secondary battery equipped with a solid electrolyte layer represented by the following formula was used.
  • All-solid-state secondary battery No. 401 was manufactured in the same manner as No. 401. 402-435 and c101-c105 were produced, respectively.
  • All-solid-state secondary battery No. 1 having the layer structure shown in FIG. 1 was prepared as follows. 501 was produced. Negative electrode sheet No. 1 for all-solid-state secondary batteries equipped with the solid electrolyte obtained above. 301 (the aluminum foil of the solid electrolyte-containing sheet has been peeled off) is cut into a disc shape with a diameter of 14.5 mm, and as shown in FIG. 2, stainless steel 2032 is assembled with a spacer and a washer (not shown in FIG. 2). I put it in a coin case 11. Next, a positive electrode sheet (positive electrode active material layer) punched out with a diameter of 14.0 mm from the positive electrode sheet for an all-solid-state secondary battery produced below was stacked on the solid electrolyte layer.
  • a positive electrode sheet positive electrode active material layer
  • an all-solid-state secondary battery laminate 12 (stainless steel foil - aluminum foil - positive electrode active material layer - solid electrolyte layer - negative electrode active material layer - copper foil). A laminate) was formed. Thereafter, by caulking the 2032 type coin case 11, all-solid-state secondary battery No. 2 shown in FIG. 501 was manufactured.
  • all-solid-state secondary battery No. 501 A positive electrode sheet for a solid secondary battery used in manufacturing No. 501 was prepared.
  • - Preparation of positive electrode composition - 180 zirconia beads with a diameter of 5 mm were placed in a 45 mL zirconia container (manufactured by Fritsch), 2.7 g of LPS synthesized in Synthesis Example A above, and KYNAR FLEX 2500-20 (trade name, PVdF-HFP: polyfluoride).
  • This container was set in a planetary ball mill P-7 (trade name) manufactured by Fritsch, and stirred at 25° C. and a rotation speed of 300 rpm for 60 minutes. After that, 7.0 g of LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NMC) was added as a positive electrode active material, and in the same way, the container was set in a planetary ball mill P-7 and heated at 25°C and the rotation speed. Mixing was continued for 5 minutes at 100 rpm to prepare a positive electrode composition.
  • NMC LiNi 1/3 Co 1/3 Mn 1/3 O 2
  • All-solid-state secondary battery No. 501 all-solid-state secondary battery negative electrode sheet No. 501 including a solid electrolyte layer was manufactured. No. 301 shown in the "Electrode active material layer (sheet No.)" column of Tables 4-2 and 4-3. All-solid-state secondary battery No. 1 was used except that an all-solid-state secondary battery negative electrode sheet having a solid electrolyte layer represented by the following was used. All-solid-state secondary battery No. 501 was manufactured in the same manner as No. 501. 502-535 and c201-c205 were produced, respectively.
  • Ionic conductivity measurement> The ionic conductivity of each manufactured all-solid-state secondary battery was measured. Specifically, for each all-solid-state secondary battery, AC impedance was measured at 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) in a constant temperature bath at 25°C. Thereby, the resistance in the layer thickness direction of the sample for ionic conductivity measurement was determined, and the ionic conductivity was determined by calculation using the following formula (C1). The results are shown in Tables 4-1 to 4-3 (collectively referred to as Table 4).
  • Ionic conductivity ⁇ (mS/cm) 1000 ⁇ sample layer thickness (cm)/[resistance ( ⁇ ) ⁇ sample area (cm 2 )]
  • the sample layer thickness is measured before putting the laminate 12 into the 2032 type coin case 11, and is the value obtained by subtracting the thickness of the current collector (total layer thickness of the solid electrolyte layer and the electrode active material layer). It is.
  • the sample area is the area of a disc-shaped sheet with a diameter of 14.5 mm. It was determined which of the following evaluation criteria the obtained ionic conductivity ⁇ was included in. Regarding the ionic conductivity ⁇ in this test, an evaluation standard of "C" or higher means a pass.
  • a polymer binder composed of a polymer having less than 30% by mass of components derived from (meth)acrylic acid in the total components of the polymer, and a content of 1.0 ⁇ 10 ⁇ 3 to 1.0 ⁇ 10 4 ppm.
  • Inorganic solid electrolyte-containing compositions using binder compositions T-1 to T-5 that do not contain metal element-containing components with a particle size of 10 ⁇ m or less as binder components can form a low-resistance constituent layer. Therefore, it is not possible to sufficiently reduce the resistance of an all-solid-state secondary battery.
  • compositions Kc11, PKc21, and NKc21 using binder composition T-1 without a metal element-containing component in combination with a polymer binder can reduce the resistance of an all-solid-state secondary battery to some extent. , cannot meet the advanced demands of recent years.
  • compositions Kc12, PKc22, and NKc22 using binder composition T-2 in which a metal element-containing component having a large particle size of 45 ⁇ m is used in combination with the polymer binder cannot suppress the increase in resistance of the all-solid-state secondary battery.
  • composition using binder composition T-3 in which a polymer binder composed of a polymer having a component derived from (meth)acrylic acid as much as 35% by mass in the total components of the polymer is used in combination with a component containing a metal element.
  • the polymer binder is considered to exhibit excessive cohesiveness, and as a result, an increase in resistance of the all-solid-state secondary battery cannot be suppressed.
  • compositions Kc14, PKc24, and NKc24 using binder composition T-4 in which the content of metal element-containing components with a particle size of 10 ⁇ m or less is too small the effect of incorporating metal element-containing components is not sufficient, and the total solid The increase in resistance of the secondary battery cannot be suppressed.
  • compositions Kc15, PKc25, and NKc25 using binder composition T-5 in which the content of metal element-containing components is too large even if the particle size is 10 ⁇ m or less, the metal element-containing components coexisting in excess cause polymerization. It is thought that the binder tends to aggregate, and as a result, an increase in resistance of the all-solid-state secondary battery cannot be suppressed.
  • a polymer binder composed of a polymer having less than 30% by mass of a component derived from (meth)acrylic acid in the total components of the polymer, and Each composition K-1 to K-33, PK-1 to using binder compositions S-1 to S-33 containing a metal element containing component with a particle size of 10 ⁇ m or less at a content of 4 ppm as a binder component.
  • PK-33 and NK-1 to NK-33 are all used as constituent layer forming materials that form at least one constituent layer of a non-aqueous secondary battery, thereby effectively suppressing an increase in resistance. It is possible to realize an all-solid-state secondary battery with sufficiently low resistance (high ionic conductivity).
  • the binder-forming polymer has a polar functional group such as a carboxy group, the interaction with the metal element-containing component will be strengthened and the cohesiveness of the polymer binder will be further increased, making it possible to further reduce battery resistance. becomes.

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PCT/JP2023/022773 2022-06-23 2023-06-20 二次電池用バインダー組成物、二次電池用固体電解質含有組成物、全固体二次電池用シート及び全固体二次電池 Ceased WO2023249014A1 (ja)

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