WO2017030154A1 - Composition d'électrolyte solide, feuille d'électrode pour batteries rechargeables tout solide, batterie rechargeable tout solide, procédé de production de feuille d'électrode pour batteries rechargeables tout solide, et procédé de fabrication de batterie rechargeable tout solide - Google Patents

Composition d'électrolyte solide, feuille d'électrode pour batteries rechargeables tout solide, batterie rechargeable tout solide, procédé de production de feuille d'électrode pour batteries rechargeables tout solide, et procédé de fabrication de batterie rechargeable tout solide Download PDF

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WO2017030154A1
WO2017030154A1 PCT/JP2016/074045 JP2016074045W WO2017030154A1 WO 2017030154 A1 WO2017030154 A1 WO 2017030154A1 JP 2016074045 W JP2016074045 W JP 2016074045W WO 2017030154 A1 WO2017030154 A1 WO 2017030154A1
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group
solid electrolyte
solid
functional group
electrolyte composition
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PCT/JP2016/074045
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English (en)
Japanese (ja)
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雅臣 牧野
宏顕 望月
智則 三村
目黒　克彦
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富士フイルム株式会社
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Priority to JP2017535555A priority Critical patent/JP6461354B2/ja
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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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M10/058—Construction or manufacture
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solid electrolyte composition, an electrode sheet for an all-solid secondary battery, an all-solid secondary battery, an electrode sheet for an all-solid secondary battery, and an all-solid secondary battery manufacturing method.
  • Electrolytic solutions have been used for lithium ion batteries. Attempts have been made to replace the electrolytic solution with a solid electrolyte to obtain an all-solid-state secondary battery in which all constituent materials are solid.
  • An advantage of the technology using an inorganic solid electrolyte is the reliability of the overall performance of the battery. For example, a flammable material such as a carbonate-based solvent is applied as a medium to an electrolytic solution used in a lithium ion secondary battery.
  • Various safety measures have been taken for lithium ion secondary batteries. However, there is a risk of inconvenience during overcharging, and further measures are desired.
  • An all-solid-state secondary battery that can make the electrolyte nonflammable is positioned as a fundamental solution.
  • a further advantage of the all-solid-state secondary battery is that it is suitable for increasing the energy density by stacking electrodes. Specifically, a battery having a structure in which an electrode and an electrolyte are directly arranged in series can be obtained. At this time, since the metal package for sealing the battery cell, the copper wire and the bus bar for connecting the battery cell can be omitted, the energy density of the battery is greatly increased. In addition, good compatibility with the positive electrode material capable of increasing the potential is also mentioned as an advantage.
  • Patent Document 1 discloses that an anhydrous sulfuric acid or an anhydrous sulfuric acid-electron donating compound complex is added to a carbon-carbon double bond in a molecule as a binder for constituting at least one of an electrolyte layer and / or an electrode. All-solid lithium batteries containing a polymer are described.
  • the invention described in Patent Document 1 aims to improve the charge / discharge cycle characteristics of an all-solid-state lithium battery using a sulfonated binder.
  • the all-solid-state lithium battery described in the same document has a low binding property between solid particles such as a solid electrolyte, which causes a minute gap between the solid particles and causes a decrease in ion conductivity.
  • solid-solid interface In order to prevent the generation of the gap and increase the lithium ion conductivity between solid particles (solid-solid interface), it is necessary to pressurize the all-solid-state secondary battery during use.
  • the present invention can be used to form a layer (a positive electrode active material layer, a solid electrolyte layer and / or a negative electrode active material layer) of an all-solid-state secondary battery, thereby enhancing the binding between solid particles in the layer.
  • a solid electrolyte composition capable of realizing excellent ionic conductivity between solid particles regardless of pressure, an electrode sheet for an all-solid secondary battery and an all-solid secondary battery using the solid electrolyte composition This is the issue.
  • this invention makes it a subject to provide the manufacturing method of the electrode sheet for all-solid-state secondary batteries using this solid electrolyte composition, and an all-solid-state secondary battery.
  • pressurization means that the all-solid-state secondary battery is driven without pressurization or the all-solid-state secondary battery is driven under a pressure of 1 MPa or less. Even when an atmospheric pressure of 0.1 MPa and a pressure higher than the atmospheric pressure are applied (up to 1 MPa), the pressure is not applied for the purpose of applying the pressure to the sheet forming process (for example, laminating process) of the battery. Is not applicable.
  • pressurization means applying a pressure exceeding 1 MPa, or driving a battery by applying a pressure exceeding 1 MPa.
  • a functional block polymer (block copolymer) having an affinity for at least one of an electrode active material and a specific inorganic solid electrolyte, and an inorganic solid electrolyte
  • a solid electrolyte composition containing the above has excellent dispersion stability of solid particles. The reason for this is not clear yet, but in an all-solid-state secondary battery produced using this solid electrolyte composition, the distance of solid particles in each layer constituting the all-solid-state secondary battery becomes uniform, which It is considered that a good interface is formed between solid particles in combination with the action (affinity) of a specific functional group that can exist at a high density because it is a polymer. As a result, the all-solid-state secondary battery produced using this solid electrolyte composition has excellent binding properties and can exhibit ionic conductivity comparable to that of the pressurized state without being pressurized.
  • the present invention has been made based on these findings.
  • a solid electrolyte composition comprising a block polymer and an inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the Periodic Table,
  • the block polymer includes at least one block composed of repeating units having at least one functional group,
  • a solid electrolyte composition, wherein the functional group is a functional group selected from the following functional group group (I) having an affinity for an electrode active material and / or the following functional group group (II) having an affinity for an inorganic solid electrolyte.
  • the block polymer is A block comprising a repeating unit having at least one functional group selected from the functional group (I);
  • the solid electrolyte composition according to ⁇ 1> comprising a block composed of a repeating unit having at least one functional group selected from the functional group group (II).
  • ⁇ 3> The solid electrolyte composition according to ⁇ 1> or ⁇ 2>, in which at least one of the end portions of the main chain of the block polymer has a functional group selected from the functional group group (I) and / or (II).
  • the content of the repeating unit having at least one functional group selected from the functional group (I) and / or (II) is 100 mol of all repeating units.
  • ⁇ 5> The solid according to any one of ⁇ 1> to ⁇ 4>, wherein the group having a ring structure of three or more rings is a residue of a compound represented by the following general formula (1) or (2) Electrolyte composition.
  • Ar represents a benzene ring.
  • n represents an integer of 0 to 8.
  • R 11 to R 16 each independently represents a hydrogen atom or a substituent.
  • X 1 and X 2 each independently represent a hydrogen atom or a substituent.
  • groups adjacent to each other may be bonded to form a 5- or 6-membered ring.
  • any one of the substituents R 11 to R 13 is — (Ar 1 ) m-Rxx, or any two of R 11 to R 13 are bonded to each other; -(Ar 1 ) m- is formed.
  • Ar 1 represents a phenylene group
  • m represents an integer of 2 or more
  • Rxx represents a hydrogen atom or a substituent.
  • Y 1 and Y 2 each independently represent a hydrogen atom, a methyl group or a formyl group.
  • R 21 , R 22 , R 23 and R 24 each independently represent a substituent
  • a, b, c and d each independently represent an integer of 0 to 4.
  • the A ring may be a saturated ring, an unsaturated ring having 1 or 2 double bonds, or an aromatic ring
  • the B ring and the C ring are unsaturated rings having 1 or 2 double bonds. It may be.
  • adjacent substituents may be bonded to form a ring.
  • ⁇ 6> The solid electrolyte composition according to any one of ⁇ 1> to ⁇ 5>, wherein the block polymer includes a block composed of a repeating unit having at least one substituent selected from the following substituent group (a).
  • the block polymer is A block comprising a repeating unit having at least one functional group selected from the functional group (I); A block comprising a repeating unit having at least one substituent selected from the substituent group (a); A block comprising a repeating unit having at least one functional group selected from the functional group group (II),
  • the solid electrolyte composition according to any one of ⁇ 1> to ⁇ 6>, which is included in this order from any one of the end portions of the main chain.
  • ⁇ 9> The solid electrolyte composition according to any one of ⁇ 1> to ⁇ 8>, wherein the dispersity of the block polymer is less than 1.5.
  • ⁇ 10> The solid electrolyte composition according to any one of ⁇ 1> to ⁇ 9>, wherein one of the terminal ends of the main chain of the block polymer is a halogen atom.
  • ⁇ 11> The solid electrolyte composition according to any one of ⁇ 1> to ⁇ 10>, wherein the number average molecular weight of the block polymer is 1,000 to 500,000.
  • ⁇ 12> The solid electrolyte composition according to any one of ⁇ 1> to ⁇ 11>, wherein the content of the block polymer with respect to 100 parts by mass of the inorganic solid electrolyte is 0.01 to 20 parts by mass.
  • ⁇ 13> The solid electrolyte composition according to any one of ⁇ 1> to ⁇ 12>, containing a lithium salt.
  • ⁇ 14> The solid electrolyte composition according to any one of ⁇ 1> to ⁇ 13>, wherein the inorganic solid electrolyte is a sulfide-based inorganic solid electrolyte.
  • the solid electrolyte composition according to any one of ⁇ 1> to ⁇ 14> including at least one selected from the group consisting of an ether compound solvent, an amide compound solvent, an aromatic compound solvent, and an aliphatic compound solvent object.
  • An electrode sheet for an all-solid-state secondary battery comprising a solid electrolyte layer containing a block polymer and an inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table.
  • the block polymer includes at least one block composed of repeating units having at least one functional group,
  • An all-solid secondary battery in which the functional group is a functional group selected from the following functional group group (I) having an affinity for an electrode active material and / or the following functional group group (II) having an affinity for an inorganic solid electrolyte Electrode sheet.
  • ⁇ 17> A method for producing an electrode sheet for an all-solid-state secondary battery, comprising a step of applying a wet slurry to the solid electrolyte composition according to any one of ⁇ 1> to ⁇ 15> and a step of drying the slurry.
  • a method for producing an all-solid secondary battery comprising producing an all-solid secondary battery having a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order via the production method according to ⁇ 17>.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • acryl or “(meth) acryl” is described, it is used in the meaning including both methacryl and acryl.
  • acryloyl or “(meth) acryloyl” is described, it is used in the meaning including both methacryloyl and acryloyl.
  • group having three or more ring structures refers to a group in which at least one hydrogen atom or substituent is eliminated from a compound having a ring structure composed of three or more rings. .
  • the “residue of the compound represented by the general formula (1) or (2)” is a group in which at least one hydrogen atom or substituent is eliminated from the compound represented by the general formula (1) or (2).
  • compounds and groups that do not specify substitution or unsubstituted have a substituent represented by R 11 to R 16 , X 1 , X 2 and Rxx in the general formula (1) described later. Also good.
  • the solid electrolyte composition of the present invention is excellent in dispersion stability, and can be used to form a layer of an all-solid secondary battery, thereby enhancing the binding between solid particles in the layer, regardless of pressure. Excellent ion conductivity between solid particles can be realized.
  • the electrode sheet for an all-solid secondary battery and the all-solid-state secondary battery of the present invention are excellent in the binding property between the solid particles in the layer, and excellent ions between the solid particles regardless of pressure. Conductivity can be realized.
  • the electrode sheet for the all-solid-state secondary battery and the all-solid-state secondary battery of the present invention having the above characteristics are manufactured. be able to.
  • FIG. 1 is a longitudinal sectional view schematically showing an all solid state secondary battery according to a preferred embodiment of the present invention.
  • FIG. 2 is a longitudinal sectional view schematically showing the test apparatus used in the examples.
  • the solid electrolyte composition of the present invention contains a block polymer and an inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table.
  • the block polymer includes at least one block (partial structure) composed of a repeating unit having at least one functional group.
  • This functional group is selected from the functional group group (I) having affinity with the electrode active material and / or the following functional group group (II) having affinity with the inorganic solid electrolyte.
  • the functional group belonging to the functional group group (I) and / or (II) is also referred to as a specific functional group.
  • R represents a hydrogen atom, an alkyl group or an aryl group.
  • the alkyl group or aryl group represented by R is preferably an alkyl group or aryl group represented by R 11 described later.
  • block polymer that can be used in the present invention preferably includes a block composed of a repeating unit having a specific substituent described later in order to further improve the dispersion stability of the solid electrolyte composition.
  • “having affinity with the electrode active material” means chemical bonding (covalent bond, ionic bond, hydrogen bond, etc.) or physical interaction ( ⁇ - ⁇ mutual) with the particle surface of the electrode active material. Action, n- ⁇ interaction, hydrophilic / hydrophilic interaction, hydrophobic / hydrophobic interaction, intermolecular force, etc.).
  • “having affinity with an inorganic solid electrolyte” indicates that the inorganic solid electrolyte can be dissolved and compatible with the chemical bond and physical interaction described above.
  • the density of the specific functional group can be increased (high concentration can be achieved), and the adsorption efficiency and adhesion of the block polymer to the solid particles can be improved. it can.
  • the adhesion By increasing the adhesion, the binding property between the solid particles can be improved and the solid particle interface can be reduced. As a result, an increase in resistance at the solid particle interface can be suppressed, and the ionic conductivity of the all-solid secondary battery can be increased.
  • 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 this embodiment has a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 in this order as viewed from the negative electrode side. .
  • Each layer is in contact with each other and has a laminated structure.
  • the solid electrolyte composition of the present invention can be preferably used as a molding material for the negative electrode active material layer, the positive electrode active material layer, and the solid electrolyte layer.
  • the all-solid-state secondary battery having the layer configuration shown in FIG. 1 when putting the all-solid-state secondary battery having the layer configuration shown in FIG. 1 into a 2032 type coin case, the all-solid-state secondary battery having the layer configuration shown in FIG. A battery produced by placing an electrode sheet for an all-solid secondary battery in a 2032 type coin case may be referred to as an all-solid secondary battery.
  • the thicknesses of the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 are not particularly limited. In consideration of general battery dimensions, the thickness 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, it is more preferable that the thickness of at least one of the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 is 50 ⁇ m or more and less than 500 ⁇ m. In this specification, the positive electrode active material layer and the negative electrode active material layer may be collectively referred to as an electrode layer.
  • the electrode active material that can be used in the present invention includes a positive electrode active material contained in the positive electrode active material layer and a negative electrode active material contained in the negative electrode active material layer. May be simply referred to as an active material or an electrode active material.
  • solid electrolyte composition that can be suitably used for the production of the all-solid-state secondary battery of the present invention will be described.
  • the main chain skeleton of the block polymer used in the present invention is not particularly limited, but is preferably a copolymer skeleton composed of blocks obtained by polymerizing ethylenically unsaturated monomers.
  • An ethylenically unsaturated monomer is a compound having at least one, preferably one, polymerizable ethylenically unsaturated bond (C ⁇ C).
  • the block polymer has a plurality of types of structures (blocks) in which the same type of monomer (monomer) is repeated for a long time. Generally, it consists of two or more different monomer repeating units and does not include a single polymer (homopolymer).
  • the block polymer used in the present invention can be synthesized, for example, by living radical polymerization.
  • the types of living radical polymerization include atom transfer radical polymerization (ATRP), reversible non-cleavable chain transfer polymerization (reversible addition / fragmentation chain transfer polymerization nitridation: RAFT) Polymerization (NMP).
  • ATRP atom transfer radical polymerization
  • RAFT reversible non-cleavable chain transfer polymerization
  • NMP Polymerization
  • a normal radically polymerizable monomer can be used.
  • the specific functional group and / or the specific substituent is preferably bonded to these monomers.
  • the block polymer used in the present invention preferably contains at least one block component composed of a repeating unit represented by any one of the following formulas (U1) to (U3).
  • R 1 represents a hydrogen atom or an alkyl group
  • R 2 represents a hydrogen atom, a specific functional group, or a specific substituent described later
  • L 1 represents a divalent linking group
  • m 1 represents 0 or 1.
  • the carbon number of the alkyl group is preferably 1 to 25, more preferably 1 to 15, further preferably 1 to 5, and particularly preferably 1. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, octyl, dodecyl, and stearyl.
  • divalent linking group examples include an alkylene group, an arylene group, —O—, —C ( ⁇ O) —, —NH—, and a linking group obtained by combining these.
  • the carbon number of the alkylene group is preferably 1 to 8, more preferably 1 to 5, and particularly preferably 1 to 3. Examples include methylene, ethylene, propylene, isopropylene, and tetramethylene.
  • the carbon number of the arylene group is preferably 6 to 12, more preferably 6 to 8, and particularly preferably 6. Examples thereof include phenylene and naphthylene.
  • R 3 , L 2 and m2 have the same meanings as R 1 , L 1 and m1 in formula (U1), respectively, and preferred ranges are also the same.
  • R 4 represents a hydrogen atom or an alkyl group. Examples of the alkyl group include an alkyl group represented by R 1 in the formula (U1), and an alkyl group having 1 to 5 carbon atoms is preferable.
  • R 5 , R 6 , L 3 and m3 have the same meanings as R 1 , R 2 , L 1 and m1 in formula (U1), respectively, and the preferred ranges are also the same.
  • the block polymer used for this invention may contain the block component which consists of a repeating unit which does not have a specific functional group group and / or a specific substituent.
  • a block component formed from an unsubstituted alkyl methacrylate having a low carbon number or a hydrocarbon radical polymerization monomer (such as styrene) can be used.
  • the block polymer used in the present invention may be linear or branched. Each block represents a single polymer mass, and one block generally has a number average molecular weight of 500 to 50,000, and the degree of polymerization of the monomer is preferably 5 to 200.
  • the structure of the end portion of the main chain of the block polymer used in the present invention is not particularly limited, but preferably has a functional group, a substituent or a halogen atom.
  • the main chain terminal part has a functional group, a substituent or a halogen atom.
  • the main chain terminal part is a functional group, a substituent or a halogen atom, and the main chain terminal part is a divalent linking group.
  • the divalent linking group include L 1 in the above formula (U1).
  • the divalent linking group may have a substituent.
  • the divalent linking group —CH 2 CH 2 —O—C ( ⁇ O) —C (CH 3 ) 2- .
  • a specific functional group is preferred as the functional group of the main chain terminal.
  • substituents include specific substituents described below and substituents represented by R 11 to R 16 , X 1 , X 2 and Rxx in general formula (1) described below, and specific substituents are preferable.
  • halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a bromine atom is preferable.
  • At least one, preferably one of the end portions of the main chain of the block polymer used in the present invention has a specific functional group or a specific substituent.
  • one of the main chain terminal parts of the block polymer used for this invention has a halogen atom.
  • halogen atoms F, Cl, Br, I
  • ATRP halogen atoms
  • 2-bromoisobutyryl bromide and a small molecule having a specific functional group are esterified to synthesize a specific functional group or specific substituent-containing initiator in which a halogen is bonded to a tertiary carbon.
  • dithiocarboxylic acid can be introduced into the end of the main chain by RAFT.
  • nitroxide can be introduced into the end of the main chain by NMP.
  • the main chain terminal portion of the block polymer used in the present invention can be changed to various functional groups or substituents by post-treatment after completion of the polymerization. For example, if an untreated block polymer on the right end is post-treated in the presence of an azo-based thermal polymerization initiator or a peroxide-based thermal polymerization initiator and no monomer, the radical active right end is left behind from the polymerization initiator. It is possible to obtain a block polymer which is substituted with a group and has a radically active end blocked (ie, a dead activated polymer which does not extend further). By the method as described above, the main chain terminal portion of the block polymer used in the present invention can be made into any functional group or substituent.
  • the number average molecular weight of the block polymer used in the present invention is preferably 1,000 to 500,000, more preferably 1,000 to 100,000, still more preferably 1,000 to 10,000, and 1,000 to 5 1,000 is particularly preferred.
  • the number average molecular weight of the block polymer and the mass average molecular weight necessary for calculating the degree of dispersion described later can be measured with reference to the measuring methods described in the Examples section.
  • the repeating unit constituting the block polymer that can be used in the present invention has at least one specific functional group.
  • the block polymer used in the present invention is an electrode. Shows strong binding to active materials.
  • the functional group belonging to the functional group (I) has high affinity with the electrode active material, among them, a hydroxyl group, a carboxy group, an alkoxy group, or a group having a ring structure of 3 or more rings is preferable.
  • the electrode active material is a positive electrode active material
  • a hydroxy group, a carboxy group, or an alkoxy group is preferable because the surface of the active material is a metal oxide and is hydrophilic.
  • the electrode active material is a negative electrode active material, the surface of the active material is hydrophobic and has a ⁇ plane, such as graphite. Therefore, an alkoxy group and a group having a ring structure of three or more rings are preferable.
  • the group having 3 or more ring structures is preferably a residue of a compound represented by the following general formula (1) or (2).
  • Ar represents a benzene ring.
  • n represents an integer of 0 to 8.
  • R 11 to R 16 each independently represents a hydrogen atom or a substituent.
  • X 1 and X 2 each independently represent a hydrogen atom or a substituent.
  • groups adjacent to each other may be bonded to form a 5- or 6-membered ring.
  • any one substituent of R 11 to R 16 is — (Ar 1 ) m-Rxx, or any two of R 11 to R 16 are bonded to each other; -(Ar 1 ) m- is formed.
  • Ar 1 represents a phenylene group
  • m represents an integer of 2 or more
  • Rxx represents a hydrogen atom or a substituent.
  • n 1, at least two adjacent R 11 to R 16 , X 1 and X 2 are bonded to form a benzene ring.
  • R 11 to R 16 , X 1 , X 2 and Rxx an alkyl group, aryl group, heteroaryl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, Arylthio group, heteroarylthio group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, hydroxy group, carboxy group or salt thereof, sulfo group or salt thereof, amino group , Mercapto groups, amide groups, formyl groups, cyano groups, halogen atoms, (meth) acryloyl groups, (meth) acryloyloxy groups, (meth) acrylamide groups, epoxy groups, oxetanyl groups, and combinations thereof. .
  • a group in which an alkyl group and a hydroxy group or a (meth) acryloyloxy group are combined that is, an alkyl group having a hydroxy group and an alkyl group having a (meth) acryloyloxy group are preferable.
  • the formyl group is included in the acyl group.
  • the carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 25, still more preferably 1 to 20, and particularly preferably 1 to 8. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, octyl, dodecyl, stearyl, benzyl, naphthylmethyl, pyrenylmethyl and pyrenylbutyl.
  • the alkyl group preferably contains a double bond or triple bond unsaturated carbon bond inside.
  • the carbon number of the aryl group is preferably 6-30, more preferably 6-26, and particularly preferably 6-15. Specific examples include phenyl, naphthyl, anthracene, terphenyl, tolyl, xylyl, methoxyphenyl, cyanophenyl, and nitrophenyl.
  • the carbon number of the heteroaryl group is preferably 1 to 30, more preferably 1 to 26, and particularly preferably 1 to 15. Specific examples include furan, pyridine, thiophene, pyrrole, triazine, imidazole, tetrazole, pyrazole, thiazole and oxazole.
  • the carbon number of the alkenyl group is preferably 2 to 30, more preferably 2 to 25, and particularly preferably 2 to 20. Specific examples include vinyl and propenyl.
  • the carbon number of the alkynyl group is preferably 2 to 30, more preferably 2 to 25, and particularly preferably 2 to 20. Specific examples include ethynyl, propynyl and phenylethynyl.
  • Alkoxy group The alkyl group constituting the alkoxy group has the same meaning as the above alkyl group.
  • aryl group which comprises an aryloxy group is synonymous with the said aryl group.
  • heteroaryl group which comprises a heteroaryloxy group is synonymous with the said heteroaryl group.
  • alkyl group which comprises an alkylthio group is synonymous with the said alkyl group.
  • Arylthio group The aryl group constituting the arylthio group has the same meaning as the above aryl group.
  • heteroaryl group which comprises a heteroarylthio group is synonymous with the said heteroaryl group.
  • the number of carbon atoms is preferably 1-30, more preferably 1-25, still more preferably 1-20.
  • the acyl group includes a formyl group, an aliphatic carbonyl group, an aromatic carbonyl group, and a heterocyclic carbonyl group.
  • the following groups are mentioned. Formyl, acetyl (methylcarbonyl), benzoyl (phenylcarbonyl), ethylcarbonyl, acryloyl, octylcarbonyl, dodecylcarbonyl (stearic acid residue), linoleic acid residue, linolenic acid residue
  • Acyloxy group The number of carbon atoms is preferably 1-30, more preferably 1-25, still more preferably 1-20. Specific examples of the acyl group are specific examples of the acyl group constituting the acyloxy group.
  • Alkoxycarbonyl group The carbon number is preferably 2 to 30, more preferably 2 to 25, and still more preferably 2 to 20. Specific examples of the alkyl group constituting the alkoxycarbonyl group include specific examples of the alkyl group.
  • Aryloxycarbonyl group The number of carbon atoms is preferably 7 to 30, more preferably 7 to 25, and still more preferably 7 to 20. Specific examples of the aryl group constituting the aryloxycarbonyl group include the specific examples of the aryl group.
  • Alkylcarbonyloxy group the number of carbon atoms is preferably 2 to 30, more preferably 2 to 25, still more preferably 2 to 20.
  • Specific examples of the alkyl group constituting the alkylcarbonyloxy group include the specific examples of the alkyl group.
  • Arylcarbonyloxy group The number of carbon atoms is preferably 7 to 30, more preferably 7 to 25, and still more preferably 7 to 20. Specific examples of the aryl group that constitutes the arylcarbonyloxy group include the specific examples of the aryl group.
  • substituents can generally be introduced by electrophilic substitution reaction, nucleophilic substitution reaction, halogenation, sulfonation, diazotization, or a combination thereof of the compound represented by the general formula (1).
  • Examples thereof include alkylation by Friedel-Craft reaction, acylation by Friedel-Craft reaction, Vilsmeier reaction, transition metal catalyzed coupling reaction and the like.
  • N is more preferably an integer of 0 to 6, particularly preferably an integer of 1 to 4.
  • the compound represented by the general formula (1) is preferably a compound represented by the following general formula (1-1) or (1-2), more preferably a compound represented by the following general formula (1-1). .
  • n1 represents an integer of 1 or more. However, when n1 is 1, in R 11 to R 16 , X 1 and X 2 , at least two adjacent to each other are bonded to form a benzene ring.
  • Rxx has the same meaning as Rxx in the general formula (1), and the preferred range is also the same.
  • R 10 represents a substituent, and nx represents an integer of 0 to 4.
  • m1 represents an integer of 3 or more.
  • Ry represents a hydrogen atom or a substituent. Here, Rxx and Ry may be combined.
  • n1 is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and particularly preferably 1.
  • m1 is preferably an integer of 3 to 10, more preferably an integer of 3 to 8, and particularly preferably an integer of 3 to 5.
  • the compound represented by the following general formula (1-1) is more preferably a compound represented by the following general formula (1-3).
  • R 12 ⁇ R 14, R 16 and X 2 are synonymous with R 12 ⁇ R 14, R 16 and X 2 in the general formula (1) and a similar preferable range .
  • R 13 , R 14 , R 16 and X 2 are more preferably a hydrogen atom
  • R 12 is more preferably an alkyl group having a hydroxy group and an alkyl group having a (meth) acryloyloxy group.
  • ring structure in the compound represented by the general formula (1) examples include anthracene, phenanthracene, pyrene, tetracene, tetraphen, chrysene, triphenylene, pentacene, pentaphen, perylene, benzo [a] pyrene, coronene, and antan.
  • Tren, corannulene, obalene, graphene, cycloparaphenylene, polyparaphenylene and cyclophen are mentioned, and pyrene is preferred.
  • the present invention is not limited to these.
  • a commercially available product can be used as the compound represented by the general formula (1).
  • Y 1 and Y 2 each independently represent a hydrogen atom, a methyl group or a formyl group.
  • R 21 , R 22 , R 23 and R 24 each independently represent a substituent, and a, b, c and d each independently represent an integer of 0 to 4.
  • the A ring may be a saturated ring, an unsaturated ring having 1 or 2 double bonds, or an aromatic ring, and the B ring and the C ring are unsaturated rings having 1 or 2 double bonds. It may be.
  • adjacent substituents may be bonded to form a ring.
  • the A ring, the C ring and the D ring are preferably saturated rings
  • the B ring is preferably an unsaturated ring having two double bonds.
  • the compound represented by the general formula (2) is a compound having a steroid skeleton.
  • the carbon numbers of the steroid skeleton are as follows.
  • the substituent in R 21 , R 22 , R 23 and R 24 may be any substituent, but an alkyl group, an alkenyl group, a hydroxy group, a formyl group, an acyl group, a carboxy group or a salt thereof, (meth) An acryl group, a (meth) acryloyloxy group, a (meth) acrylamide group, an epoxy group, and an oxetanyl group are preferable, and a ⁇ O group formed by jointly forming two substituents on the same carbon atom is preferable. Among these, a hydroxy group and an alkyl group are preferable.
  • the substituent in R 21 , R 22 and R 23 is preferably a hydroxy group
  • the substituent in R 24 is preferably an alkyl group.
  • the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms (preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms), and may have a substituent.
  • Such a substituent may be any substituent, but may be an alkyl group (preferably a methyl group), an alkenyl group, a hydroxy group, a formyl group, an acyl group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfo group.
  • the alkyl group preferably contains a double bond or triple bond unsaturated carbon bond inside.
  • the alkenyl group is preferably an alkenyl group having 1 to 12 carbon atoms and may have a substituent. Such a substituent may be any substituent, and examples thereof include an alkyl group, an alkenyl group, a hydroxy group, a formyl group, an acyl group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, and a sulfo group.
  • R 21 is preferably substituted with carbon number 3
  • R 22 is preferably substituted with carbon number 6 or 7
  • R 23 is preferably substituted with carbon number 12
  • R 24 is substituted with carbon number 17 Is preferably substituted.
  • Y 1 and Y 2 are preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
  • a is preferably an integer of 0 to 2, and more preferably 1.
  • b is preferably an integer of 0 to 2, and more preferably 0.
  • c is preferably an integer of 0 to 2, more preferably 0.
  • d is preferably an integer of 0 to 2, and more preferably 1.
  • the double bond is preferably a bond with carbon numbers 4 and 5
  • the double bond is preferably carbon numbers 5 and 6
  • the C ring is unsaturated.
  • the double bond is preferably a bond having carbon numbers 8 and 9.
  • the compound represented by the general formula (2) includes any of stereoisomers.
  • the bonding direction of the substituent is represented by ⁇ in the downward direction on the paper and ⁇ in the upward direction on the paper, it may be either ⁇ or ⁇ , or a mixture thereof.
  • the arrangement of the A / B ring, the arrangement of the B / C ring, and the arrangement of the C / D ring may be either a trans arrangement or a cis arrangement, or a mixed arrangement thereof. Absent.
  • steroids as shown below are preferable.
  • the substituents on the steroid ring are sterically controlled. From the left, there are cholestanes, cholans, pregnanes, androstanes, and estranes.
  • Specific examples of the compound represented by the general formula (2) include cholesterol, ergosterol, testosterone, estradiol, aldosterol, aldosterone, hydrocortisone, stigmasterol, thymosterol, lanosterol, 7-dehydrodesmosterol, 7-dehydrocholesterol.
  • Cholanic acid, cholic acid, lithocholic acid, deoxycholic acid, sodium deoxycholic acid, lithium deoxycholic acid, hyodeoxycholic acid, chenodeoxycholic acid, ursodeoxycholic acid, dehydrocholic acid, hookecholic acid and hyocholic acid, Cholesterol is preferred.
  • the present invention is not limited to these.
  • the functional group belonging to the functional group group (II) has physical and chemical adsorption ability with the surface of the inorganic solid electrolyte, so that the block polymer used in the present invention has a binding property to the strong inorganic solid electrolyte.
  • a hydroxy group, a carboxy group, a cyano group, an amide group, a urea group, and a urethane group are particularly preferable because of their particularly high affinity for the inorganic solid electrolyte.
  • the functional groups belonging to the functional group groups (I) and (II) have affinity for both the electrode active material and the inorganic solid electrolyte.
  • the block polymer used in the present invention is a block composed of a repeating unit having at least one functional group selected from the functional group (I) and at least one selected from the functional group (II). It preferably includes a block composed of a repeating unit having a functional group.
  • the block polymer used in the present invention has an affinity for the electrode active material and the inorganic solid electrolyte, and is produced using the solid electrolyte composition of the present invention.
  • the adhesion rate between the solid particles can be increased. Therefore, the all-solid-state secondary battery of the present invention forms a good interface between the solid particles, and is excellent in the binding property between the solid particles and between the layers. Therefore, the all-solid-state secondary battery of the present invention can exhibit excellent ion conductivity regardless of pressurization.
  • the content of the repeating unit having the specific functional group among all the repeating units constituting the block polymer used in the present invention is all repeating units. It is preferable that it is 30 mol% or more as 100 mol%.
  • the content of the repeating unit having a specific substituent described later is 100% of all repeating units among all repeating units constituting the block polymer used in the present invention. It is preferable that it is 30 mol% or more as mol%.
  • the content ratio of each block composed of the repeating unit having the specific functional group and / or the specific substituent can be obtained by referring to the method described in the section of the examples.
  • the average particle size (volume average particle size) of the block polymer that can be used in the present invention is not particularly limited, but is preferably 1 nm to 1,000 nm, more preferably 1 nm to 100 nm, and particularly preferably 1 nm to 50 nm. When the average particle size is in the above range, both the binding property and the ion conductivity can be improved.
  • the average particle size of the block polymer can be measured in the same manner as the method for measuring the average particle size ⁇ of the binder (polymer particles) described later.
  • the block polymer that can be used in the present invention is a block comprising a repeating unit having at least one substituent selected from the following substituent group (a) (hereinafter also referred to as “specific substituent”). It is also preferable to contain. Having a substituent belonging to the substituent group (a) is preferable because the dispersion stability of the solid electrolyte composition of the present invention is further improved.
  • the specific substituent is preferably a structure that is preferably dispersed in a hydrocarbon solvent and that can dissolve a lithium salt to enable lithium ion conduction between the active material and the solid electrolyte.
  • a polyether group or a polycarbonate group having a number average molecular weight of 300 or more is preferable.
  • An alkyl group having 8 or more carbon atoms is preferable because aggregation is suppressed by steric repulsion.
  • the alkyl group in the substituent group (a) may be linear or branched.
  • the upper limit of the carbon number of the alkyl group in the substituent group (a) is not particularly limited, but is preferably 100 or less, more preferably 50 or less, and particularly preferably 30 or less. Specific examples include octyl, dodecyl, heptadecyl, nonadecyl, triacontyl, and stearyl.
  • the alkyl group may contain a double bond or triple bond unsaturated carbon bond.
  • the alkenyl group in the substituent group (a) may be linear or branched.
  • the upper limit of the carbon number of the alkenyl group in the substituent group (a) is not particularly limited, but is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. Specific examples include octenyl, dodecenyl, heptadecenyl, nonadecenyl, and triacontenyl.
  • the alkynyl group in the substituent group (a) may be linear or branched.
  • the upper limit of the carbon number of the alkynyl group in the substituent group (a) is not particularly limited, but is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. Specific examples include octynyl, dodecinyl, heptadecinyl, nonadecynyl and triacontinyl.
  • the upper limit of the number average molecular weight of the polyether group, polycarbonate group, polyester group and polysiloxane group having a number average molecular weight of 300 or more is not particularly limited, but is preferably 100,000 or less, more preferably 50,000 or less, and 30,000.
  • the polyether group refers to a monovalent or divalent group having two or more ether bonds.
  • the polycarbonate group refers to a monovalent or divalent group having two or more carbonate bonds.
  • the polyester group refers to a monovalent or divalent group having two or more ester bonds.
  • the polysiloxane group refers to a monovalent or divalent group having two or more siloxane bonds.
  • the block polymer used in the present invention comprises a block composed of a repeating unit having at least one functional group selected from the functional group group (I) and at least one substituent selected from the substituent group (a). And a block consisting of a repeating unit having at least one functional group selected from the functional group group (II) from any one of the end portions of the main chain in this order. preferable.
  • the block unit at both ends of the block polymer used in the present invention acts as a binding agent between the electrode active material and the inorganic solid electrolyte, and is positioned at the center of the block polymer while maintaining the binding state. This is because the block unit to be able to exhibit dispersibility without hindering the binding property.
  • the dispersity (mass average molecular weight: Mw / number average molecular weight: Mn) of the block polymer used in the present invention is preferably less than 1.5.
  • block polymers that can be suitably used in the present invention [Exemplary compounds (A-1) to (A-23)] are shown below, but the present invention is not limited thereto.
  • A-block-B is a mark based on the raw material basic nomenclature of the copolymer
  • -block- is a block of the repeating unit A.
  • the polymer is a block polymer composed of blocks of the repeating unit B (for example, -AAAAAAA-BBBBBBB-).
  • “*” represents a binding site with one polymer main chain terminal portion.
  • N represents an integer.
  • the other main chain terminal is a halogen atom (F, Cl, Br, I), a dithiocarboxylic acid ester or a nitroxide.
  • the above block polymers may be used alone or in combination of two or more.
  • the content of the block polymer is preferably 0.01 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, and more preferably 0.3 to 100 parts by mass of the inorganic solid electrolyte. Is more preferably 5 to 5 parts by mass, and particularly preferably 0.5 to 3 parts by mass. It is preferable to be within the above-mentioned preferable range because the binding property of the solid interface can be enhanced without impeding ion conduction.
  • the mass ratio of the total mass (total amount) of the inorganic solid electrolyte and, if necessary, the electrode active material to the mass of the block polymer [(mass of inorganic solid electrolyte + mass of electrode active material) / mass of block polymer].
  • the inorganic solid electrolyte is an inorganic solid electrolyte, and the solid electrolyte is a solid electrolyte capable of moving ions inside. Since it does not contain organic substances as the main ion conductive material, it is clearly distinguished from organic solid electrolytes (polymer electrolytes typified by PEO and the like, organic electrolyte salts typified by LiTFSI and the like). In addition, since the inorganic solid electrolyte is solid in a steady state, it is not usually dissociated or released into cations and anions.
  • inorganic electrolyte salts LiPF 6 , LiBF 4 , LiFSI, LiCl, etc.
  • the inorganic solid electrolyte is not particularly limited as long as it has ion conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table (hereinafter also referred to as metal ion conductivity). What you don't do is common.
  • the inorganic solid electrolyte has ion conductivity of ions of metals belonging to Group 1 or Group 2 of the Periodic Table.
  • a solid electrolyte material applied to this type of product can be appropriately selected and used.
  • Typical examples of inorganic solid electrolytes include (i) sulfide-based inorganic solid electrolytes and (ii) oxide-based inorganic solid electrolytes.
  • the sulfide-based inorganic solid electrolyte contains sulfur (S) and has ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and What has electronic insulation is preferable.
  • the sulfide-based inorganic solid electrolyte preferably contains at least Li, S and P as elements and has lithium ion conductivity. However, depending on the purpose or the case, other than Li, S and P may be used. An element may be included.
  • a lithium ion conductive inorganic solid electrolyte satisfying the composition represented by the following formula (A) can be mentioned.
  • L a1 M b1 P c1 S d1 A e1 (A)
  • L represents an element selected from Li, Na, and K, and Li is preferable.
  • M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge. Among them, B, Sn, Si, Al, and Ge are preferable, and Sn, Al, and Ge are more preferable, A represents I, Br, Cl, and F, I and Br are preferable, and I is particularly preferable.
  • E1 represents the composition ratio of each element, and a1: b1: c1: d1: e1 satisfies 1 to 12: 0 to 1: 1: 2 to 12: 0 to 5.
  • a1 is more preferably 1 to 9 1.5 to 4 is more preferable, b1 is preferably 0 to 0.5, d1 is further preferably 3 to 7, more preferably 3.25 to 4.5, and e1 is further preferably 0 to 3. 0 to 1 are more preferable.
  • the composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based inorganic solid electrolyte.
  • the sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass ceramic), or only a part may be crystallized.
  • glass glass
  • glass ceramic glass ceramic
  • Li—PS system glass containing Li, P and S, or Li—PS system glass ceramics containing Li, P and S can be used.
  • the sulfide-based inorganic solid electrolyte includes [1] lithium sulfide (Li 2 S) and phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), [2] at least one of lithium sulfide, simple phosphorus and simple sulfur, Or [3] It can be produced by a reaction of lithium sulfide, phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )) and at least one of simple phosphorus and simple sulfur.
  • the ratio of Li 2 S to P 2 S 5 in the Li—PS system glass and the Li—PS system glass ceramic is a molar ratio of Li 2 S: P 2 S 5 , preferably 65:35 to 85:15, more preferably 68:32 to 77:23.
  • the lithium ion conductivity can be increased.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 ⁇ 4 S / cm or more, more preferably 1 ⁇ 10 ⁇ 3 S / cm or more. Although there is no particular upper limit, it is practical that it is 1 ⁇ 10 ⁇ 1 S / cm or less.
  • the compound include those using a raw material composition containing, for example, Li 2 S and a sulfide of an element belonging to Group 13 to Group 15.
  • Li 2 S—P 2 S 5 Li 2 S—LiI—P 2 S 5 , Li 2 S—LiI—Li 2 O—P 2 S 5 , Li 2 S—LiBr—P 2 S 5 Li 2 S—Li 2 O—P 2 S 5 , Li 2 S—Li 3 PO 4 —P 2 S 5 , Li 2 S—P 2 S 5 —P 2 O 5 , Li 2 SP—P 2 S 5 —SiS 2 , 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 S—GeS 2 —ZnS, Li 2 S—Ga 2 S 3 , Li 2 S—GeS 2 —Ga 2 S 3 , Li 2 S—GeS 2 —GeS 2
  • Examples of a method for synthesizing a sulfide-based inorganic solid electrolyte material using such a raw material composition include an amorphization method.
  • Examples of the amorphization method include a mechanical milling method and a melt quenching method, and among them, the mechanical milling method is preferable. This is because processing at room temperature is possible, and the manufacturing process can be simplified.
  • Oxide-based inorganic solid electrolyte contains oxygen (O) and has ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and What has electronic insulation is preferable.
  • ⁇ 4 was filled, zb satisfies 1 ⁇ zb ⁇ 4, mb satisfies 0 ⁇ mb ⁇ 2, nb satisfies 5 ⁇ nb ⁇ 20.) Li xc B yc M cc zc O nc (M cc is C , S, Al, Si, Ga, Ge, In, and Sn, xc satisfies 0 ⁇ xc ⁇ 5, yc satisfies 0 ⁇ yc ⁇ 1, and zc satisfies 0 ⁇ zc ⁇ 1.
  • Li, P and O Phosphorus compounds containing Li, P and O are also desirable.
  • lithium phosphate Li 3 PO 4
  • LiPON obtained by replacing a part of oxygen of lithium phosphate with nitrogen
  • LiPOD 1 LiPOD 1
  • LiA 1 ON A 1 is at least one selected from Si, B, Ge, Al, C, Ga, etc.
  • the ion conductivity that affects the resistance of the battery is high and the processing is easy due to the flexibility of the particles, it is an inorganic material having ion conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table It is preferable that the solid electrolyte is a sulfide-based inorganic solid electrolyte.
  • the shape of the inorganic solid electrolyte is not particularly limited, but is preferably a particle.
  • the volume average particle diameter of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more. As an upper limit, it is preferable that it is 100 micrometers or less, and it is more preferable that it is 50 micrometers or less.
  • the measurement of the volume average particle diameter of an inorganic solid electrolyte particle is performed in the following procedures.
  • the inorganic solid electrolyte particles are prepared by diluting a 1% by weight dispersion in water (heptane in the case of a substance unstable to water) in a 20 ml sample bottle.
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes and used immediately after that.
  • a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA)
  • data was acquired 50 times using a quartz cell for measurement at a temperature of 25 ° C., Obtain the volume average particle size.
  • JISZ8828 2013 “Particle Size Analysis—Dynamic Light Scattering Method” is referred to as necessary. Five samples are prepared for each level, and the average value is adopted.
  • the concentration of the solid component in the solid electrolyte composition of the inorganic solid electrolyte is preferably 5% by mass or more at 100% by mass of the solid component when considering both the battery performance and the reduction / maintenance effect of the interface resistance. It is more preferably 10% by mass or more, and particularly preferably 20% by mass or more. As an upper limit, it is preferable that it is 99.9 mass% or less from the same viewpoint, It is more preferable that it is 99.5 mass% or less, It is especially preferable that it is 99 mass% or less.
  • the solid component refers to a component that does not disappear by volatilization or evaporation when dried at 170 ° C. for 6 hours. Typically, it refers to components other than the dispersion medium described below.
  • the said inorganic solid electrolyte may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the solid electrolyte composition of the present invention preferably contains a binder.
  • the binder that can be used in the present invention is not particularly limited as long as it is an organic polymer.
  • the binder that can be used in the present invention is preferably a binder that is usually used as a binder for a positive electrode or a negative electrode of a battery material, and is not particularly limited.
  • a binder made of a resin described below is preferable.
  • fluorine-containing resin examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and a copolymer of polyvinylidene fluoride and hexafluoropropylene (PVdF-HFP).
  • hydrocarbon-based thermoplastic resin examples include polyethylene, polypropylene, styrene butadiene rubber (SBR), hydrogenated styrene butadiene rubber (HSBR), butylene rubber, acrylonitrile butadiene rubber, polybutadiene, polyisoprene, and polyisoprene latex.
  • acrylic resin examples include poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate isopropyl, poly (meth) acrylate isobutyl, poly (meth) butyl acrylate, poly (meth) ) Hexyl acrylate, poly (meth) acrylate octyl, poly (meth) acrylate dodecyl, poly (meth) acrylate stearyl, poly (meth) acrylate 2-hydroxyethyl, poly (meth) acrylic acid, poly (meth) ) Benzyl acrylate, poly (meth) acrylate glycidyl, poly (meth) acrylate dimethylaminopropyl, and copolymers of monomers constituting these resins.
  • urethane resin examples include polyurethane.
  • copolymers with other vinyl monomers are also preferably used. Examples include poly (meth) acrylate methyl-polystyrene copolymer, poly (meth) acrylate methyl-acrylonitrile copolymer, poly (meth) acrylate butyl-acrylonitrile-styrene copolymer, and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the binder that can be used in the present invention is preferably a polymer particle, and the average particle diameter ⁇ of the polymer particle is preferably 0.01 ⁇ m to 100 ⁇ m, more preferably 0.05 ⁇ m to 50 ⁇ m, and further preferably 0.05 ⁇ m to 20 ⁇ m. preferable. It is preferable from the viewpoint of improving the output density that the average particle diameter ⁇ is in the above preferred range.
  • the average particle diameter ⁇ of the polymer particles that can be used in the present invention is based on the measurement conditions and definitions described below unless otherwise specified.
  • the polymer particles are diluted and prepared in a 20 ml sample bottle using an arbitrary solvent (an organic solvent used for preparing the solid electrolyte composition, for example, heptane).
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes and used immediately after that.
  • the electrode material is measured according to the measurement method of the average particle diameter ⁇ of the polymer particles, This can be done by excluding the measured value of the average particle diameter of the particles other than the polymer particles that has been measured in advance.
  • the structure of the polymer particle is not particularly limited as long as it is an organic polymer particle.
  • the resin constituting the organic polymer particles include the resins described as the resin constituting the binder, and preferred resins are also applied.
  • the shape of the polymer particles is not limited as long as they are solid.
  • the polymer particles may be monodispersed or polydispersed.
  • the polymer particles may be spherical or flat and may be amorphous.
  • the surface of the polymer particles may be smooth or may have an uneven shape.
  • the polymer particles may have a core-shell structure, and the core (inner core) and the shell (outer shell) may be made of the same material or different materials. Moreover, it may be hollow and the hollow ratio is not limited.
  • the polymer particles can be synthesized by a method of polymerizing in the presence of a surfactant, an emulsifier or a dispersant, or a method of depositing in a crystalline form as the molecular weight increases. Moreover, you may use the method of crushing the existing polymer mechanically, and the method of making a polymer liquid fine particle by reprecipitation.
  • the polymer particles may be commercial products, or oily latex polymer particles described in JP-A-2015-88486 and International Publication No. 2015/046314 may be used.
  • the upper limit of the glass transition temperature of the binder is preferably 50 ° C. or lower, more preferably 0 ° C. or lower, and most preferably ⁇ 20 ° C. or lower.
  • the lower limit is preferably ⁇ 100 ° C. or higher, more preferably ⁇ 70 ° C. or higher, and most preferably ⁇ 50 ° C. or higher.
  • the glass transition temperature (Tg) is measured under the following conditions using a dry sample and a differential scanning calorimeter “X-DSC7000” (trade name, manufactured by SII Nanotechnology Co., Ltd.). The measurement is performed twice on the same sample, and the second measurement result is adopted.
  • Measurement chamber atmosphere Nitrogen (50 mL / min) Temperature increase rate: 5 ° C / min Measurement start temperature: -100 ° C Measurement end temperature: 200 ° C
  • Sample pan Aluminum pan Mass of measurement sample: 5 mg Calculation of Tg: Tg is calculated by rounding off the decimal point of the intermediate temperature between the lowering start point and the lowering end point of the DSC chart.
  • the water concentration of the polymer (preferably polymer particles) constituting the binder that can be used in the present invention is preferably 100 ppm (mass basis) or less, and Tg is preferably 100 ° C. or less.
  • the polymer which comprises the binder which can be used for this invention may be crystallized and dried, and a polymer solution may be used as it is. It is preferable that the amount of metal catalyst (urethane-forming, polyester-forming catalyst, tin, titanium, bismuth catalyst) is small. It is preferable that the metal concentration in the copolymer be 100 ppm (mass basis) or less by reducing the amount during polymerization or removing the catalyst by crystallization.
  • the water concentration of the polymer can be measured by the same method as the method for measuring the moisture content of the solid electrolyte composition described later.
  • the solvent used for the polymerization reaction of the polymer is not particularly limited. It is desirable to use a solvent that does not react with the inorganic solid electrolyte or the active material and that does not decompose them.
  • hydrocarbon solvents toluene, heptane, xylene
  • ester solvents ethyl acetate, propylene glycol monomethyl ether acetate
  • ether solvents tetrahydrofuran, dioxane, 1,2-diethoxyethane
  • ketone solvents acetone
  • Methyl ethyl ketone Methyl ethyl ketone, cyclohexanone
  • nitrile solvents acetonitrile, propionitrile, butyronitrile, isobutyronitrile
  • halogen solvents dichloromethane, chloroform
  • the polymer constituting the binder that can be used in the present invention preferably has a mass average molecular weight of 10,000 or more, more preferably 20,000 or more, and even more preferably 50,000 or more. As an upper limit, 1,000,000 or less is preferable, 200,000 or less is more preferable, and 100,000 or less is more preferable.
  • the molecular weight of the polymer means a mass average molecular weight unless otherwise specified. The mass average molecular weight can be measured as a molecular weight in terms of polystyrene by GPC.
  • GPC apparatus HLC-8220 (trade name, manufactured by Tosoh Corporation) was used, the column was G3000HXL + G2000HXL (trade name, manufactured by Tosoh Corporation), the flow rate was 1 mL / min at 23 ° C., and RI. Will be detected.
  • the eluent can be selected from THF (tetrahydrofuran), chloroform, NMP (N-methyl-2-pyrrolidone), m-cresol / chloroform (manufactured by Shonan Wako Pure Chemical Industries, Ltd.) and dissolves. If present, use THF.
  • the concentration of the binder in the solid electrolyte composition is 0.01% by mass or more in 100% by mass of the solid component in consideration of good reduction in interface resistance when used in an all-solid secondary battery and its maintainability. Is preferable, 0.1 mass% or more is more preferable, and 1 mass% or more is further more preferable. As an upper limit, from a viewpoint of a battery characteristic, 10 mass% or less is preferable, 5 mass% or less is more preferable, and 3.5 mass% or less is further more preferable.
  • the mass ratio [(mass of inorganic solid electrolyte + mass of electrode active material) / mass of binder] of the total mass (total amount) of the inorganic solid electrolyte and the electrode active material to be included if necessary with respect to the mass of the binder is: A range of 1,000 to 1 is preferred. This ratio is more preferably 500 to 2, and further preferably 100 to 10.
  • the solid electrolyte composition of the present invention preferably contains a lithium salt.
  • a lithium salt the lithium salt normally used for this kind of product is preferable and there is no restriction
  • the content of the lithium salt is preferably 0 parts by mass or more, more preferably 5 parts by mass or more with respect to 100 parts by mass of the solid electrolyte.
  • As an upper limit 50 mass parts or less are preferable, and 20 mass parts or less are more preferable.
  • the solid electrolyte composition of the present invention contains a conductive additive.
  • a conductive support agent can be used as the conductive support agent.
  • graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black and furnace black, amorphous carbon such as needle coke, vapor-grown carbon fiber and carbon nanotubes, which are electron conductive materials
  • Carbon fibers such as graphene, carbonaceous materials such as graphene and fullerene, metal powders such as copper and nickel, and metal fibers may be used, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives may be used. It may be used.
  • 1 type may be used among these and 2 or more types may be used.
  • the positive electrode active material is preferably one that can reversibly insert and release lithium ions.
  • the material is not particularly limited, and may be a transition metal oxide or an element that can be combined with Li such as sulfur. Among them, it is preferable to use a transition metal oxide, and it is more preferable to have one or more elements selected from Co, Ni, Fe, Mn, Cu, and V as a transition metal element.
  • transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt structure, (MB) a transition metal oxide having a spinel structure, (MC) a lithium-containing transition metal phosphate compound, (MD And lithium-containing transition metal halide phosphate compounds, (ME) lithium-containing transition metal silicate compounds, and the like.
  • transition metal oxide having a layered rock salt structure LiCoO 2 (lithium cobaltate [LCO]), LiNi 2 O 2 (lithium nickelate) LiNi 0.85 Co 0.10 Al 0.05 O 2 (nickel cobalt lithium aluminum oxide [NCA]), LiNi 0.33 Co 0.33 Mn 0.33 O 2 (nickel manganese lithium cobalt oxide [NMC]), LiNi 0.5 Mn 0.5 O 2 (manganese) Lithium nickelate).
  • LCO lithium cobaltate
  • NCA nickelate
  • NMC nickel manganese lithium cobalt oxide
  • NMC nickel manganese lithium cobalt oxide
  • (MB) As specific examples of the transition metal oxide having a spinel structure, LiCoMnO 4, Li 2 FeMn 3 O 8 , Li 2 CuMn 3 O 8 , Li 2 CrMn 3 O 8, Li 2 NiMn 3 O 8, LiMn 2 O 4 is mentioned.
  • Examples of (MC) lithium-containing transition metal phosphate compounds include olivine-type iron phosphate salts such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , LiCoPO 4 and the like. And monoclinic Nasicon type vanadium phosphate salts such as Li 3 V 2 (PO 4 ) 3 (vanadium lithium phosphate).
  • the (MD) lithium-containing transition metal halogenated phosphate compound for example, Li 2 FePO 4 F such fluorinated phosphorus iron salt, Li 2 MnPO 4 hexafluorophosphate manganese salts such as F, Li 2 CoPO 4 F Cobalt fluorophosphates such as
  • Examples of the (ME) lithium-containing transition metal silicate compound include Li 2 FeSiO 4 , Li 2 MnSiO 4 , Li 2 CoSiO 4, and the like.
  • the volume average particle diameter (sphere conversion average particle diameter) of the positive electrode active material used in the all solid state secondary battery of the present invention is not particularly limited. In addition, 0.1 ⁇ m to 50 ⁇ m is preferable. In order to make the positive electrode active material have a predetermined particle size, an ordinary pulverizer or classifier may be used. The positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent. The volume average particle diameter (sphere-converted average particle diameter) of the positive electrode active material particles can be measured using a laser diffraction / scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA).
  • the concentration of the positive electrode active material is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 80% by mass in 100% by mass of the solid component in the positive electrode composition.
  • the positive electrode active materials may be used singly or in combination of two or more.
  • the negative electrode active material is preferably one that can reversibly insert and release lithium ions.
  • the material is not particularly limited, and is a carbonaceous material, a metal oxide such as tin oxide or silicon oxide, a metal composite oxide, a lithium alloy such as lithium alone or a lithium aluminum alloy, and a lithium such as Sn, Si, or In. And metals capable of forming an alloy. Of these, carbonaceous materials or lithium composite oxides are preferably used from the viewpoint of reliability. In addition, the metal composite oxide is preferably capable of inserting and extracting lithium.
  • the material is not particularly limited, but preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
  • the carbonaceous material used as the negative electrode active material is a material substantially made of carbon.
  • carbon black such as petroleum pitch, acetylene black (AB), artificial graphite such as natural graphite and vapor-grown graphite, and various synthetic resins such as PAN (polyacrylonitrile) resin and furfuryl alcohol resin are fired.
  • PAN polyacrylonitrile
  • furfuryl alcohol resin A carbonaceous material can be mentioned.
  • various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA (polyvinyl alcohol) -based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber, etc. And mesophase microspheres, graphite whiskers, flat graphite and the like.
  • carbonaceous materials can be divided into non-graphitizable carbon materials and graphite-based carbon materials depending on the degree of graphitization.
  • the carbonaceous material preferably has a face spacing, density, and crystallite size described in JP-A-62-222066, JP-A-2-6856, and 3-45473.
  • the carbonaceous material does not have to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, or the like is used. You can also.
  • an amorphous oxide is particularly preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used. It is done.
  • amorphous as used herein means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering band having a peak in the region of 20 ° to 40 ° in terms of 2 ⁇ , and is a crystalline diffraction line. You may have.
  • the strongest intensity of crystalline diffraction lines seen from 2 ° to 40 ° to 70 ° is 100 times the diffraction line intensity at the peak of the broad scattering band seen from 2 ° to 20 °. It is preferable that it is 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.
  • amorphous metal oxides and chalcogenides are more preferable, and elements in groups 13 (IIIB) to 15 (VB) of the periodic table are preferable.
  • oxides and chalcogenides composed of one kind of Al, Ga, Si, Sn, Ge, Pb, Sb, Bi or a combination of two or more kinds thereof.
  • preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , SiO, GeO, SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , Bi 2 O 3 , Bi 2 O 4 , SnSiO 3 , GeS, SnS, SnS 2 , PbS, PbS 2 , Sb 2 S 3 , Sb 2 S 5 , SnSiS 3 is preferred.
  • these may be a complex oxide with lithium oxide, for example, Li 2 SnO 2 .
  • the average particle size of the negative electrode active material is preferably 0.1 ⁇ m to 60 ⁇ m.
  • a normal pulverizer or classifier is used.
  • a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill or a sieve is preferably used.
  • wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary.
  • classification is preferably performed.
  • the classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be used both dry and wet.
  • the average particle diameter of the negative electrode active material particles can be measured by the same method as the above-described method for measuring the volume average particle diameter of the positive electrode active material.
  • artificial graphite is preferably used as the negative electrode active material.
  • the negative electrode active material containing a titanium atom is also preferably used. More specifically, since Li 4 Ti 5 O 12 has a small volume fluctuation at the time of occlusion and release of lithium ions, it is excellent in rapid charge / discharge characteristics, electrode deterioration is suppressed, and the life of the lithium ion secondary battery can be improved. This is preferable.
  • the concentration of the negative electrode active material is not particularly limited, but is preferably 10 to 80% by mass, more preferably 20 to 70% by mass in 100% by mass of the solid component in the negative electrode composition.
  • the negative electrode active materials may be used alone or in combination of two or more.
  • the solid electrolyte composition of the present invention may contain a dispersion medium. Any dispersion medium may be used as long as it can disperse the above-described components. Specific examples thereof include the following.
  • alcohol compound solvents examples include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, t-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, and sorbitol.
  • ether compound solvent examples include alkylene glycol alkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether (diglyme), triethylene glycol.
  • alkylene glycol alkyl ether ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether (diglyme), triethylene glycol.
  • amide compound solvent examples include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ⁇ -caprolactam, formamide, N-methylformamide, and acetamide. , N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide.
  • amino compound solvent examples include triethylamine, diisopropylethylamine, and tributylamine.
  • ketone compound solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diisobutyl ketone.
  • aromatic compound solvent examples include benzene, toluene, and xylene.
  • the ester compound solvent is, for example, ethyl acetate, propyl acetate, butyl acetate, ethyl formate, propyl formate, butyl formate, ethyl lactate, propylene glycol monomethyl ether acetate, methyl isobutyrate, isopropyl isobutyrate, methyl pivalate, isopropyl cyclohexanecarboxylate Is mentioned.
  • Examples of the aliphatic compound solvent include pentane, hexane, heptane, octane, decane, and cyclohexane.
  • nitrile compound solvent examples include acetonitrile, propyronitrile, and butyronitrile.
  • the said dispersion medium may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the dispersion medium preferably has a boiling point of 50 ° C. or higher, more preferably 70 ° C. or higher at normal pressure (1 atm).
  • the upper limit is preferably 250 ° C. or lower, and more preferably 220 ° C. or lower.
  • an ether compound solvent preferably dibutyl ether
  • an amide compound solvent preferably N, N-dimethylformamide
  • an aromatic compound solvent preferably xylene
  • an aliphatic compound solvent preferably, It is preferable to use at least one selected from the group consisting of heptane
  • hydrocarbon solvents include the above aromatic compound solvents and aliphatic compound solvents.
  • the water content of the solid electrolyte composition of the present invention is preferably 50 ppm or less, more preferably 40 ppm or less, and even more preferably 30 ppm or less.
  • the lower limit of the moisture content is not particularly limited, but 0.001 ppm or more is practical.
  • the water content of the solid electrolyte composition can be measured by the Karl Fischer method. For example, a trace moisture measuring device CA-200 (trade name, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) may be used as the measuring device, and Aquamicron AX (trade name, manufactured by Mitsubishi Chemical Corporation) may be used as the Karl Fischer liquid. it can.
  • the content of the dispersion medium with respect to 100 parts by mass of the total solid content of the solid electrolyte composition is preferably 10 to 300 parts by mass, and more preferably 50 to 150 parts by mass.
  • the positive and negative current collectors are preferably electron conductors that do not cause chemical changes.
  • the positive electrode current collector is preferably made by treating the surface of aluminum or stainless steel with carbon, nickel, titanium or silver in addition to aluminum, stainless steel, nickel, titanium, etc. Among them, aluminum and aluminum alloys are more preferable. preferable.
  • the current collector of the negative electrode is preferably aluminum, copper, stainless steel, nickel, or titanium, and more preferably aluminum, copper, or a copper alloy.
  • the current collector is usually in the form of a film sheet, but a net, a punched one, a lath, a porous body, a foam, a fiber group molded body, or the like can also be used.
  • the thickness of the current collector is not particularly limited, but is preferably 1 ⁇ m to 500 ⁇ m.
  • the current collector surface is roughened by surface treatment.
  • the all-solid-state secondary battery may be manufactured by a conventional method. Specifically, the solid electrolyte composition of this invention is apply
  • the electrode layer contains an active material. From the viewpoint of improving ion conductivity, the electrode layer preferably contains the inorganic solid electrolyte. Further, from the viewpoint of improving the binding property between the solid particles, between the electrodes, and between the electrode and the current collector, the electrode layer preferably contains a block polymer, and preferably contains a binder.
  • the solid electrolyte layer contains a block polymer and an inorganic solid electrolyte. From the viewpoint of improving the binding between the solid particles and between the layers, the solid electrolyte layer preferably also contains a binder.
  • a composition serving as a positive electrode material is applied on a metal foil that is a positive electrode current collector, a positive electrode active material layer is formed, and a positive electrode sheet for a battery is produced.
  • the solid electrolyte composition of the present invention is applied to form a solid electrolyte layer.
  • a composition to be a negative electrode material is applied on the solid electrolyte layer to form a negative electrode active material layer.
  • a structure of an all-solid-state secondary battery in which a solid electrolyte layer is sandwiched between a positive electrode layer and a negative electrode layer can be obtained by stacking a negative electrode side current collector (metal foil) on the negative electrode active material layer. it can.
  • coating method of said each composition should just follow a conventional method.
  • the composition for forming the positive electrode active material layer, the composition for forming the inorganic solid electrolyte layer, and the composition for forming the negative electrode active material layer may be subjected to a drying treatment after being applied.
  • a drying process may be performed.
  • the drying temperature is not particularly limited.
  • the lower limit is preferably 30 ° C or higher, more preferably 60 ° C or higher, and the upper limit is preferably 300 ° C or lower, more preferably 250 ° C or lower.
  • the all solid state secondary battery of the present invention can be applied to various uses. Although there is no particular limitation on the application mode, for example, when installed in an electronic device, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a mobile phone, a cordless phone, a pager, a handy terminal, a mobile fax machine, a mobile phone Copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, minidisc, electric shaver, transceiver, electronic notebook, calculator, portable tape recorder, radio, backup power supply, memory card, etc.
  • Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military use and space use. Moreover, it can also combine with a solar cell.
  • a solid electrolyte composition (a positive electrode or negative electrode composition) containing an electrode active material.
  • An electrode sheet for an all-solid secondary battery having a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order, At least one of a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer, An inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table;
  • a block polymer comprising a block comprising a repeating unit having a functional group selected from the following functional group group (I) having an affinity for an electrode active material and / or the following functional group group (II) having an affinity for an inorganic solid electrolyte
  • An electrode sheet for an all solid secondary battery is derived.
  • An electrode sheet for an all-solid secondary battery having a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order, All layers of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer are An electrode sheet for an all-solid secondary battery, containing the inorganic solid electrolyte and the block polymer.
  • An all-solid secondary battery configured using the electrode sheet for an all-solid secondary battery.
  • a method for producing an all-solid-state secondary battery comprising producing an all-solid-state secondary battery via the method for producing an electrode sheet for an all-solid-state secondary battery.
  • the electrode sheet for an all-solid secondary battery of the present invention was prepared not only in a sheet containing an active material such as a positive electrode sheet for an all-solid secondary battery prepared in an example described later but also in an example described later. Solid electrolyte sheets (sheets containing no active material) are also included.
  • Examples of the method for applying the solid electrolyte composition on the metal foil include coating (wet coating, spray coating, spin coating coating, slit coating, stripe coating, bar coating coating dip coating), and wet coating ( Coating) is preferred.
  • An all-solid secondary battery refers to a secondary battery in which the positive electrode, the negative electrode, and the electrolyte are all solid. In other words, it is distinguished from an electrolyte type secondary battery using a carbonate-based solvent as an electrolyte.
  • this invention presupposes an inorganic all-solid-state secondary battery.
  • the all-solid-state secondary battery includes an organic (polymer) all-solid-state secondary battery that uses a polymer compound such as polyethylene oxide as an electrolyte, and an inorganic all-solid-state that uses the above-described Li—PS glass, LLT, LLZ, or the like. It is divided into secondary batteries.
  • the application of the polymer compound to the inorganic all-solid secondary battery is not hindered, and the polymer compound can be applied as a binder for the positive electrode active material, the negative electrode active material, and the inorganic solid electrolyte.
  • the inorganic solid electrolyte is distinguished from an electrolyte (polymer electrolyte) using the above-described polymer compound as an ion conductive medium, and the inorganic compound serves as an ion conductive medium. Specific examples include the above-described Li—PS glass, LLT, and LLZ.
  • the inorganic solid electrolyte itself does not release cations (Li ions) but exhibits an ion transport function.
  • electrolyte a material that is added to the electrolytic solution or the solid electrolyte layer and serves as a source of ions that release cations (Li ions) is sometimes called an electrolyte.
  • electrolyte salt When distinguishing from the electrolyte as the above ion transport material, this is called “electrolyte salt” or “supporting electrolyte”.
  • electrolyte salt An example of the electrolyte salt is LiTFSI.
  • composition means a mixture in which two or more components are uniformly mixed. However, as long as the uniformity is substantially maintained, aggregation or uneven distribution may partially occur within a range in which a desired effect is achieved.
  • Synthesis example 1 Synthesis of Exemplary Compound (A-1) In a 300 mL three-necked flask, 3.1 g of ethyl 2-bromoisobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10.2 g of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added with propylene glycol monomethyl ether Dissolved in 50 g of acetate and bubbled with nitrogen for 10 minutes. Separately, 0.50 g of copper (I) bromide and 0.92 g of 2,2′-bipyridyl were dissolved in 3 g of propylene glycol monomethyl ether to form a copper complex.
  • ethyl 2-bromoisobutyrate manufactured by Tokyo Chemical Industry Co., Ltd.
  • acrylic acid manufactured by Wako Pure Chemical Industries, Ltd.
  • the copper complex that had been heated up to 90 ° C. while a 300 mL three-necked flask was allowed to flow with nitrogen was added.
  • the mixture was heated and stirred at 90 ° C. for 6 hours, and after consumption of the monomer was confirmed by liquid high performance chromatography (HPLC), 11.6 g of methyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was added.
  • HPLC liquid high performance chromatography
  • 11.6 g of methyl acrylate manufactured by Wako Pure Chemical Industries, Ltd.
  • the obtained polymer solution was added to 500 mL of methanol / water (4/1) to perform reprecipitation operation.
  • the polymer was collected by filtration and dried under vacuum at 120 ° C. for 6 hours to obtain a block polymer (A-1).
  • the number average molecular weight was 6,890, and the degree of dispersion was 1.43.
  • Synthesis example 2 Synthesis of Exemplary Compound (A-4) To a 300 mL three-necked flask, 4.0 g of 2-cyanoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.5 g of triethylamine, and 100 mL of tetrahydrofuran were added, and cooled to 5 ° C. in an ice bath under a nitrogen atmosphere. did. To this was added dropwise a mixture of 11.5 g of bromoisobutyric acid bromide (Tokyo Kasei Co., Ltd.) and 20 mL of tetrahydrofuran over 10 minutes. The reaction was stirred at room temperature (25 ° C.) for a further 4 hours.
  • the block polymer was synthesized by using the block polymer starting unit (2-cyanoethyl 2-bromo-2-methylpropanoate) obtained above, and adding acrylic acid, stearyl acrylate, and acrylic acid in this order.
  • the block polymer was prepared in the same manner as in Synthesis Example 1 except that polymerization was performed so that the mol% constituting the block of acid)-(stearyl acrylate)-(acrylic acid) was 30 mol% -40 mol% -30 mol%. (A-4) was obtained.
  • the number average molecular weight was 4,560, and the degree of dispersion was 1.33.
  • Synthesis example 3 Synthesis of Exemplary Compound (A-5)
  • the synthesis of the block polymer starting unit (3- (2-bromo-2-methylpropanoyloxy) propionic acid) was performed using 3-hydroxypropionic acid instead of 2-cyanoethanol. Except for the above, synthesis was performed in the same manner as in Synthesis Example 2.
  • the block polymer was synthesized using the block polymer starting unit (3- (2-bromo-2-methylpropanoyloxy) propionic acid) obtained above, and acrylic acid, dodecyl acrylate and N-isopropylacrylamide in this order.
  • Synthesis Example 2 except that the polymer was added and polymerized so that the mol% constituting the block of (acrylic acid)-(dodecyl acrylate)-(N-isopropylacrylamide) was 20 mol% -30 mol% -50 mol%
  • a block polymer (A-5) was obtained.
  • the number average molecular weight was 4,280, and the degree of dispersion was 1.49.
  • Synthesis example 4 Synthesis of Exemplary Compound (A-8) The synthesis of the block polymer starting unit (pyren-1-ylmethyl 2-bromo-2-methylpropanoate) was performed except that 1-pyrenemethanol was used instead of 2-cyanoethanol. Synthesis was performed in the same manner as in Synthesis Example 2.
  • the block polymer was synthesized using the block polymer starting unit (pyren-1-ylmethyl 2-bromo-2-methylpropanoate) obtained above, and pyren-1-ylmethyl acrylate, polyethylene glycol monomethyl ether acrylate (number average) (Molecular weight 850), acrylic acid was added in this order, and the mol% constituting the block of (pyrene-1-ylmethyl acrylate)-(polyethylene glycol monomethyl ether acrylate)-(acrylic acid) was 30 mol% -40 mol%
  • a block polymer (A-8) was obtained in the same manner as in Synthesis Example 2 except that the polymerization was performed so that the concentration was ⁇ 30 mol%.
  • the number average molecular weight was 8,520, and the degree of dispersion was 1.43.
  • Synthesis example 5 Synthesis of Exemplary Compound (A-11) The synthesis of the block polymer starting unit (cholesteryl 2-bromo-2-methylpropanoate) was the same as in Synthesis Example 2 except that cholesterol was used instead of 2-cyanoethanol. was synthesized.
  • the block polymer was synthesized using the block polymer starting unit (cholesteryl 2-bromo-2-methylpropanoate) obtained above, cholesteryl acrylate, polyethylene glycol monomethyl ether acrylate (number average molecular weight 850), 2-methacryloyl Block of Roxyethylphthalic acid (CB-12: trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) in this order (cholesteryl acrylate)-(polyethylene glycol monomethyl ether acrylate)-(2-methacryloyloxyethylphthalic acid)
  • a block polymer (A-11) was obtained in the same manner as in Synthetic Example 2 except that the polymerization was performed so that the mol% constituting the polymer was 30 mol% -40 mol% -30 mol%.
  • the number average molecular weight was 6,190, and the degree of dispersion was 1.39.
  • the weight average molecular weight and the number average molecular weight are those converted to standard polystyrene by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • said dispersion degree was computed by the mass average molecular weight / number average molecular weight.
  • the content ratio of each repeating unit constituting the exemplified compound synthesized above was determined from the monomer charge ratio at the time of polymerization.
  • the block polymer was diluted with a solvent (dispersion medium used in the preparation of the solid electrolyte composition. For example, heptane) to prepare a 1% by mass dispersion in a 20 ml sample bottle.
  • the diluted dispersion sample was irradiated with 1 kHz ultrasonic waves for 10 minutes and used for the test immediately after that.
  • LA-920 laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA)
  • Li 2 S lithium sulfide
  • P 2 S 5 diphosphorus pentasulfide
  • Table 1 summarizes the composition and components of the solid electrolyte composition.
  • the solid electrolyte compositions S-2 to S-10 are solid electrolyte compositions of the present invention
  • the solid electrolyte compositions T-1 to T-3 are comparative solid electrolyte compositions.
  • composition for positive electrode- In a planetary mixer (TK Hibismix, trade name, manufactured by Primix), 5 parts by mass of acetylene black, 270 parts by mass of N-methylpyrrolidone, and 100 parts by mass of the positive electrode active material described in the column of the composition for positive electrode in Table 2 below And 75 mass parts of solid electrolyte compositions were added, and it stirred for 1 hour at the rotation speed of 40 rpm and the temperature of 25 degreeC, and prepared the composition for positive electrodes described in Table 2 below.
  • TK Hibismix trade name, manufactured by Primix
  • composition for negative electrode- In a planetary mixer (TK Hibismix, trade name, manufactured by Primix Co., Ltd.), 5 parts by mass of acetylene black, 270 parts by mass of N-methylpyrrolidone, 100 parts by mass of the negative electrode active material described in the column of the composition for negative electrode in Table 2 below And 75 mass parts of solid electrolyte compositions were added, and it stirred for 1 hour at the rotation speed of 40 rpm and the temperature of 25 degreeC, and prepared the composition for negative electrodes described in Table 2 below.
  • TK Hibismix trade name, manufactured by Primix Co., Ltd.
  • the solid electrolyte composition S-1 was applied onto an aluminum foil having a thickness of 20 ⁇ m with an applicator (trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.), heated at 80 ° C. for 1 hour, and then further 120 The dispersion medium was dried by heating at 0 ° C. for 1 hour. Thereafter, using a heat press machine, the solid electrolyte layer was pressurized while being heated (150 ° C.) (30 MPa, 10 seconds). 101 solid electrolyte sheet was obtained. The film thickness of the solid electrolyte layer was 50 ⁇ m.
  • test no In the same manner as the solid electrolyte sheet of No. 101, Test No. Solid electrolyte sheets of 104, 106, 108, 110, c11 and c12 were produced.
  • composition for an all-solid-state secondary battery positive electrode prepared above was applied onto an aluminum foil (current collector) having a thickness of 20 ⁇ m with an applicator (trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.). After heating at 1 ° C. for 1 hour, the coating solvent was dried by further heating at 110 ° C. for 1 hour. Then, using a heat press machine, pressurizing while heating (120 ° C.) (10 MPa, 1 minute) to produce a positive electrode sheet for an all-solid-state secondary battery having a positive electrode active material layer / aluminum foil laminated structure having a thickness of 170 ⁇ m. did.
  • the solid electrolyte composition described in the column of the solid electrolyte composition in Table 2 below was applied with an applicator (trade name: SA-201 Baker type applicator, Tester Sangyo Co., Ltd.). And heated at 80 ° C. for 1 hour and further heated at 110 ° C. for 1 hour to form a solid electrolyte layer having a thickness of 50 ⁇ m. Thereafter, the negative electrode composition prepared above was further applied, heated at 80 ° C. for 1 hour, and further heated at 110 ° C. for 1 hour to form a negative electrode active material layer having a thickness of 100 ⁇ m.
  • a copper foil having a thickness of 20 ⁇ m was combined on the negative electrode active material layer, and pressure (10 MPa, 1 minute) was applied while heating (120 ° C.) using a heat press machine.
  • 102, 103, 105, 107, 109, 111 to 118 and c13 to c15 all-solid-state secondary battery electrode sheets were produced.
  • the electrode sheet for an all-solid-state secondary battery has the configuration shown in FIG. 1, and is a laminated structure of copper foil / negative electrode active material layer / inorganic solid electrolyte layer / positive electrode sheet for all-solid-state secondary battery (positive electrode active material layer / aluminum foil).
  • the positive electrode active material layer, the negative electrode active material layer, and the inorganic solid electrolyte layer were prepared so as to have film thicknesses of 150 ⁇ m, 100 ⁇ m, and 50 ⁇ m in order, respectively. Was made so that the film thickness was ⁇ 10%.
  • LMO LiMn 2 O 4 lithium manganate
  • LTO Li 4 Ti 5 O 12 lithium titanate (trade name “Enamite LT-106”, manufactured by Ishihara Sangyo Co., Ltd.)
  • LCO LiCoO 2 lithium cobaltate
  • NMC LiNi 0.33 Co 0.33 Mn 0.33 O 2 nickel manganese lithium cobaltate
  • Graphite Artificial graphite (trade name: SMG-HP2K manufactured by Hitachi Chemical)
  • a group having a ring structure having three or more rings has a skeletal structure (see the exemplified compounds (A-1) to (A-23) above).
  • exemplary compound (A-1) has one block composed of repeating units having a carboxy group belonging to functional group (I) and (II). In such a case (for example, test No. 101), the carboxy group is described in the column “functional group (I)”.
  • the exemplified compound (A-4) has two blocks composed of repeating units having a carboxy group belonging to the functional group groups (I) and (II).
  • the carboxy group is described in the column of “functional group (I)” and “functional group (II)”.
  • the solid electrolyte composition, the positive electrode composition, and the negative electrode composition that satisfy the provisions of the present invention are excellent in dispersion stability.
  • the dispersion stability of the solid electrolyte composition, the positive electrode composition, and the negative electrode composition that did not satisfy the provisions of the present invention was below the acceptable level.
  • Test No. 1 of the present invention produced above. 101-118 and test No. for comparison.
  • a binding test was performed on each of the sheets c11 to c14.
  • a coin battery or an all-solid secondary battery was produced using each sheet, and the ionic conductivity was measured.
  • the test method and measurement method are described below. The test and measurement results are summarized in Table 4 below.
  • the battery thus produced was used for measurement of ionic conductivity in a state where no pressure was applied, that is, in a “non-pressurized” state described in Table 4 below. Further, it was sandwiched between jigs capable of applying pressure between the electrodes from the outside of the battery thus produced, and used for measurement of ion conductivity in the “pressurized” state described in Table 4 below.
  • the pressure between the electrodes was 49 MPa.
  • 11 is an upper support plate
  • 12 is a lower support plate
  • 13 is a battery (coin battery or all-solid secondary battery)
  • 14 is a coin case
  • 15 is a sheet (solid electrolyte sheet or electrode sheet for all-solid secondary battery)
  • S I is a screw.
  • the sample film thickness means the thickness of the solid electrolyte layer or the total thickness of the three layers of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer.
  • the sample area means the surface area of the solid electrolyte layer.
  • the coin battery and the all-solid secondary battery produced from the solid electrolyte composition satisfying the provisions of the present invention are excellent in binding properties and are in a pressurized state even in a non-pressurized state. It turns out that there exists the same level of ionic conductivity.
  • the coin battery and the all-solid secondary battery produced from the solid electrolyte composition that does not satisfy the provisions of the present invention have insufficient binding properties.
  • the ionic conductivity was significantly inferior in the non-pressurized state compared to the pressurized state.

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Abstract

La présente invention porte sur une composition d'électrolyte solide qui contient un polymère séquencé et un électrolyte solide inorganique qui possède une conductivité d'ions d'un métal du groupe 1 ou du groupe 2 du tableau périodique, et le polymère séquencé contenant au moins un bloc qui est composé d'une unité répétitive ayant au moins un groupe fonctionnel qui est choisi dans le groupe constitué de groupes fonctionnels spécifiques ; une feuille d'électrode pour batteries rechargeables tout solide, qui utilise cette composition d'électrolyte solide ; une batterie rechargeable tout solide ; un procédé de production de feuille d'électrode pour batteries rechargeables tout solide ; et un procédé de fabrication de batterie secondaire tout solide.
PCT/JP2016/074045 2015-08-18 2016-08-17 Composition d'électrolyte solide, feuille d'électrode pour batteries rechargeables tout solide, batterie rechargeable tout solide, procédé de production de feuille d'électrode pour batteries rechargeables tout solide, et procédé de fabrication de batterie rechargeable tout solide WO2017030154A1 (fr)

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CN109599561A (zh) * 2017-09-30 2019-04-09 宁德时代新能源科技股份有限公司 全固态锂离子二次电池用粘结剂、电解质膜片、电极膜片、电池及制备方法
WO2019073692A1 (fr) * 2017-10-11 2019-04-18 学校法人福岡大学 Composition de modification de surface, objet modifié et procédé de production associé
CN109755643A (zh) * 2018-12-28 2019-05-14 浙江大学 一种富氧的聚合物电解质及其制备方法和应用
JP2019121603A (ja) * 2017-12-28 2019-07-22 財團法人工業技術研究院Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ 電解質、電解質に用いる組成物、およびそれを用いたリチウム電池
WO2019203334A1 (fr) * 2018-04-20 2019-10-24 富士フイルム株式会社 Composition d'électrolyte solide, feuille de batterie secondaire tout solide, batterie secondaire tout solide, et procédé de fabrication d'une feuille de batterie secondaire tout solide ou d'une batterie secondaire tout solide
WO2020022205A1 (fr) * 2018-07-25 2020-01-30 富士フイルム株式会社 Composition d'électrolyte solide, feuille contenant un électrolyte solide, feuille d'électrode de batterie secondaire tout solide, batterie secondaire tout solide, procédés de production de feuille contenant un électrolyte solide et batterie secondaire tout solide, et procédé de production de liant particulaire
JPWO2021060541A1 (fr) * 2019-09-27 2021-04-01
WO2021085549A1 (fr) * 2019-10-30 2021-05-06 富士フイルム株式会社 Composition contenant un électrolyte solide inorganique, feuille pour batterie secondaire entièrement solide et batterie secondaire entièrement solide, et procédés de fabrication de feuille pour batterie secondaire entièrement solide et pour fabrication de batterie secondaire entièrement solide
CN113851650A (zh) * 2020-06-28 2021-12-28 比亚迪股份有限公司 正极片、全固态锂电池
KR20230074542A (ko) 2020-12-25 2023-05-30 후지필름 가부시키가이샤 무기 고체 전해질 함유 조성물, 전고체 이차 전지용 시트 및 전고체 이차 전지, 및, 전고체 이차 전지용 시트 및 전고체 이차 전지의 제조 방법

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CN109599561A (zh) * 2017-09-30 2019-04-09 宁德时代新能源科技股份有限公司 全固态锂离子二次电池用粘结剂、电解质膜片、电极膜片、电池及制备方法
WO2019073692A1 (fr) * 2017-10-11 2019-04-18 学校法人福岡大学 Composition de modification de surface, objet modifié et procédé de production associé
JP2019121603A (ja) * 2017-12-28 2019-07-22 財團法人工業技術研究院Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ 電解質、電解質に用いる組成物、およびそれを用いたリチウム電池
JPWO2019203334A1 (ja) * 2018-04-20 2021-05-13 富士フイルム株式会社 固体電解質組成物、全固体二次電池用シート、及び全固体二次電池、並びに、全固体二次電池用シート若しくは全固体二次電池の製造方法
WO2019203334A1 (fr) * 2018-04-20 2019-10-24 富士フイルム株式会社 Composition d'électrolyte solide, feuille de batterie secondaire tout solide, batterie secondaire tout solide, et procédé de fabrication d'une feuille de batterie secondaire tout solide ou d'une batterie secondaire tout solide
WO2020022205A1 (fr) * 2018-07-25 2020-01-30 富士フイルム株式会社 Composition d'électrolyte solide, feuille contenant un électrolyte solide, feuille d'électrode de batterie secondaire tout solide, batterie secondaire tout solide, procédés de production de feuille contenant un électrolyte solide et batterie secondaire tout solide, et procédé de production de liant particulaire
CN112470316A (zh) * 2018-07-25 2021-03-09 富士胶片株式会社 固体电解质组合物、含固体电解质的片材、全固态二次电池用电极片及全固态二次电池、含固体电解质的片材及全固态二次电池的制造方法以及粒子状粘合剂的制造方法
JPWO2020022205A1 (ja) * 2018-07-25 2021-04-08 富士フイルム株式会社 固体電解質組成物、固体電解質含有シート、全固体二次電池用電極シート及び全固体二次電池、固体電解質含有シート及び全固体二次電池の製造方法、並びに、粒子状バインダーの製造方法
US20210143472A1 (en) * 2018-07-25 2021-05-13 Fujifilm Corporation Solid electrolyte composition, solid electrolyte-containing sheet, electrode sheet for all-solid state secondary battery, all-solid state secondary battery, method of manufacturing solid electrolyte-containing sheet, method of manufacturing all-solid state secondary battery, and method of manufacturing particle binder
CN109575267A (zh) * 2018-12-03 2019-04-05 上海交通大学 聚醚基聚合物、交联网络聚合物及电化学器件
CN109575267B (zh) * 2018-12-03 2020-12-18 上海交通大学 聚醚基聚合物、交联网络聚合物及电化学器件
CN109755643B (zh) * 2018-12-28 2020-11-10 浙江大学 一种富氧的聚合物电解质及其制备方法和应用
CN109755643A (zh) * 2018-12-28 2019-05-14 浙江大学 一种富氧的聚合物电解质及其制备方法和应用
JPWO2021060541A1 (fr) * 2019-09-27 2021-04-01
JP7373577B2 (ja) 2019-09-27 2023-11-02 富士フイルム株式会社 無機固体電解質含有組成物、全固体二次電池用シート、全固体二次電池用電極シート及び全固体二次電池、並びに、全固体二次電池用シート及び全固体二次電池の製造方法
WO2021085549A1 (fr) * 2019-10-30 2021-05-06 富士フイルム株式会社 Composition contenant un électrolyte solide inorganique, feuille pour batterie secondaire entièrement solide et batterie secondaire entièrement solide, et procédés de fabrication de feuille pour batterie secondaire entièrement solide et pour fabrication de batterie secondaire entièrement solide
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JP7263536B2 (ja) 2019-10-30 2023-04-24 富士フイルム株式会社 無機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、並びに全固体二次電池用シート及び全固体二次電池の製造方法
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KR20230074542A (ko) 2020-12-25 2023-05-30 후지필름 가부시키가이샤 무기 고체 전해질 함유 조성물, 전고체 이차 전지용 시트 및 전고체 이차 전지, 및, 전고체 이차 전지용 시트 및 전고체 이차 전지의 제조 방법

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