WO2021060541A1 - 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 - Google Patents

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 Download PDF

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WO2021060541A1
WO2021060541A1 PCT/JP2020/036472 JP2020036472W WO2021060541A1 WO 2021060541 A1 WO2021060541 A1 WO 2021060541A1 JP 2020036472 W JP2020036472 W JP 2020036472W WO 2021060541 A1 WO2021060541 A1 WO 2021060541A1
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solid electrolyte
inorganic solid
active material
secondary battery
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French (fr)
Japanese (ja)
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安田　浩司
宏顕 望月
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Fujifilm Corp
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Fujifilm Corp
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Priority to CN202080066902.9A priority Critical patent/CN114531927B/zh
Priority to JP2021548468A priority patent/JP7373577B2/ja
Priority to KR1020227009358A priority patent/KR20220050191A/ko
Publication of WO2021060541A1 publication Critical patent/WO2021060541A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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 an inorganic solid electrolyte-containing composition, an all-solid-state secondary battery sheet, an all-solid-state secondary battery electrode sheet and an all-solid-state secondary battery, and an all-solid-state secondary battery sheet and an all-solid-state secondary battery. Regarding the manufacturing method.
  • the negative electrode, electrolyte, and positive electrode of the all-solid-state secondary battery are all solid, which can greatly improve the safety and reliability of batteries using organic electrolytes. It is also said that it will be possible to extend the service life. Further, the all-solid-state secondary battery can have a structure in which electrodes and electrolytes are directly arranged side by side and arranged in series. Therefore, it is possible to increase the energy density as compared with a secondary battery using an organic electrolytic solution, and it is expected to be applied to an electric vehicle, a large storage battery, or the like.
  • solid particle materials such as an inorganic solid electrolyte, an active material, and a conductive auxiliary agent are used as substances forming the constituent layers (solid electrolyte layer, negative electrode active material layer, positive electrode active material layer, etc.). Used. Therefore, as the material for forming such a constituent layer (constituent layer forming material), in addition to the solid particle material, a material such as a binder for binding the solid particle material and a dispersant for dispersing in the dispersion medium is usually used. Be done.
  • Patent Document 1 describes a positive electrode active material, an inorganic solid electrolyte having conductivity of an ion of a metal belonging to Group 1 or Group 2 of the Periodic Table, a conductive auxiliary agent, and a compound having a specific functional group.
  • a material for a positive electrode containing a dispersant containing the above is described.
  • Patent Document 2 describes (A) an inorganic solid electrolyte having conductivity of an ion of a metal belonging to Group 1 or Group 2 of the Periodic Table, and (B) a fluorine-containing compound satisfying a specific condition at a specific content. And (C) a dispersion medium are described.
  • Patent Document 3 describes an inorganic solid electrolyte (A) having conductivity of an ion of a metal belonging to Group 1 or Group 2 of the periodic table, and a compound (B) represented by a specific formula as a polymer dispersant.
  • a solid electrolyte composition comprising and is described.
  • a material using a solid electrolyte in which the solid electrolyte is surface-treated in advance is also proposed, instead of a substance in which the constituent layer forming material is used in combination with an inorganic solid electrolyte or the like.
  • Patent Document 4 contains a coated solid electrolyte for a lithium battery in which the surface of a sulfide-based solid electrolyte containing at least lithium and phosphorus is coated with a fluorine-containing silane compound or a fluorine-containing acrylic resin, and a binder. The solution to be used is described.
  • a constituent layer formed of a solid particle material in general, an interfacial contact state between solid particles (for example, between inorganic solid electrolytes, between inorganic solid electrolytes and active materials, and between active materials). Is not enough. Further, the constituent layers of the all-solid secondary battery, particularly the active material layer, repeat expansion and contraction (contraction and expansion of the active material due to the release and absorption of metal ions belonging to Group 1 or Group 2 of the Periodic Table) by charging and discharging. Then, the contact state between the solid particles gradually decreases.
  • the (negative electrode) active material that can be alloyed with lithium exhibits high ionic conductivity and is attracting attention because it contributes to the improvement of basic battery performance, but on the other hand, it is a solid with large expansion and contraction due to charging and discharging.
  • the contact state between particles is significantly reduced. It is considered that such a decrease in the contact state between the solid particles is caused by the gradual formation of voids between the solid particles in the constituent layer, which not only increases the resistance of the all-solid secondary battery but also increases the resistance. It also reduces cycle characteristics.
  • the present invention provides an inorganic solid electrolyte-containing composition capable of realizing a constituent layer capable of suppressing the generation of voids due to charging and discharging of the all-solid secondary battery by using it as a constituent layer forming material of the all-solid secondary battery. Is an issue. Further, the present invention uses the inorganic solid electrolyte-containing composition to form an all-solid-state secondary battery sheet, an all-solid-state secondary battery electrode sheet, an all-solid-state secondary battery, an all-solid-state secondary battery sheet, and the like. An object of the present invention is to provide a method for manufacturing an all-solid-state secondary battery.
  • the present inventors have made an inorganic solid electrolyte-containing composition using a compound (SA) having a specific molecular structure and having a specific functional group introduced in combination with the inorganic solid electrolyte. It has been found that by using a compound as a material for forming a constituent layer of an all-solid secondary battery, it is possible to realize a constituent layer in which the frictional resistance between solid particles is reduced and voids are less likely to be generated when the constituent layer expands and contracts due to charging and discharging. ..
  • SA compound having a specific molecular structure and having a specific functional group introduced in combination with the inorganic solid electrolyte.
  • the constituent layer formed of the inorganic solid electrolyte-containing composition as the seat for the all-solid-state secondary battery or the constituent layer of the all-solid-state secondary battery, the resistance of the all-solid-state secondary battery can be reduced and the cycle characteristics can be reduced. It was found that it is possible to improve.
  • the present invention has been further studied based on these findings and has been completed.
  • ⁇ 1> Contains an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and at least one compound (SA) selected from the following (A) to (C).
  • Inorganic solid electrolyte-containing composition (A): Compound formula represented by the following formula (1) (1) RAX
  • R has no fluorine atom and does not have an aliphatic hydrocarbon group having 6 or more carbon atoms (however, does not contain a steroid ring structure), or a fluorinated hydrocarbon group and a fluorine atom. Indicates a group containing a hydrocarbon group.
  • A represents a divalent linking group that does not contain an aromatic ring structure.
  • X represents a functional group represented by the following functional group group (I).
  • B Perfluoropolyether, polychlorotrifluoroethylene or polytetrafluoroethylene
  • C having at least one functional group among the functional groups contained in the following functional group group (I): The following functional group group ( Organopolysiloxane having at least one functional group among the functional groups contained in I) ⁇ Functional group group (I)> Acid group, group having basic nitrogen atom, amide group, urea group, urethane group, alkoxysilyl group, epoxy group, isocyanate group, hydroxyl group, or (meth) acryloyloxy group ⁇ 2> Solid of inorganic solid electrolyte-containing composition The ratio of the content [SE] of the inorganic solid electrolyte to the total content [SA] of the compound (SA) in 100% by mass of the component: [SA] / [SE]
  • the inorganic solid electrolyte-containing composition according to ⁇ 3> which is 0.2 to 5.
  • ⁇ 6> The inorganic solid electrolyte-containing composition according to ⁇ 5>, wherein the active material is an active material containing a silicon element or a tin element.
  • the active material is an active material containing a silicon element or a tin element.
  • SA contains a compound represented by the formula (1).
  • ⁇ 8> The composition containing an inorganic solid electrolyte according to any one of ⁇ 1> to ⁇ 7>, wherein the inorganic solid electrolyte is a sulfide-based inorganic solid electrolyte.
  • a dispersion medium is selected from a ketone compound, an aliphatic compound, and an ester compound.
  • An electrode sheet for an all-solid secondary battery having an active material layer composed of the inorganic solid electrolyte-containing composition according to ⁇ 5> or ⁇ 6> above.
  • An all-solid-state secondary battery including a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order.
  • the all-solid state in which at least one layer of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is a layer composed of the inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 10>. Secondary battery.
  • ⁇ 14> A method for producing a sheet for an all-solid secondary battery, which forms a film of the inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 10> above.
  • ⁇ 15> A method for manufacturing an all-solid-state secondary battery, wherein the all-solid-state secondary battery is manufactured through the manufacturing method according to ⁇ 14> above.
  • the inorganic solid electrolyte-containing composition of the present invention as a material for forming a constituent layer of an all-solid secondary battery, it is possible to realize a constituent layer capable of suppressing the generation of voids due to charging and discharging of the all-solid secondary battery.
  • the sheet for an all-solid-state secondary battery and the electrode sheet for an all-solid-state secondary battery of the present invention can be used as a constituent layer of an all-solid-state secondary battery to exhibit low resistance and excellent cycle characteristics. The next battery can be realized.
  • the all-solid-state secondary battery of the present invention exhibits low resistance and excellent cycle characteristics.
  • each of the manufacturing methods for the all-solid-state secondary battery sheet and the all-solid-state secondary battery of the present invention can manufacture the all-solid-state secondary battery sheet and the all-solid-state secondary battery exhibiting the above-mentioned excellent characteristics.
  • the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the indication of a compound is used to mean that the compound itself, a salt thereof, and an ion thereof are included.
  • it is meant to include a derivative which has been partially changed, such as by introducing a substituent, as long as the effect of the present invention is not impaired.
  • (meth) acrylic means one or both of acrylic and methacrylic. The same applies to (meth) acrylate.
  • substituents for which substitution or non-substitution is not specified may have an appropriate substituent in the group. Therefore, in the present invention, even if it is simply described as a YYY group, this YYY group includes a mode having a substituent in addition to a mode having no substituent. This is also synonymous with compounds that do not specify substitution or non-substitution.
  • Preferred substituents include, for example, Substituent Z, which will be described later.
  • the respective substituents or the like may be the same or different from each other.
  • the polymer means a polymer, but is synonymous with a so-called polymer compound.
  • the polymer binder also simply referred to as a binder
  • the polymer binder means a binder composed of a polymer, and includes the polymer itself and a binder formed containing the polymer.
  • the inorganic solid electrolyte-containing composition of the present invention comprises an inorganic solid electrolyte having conductivity of an ion of a metal belonging to Group 1 or Group 2 of the periodic table, and at least selected from (A) to (C) described later. Contains one compound (SA).
  • SA an inorganic solid electrolyte having conductivity of an ion of a metal belonging to Group 1 or Group 2 of the periodic table, and at least selected from (A) to (C) described later.
  • SA the content state of the inorganic solid electrolyte and the compound (SA) is not particularly limited, and the solid particles such as the inorganic solid electrolyte and the compound (SA) are independently present (dispersed). May be. That is, the compound (SA) may or may not be adsorbed or adhered to the surface of the solid particles, but is preferably adsorbed or adhered.
  • the composition containing an inorganic solid electrolyte of the present invention can form a constituent layer in which voids are unlikely to be generated even if the all-solid secondary battery is repeatedly charged and discharged, and an active material layer that expands and contracts due to charging and discharging, particularly a negative electrode having a large expansion and contraction. It is possible to suppress the generation of voids in the active material layer as well, and maintain the desired contact state between the solid particles.
  • the all-solid-state secondary battery provided with such a constituent layer can reduce the resistance and improve the cycle characteristics by using the composition containing the inorganic solid electrolyte of the present invention as the constituent layer-forming material of the all-solid-state secondary battery. realizable.
  • the compound (SA) described later in combination with the inorganic solid electrolyte in the composition containing the inorganic solid electrolyte of the present invention.
  • the compound (SA) used in combination with solid particles such as an inorganic solid electrolyte (furthermore, an active material and a conductive auxiliary agent that can coexist) is functional. It is a group of solid particles (particularly inorganic solid electrolytes), usually attached to or adsorbed on its surface.
  • the active material layer will be specifically described.
  • the active material layer expanded by charging an all-solid-state secondary battery shifts to a highly dense state by discharging so that solid particles do not generate voids. Since the all-solid-state secondary battery is usually pressure-constrained, shrinkage to a dense active material layer is promoted.
  • Such shrinkage to the dense active material layer can be repeatedly realized as long as the compound (SA) is interposed between the solid particles.
  • the constituent layer containing the compound (SA) can suppress the generation of voids due to charging / discharging of the all-solid-state secondary battery, particularly voids during contraction, and as a result, charge / discharge the all-solid-state secondary battery. Even so, the desired contact state between the solid particles can be maintained. Therefore, the all-solid-state secondary battery provided with the constituent layer formed of the inorganic solid electrolyte-containing composition of the present invention can achieve both low resistance and cycle characteristics at a high level.
  • the above-mentioned action and effect of the present invention are further excellent by using a polymer binder in combination, particularly by using an inorganic solid electrolyte, the above compound (SA) and a polymer binder in a specific content ratio. It becomes a thing.
  • the inorganic solid electrolyte-containing composition of the present invention is a material for forming a solid electrolyte layer or an active material layer of an all-solid secondary battery sheet (including an electrode sheet for an all-solid secondary battery) or an all-solid secondary battery. It can be preferably used as a constituent layer forming material). In particular, it can be preferably used as a material for forming a negative electrode sheet for an all-solid secondary battery or a negative electrode active material layer containing a negative electrode active material having a large expansion and contraction due to charging and discharging. Low resistance and high cycle characteristics can be achieved.
  • the inorganic solid electrolyte-containing composition of the present invention is preferably a non-aqueous composition.
  • the non-aqueous composition includes not only a water-free aspect but also a form in which the water content (also referred to as water content) is preferably 500 ppm or less.
  • the water content is more preferably 200 ppm or less, further preferably 100 ppm or less, and particularly preferably 50 ppm or less.
  • the water content indicates the amount of water contained in the inorganic solid electrolyte-containing composition (mass ratio to the inorganic solid electrolyte-containing composition).
  • the mixture is filtered through a 0.02 ⁇ m membrane filter and curled fisher.
  • the value shall be the value measured using titration.
  • the composition containing an inorganic solid electrolyte of the present invention also includes an embodiment containing an active material, a conductive additive, and the like in addition to the inorganic solid electrolyte (the composition of this embodiment is referred to as an electrode composition).
  • the composition of this embodiment is referred to as an electrode composition.
  • the inorganic solid electrolyte-containing composition of the present invention contains an inorganic solid electrolyte.
  • the inorganic solid electrolyte is an inorganic solid electrolyte
  • the solid electrolyte is a solid electrolyte capable of transferring ions inside the solid electrolyte. Since it does not contain organic substances as the main ionic conductive material, it is an organic solid electrolyte (polymer electrolyte typified by polyethylene oxide (PEO), organic typified by lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), etc. It is clearly distinguished from electrolyte salts).
  • PEO polyethylene oxide
  • LiTFSI lithium bis (trifluoromethanesulfonyl) imide
  • the inorganic solid electrolyte is a solid in a steady state, it is usually not dissociated or liberated into cations and anions. In this respect, it is clearly distinguished from the electrolyte or inorganic electrolyte salts (LiPF 6 , LiBF 4 , Lithium bis (fluorosulfonyl) imide (LiFSI), LiCl, etc.) that are dissociated or liberated into cations and anions in the polymer. Will be done.
  • the inorganic solid electrolyte is not particularly limited as long as it has the conductivity of the ions of the metal belonging to Group 1 or Group 2 of the periodic table, and is generally one having no electron conductivity.
  • the inorganic solid electrolyte preferably has lithium ion ionic conductivity.
  • a solid electrolyte material usually used for an all-solid secondary battery can be appropriately selected and used.
  • examples of the inorganic solid electrolyte include (i) a sulfide-based inorganic solid electrolyte, (ii) an oxide-based inorganic solid electrolyte, (iii) a halide-based inorganic solid electrolyte, and (iv) a hydride-based inorganic solid electrolyte.
  • the sulfide-based inorganic solid electrolyte is preferable from the viewpoint that a better interface can be formed between the active material and the inorganic solid electrolyte.
  • the sulfide-based inorganic solid electrolyte contains a sulfur atom, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. Those having sex are preferable.
  • the sulfide-based inorganic solid electrolyte preferably contains at least Li, S and P as elements and has lithium ion conductivity, but other than Li, S and P may be used depending on the purpose or case. It may contain elements.
  • Examples of the sulfide-based inorganic solid electrolyte include a lithium ion conductive inorganic solid electrolyte satisfying the composition represented by the following formula (S1).
  • L a1 M b1 P c1 S d1 A e1 (S1)
  • L represents an element selected from Li, Na and K, with Li being preferred.
  • M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al and Ge.
  • A represents an element selected from I, Br, Cl and F.
  • a1 to e1 indicate the composition ratio of each element, and a1: b1: c1: d1: e1 satisfy 1 to 12: 0 to 5: 1: 2 to 12: 0 to 10.
  • a1 is preferably 1 to 9, more preferably 1.5 to 7.5.
  • b1 is preferably 0 to 3, more preferably 0 to 1.
  • d1 is preferably 2.5 to 10, more preferably 3.0 to 8.5.
  • e1 is preferably 0 to 5, more preferably 0 to 3.
  • composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based inorganic solid electrolyte as described below.
  • the sulfide-based inorganic solid electrolyte may be non-crystal (glass) or crystallized (glass-ceramic), or only a part thereof may be crystallized.
  • Li-PS-based glass containing Li, P and S, or Li-PS-based glass ceramics containing Li, P and S can be used.
  • Sulfide-based inorganic solid electrolytes include, for example, lithium sulfide (Li 2 S), phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), simple phosphorus, simple sulfur, sodium sulfide, hydrogen sulfide, and lithium halide (for example). It can be produced by the reaction of at least two or more raw materials in sulfides of LiI, LiBr, LiCl) and the element represented by M (for example, SiS 2 , SnS, GeS 2).
  • the ratio of Li 2 S and P 2 S 5 is, Li 2 S: at a molar ratio of P 2 S 5, preferably 60: 40 ⁇ It is 90:10, more preferably 68:32 to 78:22.
  • the lithium ion conductivity can be made high.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 -4 S / cm or more, and more preferably 1 ⁇ 10 -3 S / cm or more. There is no particular upper limit, but it is practical that it is 1 ⁇ 10 -1 S / cm or less.
  • Li 2 S-P 2 S 5 Li 2 S-P 2 S 5 -LiCl, Li 2 S-P 2 S 5 -H 2 S, Li 2 S-P 2 S 5 -H 2 S-LiCl, Li 2 S-LiI-P 2 S 5 , Li 2 S-LiI-Li 2 O-P 2 S 5 , Li 2 S-LiBr-P 2 S 5 , Li 2 S-Li 2 O-P 2 S 5 , Li 2 S-Li 3 PO 4- P 2 S 5 , Li 2 S-P 2 S 5- P 2 O 5 , Li 2 S-P 2 S 5- SiS 2 , Li 2 S-P 2 S 5- SiS 2 -LiCl, Li 2 S-P 2 S 5 -SnS, Li 2 S-P 2 S 5 -Al 2 S 3, Li 2 S-GeS 2, Li 2
  • the mixing ratio of each raw material does not matter.
  • an amorphization method can be mentioned.
  • the amorphization method include a mechanical milling method, a solution method and a melt quenching method. This is because processing at room temperature is possible and the manufacturing process can be simplified.
  • the oxide-based inorganic solid electrolyte contains an oxygen atom, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. Those having sex are preferable.
  • the oxide-based inorganic solid electrolyte preferably has an ionic conductivity of 1 ⁇ 10 -6 S / cm or more, more preferably 5 ⁇ 10 -6 S / cm or more, and 1 ⁇ 10 -5 S / cm or more. It is particularly preferable that it is / cm or more.
  • the upper limit is not particularly limited, but it is practical that it is 1 ⁇ 10 -1 S / cm or less.
  • Li xa La ya TiO 3 [xa satisfies 0.3 ⁇ xa ⁇ 0.7, and ya satisfies 0.3 ⁇ ya ⁇ 0.7.
  • LLT Li xb Layb Zr zb M bb mb Onb
  • M bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In and Sn.
  • Xb satisfies 5 ⁇ xb ⁇ 10, yb satisfies 1 ⁇ yb ⁇ 4, zb satisfies 1 ⁇ zb ⁇ 4, mb satisfies 0 ⁇ mb ⁇ 2, and nb satisfies 5 ⁇ nb ⁇ 20. Satisfy.); Li xc Byc M cc zc Onc (M cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In and Sn.
  • Xc is 0 ⁇ xc ⁇ 5 , Yc satisfies 0 ⁇ yc ⁇ 1, zc satisfies 0 ⁇ zc ⁇ 1, nc satisfies 0 ⁇ nc ⁇ 6); Li xd (Al, Ga) yd (Ti, Ge) zd Si.
  • Li xf Si yf O zf (xf satisfies 1 ⁇ xf ⁇ 5, yf satisfies 0 ⁇ yf ⁇ 3 , Zf satisfies 1 ⁇ zf ⁇ 10); Li xg S yg O zg (xg satisfies 1 ⁇ xg ⁇ 3, yg satisfies 0 ⁇ yg ⁇ 2, and zg satisfies 1 ⁇ zg ⁇ 10.
  • Li 7 La 3 Zr 2 O 12 (LLZ) having a garnet-type crystal structure.
  • Phosphorus compounds containing Li, P and O are also desirable.
  • lithium phosphate Li 3 PO 4
  • LiPON in which a part of oxygen of lithium phosphate is replaced with nitrogen
  • LiPOD 1 (D 1 is preferably Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and one or more elements selected from Au) and the like.
  • LiA 1 ON (A 1 is one or more elements selected from Si, B, Ge, Al, C and Ga) and the like can also be preferably used.
  • the halide-based inorganic solid electrolyte contains a halogen atom, has the conductivity of an ion of a metal belonging to Group 1 or Group 2 of the Periodic Table, and has electrons. Insulating compounds are preferred.
  • the halide-based inorganic solid electrolyte is not particularly limited, and examples thereof include compounds such as Li 3 YBr 6 and Li 3 YCl 6 described in LiCl, LiBr, LiI, ADVANCED MATERIALS, 2018, 30, 1803075. Of these, Li 3 YBr 6 and Li 3 YCl 6 are preferable.
  • the hydride-based inorganic solid electrolyte contains a hydrogen atom, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. A compound having a property is preferable.
  • the hydride-based inorganic solid electrolyte is not particularly limited, and examples thereof include LiBH 4 , Li 4 (BH 4 ) 3 I, and 3 LiBH 4- LiCl.
  • the inorganic solid electrolyte is preferably particles.
  • the particle size (volume average particle size) 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.
  • the upper limit is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • the particle size of the inorganic solid electrolyte is measured by the following procedure. Inorganic solid electrolyte particles are prepared by diluting 1% by mass of a dispersion in a 20 mL sample bottle with water (heptane in the case of a water-unstable substance).
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes, and immediately after that, it is used for the test.
  • data was captured 50 times using a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA) using a measuring quartz cell at a temperature of 25 ° C. Obtain the volume average particle size.
  • JIS Japanese Industrial Standards
  • Z 8828 2013 "Particle size analysis-Dynamic light scattering method” as necessary. Five samples are prepared for each level and the average value is adopted.
  • the inorganic solid electrolyte may contain one kind or two or more kinds.
  • the mass (mg) (grain amount) of the inorganic solid electrolyte per unit area (cm 2) of the solid electrolyte layer is not particularly limited. It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm 2 .
  • the amount of the inorganic solid electrolyte is preferably such that the total amount of the active material and the inorganic solid electrolyte is in the above range.
  • the content of the inorganic solid electrolyte in the composition containing the inorganic solid electrolyte is not particularly limited, but is 50% by mass or more at 100% by mass of the solid content in terms of binding property and dispersibility. Is more preferable, 70% by mass or more is more preferable, and 90% by mass or more is particularly preferable. From the same viewpoint, the upper limit is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less.
  • the content of the inorganic solid electrolyte in the inorganic solid electrolyte-containing composition is such that the total content of the active material and the inorganic solid electrolyte is in the above range. Is preferable.
  • the solid content refers to a component that does not disappear by volatilizing or evaporating when the inorganic solid electrolyte-containing composition is dried at 150 ° C. for 6 hours under an atmospheric pressure of 1 mmHg and a nitrogen atmosphere. .. Typically, it refers to a component other than the dispersion medium described later.
  • the inorganic solid electrolyte-containing composition of the present invention contains any one or more of the following compounds (A) to (C) as a specific compound (SA).
  • the compounds included in the above (A), (B) or (C) may be collectively referred to as the compound group (A), (B) or (C) for convenience.
  • the number of compounds (SA) contained in the inorganic solid electrolyte-containing composition of the present invention may be one or more, and may be, for example, one to three. When a plurality of compounds are contained, they may be selected from the same compound group (any of (A) to (C)) or may be selected from different compound groups.
  • each of the following compounds (A) to (C) can suppress the generation of voids due to charging and discharging of the all-solid secondary battery by being used in combination with the inorganic solid electrolyte in the constituent layer. Shows action and effect. Compound (A) is preferable because it is excellent in this action and effect.
  • the functional group contained in the compound (SA) is at least one of the functional groups contained in the following functional group group (I).
  • the functional groups contained in the following group (I) have a property of interacting with and adsorbing an inorganic solid electrolyte, an active material, a conductive auxiliary agent and the like. This interaction is not particularly limited, but is, for example, due to a hydrogen bond, an acid-base ionic bond, a covalent bond, a ⁇ - ⁇ interaction due to an aromatic ring, or a hydrophobic-hydrophobic interaction. Things etc. can be mentioned.
  • the chemical structure of the functional groups may or may not change.
  • the functional group in the above-mentioned ⁇ - ⁇ interaction or the like, the functional group usually does not change and the structure as it is is maintained.
  • an active hydrogen such as a carboxylic acid group is usually released as an anion (the functional group is changed) to bond with the solid particle.
  • the number of functional groups contained in one molecule of the compound is not particularly limited as long as it is 1 or more, and is appropriately set.
  • the number of functional groups contained in compound (A) can be 1 to 6, and 1 or 2 is more preferable.
  • the number of functional groups of the compound (B) and the compound (C) cannot be uniquely determined by the polymer structure, and can be, for example, 1 to 100, and the compound (B) may have one or two. preferable.
  • the acidic group is not particularly limited, for example, a carboxylic acid group (-COOH), a sulfonic acid group (sulfo group: -SO 3 H), phosphoric acid group (phospho group: -OPO (OH) 2), phosphonic acid Examples thereof include a group and a phosphinic acid group, and a carboxylic acid group is preferable.
  • the amino group is synonymous with the amino group of the substituent Z described later, but an unsubstituted amino group or an alkylamino group is preferable.
  • Each of the three Rs of the amidine group indicates a hydrogen atom or a substituent (for example, a group selected from the substituent Z described later).
  • Examples of the urea group include -NR 15 CONR 16 R 17 (where R 15 , R 16 and R 17 are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and 7 carbon atoms.
  • the above-mentioned Aralkyl group is represented.) Is given as a preferable example.
  • -NR 15 CONHR 17 (where R 15 and R 17 represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms). ) Is more preferable, and ⁇ NHCONHR 17 (where R 17 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms) is particularly preferable. ..
  • urethane group for example, -NHCOOR 18 , -NR 19 COOR 20 , -OCONHR 21 , -OCONR 22 R 23 (where R 18 , R 19 , R 20 , R 21 , R 22 and R 23 have carbon atoms.
  • Preferred examples include groups containing at least an imino group and a carbonyl group, such as an alkyl group of 1 to 20, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms.
  • -NHCOOR 18 and -OCONHR 21 represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms.
  • Etc. are more preferable, and -NHCOOR 18 and -OCONHR 21 (where R 18 and R 21 represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms). Etc. are particularly preferable.
  • the amide group is not particularly limited, but includes, for example, a carbonyl group and an amino group or an imino group such as -CONR 16 R 17 and -NR 15- COR 18 (R 15 to R 18 are as described above).
  • a group containing the above is given as a preferable example.
  • Examples of the amide group is preferably an -NR 15 -COR 18, -NHCOR 18 is more preferable.
  • the alkoxysilyl group is not particularly limited, and examples thereof include mono-, di-, and tri-alkoxysilyl groups, preferably an alkoxysilyl group having 1 to 20 carbon atoms, and more preferably an alkoxysilyl group having 1 to 6 carbon atoms. ..
  • methoxysilyl, ethoxysilyl, t-butoxysilyl, cyclohexylsilyl, and each group exemplified by Substituent Z described later can be mentioned.
  • Examples of the (meth) acryloyloxy group include acryloyloxy and methacryloyloxy.
  • Acidic groups groups having a basic nitrogen atom, hydroxyl groups and the like may form salts.
  • the functional group contained in the compound (SA) is preferably an acidic group, an alkoxysilyl group, an amide group, a urea group, a urethane group or an epoxy group, and more preferably an acidic group.
  • the compound (A) is a compound represented by the following (1). Equation (1) RAX
  • R has no fluorine atom and does not have an aliphatic hydrocarbon group having 6 or more carbon atoms (however, does not contain a steroid ring structure), or a fluorinated hydrocarbon group and a fluorine atom. Indicates a group containing a hydrocarbon group.
  • A represents a divalent linking group that does not contain an aromatic ring structure.
  • X represents the functional group represented by the functional group group (I).
  • R includes an aliphatic hydrocarbon group having 6 or more carbon atoms (however, it does not contain a steroid ring structure) having no fluorine atom (referred to as the first form for convenience) and a fluorinated hydrocarbon group. It takes either group in a form containing a hydrocarbon group having no fluorine atom (referred to as a second form for convenience).
  • R is an aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group that can be taken as R is not particularly limited, and may be an aliphatic saturated hydrocarbon group (alkyl group) or an aliphatic unsaturated hydrocarbon group (alkenyl group, alkynyl group). Of these, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable. Further, the aliphatic hydrocarbon group may be linear, branched or cyclic, and may partially contain a cyclic structure. However, this aliphatic hydrocarbon group does not contain the steroid ring structure (steroid skeleton) shown below.
  • the absence of a steroid ring structure means that the aliphatic hydrocarbon group does not contain a steroid ring structure in its structure, and that the aliphatic hydrocarbon group itself is not a group of a steroid ring structure.
  • the aliphatic hydrocarbon group preferably does not contain a cyclic structure, and a non-cyclic hydrocarbon group (linear or branched hydrocarbon group) is more preferable.
  • a fused ring structure preferably two or more rings, more preferably three or more rings, is not contained. This fused ring structure may be aliphatic or aromatic.
  • the aliphatic hydrocarbon group is preferably linear or branched, and more preferably linear, in terms of reducing frictional resistance against solid particles.
  • the aliphatic hydrocarbon group has 6 or more carbon atoms, and is preferably 8 or more, more preferably 12 or more, still more preferably 18 or more, in terms of reduction of frictional resistance of solid particles and cycle characteristics.
  • the upper limit of the number of carbon atoms is not particularly limited, but is preferably 30 or less, more preferably 25 or less, and even more preferably 22 or less.
  • the carbon number of the aliphatic hydrocarbon group means the carbon number of the carbon atom constituting the aliphatic hydrocarbon group, and when the aliphatic hydrocarbon group has a substituent, includes the number of carbon atoms constituting the substituent. Absent.
  • the aliphatic hydrocarbon group when it is a branched hydrocarbon group, it contains the number of carbon atoms constituting the branched chain (for example, when it is a 2-ethylhexyl group, the number of carbon atoms is 8).
  • the aliphatic hydrocarbon group may have a substituent, but does not have a fluorine atom and a steroid ring structure as a substituent.
  • the substituent which the aliphatic hydrocarbon group may have is not particularly limited as long as the effect of the present invention is not impaired.
  • a substituent Z described later can be mentioned, and a group other than the functional group contained in the functional group group (I) and a group other than the aryl group are preferable. That is, it is preferable that the aliphatic hydrocarbon group does not have a functional group, an aryl group or a group containing these as a substituent contained in the functional group group (I).
  • the group containing a fluorinated hydrocarbon group and a hydrocarbon group having no fluorine atom which can be taken as R, is composed of a fluorinated hydrocarbon group and a hydrocarbon group having no fluorine atom.
  • Both forms include a group and a group further containing another group of other groups (ie, another group other than the fluorinated hydrocarbon group and other than the hydrocarbon group having no fluorine atom).
  • Another group is usually attached between a fluorinated hydrocarbon group and a hydrocarbon group that does not have a fluorine atom.
  • the other group is not particularly limited, and examples thereof include a linking group that can be taken as A, which will be described later.
  • a group composed of a fluorinated hydrocarbon group and a hydrocarbon group having no fluorine atom is preferable.
  • the hydrocarbon group before fluorination and the hydrocarbon group having no fluorine atom constituting the fluorinated hydrocarbon group are not particularly limited and may be an aromatic hydrocarbon group, but may be an aliphatic hydrocarbon group. It is preferable to have. Thereby, the frictional resistance of the solid particles can be reduced.
  • the aliphatic hydrocarbon group is not particularly limited, and may be an aliphatic saturated hydrocarbon group or an aliphatic unsaturated hydrocarbon group. Of these, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic, and may partially contain a cyclic structure, but linear or branched is preferable, and linear is more preferable.
  • the aliphatic hydrocarbon group in the second form may contain a steroid ring structure.
  • the fluorinated hydrocarbon group in the second form is a fluorinated hydrocarbon group, and the number of carbon atoms thereof is not particularly limited.
  • the number of carbon atoms of the fluorinated hydrocarbon group can be, for example, 1 or more, and 2 or more is preferable, and 4 or more is more preferable, and 5 or more is preferable in terms of reduction of frictional resistance, low resistance and cycle characteristics of solid particles. The above is more preferable.
  • the upper limit of the number of carbon atoms is not particularly limited, but is preferably 20 or less, more preferably 15 or less, and even more preferably 8 or less.
  • all the hydrogen atoms of the hydrocarbon group before fluorination may be substituted with a fluorine atom (perfluorohydrocarbon group), and a part thereof is substituted with a fluorine atom. You may.
  • a perfluorohydrocarbon group is preferable because the frictional resistance of the solid particles can be effectively reduced.
  • the remaining hydrogen atom may be substituted with a substituent other than the fluorine atom.
  • the hydrocarbon group having no fluorine atom in the second form may be a hydrocarbon group other than the fluorinated hydrocarbon group and may have a substituent, but is a hydrocarbon group having no substituent. (Unsubstituted hydrocarbon group) is preferable.
  • the number of carbon atoms of the hydrocarbon group having no fluorine atom can be, for example, 1 or more, and is preferably 2 or more in terms of reduction of frictional resistance, low resistance, and cycle characteristics of solid particles.
  • the upper limit of the number of carbon atoms is not particularly limited, but is preferably 20 or less, more preferably 10 or less, and even more preferably 6 or less.
  • the combination of the fluorinated hydrocarbon group and the hydrocarbon group having no fluorine atom in the second form is not particularly limited, and examples thereof include the above-mentioned preferable combinations of the fluorinated hydrocarbon groups.
  • both the hydrocarbon group constituting the fluorinated hydrocarbon group and the hydrocarbon group having no fluorine atom are preferably an aliphatic hydrocarbon group, more preferably an alkyl group, and directly. It is more preferably a chain or branched alkyl group, and particularly preferably a linear alkyl group.
  • the fluorinated hydrocarbon group and the hydrocarbon group having no fluorine atom and the bonding mode are not particularly limited, and the other hydrocarbon group is bonded as a side chain of one hydrocarbon group (for example, the whole). (Forming a branched chain hydrocarbon group), but it is preferable to bond in a linear manner (preferably forming a linear hydrocarbon group as a whole). Further, any hydrocarbon group may be bonded to the linking group A of the above formula (1), but in terms of reducing the frictional resistance of the solid particles, the hydrocarbon group having no fluorine atom is the linking group A. It is preferable that the fluorinated hydrocarbon group is terminal (free).
  • the total number of carbon atoms as a group containing a fluorinated hydrocarbon group and a hydrocarbon group having no fluorine atom is within the total number of carbon atoms that can be taken by the fluorinated hydrocarbon group and the hydrocarbon group having no fluorine atom. Is appropriately determined, and is preferably synonymous with the range of carbon numbers of the aliphatic hydrocarbon group in the first form. In the present invention, the meaning of the total carbon number is synonymous with the meaning of the carbon number of the aliphatic hydrocarbon group in the first form, and does not include the number of carbon atoms constituting the substituent.
  • the hydrocarbon group contains one or more heteroatoms (atoms other than carbon atom and other than hydrogen atom, for example, oxygen atom, sulfur atom, nitrogen atom, silicon atom) inside the molecular chain.
  • heteroatoms atoms other than carbon atom and other than hydrogen atom, for example, oxygen atom, sulfur atom, nitrogen atom, silicon atom
  • a in the formula (1) represents a divalent linking group that does not contain an aromatic ring structure, and is preferably an aliphatic group.
  • the linking group that can be used as A is not particularly limited, but is, for example, an alkylene group (preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms), an alkenylene group (2 carbon atoms). ⁇ 18 is preferred, 2-10 is more preferred, 2-6 is even more preferred), oxygen atom, sulfur atom, imino group (-NR N- ), carbonyl group, phosphoric acid linking group (-OP (OH)). Examples thereof include (O) -O-), a phosphonic acid linking group (-P (OH) (O) -O-), or a group related to a combination thereof.
  • the alkylene group and the alkenylene group that can be used as the linking group may be linear, branched or cyclic, respectively, but the alkylene group is linear or branched in terms of reducing the frictional resistance of the solid particles.
  • the alkenylene group is preferably linear.
  • Examples of the cyclic alkylene group include a cyclohexane ring group and a norbornane ring group, and examples of the cyclic alkenylene group include a cyclohexene ring group and a norbornene ring group.
  • a group formed by combining an alkylene group, an alkenylene group, a carbonyl group, an oxygen atom, a sulfur atom and an imino group is preferable, and an alkylene group, an alkenylene group, a carbonyl group, an oxygen atom and an imino group are preferable.
  • a group containing an —CO—O— group is more preferable, and a group composed of a combination of a —CO—O— group and an alkylene group or an alkenylene group is particularly preferable.
  • the -CO-O- group is preferably bonded to R in the formula (1), and the oxygen atom in the -CO-O- group is the R in the formula (1). It is more preferable to combine with.
  • the group containing the —CO—O— group include, but are not limited to, those shown in each compound used in the examples.
  • the total number of atoms constituting the linking group is preferably 1 to 36, more preferably 1 to 24, further preferably 1 to 12, and preferably 1 to 6. Especially preferable.
  • the number of connecting atoms of the linking group is preferably 10 or less, more preferably 8 or less. The lower limit is 1 or more.
  • the number of connected atoms is the minimum number of atoms connecting R and X in the formula (1).
  • the number of atoms constituting the linking group is 19, but the number of linking atoms is It becomes 4.
  • the linking group that can be taken as A is preferably an alkylene group, an oxygen atom, or a group formed by combining an —CO—O— group with an alkylene group or an alkenylene group, and the alkylene group is used in terms of reducing the frictional resistance of the solid particles. More preferred.
  • the RA-group has a single group (excluding the aralkyl group)
  • the minimum unit of the linking group contained in the single group is A, and the rest is R. ..
  • RA-group is an alkyl group as a whole (undecanyl group in the compound A-01 used in the examples)
  • A is a methylene group (the smallest unit of an alkylene group as a linking group), and the remaining groups.
  • R be (a decanyl group in compound A-01).
  • the linking group that can be taken as A may have a substituent, but it is preferable that it does not have a substituent.
  • Examples of the substituent that A may have include a substituent Z other than the functional group selected from the functional group group (I) and which can be taken as R.
  • X in the formula (1) indicates a functional group contained in the above-mentioned functional group group (I).
  • the functional groups are as described above, and the preferred ones are also the same.
  • the compound (A) may have a substituent.
  • the substituent is not particularly limited as long as the effect of the present invention is not impaired, and examples thereof include a substituent Z described later, a group other than the functional group included in the functional group group (I), and an aryl group. Groups other than are preferred.
  • Compound (A) is preferably a low molecular weight compound, and its molecular weight is appropriately determined. The molecular weight can be, for example, 150 to 1000.
  • Compound (B) is perfluoropolyether, polychlorotrifluoroethylene or polytetrafluoroethylene, and perfluoropolyether is preferable.
  • the perfluoropolyether is not particularly limited, and examples thereof include polymers containing alkylene oxide, arylene oxide and the like as constituents.
  • the compound (B) is not particularly limited as long as it is a polymer having a fluorinated constituent component.
  • the number of carbon atoms of the alkylene group in the alkylene oxide is not particularly limited, and may be, for example, 1 to 10, preferably 1 to 6.
  • the carbon number of the arylene group in the arylene oxide is not particularly limited, and may be, for example, 6 to 10.
  • Compound (B) has a functional group selected from the functional group group (I).
  • the functional group may be introduced into any of the constituent components forming the compound (B), but it is preferably introduced at the end of the main chain of the polymerized chain.
  • the number average molecular weight of compound (B) is not particularly limited, but can be, for example, 1000 to 50,000.
  • the perfluoropolyether include those manufactured by Fluorolink (registered commercial law) series (PFPE, manufactured by Solvay) and MORESCO.
  • Examples of polychlorotrifluoroethylene include neochlorotrifluoroethylene PCTFE M series (manufactured by Daikin Corporation).
  • polytetrafluoroethylene include Polyflon PTFE series (manufactured by Daikin Corporation) and those manufactured by Shamlock Technologies.
  • the organopolysiloxane of compound (C) is not particularly limited, but is a polymer having a siloxane structure and having at least one functional group among the functional groups contained in the functional group group (I).
  • Examples of the siloxane structure of the organopolysiloxane include structural units represented by —Si (RS 2) —O—.
  • RS represents a hydrogen atom or a substituent, and the substituent is not particularly limited, and a hydroxy group or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, 1 to 3).
  • an alkenyl group preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms
  • an alkoxy group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms.
  • 1, 1 to 6 are more preferable, 1 to 3 are particularly preferable
  • an aryl group (6 to 22 carbon atoms are preferable, 6 to 14 is more preferable, 6 to 10 is particularly preferable), and an aryloxy group (carbon number is particularly preferable).
  • 6 to 22 is preferable, 6 to 14 is more preferable, 6 to 10 is particularly preferable)
  • an arylyl group (7 to 23 carbon atoms are preferable, 7 to 15 is more preferable, and 7 to 11 is particularly preferable), and further.
  • Examples thereof include a substituent represented by the substituent ZC or —R 11- X in the formula (2) described later.
  • a substituent represented by the substituent ZC or —R 11- X in the formula (2) described later examples thereof include a substituent represented by the substituent ZC or —R 11- X in the formula (2) described later.
  • an alkyl group having 1 to 3 carbon atoms, a phenyl group, a substituent ZC or a group represented by -R 11- X is more preferable, and an alkyl group having 1 to 3 carbon atoms or -R 11- X is represented. Groups are even more preferred.
  • the siloxane structure is preferably a polymer chain having two or more structural units, and the degree of polymerization of all the structural units forming the polymer chain is not particularly limited, but is preferably 1 to 1000, and is preferably 1 to 500. Is more preferable, and 1 to 200 is particularly preferable.
  • the number average molecular weight of the polymerized chain is not particularly limited, and is preferably 400 or more, more preferably 800 or more, and further preferably 2,000 or more.
  • the upper limit is not particularly limited, and is preferably 500,000 or less, more preferably 100,000 or less, and particularly preferably 50,000 or less.
  • the number average molecular weight of the polymerized chain can be measured as a standard polystyrene-equivalent number average molecular weight, as will be described later.
  • the organopolysiloxane is preferably a polymer represented by the following formula (2).
  • R 15 represents an alkyl group or an aryl group, and an alkyl group is preferable.
  • the alkyl group and aryl group that can be taken as R 15 are synonymous with the alkyl group and aryl group that can be taken as RS in the structural unit, respectively, and the preferred ones are also the same.
  • R 15 is methyl are particularly preferred. Same silicon atoms bonded two R 15 are each, may be the same or different, are preferably both methyl.
  • R 16 represents an alkyl group or an aryl group, and an alkyl group is preferable. Two R 16 attached to the same silicon atom, respectively, may be the same or different.
  • the alkyl group and aryl group that can be taken as R 16 are synonymous with the alkyl group and aryl group that can be taken as RS in the structural unit, respectively, and the preferred ones are also the same.
  • R 11 represents a linking group.
  • the linking group that can be used as R 11 is not particularly limited, and is, for example, an alkylene group having 1 to 30 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 24 carbon atoms, and 3 to 12 carbon atoms.
  • R S2 is hydrogen or an alkyl group having 1 to 6 carbon atoms), a carbonyl group, an imino group (-NR N -: R N represents a hydrogen atom, an alkyl group or carbon number of 1 to 6 carbon atoms 6 to 10 aryl groups), or a linking group in which two or more (preferably 2 to 10) of these are combined is preferable.
  • R N represents a hydrogen atom, an alkyl group or carbon number of 1 to 6 carbon atoms 6 to 10 aryl groups
  • a linking group in which two or more (preferably 2 to 10) of these are combined is preferable.
  • an alkylene group, an imino group, an ether group, a sulfide group or a carbonyl group, or a linking group in which two or more (preferably 2 to 5) of these are combined is preferable.
  • X is synonymous with X in the above formula (1).
  • ZC represents a group represented by the following formula (Z).
  • R 17 and R 18 represent alkyl or aryl groups, respectively.
  • the alkyl and aryl groups that can be taken as R 17 and R 18 are synonymous with the alkyl and aryl groups that can be taken as RS in the siloxane structure, respectively, and the preferred ones are also the same.
  • R 17 and R 18 may be the same or different.
  • R 19 represents an unsubstituted alkyl group having 1 to 4 carbon atoms.
  • y2 is an integer of 1 to 100, preferably an integer of 1 to 50, and more preferably an integer of 1 to 20.
  • x1, x2 and x3 are integers of 0 or more, respectively.
  • x1 is preferably an integer of 0 to 50, more preferably an integer of 0 to 20.
  • x2 is preferably an integer of 0 to 50, more preferably an integer of 0 to 20.
  • x3 is preferably an integer of 1 to 500, and more preferably an integer of 1 to 200.
  • x4 an integer of 0 to 200 is preferable, an integer of 0 to 100 is more preferable, and an integer of 0 to 30 is more preferable.
  • x1, x2, x3 and x4 are integers of 1 to 500, preferably integers of 1 to 200, and more preferably integers of 1 to 100.
  • x1 and x3 takes an integer of 2 or more, respectively, in Formula 2, two ZC or R 15 attached to the same silicon atom may be the same or different from each other.
  • y1 is an integer of 1 to 30, preferably an integer of 1 to 20, and more preferably an integer of 1 to 10.
  • Y represents the group represented by -R 11- X or R 16 described above, and the two Ys may be the same or different, respectively.
  • polymer represented by formula (2) has a group represented by at least one -R 11 -X in the molecule, for example, in the formula (2), X 4 and y1 is at least 1 At least one of the two Ys has a group represented by -R 11-X. That is, if x4 is 0, then any one of the two Ys represents a group represented by -R 11- X, or if both Ys are R 16 , then x4 and y1 are It is an integer of 1 or more.
  • the above compounds (A) to (C) may be commercially available products or may be appropriately synthesized.
  • the synthesis method is not particularly limited, and a known method can be selected and conditions can be set as appropriate.
  • -Substituent Z- Alkyl groups preferably alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • alkenyl groups preferably alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • an alkenyl group having 2 to 20 carbon atoms for example, vinyl, allyl, oleyl, etc.
  • an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms, for example, ethynyl, butadynyl, phenylethynyl, etc.
  • a cycloalkyl group having 3 to 20 carbon atoms for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc., is usually used in the present specification to include a cycloalkyl group.
  • An aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), an aralkyl group (preferably having 7 carbon atoms).
  • ⁇ 23 aralkyl groups eg, benzyl, phenethyl, etc.
  • heterocyclic groups preferably heterocyclic groups having 2 to 20 carbon atoms, more preferably 5 or 5 having at least one oxygen atom, sulfur atom, nitrogen atom. It is a 6-membered heterocyclic group.
  • the heterocyclic group includes an aromatic heterocyclic group and an aliphatic heterocyclic group.
  • a tetrahydropyran ring group for example, a tetrahydropyran ring group, a tetrahydrofuran ring group, 2-pyridyl, 4-pyridyl, 2-. Imidazolyl, 2-benzoimidazolyl, 2-thiazolyl, 2-oxazolyl, pyrrolidone group, etc.), alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, for example, methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryloxy group.
  • an aryloxy group having 6 to 26 carbon atoms for example, phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.
  • a heterocyclic oxy group a group in which an —O— group is bonded to the heterocyclic group
  • an alkoxycarbonyl group preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, for example, ethoxycarbonyl, 2-ethylhexyloxycarbonyl.
  • aryloxycarbonyl groups preferably aryloxycarbonyl groups with 6-26 carbon atoms, such as phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-me Chilphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc.
  • heterocyclic oxycarbonyl group group in which -O-CO- group is bonded to the above heterocyclic group
  • amino group preferably amino group having 0 to 20 carbon atoms, alkyl It contains an amino group and an arylamino group, and includes, for example, amino (-NH 2 ), N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anirino, etc., and a sulfamoyl group (preferably having 0 to 20 carbon atoms).
  • Sulfamoyl group of, for example, N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc. acyl group (alkylcarbonyl group, alkenylcarbonyl group, alkynylcarbonyl group, arylcarbonyl group, heterocyclic carbonyl group, etc.
  • an acyl group having 1 to 20 carbon atoms for example, acetyl, propionyl, butyryl, octanoyl, hexadecanoyl, acryloyl, methacryloyl, crotonoyle, benzoyl, naphthoyl, nicotineol, etc., and an acyloxy group (alkylcarbonyloxy group, alkenylcarbonyloxy).
  • heterocyclic thio group group in which -S- group is bonded to the above heterocyclic group
  • alkylsulfonyl group preferably alkylsulfonyl group having 1 to 20 carbon atoms.
  • RP is a hydrogen atom or a substituent (preferably a group selected from the substituent Z). Further, each group listed in these substituents Z may be further substituted with the above-mentioned substituent Z.
  • the alkyl group, alkylene group, alkenyl group, alkenylene group, alkynyl group and / or alkynylene group and the like may be cyclic or chain-like, or may be linear or branched.
  • the content of the compound (SA) in the inorganic solid electrolyte-containing composition is not particularly limited, but is 0.1% by mass or more at 100% by mass of the solid content in terms of reducing the frictional resistance of the solid particles. It is preferably 0.2% by mass or more, and particularly preferably 0.4% by mass or more.
  • the upper limit is preferably 10% by mass or less, more preferably 4% by mass or less, further preferably 2.5% by mass or less, and 1.2% by mass in terms of reducing battery resistance. It is particularly preferable that it is% or less.
  • the ratio of the content [SE] of the inorganic solid electrolyte to the total content [SA] of the compound (SA) in 100% by mass of the solid content: [SA] / [SE]. ] is not particularly limited, but is preferably 0.0003 to 0.11 in terms of reduction of frictional resistance of solid particles, reduction of resistance, and cycle characteristics, and further reduction of frictional resistance of solid particles. In terms of achieving both low resistance and improvement of cycle characteristics at a high level, it is more preferably 0.003 to 0.05, further preferably 0.007 to 0.05, and 0.01 to 0. It is particularly preferable that it is 03.
  • the inorganic solid electrolyte-containing composition of the present invention contains the following polymer binder
  • the total content of the polymer binder content [BR] and the compound (SA) in 100% by mass of the solid content of the inorganic solid electrolyte-containing composition is contained.
  • the ratio with the amount [SA]: [BR] / [SA] is not particularly limited, but is preferably 0.05 to 15 in terms of reducing the frictional resistance of the solid particles, lowering the resistance, and the cycle characteristics. , 0.1 to 10 is more preferable, and 0.2 to 5 is further preferable, in that the frictional resistance of the solid particles can be further reduced, and the resistance can be lowered and the cycle characteristics can be improved at a high level. It is preferably 0.8 to 5, and particularly preferably 0.8 to 5.
  • the inorganic solid electrolyte-containing composition of the present invention preferably contains a polymer binder.
  • a polymer binder By containing the polymer binder, the binding property of the solid particles can be improved, which contributes to the improvement of the cycle characteristics and the like.
  • the polymer forming the polymer binder is not particularly limited, and examples thereof include various polymers usually used for the constituent layers of the all-solid-state secondary battery. For example, sequential polymerization (polycondensation, polyaddition or addition condensation) polymer such as polyurethane, polyurea, polyamide, polyimide, polyester, polyether, polycarbonate, etc., and further, fluoropolymer (fluorine-containing polymer), hydrocarbon polymer, etc. Examples thereof include chain polymerization polymers such as vinyl polymers and (meth) acrylic polymers.
  • polyurethane, polyurea, polyamide, and polyimide polymers that can be used as step-growth polymerization polymers include a polymer having a hard segment and a soft segment described in JP-A-2015-08480, and International Publication No. 2018/147051. No., each polymer and the like described in International Publication No. 2018/020827 and International Publication No. 2015/046313 can be mentioned.
  • fluoropolymer examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), a copolymer of polyvinylidene fluoride and hexafluoropropylene (PVdF-HFP), polyvinylidene fluoride and hexafluoro.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • PVdF-HFP a copolymer of polyvinylidene fluoride and hexafluoropropylene
  • PVdF-HFP-TFE a copolymer of propylene and tetrafluoroethylene
  • the copolymerization ratio [PVdF: HFP] (mass ratio) of PVdF and HFP is not particularly limited, but is preferably 9: 1 to 5: 5, and more preferably 9: 1 to 7: 3.
  • the copolymerization ratio [PVdF: HFP: TFE] (mass ratio) of PVdF, HFP, and TFE is not particularly limited, but may be 20 to 60:10 to 40: 5 to 30. preferable.
  • hydrocarbon polymer examples include polyethylene, polypropylene, natural rubber, polybutadiene, polyisoprene, polystyrene, polystyrene butadiene copolymer, styrene-based thermoplastic elastomer, polybutylene, acrylonitrile butadiene copolymer, or hydrogenation thereof (hydrogenation). Chemistry) Polymers can be mentioned.
  • the styrene-based thermoplastic elastomer or its hydride is not particularly limited, and for example, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), styrene-isobutylene.
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • styrene-isobutylene styrene-isobutylene.
  • SIBS styrene block copolymer
  • SIBS hydrogenated SIS
  • SBS styrene-butadiene-styrene block copolymer
  • SEEPS hydrogenated SBS
  • SEPS styrene-ethylene-ethylene-propylene-styrene block copolymer
  • SEPS ethylene-propylene-styrene block copolymer
  • SBR styrene-butadiene rubber
  • HSBR hydride styrene-butadiene rubber
  • the hydrocarbon polymer having no unsaturated group (for example, 1,2-butadiene constituent) bonded to the main chain is preferable in that the formation of chemical crosslinks can be suppressed.
  • the vinyl-based polymer include polymers containing, for example, 50 mol% or more of vinyl-based monomers other than the (meth) acrylic compound (M1).
  • the vinyl-based monomer include vinyl compounds described later.
  • Specific examples of the vinyl polymer include polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, and a copolymer containing these.
  • this vinyl-based polymer is a constituent component derived from the (meth) acrylic compound (M1) that forms the (meth) acrylic polymer described later, and further a constituent component derived from the macromonomer described later. It is preferable to have (MM).
  • the content of the constituent component derived from the vinyl-based monomer is preferably the same as the content of the constituent component derived from the (meth) acrylic compound (M1) in the (meth) acrylic polymer.
  • the content of the constituent component derived from the (meth) acrylic compound (M1) is not particularly limited as long as it is less than 50 mol% in the polymer, but is preferably 0 to 40 mol%, and is preferably 5 to 35 mol%. Is more preferable.
  • the content of the component (MM) is preferably the same as the content in the (meth) acrylic polymer.
  • the (meth) acrylic polymer is at least one (meth) acrylic compound (M1) selected from a (meth) acrylic acid compound, a (meth) acrylic acid ester compound, a (meth) acrylamide compound and a (meth) acrylonitrile compound. ) Is (co) polymerized to obtain a polymer. Further, a (meth) acrylic polymer composed of a copolymer of the (meth) acrylic compound (M1) and another polymerizable compound (M2) is also preferable.
  • M1 selected from a (meth) acrylic acid compound, a (meth) acrylic acid ester compound, a (meth) acrylamide compound and a (meth) acrylonitrile compound.
  • the other polymerizable compound (M2) is not particularly limited, and examples thereof include vinyl compounds such as styrene compounds, vinylnaphthalene compounds, vinylcarbazole compounds, allyl compounds, vinyl ether compounds, vinyl ester compounds, and dialkyl itaconate compounds.
  • vinyl compound examples include "vinyl-based monomers” described in JP-A-2015-88486.
  • a (meth) acrylic polymer having a component (MM) derived from a macromonomer is also preferable.
  • a (meth) acrylic polymer for example, a macromonomer having a mass average molecular weight of 1,000 or more is incorporated as a side chain component described in International Publication No.
  • the content of the constituent component derived from the (meth) acrylic compound (M1) is preferably 50 mol% or more, and the content of the other polymerizable compound (M2) is not particularly limited. However, for example, it can be 50 mol% or less, and preferably less than 50 mol%.
  • the content of the component (MM) is preferably 1 to 70% by mass.
  • polyurethane, fluorine-based polymer or hydrocarbon-based polymer is preferable, polyurethane, PVdF-HFP, SEBS, SBS, SBR or HSBR is more preferable, polyurethane, PVdF-HFP or SEBS is more preferable, and polyurethane or PVdF- HFP is particularly preferred.
  • the main chain forming the step-growth polymerization polymer is not particularly limited, but two or more kinds of constituents represented by any of the following formulas (I-1) to (I-4) (preferably 2 to 8 kinds, More preferably, 2 to 4 types) combined with a main chain or a carboxylic acid dianhydride represented by the following formula (I-5) and a diamine compound leading to a constituent component represented by the following formula (I-6).
  • a main chain obtained by sequentially polymerizing the above is preferable.
  • the polymer having such a main chain include polyurethane, polyurea, polyamide, polyimide, polyester and polycarbonate. The combination of each component is appropriately selected according to the polymer species.
  • the main chain made of polycarbonate, a configuration component formula (I-3) as a constituent or R P1 is represented by the following formula was introduced oxygen atoms at both ends of R P1 (I-2)
  • Examples thereof include a main chain having a constituent component represented by the following formula (I-2) and a constituent component represented by the following formula (I-3).
  • One kind of component in the combination of components means the number of kinds of components represented by any one of the following formulas, and has two kinds of components represented by one of the following formulas. However, it is not interpreted as two kinds of constituents.
  • RP1 and RP2 each indicate a molecular chain having a molecular weight or mass average molecular weight of 20 or more and 200,000 or less.
  • the molecular weight of this molecular chain cannot be uniquely determined because it depends on the type and the like, but for example, 30 or more is preferable, 50 or more is more preferable, 100 or more is further preferable, and 150 or more is particularly preferable.
  • the upper limit is preferably 100,000 or less, more preferably 10,000 or less.
  • the molecular weight of the molecular chain is measured for the starting compound before it is incorporated into the main chain of the polymer.
  • the molecular chains that can be taken as RP1 and RP2 are not particularly limited, but hydrocarbon chains, polyalkylene oxide chains, polycarbonate chains or polyester chains are preferable, hydrocarbon chains or polyalkylene oxide chains are more preferable, and hydrocarbon chains. , Polyester oxide chains or polypropylene oxide chains are more preferred.
  • the hydrocarbon chain that can be taken as RP1 and RP2 means a chain of hydrocarbons composed of carbon atoms and hydrogen atoms, and more specifically, at least two compounds composed of carbon atoms and hydrogen atoms. It means a structure in which an atom (for example, a hydrogen atom) or a group (for example, a methyl group) is eliminated.
  • the hydrocarbon chain also includes a chain having a group containing an oxygen atom, a sulfur atom or a nitrogen atom in the chain, for example, a hydrocarbon group represented by the following formula (M2).
  • M2 hydrocarbon group represented by the following formula
  • This hydrocarbon chain may have a carbon-carbon unsaturated bond and may have a ring structure of an aliphatic ring and / or an aromatic ring. That is, the hydrocarbon chain may be a hydrocarbon chain composed of a hydrocarbon selected from an aliphatic hydrocarbon and an aromatic hydrocarbon.
  • Such a hydrocarbon chain may be any one that satisfies the above molecular weight, and both a chain composed of a low molecular weight hydrocarbon group and a hydrocarbon chain composed of a hydrocarbon polymer (also referred to as a hydrocarbon polymer chain).
  • hydrocarbon chains include hydrocarbon chains.
  • a low molecular weight hydrocarbon chain is a chain composed of ordinary (non-polymerizable) hydrocarbon groups, and examples of the hydrocarbon groups include aliphatic or aromatic hydrocarbon groups, and specific examples thereof.
  • Is an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), an arylene group (preferably 6 to 22 carbon atoms, preferably 6 to 14 carbon atoms, 6 to 10 carbon atoms). Is more preferable), or a group consisting of a combination thereof is preferable.
  • This hydrocarbon chain may have a polymerized chain (eg, (meth) acrylic polymer) as a substituent.
  • the aliphatic hydrocarbon group is not particularly limited, and for example, from a hydrogen-reduced product of an aromatic hydrocarbon group represented by the following formula (M2), or a partial structure of a known aliphatic diisosoane compound (for example, from isophorone). Narumoto) and the like.
  • the hydrocarbon group contained in each of the constituent components of each of the examples described later can also be mentioned.
  • the aromatic hydrocarbon group include a hydrocarbon group contained in each of the constituent components described below, and an arylene group (for example, one or more hydrogen atoms from the aryl group mentioned in Substituent Z described later).
  • the removed group specifically a phenylene group, a trilene group or a xylylene group
  • X represents a single bond, -CH 2- , -C (CH 3 ) 2- , -SO 2- , -S-, -CO- or -O-, and is a viewpoint of binding property. Therefore, -CH 2- or -O- is preferable, and -CH 2- is more preferable.
  • the above-mentioned alkylene group exemplified here may be substituted with a substituent Z, preferably a halogen atom (more preferably a fluorine atom).
  • RM2 to RM5 each represent a hydrogen atom or a substituent, and a hydrogen atom is preferable.
  • the substituent that can be taken as RM2 to RM5 is not particularly limited, and examples thereof include a substituent Z described later.
  • a substituent Z described later for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, and -OR M6. , -N (R M6) 2, -SR M6 (R M6 represents a substituent, preferably an aryl group having an alkyl group or a C 6-10 having 1 to 20 carbon atoms.), a halogen atom (e.g., Fluorine atom, chlorine atom, bromine atom) are preferably mentioned.
  • a halogen atom e.g., Fluorine atom, chlorine atom, bromine atom
  • the ⁇ N ( RM6 ) 2 is an alkylamino group (preferably 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms) or an arylamino group (preferably 6 to 40 carbon atoms, 6 to 20 carbon atoms). More preferred).
  • a hydrocarbon polymer chain may be a polymer chain in which (at least two) polymerizable hydrocarbons are polymerized, and may be a chain composed of a hydrocarbon polymer having a larger number of carbon atoms than the above-mentioned low molecular weight hydrocarbon chain.
  • the chain is not particularly limited, but is preferably a chain composed of a hydrocarbon polymer composed of 30 or more, more preferably 50 or more carbon atoms.
  • the upper limit of the number of carbon atoms constituting the hydrocarbon polymer is not particularly limited, and may be, for example, 3,000.
  • the hydrocarbon polymer chain is preferably a chain composed of an aliphatic hydrocarbon having a main chain satisfying the above number of carbon atoms, and is composed of an aliphatic saturated hydrocarbon or an aliphatic unsaturated hydrocarbon. It is more preferable that the chain is made of a polymer (preferably an elastomer). Specific examples of the polymer include a diene polymer having a double bond in the main chain and a non-diene polymer having no double bond in the main chain.
  • the diene polymer examples include a styrene-butadiene polymer, a styrene-ethylene-butadiene copolymer, a copolymer of isobutylene and isoprene (preferably butyl rubber (IIR)), a butadiene polymer, an isoprene polymer, and ethylene.
  • IIR butyl rubber
  • -Propylene-diene copolymer and the like can be mentioned.
  • the non-diene polymer examples include olefin polymers such as an ethylene-propylene copolymer and a styrene-ethylene-butylene copolymer, and hydrogen-reduced products of the diene polymer.
  • Hydrocarbon chain which can be taken as R P1 and R P2 may have a substituent as described later, it is preferable to have an ether group or carbonyl group, or both.
  • the hydrocarbon chain can take as R P2 of constituents formula (I-3) or formula (I-4) may include an ether group or carbonyl group, or both (e.g., -CO-O- groups It is preferable to have a carboxy group). It is preferable that the ends of the ether group and the carbonyl group have an atom such as a hydrogen atom or a substituent (for example, a substituent Z described later).
  • the hydrocarbon to be a hydrocarbon chain preferably has a reactive group at its terminal, and more preferably has a polycondensable terminal reactive group.
  • the polycondensation or polyaddition-capable terminal reactive group forms a group bonded to RP1 or RP2 of each of the above formulas by polycondensation or polyaddition.
  • Examples of such a terminal reactive group include an isocinate group, a hydroxy group, a carboxy group, an amino group and an acid anhydride, and a hydroxy group is preferable.
  • hydrocarbon polymers having terminal reactive groups examples include NISSO-PB series (manufactured by Nippon Soda Co., Ltd.), clay sole series (manufactured by Tomoe Kosan Co., Ltd.), and PolyVEST-HT series (manufactured by Idemitsu Kosan Co., Ltd.).
  • Poly-bd series manufactured by Idemitsu Kosan Co., Ltd.
  • poly-ip series manufactured by Idemitsu Kosan Co., Ltd.
  • EPOL manufactured by Idemitsu Kosan Co., Ltd.
  • Polytail series manufactured by Mitsubishi Chemical Co., Ltd.
  • polyalkylene oxide chain examples include chains composed of known polyalkyleneoxy groups.
  • the number of carbon atoms of the alkyleneoxy group in the polyalkyleneoxy chain is preferably 1 to 10, more preferably 1 to 6, and further preferably 2 or 3 (polyethylene oxy chain or polypropylene oxy chain).
  • the polyalkyleneoxy chain may be a chain composed of one type of alkyleneoxy group or a chain composed of two or more types of alkyleneoxy groups (for example, a chain composed of an ethyleneoxy group and a propyleneoxy group).
  • Examples of the polycarbonate chain or polyester chain include known chains made of polycarbonate or polyester.
  • the polyalkyleneoxy chain, the polycarbonate chain, or the polyester chain each preferably has an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms) at the terminal.
  • Polyalkyleneoxy chain can be taken as R P1 and R P2, end of the polycarbonate chain and a polyester chain, appropriately changing the constituents as R P1 and R P2 are represented by the formulas above the embeddable ordinary chemical structure be able to.
  • polyalkyleneoxy chain terminal oxygen atoms are incorporated as R P1 or R P2 of the removed with the component.
  • RN is a hydrogen atom
  • RN are hydrogen atoms, inside or at the end of the alkyl group contained in the molecular chain. It may have an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms).
  • RP1 and RP2 are divalent molecular chains, but at least one hydrogen atom is substituted with -NH-CO-, -CO-, -O-, -NH- or -N ⁇ .
  • the molecular chain may be trivalent or higher.
  • R P1 among the molecular chain is preferably a hydrocarbon is a chain, more preferably a hydrocarbon chain of low molecular weight, more preferably a hydrocarbon chain comprised of hydrocarbon groups aliphatic or aromatic, Hydrocarbon chains consisting of aromatic hydrocarbon groups are particularly preferred.
  • RP2 is preferably a low molecular weight hydrocarbon chain (more preferably an aliphatic hydrocarbon group) or a molecular chain other than a low molecular weight hydrocarbon chain, and is preferably a low molecular weight hydrocarbon chain and a low molecular weight hydrocarbon chain.
  • a mode containing each molecular chain other than the hydrocarbon chain having a molecular weight is more preferable.
  • formula (I-3), component represented by any one of formula (I-4) and formula (I-6) are components R P2 is a hydrocarbon group chain of low molecular weight And, RP2 contains at least two kinds of constituents which are molecular chains other than low molecular weight hydrocarbon chains.
  • constituent components represented by the above formula (I-1) are shown below.
  • the raw material compound (diisocyanate compound) for deriving the constituent component represented by the above formula (I-1) include the diisocyanate compound represented by the formula (M1) described in International Publication No. 2018/20827. Specific examples thereof include polypeptide 4,4'-diphenylmethane diisocyanate and the like.
  • the constituent component represented by the formula (I-1) and the raw material compound derived from the constituent component are not limited to those described in the following specific examples and the above documents.
  • the raw material compound (carboxylic acid or its acid chloride, etc.) that derives the constituents represented by the above formula (I-2) is not particularly limited, and is described in, for example, paragraph [0074] of International Publication No. 2018/020827. , Carboxylic acid or acid chloride compounds and specific examples thereof.
  • the constituents represented by the above formula (I-3) or formula (I-4) are shown below.
  • the raw material compound (diol compound or diamine compound) for deriving the constituent component represented by the above formula (I-3) or the above formula (I-4) is not particularly limited, and for example, International Publication No. 2018 / Examples of each compound described in No. 020827 and specific examples thereof are given, and dihydroxyoxamide is also mentioned.
  • the constituent components represented by the formula (I-3) or the formula (I-4) and the raw material compounds derived thereto are not limited to those described in the following specific examples and the above documents.
  • the number of repetitions is an integer of 1 or more, and is appropriately set within a range satisfying the molecular weight or the number of carbon atoms of the molecular chain.
  • R P3 represents an aromatic or aliphatic linking group (tetravalent), preferred linking group represented by any one of the following formulas (i) ⁇ (iix).
  • X 1 represents a single bond or a divalent linking group.
  • divalent linking group an alkylene group having 1 to 6 carbon atoms (for example, methylene, ethylene, propylene) is preferable.
  • propylene 1,3-hexafluoro-2,2-propanediyl is preferable.
  • RX and RY represent hydrogen atoms or substituents, respectively.
  • * indicates the binding site with the carbonyl group in formula (1-5).
  • the substituents can take as R X and R Y, not particularly limited, include later-described substituent Z, an alkyl group (carbon number is preferably from 1 to 12, more preferably 1 to 6, 1-3 More preferably) or an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, even more preferably 6 to 10 carbon atoms).
  • the carboxylic acid dianhydride represented by the above formula (I-5) and the raw material compound (diamine compound) leading to the constituent components represented by the above formula (I-6) are not particularly limited, and are not particularly limited, for example. Examples thereof include the compounds described in WO2018 / 020827 and WO2015 / 046313 and specific examples thereof.
  • RP1 , RP2 and RP3 may each have a substituent.
  • substituent group is not particularly limited, for example, include substituents Z to be described later, the substituents which can take as R M2 are preferably exemplified.
  • the polyurethane is represented by the above formula (I-3) or the formula (I-4), preferably the formula (I-3).
  • RP2 is a chain composed of a low molecular weight hydrocarbon group (as a functional group, preferably has an ether group, a group having a carbonyl group, or both, and more preferably a group containing a carboxy group).
  • a component preferably a component represented by the following formula (I-3A)
  • RP2 is the above-mentioned hydrocarbon polymer chain as a molecular chain (preferably represented by the following formula (I-3C)). that a component)
  • it R P2 is to have at least one of the components as a molecular chain which is the polyalkylene oxide chain component (preferably the following formula (I-3B) represented by) preferable.
  • RP1 is as described above.
  • RP2A represents a chain composed of low molecular weight hydrocarbon groups (preferably an aliphatic hydrocarbon group), and is preferably selected from the functional group group (Ia) described later as the functional group. It has at least one group, more preferably a group containing an ether group and / or a carbonyl group, and more preferably a carboxy group. Examples thereof include bis (hydroxymethyl) acetic acid compounds such as 2,2-bis (hydroxymethyl) butyric acid.
  • RP2B represents a polyalkyleneoxy chain.
  • RP2C represents a hydrocarbon polymer chain.
  • R P2A hydrocarbon group of low molecular weight
  • R P2C hydrocarbon polymer chain which can be taken as a polyalkyleneoxy chain
  • R P2C hydrocarbon polymer chain which can be taken as a polyalkyleneoxy chain
  • R P2B are respectively taken as R P2 in the above formula (I-3)
  • R P2A hydrocarbon group of low molecular weight
  • R P2C hydrocarbon polymer chain which can be taken as a polyalkyleneoxy chain
  • R P2C can take as R P2B
  • Polyurethane preferably has a constituent component including a polyether structure in the main chain.
  • a polyether structure refers to a structure in which two or more alkyleneoxy groups are linked (also referred to as a polyalkyleneoxy chain or an alkylene oxide chain), for example,-(O-alkylene group) n-.
  • the structure (n indicates the degree of polymerization and is a number of 2 or more) is shown.
  • This "polyether structure” may be a single polyalkyleneoxy chain or a structure derived from a copolymer of at least two polyalkyleneoxy chains (having different chemical structures).
  • the constituent component containing the polyether structure is not particularly limited, and examples thereof include a constituent component derived from a polyether polyol such as polyalkylene glycol and a constituent component derived from a polyether polyamine or the like.
  • "at least two kinds" of the polyether structure means a polyether having a chemical structure (alkylene groups) different from each other regardless of the difference in the constituent components forming the main chain and the position incorporated in the main chain. This means that the number of types of structures is at least two, and even if a polyether structure having the same chemical structure is incorporated into different constituent components or a plurality of types are incorporated into one constituent component, 1 Seed.
  • the number of types of the polyether structure contained in the polyurethane may be 2 or more, preferably 2 or 3 types, and more preferably 2 types.
  • Alkyleneoxy group forming a polyether structure is not particularly limited, and for example include polyalkylene oxide chain can take as the R P2, it is preferred that the number of carbon atoms in the alkylene group of the alkylene group is 1 to 6 It is more preferably 2 to 4.
  • the combination of the polyether structures is not particularly limited, but at least two types of polyether structures selected from the polyethylene oxy chain, the polypropylene oxy chain and the polytetramethylene oxy chain are preferable.
  • a combination containing a polyethylene oxy chain and a polypropylene oxy chain or a polytetramethylene oxy chain is more preferable, and a combination containing a polyethylene oxy chain and a polypropylene oxy chain is further preferable.
  • the (number average) molecular weight of at least two types of polyether structures is not particularly limited, but is preferably 400 or less, more preferably 350 or less, further preferably 300 or less, and more preferably 250 or less. Is particularly preferred.
  • the lower limit of the (number average) molecular weight is not particularly limited, but is actually preferably 100 or more, and more preferably 150 or more.
  • the (number average) molecular weight of at least two types of polyether structures means the sum of the products of the (number average) molecular weight of each polyether structure and the mole fraction.
  • the (number average) molecular weight of each polyether structure is determined by a compound (usually a hydrogen atom bonded to each end) that leads to a component containing the polyether structure (rather than being incorporated into the main chain) by the method described below. It is a value measured for a compound (for example, a polyether polyol described later).
  • the (number average) molecular weight of each polyether structure is not particularly limited, but is appropriately set within a range satisfying the above-mentioned "number average molecular weight of at least two types of polyether structures". Further, the degree of polymerization of each polyether structure is not particularly limited as long as it is 2 or more, and is appropriately set within a range satisfying the above-mentioned "number average molecular weight of at least two types of polyether structures”. The degree of polymerization depends on the number of carbon atoms of the alkyleneoxy group and the like, but is preferably 2 to 10, more preferably 3 to 8, and even more preferably 2 to 5. Examples of the constituent component containing the polyether structure include the constituent component represented by the following formula (I-7).
  • X represents a group containing a single bond, an oxygen atom or a nitrogen atom, or a linking group
  • RP4A and RP4B represent alkylene groups different from each other.
  • n1 and n2 indicate the degree of polymerization.
  • X is appropriately selected according to the terminal group of the alkyleneoxy chain in the above formula. For example, when the end of the alkyleneoxy group is an oxygen atom, it becomes a group containing a single bond or a linking group, and when the end of the alkyleneoxy group is an alkylene group, it becomes a group containing an oxygen atom or a nitrogen atom or a linking group.
  • Examples of the group containing a linking group that can be taken as X include a group consisting of a linking group and a group in which a linking group and an oxygen atom or a nitrogen atom are combined.
  • the linking group is not particularly limited, and examples thereof include a group obtained by removing one hydrogen atom from each group listed in Substituent Z, and preferably an alkylene group which can be taken as RP4A or RP4B. ..
  • the two Xs in the constituents represented by the above formula (I-7) may be the same or different.
  • the alkylene group that can be taken as RP4A and RP4B is not particularly limited, but is synonymous with the above-mentioned alkylene group in the alkyleneoxy group forming the polyether structure, and the preferred one is also the same.
  • the combination of R P4A and R P4B is synonymous with the combination described in the above-mentioned combination of polyether structures, and the preferred one is also the same.
  • n1 and n2 indicate the degree of polymerization, respectively, n1 is a number of 2 or more, n2 is a number of 0 or more than 1, and can be a number of 2 or more.
  • the component represented by the formula (I-7) is a component containing a single polyalkyleneoxy chain.
  • the main chain of polyurethane has at least two different constituents represented by the above formula (I-7), preferably two or three types, and more preferably two types.
  • the constituent component represented by the formula (I-7) is preferably a constituent component derived from at least two kinds selected from polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol.
  • the (number average) molecular weight of two or more different constituents represented by the formula (I-7) and the (number average) molecular weight of each constituent are the above-mentioned at least two types of polyether structures, respectively. It is synonymous with the (number average) molecular weight of, and the preferred range is also the same.
  • n1 in two or more different constituents represented by the formula (I-7) is appropriately set within a range satisfying the (number average) molecular weight, and has the same meaning as the degree of polymerization of the above-mentioned polyether structure. And the preferred range is the same.
  • the constituent component represented by the formula (I-7) is a constituent component containing a copolymer of two types of polyalkyleneoxy chains.
  • the bonding mode of the two polyalkyleneoxy chains in the copolymer is not particularly limited, and may be a random bond, a block bond, or an alternating bond.
  • the main chain of polyurethane may have at least one kind of constituent component represented by the above formula (I-7), and preferably one kind.
  • examples of the constituent component represented by the formula (I-7) include a constituent component composed of a polyethylene oxy chain and a copolymer of a polypropylene oxy chain.
  • the (number average) molecular weight of the constituents represented by the formula (I-7) is synonymous with the (number average) molecular weight of at least two of the above-mentioned polyether structures, and the preferable range is also the same. Further, the (number average) molecular weights of the two polyalkyleneoxy chains are synonymous with the (number average) molecular weights of the above-mentioned respective polyether structures, and the preferable ranges are also the same. When having a plurality of the same polyalkyleneoxy chains, the (number average) molecular weight of the polyalkyleneoxy chains shall be the total molecular weight.
  • n1 and n2 are appropriately set within a range satisfying the (number average) molecular weight, respectively, and have the same meaning as the degree of polymerization of the above-mentioned polyether structure, and the preferable range is also the same.
  • the above formula (I-7) defines a component containing two types of polyether structures (alkyleneoxy chains), but in the present invention, the component containing a polyether structure, the above formula (I-7), is used.
  • the constituent component represented may contain three or more types of polyether structures.
  • Polyurethane may have components other than the components represented by the above formulas.
  • a constituent component is not particularly limited as long as it can be sequentially polymerized with the raw material compound that derives the constituent component represented by each of the above formulas.
  • the (total) content of the components represented by the above formulas (1-1) to (I-7) in the polyurethane is not particularly limited, but is preferably 5 to 100% by mass, and 10 to 10 to 100% by mass. It is more preferably 100% by mass, further preferably 50 to 100% by mass, and even more preferably 80 to 100% by mass.
  • the upper limit of this content may be, for example, 90% by mass or less regardless of the above 100% by mass.
  • the content of the constituent components other than the constituent components represented by the above formulas in the polyurethane is not particularly limited, but is preferably 50% by mass or less.
  • the polyurethane has a component represented by any of the above formulas (I-1) to (I-6), its content is not particularly limited and can be set in the following range. That is, the content of the component represented by the formula (I-1) or the formula (I-2) or the component derived from the carboxylic acid dianhydride represented by the formula (I-5) in the polyurethane is The content is not particularly limited, and is preferably 10 to 50 mol%, more preferably 20 to 50 mol%, still more preferably 30 to 50 mol%.
  • the content of the constituents represented by the formula (I-3), the formula (I-4) or the formula (I-6) in the polyurethane is not particularly limited and is 0 to 50 mol%. Is more preferable, and it is more preferably 5 to 40 mol%, further preferably 10 to 30 mol%.
  • the component in which RP2 is a chain composed of a low molecular weight hydrocarbon group (for example, represented by the above formula (I-3A)).
  • the content of the constituent components in the polyurethane is not particularly limited, but is, for example, preferably 0 to 50 mol%, more preferably 1 to 30 mol%, and 2 to 20 mol%. More preferably, it is more preferably 4 to 10 mol%.
  • the component in which RP2 is the polyalkyleneoxy chain as a molecular chain for example, represented by the above formula (I-3B)).
  • the content of the component) in the polyurethane is not particularly limited, but is preferably, for example, 0 to 50 mol%, more preferably 0 to 45 mol%, and 0 to 43 mol%. Is more preferable.
  • the component in which RP2 is the hydrocarbon polymer chain as a molecular chain for example, represented by the above formula (I-3C)
  • the content of the constituent component) in the polyurethane is not particularly limited, but is preferably, for example, 0 to 50 mol%, more preferably 1 to 45 mol%, and 3 to 40 mol%. Is even more preferable, 3 to 30 mol% is further preferable, 3 to 20 mol% is particularly preferable, and 3 to 10 mol% is most preferable.
  • the (total) content of the component having a polyether structure, for example, the component represented by the formula (I-7) in polyurethane is not particularly limited, but is preferably 10 to 60 mol%, for example. , 20-55 mol%, more preferably 30-50 mol%, and particularly preferably 35-45 mol%.
  • the content of each constituent is appropriately determined within a range satisfying the above (total) content.
  • the content of one constituent preferably a constituent having a polyether structure formed of an alkyleneoxy group having a large molecular weight).
  • the content of the other component is preferably, for example, 10 to 50 mol%, preferably 15 to 40 mol%. It is more preferably present, and further preferably 20 to 30 mol%.
  • the ratio of the content of one component to the other component [one component: the other component] is not particularly limited, but is preferably, for example, 10:90 to 80:20. It is more preferably 20:80 to 70:30.
  • polyurethane has three or more different constituents represented by the formula (I-7)
  • a constituent having a polyether structure formed of an alkyleneoxy group having the smallest molecular weight is used as the other constituent.
  • the other constituents are one of the above constituents.
  • the component represented by the formula (I-7) also corresponds to the component represented by the formula (I-3B)
  • the content of the component represented by the formula (I-7) is Regardless of the content of the component represented by the formula (I-3B), the content described by the component represented by the formula (I-7) is used.
  • -Functional group- Polyurethane preferably has a functional group for enhancing the wettability or adsorptivity of solid particles such as an inorganic solid electrolyte to the surface.
  • a functional group include a group that exhibits a physical interaction such as a hydrogen bond on the surface of a solid particle and a group that can form a chemical bond with a group existing on the surface of the solid particle. It is more preferable to have at least one group selected from the following functional group group (Ia).
  • Ia functional group
  • the group capable of forming a salt such as a carboxy group, a sulfonic acid group, a phosphoric acid group, a hydroxy group, and a sulfanyl group may be a salt thereof, and examples thereof include a sodium salt and a calcium salt.
  • the alkoxysilyl group may be a silyl group in which a Si atom is substituted with at least one alkoxy group (preferably having 1 to 12 carbon atoms), and other substituents on the Si atom include an alkyl group and an aryl. The group and the like can be mentioned.
  • the alkoxysilyl group for example, the description of the alkoxysilyl group in the substituent Z described later can be preferably applied.
  • the group having a condensed ring structure of 3 or more rings is preferably a group having a cholesterol ring structure or a group having a condensed ring structure of 3 or more aromatic rings, and a cholesterol residue or a pyrenyl group is more preferable.
  • Carboxy group, a sulfonic acid group (-SO 3 H), phosphoric acid group (-PO 4 H 2), hydroxy group and an alkoxysilyl group has a high adsorptivity of the inorganic solid electrolyte or the cathode active material, 3 or more rings condensed
  • a group having a ring structure has high adsorptivity with a negative electrode active material or the like.
  • the amino group (-NH 2 ), sulfanil group and isocyanato group have high adsorptivity with the inorganic solid electrolyte.
  • Polyurethane may have a functional group selected from the functional group group (Ia) in any of the constituent components forming the polymer, and may have a functional group in either the main chain or the side chain of the polymer. Good.
  • the constituent component having the functional group include the constituent component represented by the formula (I-3A).
  • the content of the functional group selected from the functional group group (Ia) in the polyurethane is not particularly limited, but for example, the polyurethane is composed of the constituent components having the functional group selected from the functional group group (Ia).
  • the ratio in the total components is preferably 0.01 to 50 mol%, preferably 0.02 to 49 mol%, more preferably 0.1 to 40 mol%, further preferably 1 to 30 mol%, and 3 to 3 to 30 mol%. 25 mol% is particularly preferred.
  • Polyurethane (each constituent and raw material compound) may have a substituent.
  • the substituent is not particularly limited, but preferably, a group selected from the following substituent Z can be mentioned.
  • Polyurethane can be synthesized by selecting a raw material compound by a known method according to the type of bond possessed by the main chain and subjecting the raw material compound to polyaddition or polycondensation.
  • a synthesis method for example, International Publication No. 2018/151118 can be referred to.
  • each polyurethane described in International Publication No. 2018/020827, International Publication No. 2015/046313, and JP-A-2015-08480 has two types of polyether structures as main chains. Examples include those incorporated.
  • the water concentration of the polymer binder is preferably 100 ppm (mass basis) or less.
  • the fluorine-based copolymer may be crystallized and dried, or the polymer binder dispersion may be used as it is.
  • the fluorine-based copolymer is preferably amorphous.
  • the term "amorphous" as a polymer typically means that no endothermic peak due to crystal melting is observed when measured at the glass transition temperature.
  • the shape of the polymer binder is not particularly limited, but may be in the form of particles.
  • the particle shape at this time may be flat, amorphous, or the like, but is preferably spherical or granular.
  • the particle size of the particulate polymer binder is not particularly limited, but is preferably 0.1 nm or more, more preferably 1 nm or more, further preferably 5 nm or more, and particularly preferably 10 nm or more. It is preferably 50 nm or more, and most preferably 50 nm or more.
  • the upper limit value is preferably 1.0 ⁇ m or less, more preferably 700 nm or less, and particularly preferably 500 nm or less.
  • the average particle size of the composite polymer particles can be measured in the same manner as the average particle size of the inorganic solid electrolyte.
  • the average particle size of the polymer binder in the constituent layers of the all-solid-state secondary battery is measured in advance by, for example, disassembling the battery and peeling off the constituent layer containing the polymer binder, and then measuring the constituent layers. It can be measured by excluding the measured value of the particle size of the particles other than the polymer binder.
  • the mass average molecular weight of the polymer is not particularly limited, but for example, 5,000 or more is preferable, 10,000 or more is more preferable, 20,000 or more is further preferable, and 50,000 or more is particularly preferable.
  • the upper limit is substantially 5,000,000 or less, preferably 3,000,000 or less, more preferably 1,000,000 or less, and particularly preferably 500,000 or less.
  • the molecular weights of the polymer and the polymerized chain refer to the mass average molecular weight or the number average molecular weight in terms of standard polystyrene by gel permeation chromatography (GPC) unless otherwise specified.
  • GPC gel permeation chromatography
  • the measuring method basically, the value measured by the method of the following condition 1 or condition 2 (priority) is used. However, depending on the type of polymer, an appropriate eluent may be appropriately selected and used.
  • Condition 1 Column: Connect two TOSOH TSKgel Super AWM-H (trade name, manufactured by Tosoh Corporation) Carrier: 10 mM LiBr / N-methylpyrrolidone Measurement temperature: 40 ° C.
  • Carrier flow rate 1.0 ml / min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector (condition 2) Column: A column connected with TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 (all trade names, manufactured by Tosoh Corporation) is used.
  • Carrier tetrahydrofuran Measurement temperature: 40 ° C
  • Carrier flow rate 1.0 ml / min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector
  • the polymer forming the polymer binder may be a non-crosslinked polymer or a crosslinked polymer. Further, when the cross-linking of the polymer proceeds by heating or application of a voltage, the molecular weight may be larger than the above molecular weight. Preferably, the polymer has a mass average molecular weight in the above range at the start of use of the all-solid-state secondary battery.
  • the composition containing an inorganic solid electrolyte of the present invention may contain one type of polymer binder or a plurality of types.
  • the content of the polymer binder in the inorganic solid electrolyte-containing composition is not particularly limited, but may be 0.1 to 10.0% by mass with respect to 100% by mass of the solid content in terms of binding property and resistance. It is preferably 0.2 to 5.0% by mass, more preferably 0.3 to 4.0% by mass.
  • the mass ratio of the total mass (total mass) of the inorganic solid electrolyte and the active material to the mass of the binder [(mass of the inorganic solid electrolyte + mass of the active material) / (total mass of the binder)] is 1,000.
  • the range of ⁇ 1 is preferable. This ratio is more preferably 500 to 2, and even more preferably 100 to 10.
  • the composition containing an inorganic solid electrolyte of the present invention may be a solid mixture without containing a dispersion medium for dispersing each of the above components, but it is preferable to contain a dispersion medium, and solid particles such as an inorganic solid electrolyte are used as a dispersion medium. It is preferably a slurry dispersed therein.
  • the dispersion medium may be an organic compound that is liquid in the environment of use, and examples thereof include various organic solvents. Specifically, an alcohol compound, an ether compound, an amide compound, an amine compound, a ketone compound, and an aromatic compound. , An aliphatic compound, a nitrile compound, an ester compound and the like.
  • the dispersion medium may be a non-polar dispersion medium (hydrophobic dispersion medium) or a polar dispersion medium (hydrophilic dispersion medium), but a non-polar dispersion medium is preferable because it can exhibit excellent dispersibility.
  • the non-polar dispersion medium generally refers to a property having a low affinity for water, and in the present invention, for example, an ester compound, a ketone compound, an ether compound, a perfume compound, an aliphatic compound and the like can be mentioned.
  • alcohol compounds include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, and 2 -Methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol can be mentioned.
  • ether compound examples include alkylene glycol (diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.), alkylene glycol monoalkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc.).
  • alkylene glycol diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.
  • alkylene glycol monoalkyl ether ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc.
  • amide compound examples include N, N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, ⁇ -caprolactam, formamide, N-methylformamide and acetamide. , N-Methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.
  • Examples of the amine compound include triethylamine, diisopropylethylamine, tributylamine and the like.
  • Examples of the ketone compound include acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, cycloheptanone, dipropyl ketone, dibutyl ketone, diisopropyl ketone, diisobutyl ketone (DIBK), isobutyl propyl ketone, sec-. Examples thereof include butyl propyl ketone, pentyl propyl ketone and butyl propyl ketone.
  • Examples of the aromatic compound include benzene, toluene, xylene and the like.
  • Examples of the aliphatic compound include hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, paraffin, gasoline, naphtha, kerosene, and light oil.
  • Examples of the nitrile compound include acetonitrile, propionitrile, isobutyronitrile and the like.
  • ester compound examples include ethyl acetate, butyl acetate, propyl acetate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, butyl pentanate, ethyl isobutyrate, propyl isobutyrate, isopropyl isobutyrate, isobutyl isobutyrate, and pivalic acid.
  • Examples thereof include propyl, isopropyl pivalate, butyl pivalate, and isobutyl pivalate.
  • ether compounds, ketone compounds, aromatic compounds, aliphatic compounds and ester compounds are preferable, and ketone compounds, aliphatic compounds or ester compounds are more preferable.
  • the number of carbon atoms of the compound constituting the dispersion medium is not particularly limited, and is preferably 2 to 30, more preferably 4 to 20, further preferably 6 to 15, and particularly preferably 7 to 12.
  • the dispersion medium preferably has a boiling point of 50 ° C. or higher at normal pressure (1 atm), and more preferably 70 ° C. or higher.
  • the upper limit is preferably 250 ° C. or lower, and more preferably 220 ° C. or lower.
  • the dispersion medium may be at least one type and may be two or more types. Further, the content of the dispersion medium is not particularly limited and can be appropriately set. For example, in the composition containing an inorganic solid electrolyte, 20 to 80% by mass is preferable, 30 to 70% by mass is more preferable, and 40 to 60% by mass is particularly preferable.
  • the inorganic solid electrolyte-containing composition of the present invention may also contain an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table.
  • the active material include a positive electrode active material and a negative electrode active material, which will be described below.
  • an inorganic solid electrolyte-containing composition containing an active material positive electrode active material or negative electrode active material
  • an electrode composition positive electrode composition or negative electrode composition
  • the positive electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table, and is preferably one capable of reversibly inserting and releasing lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, and may be a transition metal oxide, an organic substance, an element that can be composited with Li such as sulfur, or the like by decomposing the battery.
  • a transition metal oxide having preferably used a transition metal oxide, a transition metal element M a (Co, Ni, Fe , Mn, 1 or more elements selected from Cu and V) the Things are more preferred.
  • this transition metal oxide contains element Mb (elements of Group 1 (Ia), Group 2 (IIa), Al, Ga, In, Ge, Sn, Pb, etc. of the periodic table of metals other than lithium. Elements such as Sb, Bi, Si, P and B) may be mixed.
  • the mixing amount is preferably 0 to 30 mol% relative to the amount of the transition metal element M a (100 mol%). That the molar ratio of li / M a was synthesized were mixed so that 0.3 to 2.2, more preferably.
  • transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt type structure, (MB) a transition metal oxide having a spinel type structure, (MC) a lithium-containing transition metal phosphoric acid compound, and (MD). ) Lithium-containing transition metal halide phosphoric acid compound, (ME) lithium-containing transition metal silicic acid compound, and the like.
  • transition metal oxide having a layered rock salt structure examples include LiCoO 2 (lithium cobalt oxide [LCO]), LiNi 2 O 2 (lithium nickel oxide), LiNi 0.85 Co 0.10 Al 0. 05 O 2 (Lithium Nickel Cobalt Oxide [NCA]), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (Lithium Nickel Manganese Cobalt Oxide [NMC]) and LiNi 0.5 Mn 0.5 O 2 ( Lithium manganese nickel oxide).
  • LiCoO 2 lithium cobalt oxide [LCO]
  • LiNi 2 O 2 lithium nickel oxide
  • LiNi 0.85 Co 0.10 Al 0. 05 O 2 Lithium Nickel Cobalt Oxide [NCA]
  • LiNi 1/3 Co 1/3 Mn 1/3 O 2 Lithium Nickel Manganese Cobalt Oxide [NMC]
  • LiNi 0.5 Mn 0.5 O 2 Lithium manganese nickel oxide
  • (MB) Specific examples of the transition metal oxide having a spinel structure, LiMn 2 O 4 (LMO) , LiCoMnO 4, Li 2 FeMn 3 O 8, Li 2 CuMn 3 O 8, Li 2 CrMn 3 O 8 and Li 2 Nimn 3 O 8 can be mentioned.
  • Examples of the (MC) lithium-containing transition metal phosphate compound include olivine-type iron phosphate salts such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , and LiCoPO 4.
  • Examples thereof include cobalt phosphates of the above, and monoclinic panocycon-type vanadium phosphate salts such as Li 3 V 2 (PO 4 ) 3 (lithium vanadium phosphate).
  • (MD) as the lithium-containing transition metal halogenated phosphate compound for example, Li 2 FePO 4 F such fluorinated phosphorus iron salt, Li 2 MnPO 4 hexafluorophosphate manganese salts such as F and Li 2 CoPO 4 F Fluorophosphate cobalts such as.
  • Examples of the (ME) lithium-containing transition metal silicic acid compound include Li 2 FeSiO 4 , Li 2 MnSiO 4 , and Li 2 CoSiO 4 .
  • a transition metal oxide having a (MA) layered rock salt type structure is preferable, and LCO or NMC is more preferable.
  • the shape of the positive electrode active material is not particularly limited, but is preferably in the form of particles.
  • the particle size (volume average particle size) of the positive electrode active material is not particularly limited. For example, it can be 0.1 to 50 ⁇ m.
  • the particle size of the positive electrode active material particles can be measured in the same manner as the particle size of the above-mentioned inorganic solid electrolyte.
  • a normal crusher or classifier is used to adjust the positive electrode active material to a predetermined particle size. For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling airflow type jet mill, a sieve, or the like is preferably used.
  • wet pulverization in which a dispersion medium such as water or methanol coexists can also be performed. It is preferable to perform classification in order to obtain a desired particle size.
  • the classification is not particularly limited and can be performed using a sieve, a wind power classifier, or the like. Both dry and wet classifications can 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 positive electrode active material one type may be used alone, or two or more types may be used in combination.
  • the mass (mg) (grain amount) of the positive electrode active material per unit area (cm 2) of the positive electrode active material layer is not particularly limited. It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm 2 .
  • the content of the positive electrode active material in the composition containing an inorganic solid electrolyte is not particularly limited, and is preferably 10 to 97% by mass, more preferably 30 to 95% by mass, and 40 to 93% by mass in terms of solid content of 100% by mass. More preferably, 50 to 90% by mass is particularly preferable.
  • the negative electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table, and is preferably one capable of reversibly inserting and releasing lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, and is a negative electrode activity capable of forming an alloy with a carbonaceous material, a metal oxide, a metal composite oxide, a single lithium substance, a lithium alloy, or lithium. Examples include substances. Of these, carbonaceous materials, metal composite oxides, or elemental lithium are preferably used from the viewpoint of reliability.
  • An active material that can be alloyed with lithium is preferable in that the capacity of the all-solid-state secondary battery can be increased.
  • a negative electrode active material capable of forming an alloy with lithium can be used as the negative electrode active material. This makes it possible to increase the capacity of the all-solid-state secondary battery and extend the life of the battery.
  • the carbonaceous material used as the negative electrode active material is a material substantially composed of carbon.
  • carbon black such as acetylene black (AB), graphite (artificial graphite such as natural graphite and vapor-grown graphite), and PAN (polyacrylonitrile) -based resin or furfuryl alcohol resin.
  • a carbonaceous material obtained by firing a resin can be mentioned.
  • various carbon fibers such as PAN-based carbon fibers, cellulose-based carbon fibers, pitch-based carbon fibers, vapor-grown carbon fibers, dehydrated PVA (polypoly alcohol) -based carbon fibers, lignin carbon fibers, graphitic carbon fibers, and activated carbon fibers.
  • carbonaceous materials can also be divided into non-graphitizable carbonaceous materials (also referred to as hard carbon) and graphite-based carbonaceous materials depending on the degree of graphitization. Further, the carbonaceous material preferably has the interplanar spacing or density and the size of crystallites described in JP-A-62-22066, JP-A-2-6856, and JP-A-3-45473.
  • the carbonaceous material does not have to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, and the like should be used. You can also.
  • As the carbonaceous material hard carbon or graphite is preferably used, and graphite is more preferably used.
  • the metal or semi-metal element oxide applied as the negative electrode active material is not particularly limited as long as it is an oxide capable of storing and releasing lithium, and is a composite of a metal element oxide (metal oxide) and a metal element.
  • metal oxide metal oxide
  • examples thereof include oxides or composite oxides of metal elements and semi-metal elements (collectively referred to as metal composite oxides) and oxides of semi-metal elements (semi-metal oxides).
  • metal composite oxides oxides or composite oxides of metal elements and semi-metal elements
  • oxides of semi-metal elements semi-metal elements
  • amorphous oxides are preferable, and chalcogenides, which are reaction products of metal elements and elements of Group 16 of the Periodic Table, are also preferable.
  • the metalloid element means an element exhibiting properties intermediate between a metalloid element and a non-metalloid element, and usually contains six elements of boron, silicon, germanium, arsenic, antimony and tellurium, and further selenium. , Polonium and Astatine.
  • amorphous means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering band having an apex in a region of 20 ° to 40 ° in 2 ⁇ value, and a crystalline diffraction line is used. You may have.
  • the strongest intensity of the crystalline diffraction lines seen at a 2 ⁇ value of 40 ° to 70 ° is 100 times or less of the diffraction line intensity at the apex of the broad scattering band seen at a 2 ⁇ value of 20 ° to 40 °. It is preferable that it is 5 times or less, and it is particularly preferable that it does not have a crystalline diffraction line.
  • the amorphous oxide of the metalloid element or the chalcogenide is more preferable, and the elements of the groups 13 (IIIB) to 15 (VB) of the periodic table (for example).
  • Al, Ga, Si, Sn, Ge, Pb, Sb and Bi) alone or a combination of two or more (composite) oxides, or chalcogenides are particularly preferred.
  • preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , GeO, PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2.
  • Negative electrode active materials that can be used in combination with amorphous oxides such as Sn, Si, and Ge include carbonaceous materials that can occlude and / or release lithium ions or lithium metals, lithium alone, lithium alloys, and lithium.
  • a negative electrode active material that can be alloyed with the above is preferably used.
  • the oxide of a metal or a metalloid element contains at least one of titanium and lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
  • the lithium-containing metal composite oxide include a composite oxide of lithium oxide and the metal (composite) oxide or the chalcogenide, and more specifically, Li 2 SnO 2.
  • the negative electrode active material for example, a metal oxide, contains a titanium element (titanium oxide).
  • Li 4 Ti 5 O 12 lithium titanate [LTO]
  • Li 4 Ti 5 O 12 has excellent rapid charge / discharge characteristics because the volume fluctuation during storage and release of lithium ions is small, and deterioration of electrodes is suppressed and lithium ion secondary It is preferable in that the life of the battery can be improved.
  • the lithium alloy as the negative electrode active material is not particularly limited as long as it is an alloy usually used as the negative electrode active material of the secondary battery, and examples thereof include a lithium aluminum alloy.
  • the negative electrode active material that can be alloyed with lithium is not particularly limited as long as it is usually used as the negative electrode active material of the secondary battery. Such an active material has a large expansion and contraction due to charging and discharging of the all-solid secondary battery and accelerates the deterioration of the cycle characteristics. However, since the inorganic solid electrolyte-containing composition of the present invention contains the above-mentioned compound (SA). , Deterioration of cycle characteristics can be suppressed.
  • SA compound
  • Examples of such an active material include a (negative electrode) active material having a silicon element or a tin element (alloy, etc.), and metals such as Al and In, and a negative electrode active material having a silicon element that enables a higher battery capacity.
  • a silicon element-containing active material is preferable, and a silicon element-containing active material having a silicon element content of 50 mol% or more of all the constituent elements is more preferable.
  • a negative electrode containing these negative electrode active materials for example, a Si negative electrode containing a silicon element-containing active material, a Sn negative electrode containing a tin element active material, etc.
  • a carbon negative electrode graphite, acetylene black, etc.
  • silicon element-containing active material examples include silicon materials such as Si and SiOx (0 ⁇ x ⁇ 1), and silicon-containing alloys containing titanium, vanadium, chromium, manganese, nickel, copper, lanthanum, and the like (for example,).
  • LaSi 2 , VSi 2 , La-Si, Gd-Si, Ni-Si) or organized active material (eg LaSi 2 / Si), as well as other silicon and tin elements such as SnSiO 3 , SnSiS 3 Examples include active materials containing.
  • SiOx itself can be used as a negative electrode active material (semi-metal oxide), and since Si is generated by the operation of an all-solid-state secondary battery, a negative electrode active material that can be alloyed with lithium (its). It can be used as a precursor substance).
  • the negative electrode active material having a tin element include Sn, SnO, SnO 2 , SnS, SnS 2 , and the active material containing the silicon element and the tin element.
  • a composite oxide with lithium oxide for example, Li 2 SnO 2 can also be mentioned.
  • the above-mentioned negative electrode active material can be used without particular limitation, but in terms of battery capacity, a negative electrode active material that can be alloyed with silicon is a preferred embodiment as the negative electrode active material.
  • a negative electrode active material that can be alloyed with silicon is a preferred embodiment as the negative electrode active material.
  • the above-mentioned silicon material or silicon-containing alloy (alloy containing a silicon element) is more preferable, and it is further preferable to contain silicon (Si) or a silicon-containing alloy.
  • the chemical formula of the compound obtained by the above firing method can be calculated from the inductively coupled plasma (ICP) emission spectroscopic analysis method as a measuring method and the mass difference of the powder before and after firing as a simple method.
  • ICP inductively coupled plasma
  • the shape of the negative electrode active material is not particularly limited, but it is preferably in the form of particles.
  • the volume average particle size of the negative electrode active material is not particularly limited, but is preferably 0.1 to 60 ⁇ m.
  • the volume average particle size of the negative electrode active material particles can be measured in the same manner as the average particle size of the inorganic solid electrolyte. In order to obtain a predetermined particle size, a normal crusher or classifier is used as in the case of the positive electrode active material.
  • the negative electrode active material may be used alone or in combination of two or more.
  • the mass (mg) (grain amount) of the negative electrode active material per unit area (cm 2) of the negative electrode active material layer is not particularly limited. It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm 2 .
  • the content of the negative electrode active material in the inorganic solid electrolyte-containing composition is not particularly limited, and is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and 30 to 30% by mass, based on 100% by mass of the solid content. It is more preferably 80% by mass, and even more preferably 40 to 75% by mass.
  • the negative electrode active material layer when the negative electrode active material layer is formed by charging the secondary battery, instead of the negative electrode active material, a metal belonging to Group 1 or Group 2 of the periodic table generated in the all-solid-state secondary battery is used. Ions can be used. A negative electrode active material layer can be formed by combining these ions with electrons and precipitating them as a metal.
  • the surfaces of the positive electrode active material and the negative electrode active material may be surface-coated with another metal oxide.
  • the surface coating agent include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si or Li. Specific examples thereof include spinel titanate, tantalum oxide, niobate oxide, lithium niobate compound and the like.
  • the surface of the electrode containing the positive electrode active material or the negative electrode active material may be surface-treated with sulfur or phosphorus.
  • the surface of the positive electrode active material or the particle surface of the negative electrode active material may be surface-treated with active light rays or an active gas (plasma or the like) before and after the surface coating.
  • the inorganic solid electrolyte-containing composition of the present invention preferably contains a conductive auxiliary agent, and for example, a silicon atom-containing active material as a negative electrode active material is preferably used in combination with a conductive auxiliary agent.
  • the conductive auxiliary agent is not particularly limited, and those known as general conductive auxiliary agents can be used.
  • graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black and furnace black, amorphous carbon such as needle coke, vapor-grown carbon fibers or carbon nanotubes, which are electron conductive materials.
  • It may be a carbon fiber such as graphene or fullerene, a metal powder such as copper or nickel, or a metal fiber, and a conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, or polyphenylene derivative. May be used.
  • a conductive auxiliary agent when the active material and the conductive auxiliary agent are used in combination, among the above conductive auxiliary agents, when the battery is charged and discharged, the ions of a metal belonging to Group 1 or Group 2 of the periodic table (preferably Li).
  • a conductive auxiliary agent is one that does not insert and release ions) and does not function as an active material.
  • conductive auxiliary agents those that can function as active materials in the active material layer when the battery is charged and discharged are classified as active materials instead of conductive auxiliary agents. Whether or not the battery functions as an active material when it is charged and discharged is not unique and is determined by the combination with the active material.
  • the conductive auxiliary agent may contain one kind or two or more kinds.
  • the shape of the conductive auxiliary agent is not particularly limited, but is preferably in the form of particles.
  • the content of the conductive auxiliary agent in the inorganic solid electrolyte-containing composition is preferably 0 to 10% by mass based on 100% by mass of the solid content.
  • the inorganic solid electrolyte-containing composition of the present invention preferably contains a lithium salt (supporting electrolyte).
  • the lithium salt the lithium salt usually used for this kind of product is preferable, and there is no particular limitation.
  • the lithium salt described in paragraphs 882 to 985 of JP-A-2015-084886 is preferable.
  • the content of the lithium salt is preferably 0.1 part by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the solid electrolyte.
  • the upper limit is preferably 50 parts by mass or less, more preferably 20 parts by mass or less.
  • the inorganic solid electrolyte-containing composition of the present invention can appropriately contain a dispersant.
  • the inorganic solid electrolyte-containing composition of the present invention contains a polymer binder, since this poster also functions as a dispersant, it does not have to contain a dispersant other than this polymer binder, but it does contain a dispersant. You may.
  • the dispersant those usually used for all-solid-state secondary batteries can be appropriately selected and used. Generally, compounds intended for particle adsorption, steric repulsion and / or electrostatic repulsion are preferably used.
  • the composition containing an inorganic solid electrolyte of the present invention contains, as other components other than the above components, an ionic liquid, a thickener, and a cross-linking agent (such as those that undergo a cross-linking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization).
  • a cross-linking agent such as those that undergo a cross-linking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization.
  • Polymerization initiators such as those that generate acids or radicals by heat or light
  • defoaming agents leveling agents, dehydrating agents, antioxidants and the like
  • the ionic liquid is contained in order to further improve the ionic conductivity, and known ones can be used without particular limitation.
  • a polymer other than the polymer contained in the above-mentioned binder, a commonly used binder and the like may be contained.
  • the composition containing an inorganic solid electrolyte of the present invention comprises an inorganic solid electrolyte and the above-mentioned compound (SA), preferably a polymer binder, a dispersion medium, an active material depending on the application, a conductive additive, and optionally a lithium salt.
  • SA compound
  • Any other component can be prepared, for example, as a mixture, preferably as a slurry, by mixing with various commonly used mixers.
  • the mixing method is not particularly limited, and the mixture may be mixed all at once or sequentially.
  • the mixing environment is not particularly limited, and examples thereof include under dry air and under an inert gas.
  • the sheet for an all-solid-state secondary battery of the present invention is a sheet-like molded body capable of forming a constituent layer of an all-solid-state secondary battery, and includes various aspects depending on its use.
  • a sheet preferably used for a solid electrolyte layer also referred to as a solid electrolyte sheet for an all-solid secondary battery
  • an electrode or a sheet preferably used for a laminate of an electrode and a solid electrolyte layer (an electrode for an all-solid secondary battery).
  • Sheet and the like.
  • these various sheets are collectively referred to as an all-solid-state secondary battery sheet.
  • the solid electrolyte sheet for an all-solid secondary battery of the present invention may be a sheet having a solid electrolyte layer, and even a sheet in which the solid electrolyte layer is formed on a base material does not have a base material and is a solid electrolyte layer. It may be a sheet formed of.
  • the solid electrolyte sheet for an all-solid secondary battery may have another layer in addition to the solid electrolyte layer. Examples of other layers include a protective layer (release sheet), a current collector, a coat layer, and the like.
  • the solid electrolyte sheet for an all-solid secondary battery of the present invention for example, a sheet having a layer composed of the inorganic solid electrolyte-containing composition of the present invention, a normal solid electrolyte layer, and a protective layer on a substrate in this order.
  • the solid electrolyte layer contained in the solid electrolyte sheet for an all-solid secondary battery is preferably formed of the inorganic solid electrolyte-containing composition of the present invention.
  • the content of each component in the solid electrolyte layer is not particularly limited, but is preferably synonymous with the content of each component in the solid content of the inorganic solid electrolyte-containing composition of the present invention.
  • the layer thickness of each layer constituting the solid electrolyte sheet for an all-solid-state secondary battery is the same as the layer thickness of each layer described in the all-solid-state secondary battery described later.
  • the base material is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include a material described in the current collector described later, a sheet body (plate-like body) of an organic material, an inorganic material, and the like.
  • the organic material include various polymers, and specific examples thereof include polyethylene terephthalate, polypropylene, polyethylene, and cellulose.
  • the inorganic material include glass, ceramic and the like.
  • the electrode sheet for an all-solid-state secondary battery of the present invention may be an electrode sheet having an active material layer, and the active material layer is formed on a base material (current collector).
  • the sheet may be a sheet that does not have a base material and is formed from an active material layer.
  • This electrode sheet is usually a sheet having a current collector and an active material layer, but has an embodiment having a current collector, an active material layer and a solid electrolyte layer in this order, and a current collector, an active material layer and a solid electrolyte. An embodiment having a layer and an active material layer in this order is also included.
  • the solid electrolyte layer and the active material layer of the electrode sheet are preferably formed of the inorganic solid electrolyte-containing composition of the present invention.
  • the content of each component in the solid electrolyte layer or the active material layer is not particularly limited, but preferably, the content of each component in the solid content of the inorganic solid electrolyte-containing composition (electrode composition) of the present invention. Is synonymous with.
  • the layer thickness of each layer constituting the electrode sheet of the present invention is the same as the layer thickness of each layer described in the all-solid-state secondary battery described later.
  • the electrode sheet of the present invention may have the other layers described above.
  • the all-solid-state secondary battery sheet of the present invention at least one of the solid electrolyte layer and the active material layer is formed of the inorganic solid electrolyte-containing composition of the present invention, and the active material layer preferably contains the inorganic solid electrolyte of the present invention. Formed from the composition. Therefore, the constituent layer formed of the inorganic solid electrolyte-containing composition of the present invention can realize a large layer density ratio as shown in Examples described later. By using the sheet for an all-solid-state secondary battery of the present invention as a constituent layer of an all-solid-state secondary battery, excellent cycle characteristics and low resistance of the all-solid-state secondary battery can be realized.
  • the negative electrode sheet for an all-solid secondary battery and the all-solid secondary battery in which the negative electrode active material is formed of the inorganic solid electrolyte-containing composition of the present invention may use a negative electrode active material capable of forming an alloy with lithium as the negative electrode active material. , Low resistance and high cycle characteristics can be achieved while showing high active material capacity.
  • the method for producing the sheet for an all-solid secondary battery of the present invention is not particularly limited, and the sheet can be produced by forming each of the above layers using the inorganic solid electrolyte-containing composition of the present invention.
  • the inorganic solid electrolyte-containing composition of the present invention is a solid mixture, a method of forming it by pressure molding on a base material or a current collector can be mentioned.
  • the inorganic solid electrolyte-containing composition of the present invention contains a dispersion medium, it is preferably formed (coated and dried) on a base material or a current collector (may be via another layer).
  • Examples thereof include a method of forming a layer (coating dry layer) composed of an inorganic solid electrolyte-containing composition.
  • a layer coating dry layer
  • the coating dry layer is a layer formed by applying the inorganic solid electrolyte-containing composition of the present invention and drying the dispersion medium (that is, the inorganic solid electrolyte-containing composition of the present invention is used.
  • the dispersion medium may remain as long as the effects of the present invention are not impaired, and the residual amount may be, for example, 3% by mass or less in each layer.
  • each step such as coating and drying will be described in the following method for producing an all-solid-state secondary battery.
  • the coating dry layer obtained as described above can also be pressurized.
  • the pressurizing conditions and the like will be described later in the method for manufacturing an all-solid-state secondary battery.
  • the base material, the protective layer (particularly the release sheet) and the like can be peeled off.
  • the all-solid secondary battery of the present invention comprises a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer arranged between the positive electrode active material layer and the negative electrode active material layer.
  • the positive electrode active material layer is preferably formed on the positive electrode current collector and constitutes the positive electrode.
  • the negative electrode active material layer is preferably formed on the negative electrode current collector to form the negative electrode.
  • At least one layer of the negative electrode active material layer, the positive electrode active material layer and the solid electrolyte layer is formed by the inorganic solid electrolyte-containing composition of the present invention, and the negative electrode active material layer is formed by the inorganic solid electrolyte-containing composition of the present invention.
  • the electrode is used. It is also one of the preferred embodiments that all layers are formed of the inorganic solid electrolyte-containing composition of the present invention.
  • the active material layer or solid electrolyte layer formed of the inorganic solid electrolyte-containing composition of the present invention preferably contains the component species and their content ratios in the solid content of the inorganic solid electrolyte-containing composition of the present invention. Is the same as.
  • a known material can be used.
  • the thicknesses of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer are not particularly limited.
  • each layer is preferably 10 to 1,000 ⁇ m, more preferably 20 ⁇ m or more and less than 500 ⁇ m, respectively, in consideration of the dimensions of a general all-solid-state secondary battery.
  • the thickness of at least one of the positive electrode active material layer and the negative electrode active material layer is more preferably 50 ⁇ m or more and less than 500 ⁇ m.
  • the positive electrode active material layer and the negative electrode active material layer may each have a current collector on the opposite side of the solid electrolyte layer.
  • the all-solid-state secondary battery of the present invention may be used as an all-solid-state secondary battery with the above structure, but in order to form a dry battery, it should be further enclosed in a suitable housing.
  • the housing may be made of metal or resin (plastic).
  • a metallic material for example, one made of aluminum alloy or stainless steel can be mentioned.
  • the metallic housing is divided into a positive electrode side housing and a negative electrode side housing, and electrically connected to the positive electrode current collector and the negative electrode current collector, respectively. It is preferable that the housing on the positive electrode side and the housing on the negative electrode side are joined and integrated via a gasket for preventing a short circuit.
  • FIG. 1 is a sectional view schematically showing an all-solid-state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention.
  • the all-solid-state secondary battery 10 of the present embodiment has a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 in this order when viewed from the negative electrode side. ..
  • Each layer is in contact with each other and has an adjacent structure.
  • the lithium ions (Li + ) accumulated in the negative electrode are returned to the positive electrode side, and electrons are supplied to the operating portion 6.
  • a light bulb is used as a model for the operating portion 6, and the light bulb is turned on by electric discharge.
  • the all-solid-state secondary battery having the layer structure shown in FIG. 1 When the all-solid-state secondary battery having the layer structure shown in FIG. 1 is placed in a 2032-inch coin case, the all-solid-state secondary battery is referred to as an all-solid-state secondary battery laminate, and the all-solid-state secondary battery laminate is referred to as an all-solid-state secondary battery laminate. Batteries manufactured in a 2032 type coin case are sometimes referred to as all-solid-state secondary batteries.
  • the all-solid-state secondary battery 10 In the all-solid-state secondary battery 10, all of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer are formed of the inorganic solid electrolyte-containing composition of the present invention.
  • the all-solid-state secondary battery 10 exhibits excellent battery performance.
  • the inorganic solid electrolyte, the compound (SA), and the polymer binder contained in the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 may be of the same type or different from each other.
  • either or both of the positive electrode active material layer and the negative electrode active material layer may be simply referred to as an active material layer or an electrode active material layer.
  • either or both of the positive electrode active material and the negative electrode active material may be collectively referred to as an active material or an electrode active material.
  • the constituent layer is formed of the composition containing the inorganic solid electrolyte of the present invention, an all-solid secondary battery having excellent cycle characteristics and low resistance can be realized.
  • the negative electrode active material layer can be a lithium metal layer.
  • the lithium metal layer include a layer formed by depositing or molding a lithium metal powder, a lithium foil, a lithium vapor deposition film, and the like.
  • the thickness of the lithium metal layer can be, for example, 1 to 500 ⁇ m regardless of the thickness of the negative electrode active material layer.
  • the positive electrode current collector 5 and the negative electrode current collector 1 are preferably electron conductors.
  • either or both of the positive electrode current collector and the negative electrode current collector may be collectively referred to as a current collector.
  • a current collector As a material for forming the positive electrode current collector, in addition to aluminum, aluminum alloy, stainless steel, nickel and titanium, the surface of aluminum or stainless steel is treated with carbon, nickel, titanium or silver (a thin film is formed). Of these, aluminum and aluminum alloys are more preferable.
  • As a material for forming the negative electrode current collector in addition to aluminum, copper, copper alloy, stainless steel, nickel and titanium, carbon, nickel, titanium or silver is treated on the surface of aluminum, copper, copper alloy or stainless steel. Aluminum, copper, copper alloy and stainless steel are more preferable.
  • the shape of the current collector is usually a film sheet, but a net, a punched body, a lath body, a porous body, a foam body, a molded body of a fiber group, or the like can also be used.
  • the thickness of the current collector is not particularly limited, but is preferably 1 to 500 ⁇ m. Further, it is also preferable that the surface of the current collector is made uneven by surface treatment.
  • a layer formed of a known constituent layer-forming material can be applied to the positive electrode active material layer.
  • a functional layer, a member, or the like is appropriately interposed or arranged between or outside each of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector. You may. Further, each layer may be composed of a single layer or a plurality of layers.
  • the all-solid-state secondary battery can be manufactured by a conventional method. Specifically, the all-solid-state secondary battery can be manufactured by forming each of the above layers using the inorganic solid electrolyte-containing composition or the like of the present invention. The details will be described below.
  • the inorganic solid electrolyte-containing composition of the present invention is appropriately applied onto a base material (for example, a metal foil serving as a current collector) to form a coating film (film formation).
  • a method including (via) a step a method for producing a sheet for an all-solid-state secondary battery of the present invention
  • an inorganic solid electrolyte-containing composition containing a positive electrode active material is applied as a positive electrode material (positive electrode composition) on a metal foil which is a positive electrode current collector to form a positive electrode active material layer, and the entire solid is formed.
  • a positive electrode sheet for a secondary battery is produced.
  • an inorganic solid electrolyte-containing composition for forming the solid electrolyte layer is applied onto the positive electrode active material layer to form the solid electrolyte layer.
  • an inorganic solid electrolyte-containing composition containing a negative electrode active material is applied as a negative electrode material (negative electrode composition) on the solid electrolyte layer to form a negative electrode active material layer.
  • a negative electrode current collector metal foil
  • an all-solid secondary battery having a structure in which a solid electrolyte layer is sandwiched between the positive electrode active material layer and the negative electrode active material layer can be obtained. Can be done. This can be enclosed in a housing to obtain a desired all-solid-state secondary battery.
  • a negative electrode active material layer, a solid electrolyte layer and a positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collectors are superposed to manufacture an all-solid secondary battery. You can also do it.
  • a positive electrode sheet for an all-solid-state secondary battery is produced. Further, an inorganic solid electrolyte-containing composition containing a negative electrode active material is applied as a negative electrode material (negative electrode composition) on a metal foil which is a negative electrode current collector to form a negative electrode active material layer, and the entire solid is formed. A negative electrode sheet for a secondary battery is manufactured. Next, a solid electrolyte layer is formed on the active material layer of any one of these sheets as described above.
  • the other of the positive electrode sheet for the all-solid secondary battery and the negative electrode sheet for the all-solid secondary battery is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other.
  • an all-solid-state secondary battery can be manufactured.
  • the following method can be mentioned. That is, as described above, a positive electrode sheet for an all-solid-state secondary battery and a negative electrode sheet for an all-solid-state secondary battery are produced. Separately from this, an inorganic solid electrolyte-containing composition is applied onto a base material to prepare a solid electrolyte sheet for an all-solid secondary battery composed of a solid electrolyte layer.
  • the positive electrode sheet for the all-solid-state secondary battery and the negative electrode sheet for the all-solid-state secondary battery are laminated so as to sandwich the solid electrolyte layer peeled from the base material. In this way, an all-solid-state secondary battery can be manufactured. Further, as described above, a positive electrode sheet for an all-solid-state secondary battery or a negative electrode sheet for an all-solid-state secondary battery, and a solid electrolyte sheet for an all-solid-state secondary battery are produced. Next, the positive electrode sheet for the all-solid secondary battery or the negative electrode sheet for the all-solid secondary battery and the solid electrolyte sheet for the all-solid secondary battery were brought into contact with the positive electrode active material layer or the negative electrode active material layer and the solid electrolyte layer.
  • the solid electrolyte layer is transferred to the positive electrode sheet for the all-solid-state secondary battery or the negative electrode sheet for the all-solid-state secondary battery.
  • the pressurizing method and pressurizing conditions in this method are not particularly limited, and the methods and pressurizing conditions described later in the pressurization of the applied composition can be applied.
  • the solid electrolyte layer or the like can be formed by, for example, press-molding an inorganic solid electrolyte-containing composition or the like on a substrate or an active material layer under the pressure conditions described later, or sheet molding of the solid electrolyte or the active material. You can also use the body.
  • the inorganic solid electrolyte-containing composition of the present invention may be used as any one of the positive electrode composition, the inorganic solid electrolyte-containing composition and the negative electrode composition, and the present invention may be used as the negative electrode composition. It is preferable to use the inorganic solid electrolyte-containing composition of the above, and the inorganic solid electrolyte-containing composition of the present invention can be used for any of the compositions.
  • the solid electrolyte layer or the active material layer is formed by a composition other than the solid electrolyte composition of the present invention
  • examples of the material include commonly used compositions and the like. Further, it belongs to the first group or the second group of the periodic table, which is accumulated in the negative electrode current collector by the initialization or charging during use, which will be described later, without forming the negative electrode active material layer at the time of manufacturing the all-solid secondary battery.
  • a negative electrode active material layer can also be formed by combining metal ions with electrons and precipitating them as a metal on a negative electrode current collector or the like.
  • the method for applying the composition containing an inorganic solid electrolyte is not particularly limited and can be appropriately selected.
  • coating preferably wet coating
  • spray coating spin coating coating
  • dip coating coating dip coating coating
  • slit coating stripe coating
  • bar coating coating can be mentioned.
  • the inorganic solid electrolyte-containing composition may be subjected to a drying treatment after being applied to each of them, or may be subjected to a drying treatment after being applied in multiple layers.
  • the drying temperature is not particularly limited.
  • the lower limit is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 80 ° C. or higher.
  • the upper limit is preferably 300 ° C.
  • the dispersion medium can be removed and a solid state (coating dry layer) can be obtained. Further, it is preferable because the temperature is not raised too high and each member of the all-solid-state secondary battery is not damaged. As a result, in an all-solid-state secondary battery, it is possible to obtain excellent overall performance, good binding properties, and good ionic conductivity even without pressurization.
  • the pressurizing method include a hydraulic cylinder press machine and the like.
  • the pressing force is not particularly limited, and is generally preferably in the range of 5 to 1500 MPa.
  • the applied inorganic solid electrolyte-containing composition may be heated at the same time as pressurization.
  • the heating temperature is not particularly limited, and is generally in the range of 30 to 300 ° C. It can also be pressed at a temperature higher than the glass transition temperature of the inorganic solid electrolyte.
  • the pressurization may be carried out in a state where the coating solvent or the dispersion medium has been dried in advance, or may be carried out in a state where the solvent or the dispersion medium remains.
  • each composition may be applied at the same time, and the application drying press may be performed simultaneously and / or sequentially. After coating on separate substrates, they may be laminated by transfer.
  • the atmosphere during the manufacturing process is not particularly limited, and is in the atmosphere, in dry air (dew point -20 ° C or lower), in an inert gas (for example, in argon gas, helium gas, nitrogen gas). And so on.
  • the pressing time may be short (for example, within several hours) and high pressure may be applied, or medium pressure may be applied for a long time (1 day or more).
  • an all-solid-state secondary battery other than the all-solid-state secondary battery sheet for example, in the case of an all-solid-state secondary battery, an all-solid-state secondary battery restraint (screw tightening pressure, etc.) can be used in order to continue applying a medium pressure.
  • the press pressure may be uniform or different with respect to the pressed portion such as the sheet surface.
  • the press pressure can be changed according to the area or layer thickness of the pressed portion. It is also possible to change the same part step by step with different pressures.
  • the pressed surface may be smooth or roughened.
  • the all-solid-state secondary battery manufactured as described above is preferably initialized after manufacturing or before use.
  • the initialization is not particularly limited, and can be performed, for example, by performing initial charging / discharging with the press pressure increased, and then releasing the pressure until the pressure reaches the general working pressure of the all-solid-state secondary battery.
  • the all-solid-state secondary battery of the present invention can be applied to various applications.
  • the application mode is not particularly limited, but for example, when mounted on an electronic device, a laptop computer, a pen input computer, a mobile computer, an electronic book player, a mobile phone, a cordless phone handset, a pager, a handy terminal, a mobile fax, or a mobile phone. Examples include copying, portable printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, mini discs, electric shavers, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, etc.
  • Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (pacemakers, hearing aids, shoulder massagers, etc.). Furthermore, it can be used for various munitions and space. It can also be combined with a solar cell.
  • Li 2 S lithium sulfide
  • Aldrich Corp. purity> 99.98%
  • P 2 S 5. diphosphorus pentasulfide 3.90 g was weighed, placed in an agate mortar, and mixed for 5 minutes using an agate mortar.
  • Each of the compounds represented by A-01 to A-28 is a compound represented by the above formula (1).
  • ⁇ Preparation or synthesis of each compound> (1) Compounds A-01 to A-04 and A-20 to A-24 Commercially available compounds (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were used as each compound.
  • (2) Compound A-05 Compound A-05 was synthesized according to the method described in the following literature. References: Analytical Chemistry, 1998, vol. 60,2509-2512 (3) Compounds A-06 to A-18 In the synthesis of compound A-05, compounds A-06 to A-18 were synthesized in the same manner as A-05, except that the alcohol compound forming A-06 to A-18 and the acid anhydride were changed. ..
  • B-01 and B-02 were prepared as the above-mentioned compound (B) (fluorine-based polymer).
  • B-01 Fluorolink (registered trademark) F10 (perfluoropolyether, containing phosphoric acid group, manufactured by Solvay)
  • B-02 Fluorolink (registered trademark) S10 (perfluoropolyether, containing alkoxysilyl group, manufactured by Solvay)
  • C-01 to C-04 were prepared as the above-mentioned compound (C) (organopolysiloxane).
  • C-03: X-22-164C reactive silicone oil at both ends, reactive group is methylenedioxy group, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Example 1 ⁇ Preparation of Negative Electrode Compositions S-1 to S-44 and cS-1 to cS-3> 180 zirconia beads having a diameter of 5 mm were placed in a zirconia 45 mL container (manufactured by Fritsch), 4.0 g of LPS synthesized in Synthesis Example A was added, and a solution of the compound (SA) shown in Table 1 is shown in Table 1. An amount to be the content (solid content) and 22 g of butyl butyrate were added. This container was set on a planetary ball mill P-7 (trade name) manufactured by Fritsch, and stirred at 25 ° C. and a rotation speed of 300 rpm for 60 minutes.
  • composition S-45 for negative electrode In the preparation of the negative electrode composition S-3, the binder PVdF-HFP was changed to the polyurethane binder B-1 synthesized in Synthesis Example 1 below, and the mixture amount of the binder and butyl butyrate were mixed so that the solid content was the same.
  • the negative electrode composition S-45 was prepared as a non-aqueous composition in the same manner as in the preparation of the negative electrode composition S-3 except that the amount was adjusted.
  • binder dispersion B-1 15.00 g of the polymer solution obtained above was diluted with 15.00 g of THF, and 90.00 g of butyl butyrate was added dropwise over 1 hour with stirring to obtain an emulsion of polymer B-1. This emulsion is concentrated to about 70 g, and butyl butyrate is added to bring the total amount to 100.00 g to obtain a 3% by mass butyl butyrate dispersion (binder dispersion B-1) of a binder composed of polymer B-1. It was.
  • cA-01 The compound used for the preparation of the negative electrode composition cS-2 and the preparation of the negative electrode sheet PcS-2 for an all-solid secondary battery (the chemical structure is shown below) cA-01 is the compound (SA) specified in the present invention. However, it is shown in the compound (SA) column for convenience in Table 1.
  • the content is the content in 100% by mass of the solid content of the composition for the negative electrode, and the unit is mass%.
  • the conductive auxiliary agent is acetylene black (manufactured by Denka).
  • the binder is a polymer binder made of PVdF-HFP or a polyurethane binder B-1.
  • composition containing inorganic solid electrolyte 180 zirconia beads having a diameter of 5 mm were put into a zirconia 45 mL container (manufactured by Fritsch), 4.85 g of LPS synthesized in Synthesis Example A, 0.15 g (solid content mass) of the following polymer binder solution, and 16.0 g of butyl butyrate was added. Then, this container was set in a planetary ball mill P-7 manufactured by Fritsch, and mixed at a temperature of 25 ° C. and a rotation speed of 150 rpm for 10 minutes to prepare an inorganic solid electrolyte-containing composition.
  • Polymer binder solution A polymer binder solution having a solid content concentration of 3% by mass, prepared by dissolving PVdF-HFP (KYNER FLEX 2500-20 manufactured by Arkema) in butyl butyrate.
  • the inorganic solid electrolyte-containing composition obtained above is applied onto an aluminum foil having a thickness of 20 ⁇ m using an applicator (trade name: SA-201) and heated at 80 ° C. for 2 hours to prepare the inorganic solid electrolyte-containing composition.
  • the inorganic solid electrolyte-containing composition dried at a temperature of 120 ° C. and a pressing force of 600 MPa for 10 seconds was heated and pressurized to prepare a solid electrolyte sheet for an all-solid secondary battery.
  • the layer thickness of the solid electrolyte layer was 50 ⁇ m.
  • composition for positive electrode 180 zirconia beads having a diameter of 5 mm were put into a 45 mL container made of zirconia (manufactured by Fritsch), 2.8 g of LPS synthesized in the above synthesis example A, 0.2 g (solid content mass) of the following polymer binder solution and butyric acid. 22 g of butyl was added.
  • This container was set on a planetary ball mill P-7 manufactured by Fritsch, and stirred at 25 ° C. at a rotation speed of 300 rpm for 60 minutes.
  • LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NMC, manufactured by Aldrich) was put into this container as a positive electrode active material, and similarly, the container was placed in the planetary ball mill P-7. It was set and mixed at 25 ° C. and a rotation speed of 100 rpm for 5 minutes. In this way, the composition for the positive electrode was prepared.
  • Binder solution A polymer binder solution having a solid content concentration of 3% by mass, prepared by dissolving PVdF-HFP (KYNER FLEX 2500-20 manufactured by Arkema) in butyl butyrate.
  • the positive electrode composition obtained above is applied onto an aluminum foil (positive electrode current collector) having a thickness of 20 ⁇ m using a baker type applicator (trade name: SA-201), heated at 100 ° C. for 2 hours, and the positive electrode is used.
  • the composition for use was dried (dispersion medium was removed). Then, using a heat press machine, the dried positive electrode composition is pressurized at 25 ° C. (10 MPa, 1 minute) to obtain a positive electrode sheet for an all-solid secondary battery having a positive electrode active material layer having a film thickness of 80 ⁇ m.
  • the produced positive electrode sheet for an all-solid secondary battery was punched into a disk shape having a diameter of 14.0 mm to obtain a disk-shaped positive electrode sheet.
  • the prepared negative electrode sheet for all-solid-state secondary battery having the solid-state electrolyte layer (the aluminum foil of the solid-state electrolyte sheet for all-solid-state secondary battery had been peeled off) was cut out into a disk shape having a diameter of 14.5 mm.
  • a stainless steel 2032 coin case 11 incorporating a spacer and a washer (not shown in FIG. 2) is placed so that the negative electrode current collector of the cut-out disk-shaped sheet is on the bottom side. It was.
  • a disk-shaped positive electrode sheet is laminated on the solid electrolyte layer of the disk-shaped sheet so that the solid electrolyte layer and the positive electrode active material layer are in contact with each other, and the laminate 12 for an all-solid secondary battery (aluminum foil-positive electrode active material layer- A laminated body composed of a solid electrolyte layer-negative electrode active material layer-stainless steel foil) was formed. After that, by crimping the 2032 type coin case 11, the all-solid-state secondary battery No. 2 shown in FIG. 1 to 45 and c1 to c3 were produced, respectively.
  • the all-solid-state secondary battery manufactured in this manner has the layer structure shown in FIG.
  • Table 2 shows the ratio of the content of the inorganic solid electrolyte [SE] to the content of the compound (SA) [SA] in 100% by mass of the solid content of the composition containing the inorganic solid electrolyte (negative electrode active material layer): [ SA] / [SE] and the ratio of the content [BR] of the polymer binder to the content [SA] of the compound (SA): [BR] / [SA] are calculated and shown, respectively.
  • the compound described in the "Compound (SA)" column in Table 2 indicates the compound (SA) contained in the negative electrode active material layer.
  • this centrifuge tube was set in a test tube mixer Se-04 (trade name, manufactured by Titec Co., Ltd.) and mixed for 30 minutes to prepare an inorganic solid electrolyte-containing composition.
  • the obtained inorganic solid electrolyte-containing composition was collected in an aluminum cup and dried on a hot plate at 100 ° C. for 2 hours to obtain a powder of the inorganic solid electrolyte-containing composition.
  • the powder obtained by using a press was pressed at 25 ° C. and a pressing force of 200 MPa or 600 MPa to prepare solid electrolyte molded pellets (thickness 300 to 500 ⁇ m) for evaluation, respectively.
  • the layer density of each of the produced solid electrolyte molded body pellets for evaluation was calculated by measuring the total thickness of the pellets after molding, estimating the volume, and calculating by the powder mass / pellet volume.
  • the layer density D of the pellets produced by pressing at a pressure of 200 MPa is relative to the layer density D 600 of the pellets produced by pressing at a pressure of 600 MPa.
  • the ratio of 200 : D 200 / D 600 was calculated. In this test, the closer this ratio: D 200 / D 600 is to 1, the smaller the surface resistance between the inorganic solid electrolytes, and it expands once when used as a constituent layer of an all-solid secondary battery.
  • the all-solid-state secondary battery was initialized by performing one cycle charge / discharge with one charge and one discharge as one charge / discharge cycle.
  • the initialized all-solid-state secondary battery was repeatedly charged and discharged under the same conditions as the above charging and discharging conditions.
  • the discharge capacity (initial discharge capacity) in the first cycle of charge / discharge after initialization is 100%
  • the cycle characteristics were evaluated according to which of the following evaluation criteria the number of discharge cycles was included.
  • the composition containing the inorganic solid electrolyte of the present invention in which the compound (SA) specified in the present invention is used in combination with the inorganic solid electrolyte has a large layer density ratio, and is not significantly affected by the pressure level. It can be seen that a dense constituent layer can be formed, and the constituent layer once expanded is likely to shrink into the dense constituent layer before expansion. It can be seen that the all-solid-state secondary battery of the present invention having a constituent layer formed of these inorganic solid electrolyte-containing compositions can achieve both low resistance and excellent cycle characteristics.

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PCT/JP2020/036472 2019-09-27 2020-09-25 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 Ceased WO2021060541A1 (ja)

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JPWO2023243716A1 (https=) * 2022-06-17 2023-12-21
WO2023243718A1 (ja) * 2022-06-17 2023-12-21 トヨタ自動車株式会社 リチウムイオン伝導材料及び二次電池
WO2023243721A1 (ja) * 2022-06-17 2023-12-21 トヨタ自動車株式会社 二次電池
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JPWO2023243716A1 (https=) * 2022-06-17 2023-12-21
WO2023243718A1 (ja) * 2022-06-17 2023-12-21 トヨタ自動車株式会社 リチウムイオン伝導材料及び二次電池
WO2023243721A1 (ja) * 2022-06-17 2023-12-21 トヨタ自動車株式会社 二次電池
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JP7694507B2 (ja) 2022-08-30 2025-06-18 トヨタ自動車株式会社 全固体電池およびその製造方法
JP2024146112A (ja) * 2023-03-31 2024-10-15 トヨタ自動車株式会社 二次電池システム
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