WO2020036055A1 - Composition d'électrolyte solide, feuille contenant un électrolyte solide, feuille d'électrode pour batteries secondaires entièrement solides, et batterie secondaire entièrement solide - Google Patents

Composition d'électrolyte solide, feuille contenant un électrolyte solide, feuille d'électrode pour batteries secondaires entièrement solides, et batterie secondaire entièrement solide Download PDF

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WO2020036055A1
WO2020036055A1 PCT/JP2019/029610 JP2019029610W WO2020036055A1 WO 2020036055 A1 WO2020036055 A1 WO 2020036055A1 JP 2019029610 W JP2019029610 W JP 2019029610W WO 2020036055 A1 WO2020036055 A1 WO 2020036055A1
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group
solid electrolyte
active material
solid
secondary battery
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Japanese (ja)
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宏顕 望月
陽 串田
智則 三村
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Fujifilm Corp
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Fujifilm Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a solid electrolyte composition, a solid electrolyte-containing sheet, an electrode sheet for an all-solid secondary battery, and an all-solid secondary battery.
  • a lithium ion secondary battery is a storage battery having a negative electrode, a positive electrode, and an electrolyte interposed between the negative electrode and the positive electrode, and capable of charging and discharging by reciprocating lithium ions between the two electrodes.
  • organic electrolytes have been used as electrolytes in lithium ion secondary batteries.
  • the organic electrolyte is liable to leak, and overcharging or overdischarging may cause a short circuit inside the battery and cause ignition, and further improvement in safety and reliability is required. Under such circumstances, an all-solid secondary battery using an inorganic solid electrolyte instead of an organic electrolyte has been receiving attention.
  • the negative electrode, the electrolyte, and the positive electrode are all made of solid, and can greatly improve the safety and reliability of a battery using an organic electrolyte.
  • an inorganic solid electrolyte, an active material, a binder (binder), and the like are contained as materials for forming constituent layers such as a negative electrode active material layer, a solid electrolyte layer, and a positive electrode active material layer.
  • Materials have been proposed.
  • Patent Document 1 discloses an inorganic solid electrolyte, an organic solvent, an average diameter of 0.001 to 1 ⁇ m, an average length of 0.1 to 150 ⁇ m, and a ratio of the average length to the average diameter.
  • a linear structure (specifically, nanofibers of cellulose, carbon, zinc oxide, or titanium oxide) having an electrical conductivity of 10 to 100,000 and an electric conductivity of 1 ⁇ 10 ⁇ 6 S / m or less.
  • Patent Document 2 discloses that a lithium ion conductive solid electrolyte synthesized from a plurality of compounds containing at least lithium sulfide and a polymer elastic body (specifically, a fluororesin and a polyester resin) are dry-kneaded. A solid electrolyte molded article obtained by molding the obtained mixture is described.
  • Patent Document 3 describes a non-aqueous secondary battery in which a negative electrode is an electrode formed by adhering metal particles having an average particle diameter of 1 ⁇ m or less to a current collector with a binder (specifically, polyvinylidene fluoride). ing. It is described that a non-aqueous secondary battery using this electrode as a negative electrode has a higher capacity and a smaller decrease in capacity due to charge and discharge than a conventional graphite-based electrode material.
  • a negative electrode is an electrode formed by adhering metal particles having an average particle diameter of 1 ⁇ m or less to a current collector with a binder (specifically, polyvinylidene fluoride). ing. It is described that a non-aqueous secondary battery using this electrode as a negative electrode has a higher capacity and a smaller decrease in capacity due to charge and discharge than a conventional graphite-based electrode material.
  • the constituent layers of an all-solid secondary battery are formed of solid particles such as an inorganic solid electrolyte, an active material if necessary, and a binder in the case of containing a particulate binder. Hard to form. For example, if the interface contact between the inorganic solid electrolyte and the active material is not sufficient, the interface resistance increases (the ionic conductivity and the battery capacity decrease). Further, if the binding property between the solid particles is weak, a component layer having sufficient strength cannot be obtained. Furthermore, contact failure between solid particles occurs due to contraction and expansion of the constituent layers, particularly the active material layer, associated with charge and discharge (release and absorption of lithium ions) of the all-solid secondary battery.
  • the present invention by using as a material forming the constituent layers of the all-solid secondary battery, in the obtained all-solid secondary battery, solid particles are firmly bound by suppressing an increase in interface resistance between solid particles,
  • An object of the present invention is to provide a solid electrolyte composition that can maintain excellent discharge capacity and discharge capacity density even after repeated charge and discharge.
  • Another object of the present invention is to provide a solid electrolyte-containing sheet, an electrode sheet for an all-solid secondary battery, and an all-solid secondary battery having a layer composed of the solid electrolyte composition.
  • the solid electrolyte composition prepared by combining the binder formed into a fibrous form with the inorganic solid electrolyte and the dispersing medium satisfying the requirements of (1) and (2) has a high strength in which the solid particles are firmly bound while suppressing the interfacial resistance between the solid particles. It has been found that a layer can be formed.
  • an all-solid secondary battery including this layer as a constituent layer can maintain a high discharge capacity and a high discharge capacity density even after repeated charging and discharging, and exhibit good battery life.
  • the present invention has been further studied based on these findings, and has been completed.
  • a dispersion medium comprising a polymer satisfying the following properties (P1) and (P2):
  • R 1 and R 2 represent a hydrogen atom; an alkyl group; a substituent containing a polyethylene oxide chain, a polypropylene oxide chain, a polycarbonate chain, or a polyester chain and having a weight average molecular weight of 50 to 200,000; an alcoholic hydroxyl group; Monovalent substitution having a phenolic hydroxyl group, a sulfanyl group, a carboxy group, a sulfonic acid group, a phosphoric acid group, a nitrile group, an amino group, a zwitterion-containing group, or a group comprising a metal compound having a hydroxy group or an alkoxide group Or a substituent having a carbon-carbon unsaturated group.
  • R 3 is a hydrocarbon chain; a linking group containing a polyethylene oxide chain, a polypropylene oxide chain, a polycarbonate chain or a polyester chain and having a mass average molecular weight of 50 to 200,000; an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfanyl group, a carboxy group.
  • a linking group having a group comprising a metal compound having a group, a sulfonic acid group, a phosphoric acid group, a nitrile group, an amino group, a zwitterion-containing group, or a hydroxy group or an alkoxide group; or; The following shows the linking group.
  • R 4 represents an aromatic or aliphatic linking group.
  • ⁇ 5> The solid electrolyte composition according to any one of ⁇ 1> to ⁇ 4>, containing an active material.
  • ⁇ 6> The solid electrolyte composition according to ⁇ 5>, wherein the active material is an active material that can be alloyed with lithium.
  • ⁇ 7> The solid electrolyte composition according to any one of ⁇ 1> to ⁇ 6>, wherein the polymer has a glass transition temperature of ⁇ 120 to 80 ° C.
  • ⁇ 8> The solid electrolyte composition according to any one of ⁇ 1> to ⁇ 7>, wherein the inorganic solid electrolyte is a sulfide-based solid electrolyte.
  • a solid electrolyte-containing sheet having a layer composed of the solid electrolyte composition according to any one of ⁇ 1> to ⁇ 8>.
  • An electrode sheet for an all-solid secondary battery having an active material layer constituted by the solid electrolyte composition according to ⁇ 5> or ⁇ 6>.
  • An all-solid secondary battery including a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order, All-solid secondary, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer is a layer composed of the solid electrolyte composition according to any one of ⁇ 1> to ⁇ 8>. battery.
  • the solid electrolyte composition of the present invention is a solid electrolyte layer capable of realizing excellent discharge capacity and discharge capacity density even after repeated charge and discharge by suppressing the increase in the interfacial resistance between the solid particles and firmly binding the solid particles. Can be formed. Therefore, the present invention, by using as a material for forming a constituent layer of an all-solid secondary battery, in the obtained all-solid secondary battery, suppresses an increase in interfacial resistance between the solid particles and firmly binds the solid particles. Thus, it is possible to provide a solid electrolyte composition capable of achieving excellent discharge capacity and discharge capacity density even after repeated charge and discharge.
  • a solid electrolyte-containing sheet, an electrode sheet for an all-solid secondary battery, and an all-solid secondary battery having a layer composed of the solid electrolyte composition can be provided.
  • FIG. 1 is a longitudinal sectional view schematically showing an all solid state secondary battery according to a preferred embodiment of the present invention.
  • FIG. 2 is a longitudinal sectional view schematically showing the all-solid-state secondary battery (coin battery) manufactured in the example.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
  • acryl when simply described as "acryl” or "(meth) acryl", it means acryl and / or methacryl.
  • the expression of a compound is used to include the compound itself, its salt, and its ion. Further, it is meant to include a derivative partially changed by introducing a substituent within a range in which a desired effect is exhibited.
  • substituents, linking groups, and the like which are not specified as substituted or unsubstituted means that the groups may have an appropriate substituent. Therefore, in the present specification, even when simply referred to as a YYY group, the YYY group also includes an embodiment having a substituent in addition to an embodiment having no substituent. This is synonymous with a compound for which no substitution or no substitution is specified.
  • Preferred substituents include the substituent T described below.
  • the respective substituents and the like may be the same or different from each other Means that. Further, even when not otherwise specified, when a plurality of substituents and the like are adjacent to each other, it means that they may be connected to each other or condensed to form a ring.
  • the molecular weight of a polymer and an oligomer means a mass average molecular weight in terms of standard polystyrene determined by gel permeation chromatography (GPC), unless otherwise specified.
  • the measurement method is basically a value measured by the method of the following condition 1 or condition 2 (priority).
  • an appropriate eluent can be appropriately selected depending on the type of the polymer or the like.
  • Carrier flow rate 1.0 ml / min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector (condition 2) Column: A column to which 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 solid electrolyte composition of the present invention contains an inorganic solid electrolyte, the following fibrous binder, and a dispersion medium.
  • This solid electrolyte layer composition is also referred to as an inorganic solid electrolyte containing composition in that it contains an inorganic solid electrolyte described later.
  • the fibrous binder is a binder composed of a polymer satisfying the following properties (P1) and (P2), and a fibrous binder satisfying the following properties (B1) to (B3) , A fibrous binder).
  • the inorganic solid electrolyte and the fibrous binder are in a solid state and dispersed in a dispersion medium.
  • the fibrous binder When used as a constituent layer or a dried layer of a solid electrolyte composition to be described later, it connects solid particles such as an inorganic solid electrolyte and the like, and an adjacent layer (for example, a current collector) with the solid particles.
  • the solid particles need not necessarily be bonded to each other in the dispersion state of the solid electrolyte composition. Further, the dispersion state (present state) of the fibrous binder in the solid electrolyte composition is not particularly limited.
  • the dispersed state may be a state in which the fibrous binder is present alone (dispersed) in the solid electrolyte composition, a state in which a plurality of fibrous binders are present as a fiber membrane in which the fibrous binders are aggregated or aggregated, and further, a state in which the fibrous binder is present. Any state existing as a complex may be used, and a state in which these two or more states are mixed may be used.
  • the fibrous film preferably has a (three-dimensional) network structure, and includes, for example, a nonwoven fabric (thin cotton, web) formed by overlapping or tangling a plurality of fibrous binders.
  • the composite is not particularly limited.
  • a fibrous binder or a fibrous film is incorporated between inorganic solid electrolytes (gaps or interfaces), or a fibrous binder or a fibrous film covers or surrounds the inorganic solid electrolyte Embodiments, and embodiments in which these coexist.
  • the solid electrolyte composition contains an active material or a conductive auxiliary, it is considered that the active material and the conductive auxiliary also form a complex similarly to the inorganic solid electrolyte.
  • the fibrous binder is formed of a polymer satisfying the above properties (P1) and (P2), and may be formed of one molecule of polymer. However, usually, several molecules of polymer are bundled to form a fiber. ing.
  • the constituent layer formed of the solid electrolyte composition has an increased interface resistance between solid particles (between solid particles). (Contact resistance) can be suppressed and solid particles can be firmly bound, and an all-solid secondary battery having this constituent layer can maintain excellent discharge capacity and discharge capacity density even after repeated charging and discharging.
  • the fibrous binder contained in the solid electrolyte composition of the present invention is a polymer satisfying the above properties (P1) and (P2) and a fibrous shape satisfying the above properties (B1) to (B3), as described later. You are. Therefore, a structure (for example, the above-described composite) in which a binder made of a polymer satisfying a specific elastic modulus and an elastic deformation ratio is bridged (joined) between the solid particles or between the solid particles and the current collector is formed in the solid electrolyte composition. It is thought that it is formed by.
  • the solid particles are firmly bound to each other, and when the constituent layer is formed on the current collector, the current collector and the solid particles are firmly bound to each other.
  • the all-solid-state secondary battery having the constituent layers with the improved film strength is formed of a polymer satisfying the above characteristics (P1) and (P2) even when the constituent layers, particularly the active material layer, contract and expand during charge and discharge.
  • the obtained fibrous binder can follow the volume change well or absorb the volume change, and can maintain the binding state of the solid particles. It is considered that this can suppress an increase in electric resistance and further a reduction in battery life.
  • the fibrous binder is considered to be elongated as a fiber, and to form the above-mentioned composite with the above-mentioned fiber membrane and solid particles even in the solid electrolyte layer. Therefore, the contact between the solid particles can be secured without excessively coating (adhering) the surface of the solid particles while maintaining the above-mentioned strong binding property. Thereby, it is considered that the ion conduction path is maintained, the interface resistance between the solid particles can be reduced, and the discharge capacity (discharge capacity density) can be increased.
  • the contact state between solid particles (construction amount of ion conduction path) and the binding force between solid particles are improved in a well-balanced manner, and sufficient ion It is considered that the solid particles and the like are bound with a strong binding property while the conduction path is constructed, and the interface resistance between the solid particles is reduced.
  • Each sheet or all-solid rechargeable battery provided with a constituent layer exhibiting such excellent characteristics exhibits a high discharge capacity (discharge capacity density) by suppressing an increase in electric resistance. Even if discharge is repeated, it can be maintained.
  • the solid electrolyte composition of the present invention also includes an embodiment containing, as a dispersoid, an active material and, if necessary, a conductive additive in addition to the inorganic solid electrolyte (the composition of this embodiment is also referred to as an electrode composition). ).
  • the solid electrolyte composition of the present invention follows the volume change of the negative electrode active material (negative electrode active material layer) or absorbs the volume change even when the negative electrode active material contains a large negative electrode active material due to charge and discharge. Can maintain the binding state and the contacting state, and exhibit the above-mentioned excellent effects. Therefore, an embodiment in which the solid electrolyte composition of the present invention contains a negative electrode active material is one of the preferred embodiments.
  • the solid electrolyte composition of the present invention is a non-aqueous composition.
  • the non-aqueous composition includes, in addition to an embodiment containing no water, a form having a water content of 50 ppm or less.
  • the water content is preferably 20 ppm or less, more preferably 10 ppm or less, and even more preferably 5 ppm or less.
  • the water content indicates the amount of water (mass ratio based on the solid electrolyte composition) contained in the solid electrolyte composition.
  • the water content can be determined by filtering the solid electrolyte composition through a 0.45 ⁇ m membrane filter and Karl Fischer titration.
  • the inorganic solid electrolyte is an inorganic solid electrolyte
  • the solid electrolyte is a solid electrolyte capable of moving ions inside the solid electrolyte. Since it does not contain an organic substance as a main ion conductive material, it is an organic solid electrolyte (a polymer electrolyte represented by polyethylene oxide (PEO) and the like; an organic represented by lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) and the like) Electrolyte salt). Further, since the inorganic solid electrolyte is a solid in a steady state, it is not usually dissociated or released into cations and anions.
  • PEO polyethylene oxide
  • LiTFSI lithium bis (trifluoromethanesulfonyl) imide
  • an inorganic electrolyte salt LiPF 6 , LiBF 4 , LiFSI, LiCl, etc.
  • the inorganic solid electrolyte is not particularly limited as long as it has ion conductivity of a metal belonging to Group 1 or 2 of the periodic table, and generally has no electron conductivity.
  • the inorganic solid electrolyte has ion conductivity of a metal belonging to Group 1 or 2 of the periodic table.
  • a solid electrolyte material applied to this type of product 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 solid electrolyte.
  • the inorganic solid electrolyte preferably has lithium ion ionic conductivity.
  • the sulfide-based inorganic solid electrolyte contains a sulfur atom, has ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation. Compounds having properties are preferred.
  • the sulfide-based inorganic solid electrolyte contains at least Li, S, and P as elements and preferably has lithium ion conductivity, but depending on the purpose or case, other than Li, S, and P, It may contain an element.
  • Examples of the sulfide-based inorganic solid electrolyte include a lithium-ion conductive sulfide-based inorganic solid electrolyte satisfying a composition represented by the following formula (1).
  • L represents an element selected from Li, Na and K, and Li is preferable.
  • M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al and Ge.
  • A represents an element selected from I, Br, Cl and F.
  • a1 to e1 indicate the composition ratio of each element, and a1: b1: c1: d1: e1 satisfies 1 to 12: 0 to 5: 1: 2 to 12: 0 to 10.
  • a1 is preferably 1 to 9, and more preferably 1.5 to 7.5.
  • b1 is preferably 0 to 3, and more preferably 0 to 1.
  • d1 is preferably 2.5 to 10, more preferably 3.0 to 8.5.
  • e1 is preferably from 0 to 5, more preferably from 0 to 3.
  • composition ratio of each element can be controlled by adjusting the compounding ratio of the raw material compounds when producing the sulfide-based inorganic solid electrolyte as described below.
  • the sulfide-based inorganic solid electrolyte may be non-crystalline (glass) or crystallized (glass-ceramic), or may be partially crystallized.
  • glass glass
  • glass-ceramic glass-ceramic
  • Li-PS-based glass containing Li, P and S, or Li-PS-based glass ceramic containing Li, P and S can be used.
  • the sulfide-based inorganic solid electrolyte includes, 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 among LiI, LiBr, LiCl) and the sulfide of the element represented by M (for example, SiS 2 , SnS, GeS 2 ).
  • Li 2 S lithium sulfide
  • P 2 S 5 diphosphorus pentasulfide
  • simple phosphorus simple sulfur
  • sodium sulfide sodium sulfide
  • hydrogen sulfide hydrogen sulfide
  • lithium halide for example, It can be produced by the reaction of at least two or more raw materials among LiI, LiBr, LiCl
  • M for
  • ratio between Li 2 S and P 2 S 5 is, Li 2 S: a molar ratio of P 2 S 5, preferably 60: 40 ⁇ 90:10, more preferably 68:32 to 78:22.
  • the lithium ion conductivity can be increased.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 ⁇ 4 S / cm or more, more preferably 1 ⁇ 10 ⁇ 3 S / cm or more. Although there is no particular upper limit, 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
  • 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 becomes 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 2 of the periodic table, and has electronic insulation. Compounds having properties are preferred.
  • the oxide-based inorganic solid electrolyte has an ionic conductivity of preferably 1 ⁇ 10 ⁇ 6 S / cm or more, more preferably 5 ⁇ 10 ⁇ 6 S / cm or more, and more preferably 1 ⁇ 10 ⁇ 5 S / cm. / Cm or more is particularly preferable.
  • the upper limit is not particularly limited, but is practically 1 ⁇ 10 ⁇ 1 S / cm or less.
  • a phosphorus compound containing Li, P and O is also desirable.
  • lithium phosphate Li 3 PO 4
  • LiPON in which a part of oxygen of lithium phosphate is substituted by nitrogen
  • LiPOD 1 LiPOD 1
  • a 1 ON LiA 1 ON (A 1 is at least one selected from Si, B, Ge, Al, C, Ga, and the like) can be preferably used.
  • Halide-based inorganic solid electrolyte contains a halogen atom, has ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation. Compounds having properties are preferred.
  • the halide-based inorganic solid electrolyte is not particularly limited, and examples thereof include compounds such as LiCl, LiBr, LiI, and Li 3 YBr 6 and Li 3 YCl 6 described in ADVANCED MATERIALS, 2018, 30, 1803075. Among them, 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 2 of the periodic table, and has electronic insulation. Compounds having properties are preferred.
  • the hydride-based inorganic solid electrolyte is not particularly limited, and examples thereof include LiBH 4 , Li 4 (BH 4 ) 3 I, 3LiBH 4 -LiCl, and the like.
  • the inorganic solid electrolyte is preferably particles.
  • the average particle size (volume average particle size) of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more.
  • the upper limit is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less.
  • the measurement of the average particle size of the inorganic solid electrolyte is performed according to the following procedure.
  • the inorganic solid electrolyte particles are diluted with water (heptane in the case of a substance unstable to water) to prepare a 1% by mass dispersion liquid in a 20 mL sample bottle.
  • the dispersion sample after dilution is irradiated with 1 kHz ultrasonic wave for 10 minutes and used immediately after the test.
  • data was taken 50 times at a temperature of 25 ° C. using a laser diffraction / scattering type particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA) using a quartz cell for measurement. Obtain the volume average particle size.
  • JIS 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 one kind may be used alone, or two or more kinds may be used in combination.
  • the content of the inorganic solid electrolyte in the solid electrolyte composition is not particularly limited, but may be 50% by mass or more at a solid content of 100% by mass in terms of dispersibility, reduction in interface resistance, and binding properties. Preferably, it is more preferably 70% by mass or more, even more preferably 90% by mass or more. From the same viewpoint, the upper limit is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less.
  • the content of the inorganic solid electrolyte in the solid electrolyte composition is the total content of the inorganic solid electrolyte and the active material.
  • the solid content refers to a component which does not disappear by volatilization or evaporation when the solid electrolyte composition is dried at 150 ° C. for 6 hours under a nitrogen atmosphere under a pressure of 1 mmHg. .
  • it refers to components other than the dispersion medium described below.
  • the fibrous binder contained in the solid electrolyte composition of the present invention is a fibrous (high aspect ratio wire material) binder satisfying the following properties (B1) to (B3).
  • a fibrous binder is used as a binder contained in the solid electrolyte composition, a layer excellent in the contact state and binding force between the solid particles can be formed, and excellent battery performance is maintained even after repeated charge and discharge. The effect that an all-solid-state secondary battery can be obtained is obtained.
  • Ratio L / D of average length L to average diameter D 10 to 100,000
  • the average diameter D of the fibrous binder is 0.001 to 10 ⁇ m, and the above effects (improvement of the contact state between solid particles and binding force, and excellent battery performance when charge and discharge are repeated) are at a higher level.
  • the average length L of the fibrous binder is from 0.1 ⁇ m to 1,000 mm, and is preferably from 0.5 ⁇ m to 100 mm, and more preferably from 1 ⁇ m to 10 mm, from the viewpoint that the above effects can be achieved at a higher level.
  • the ratio L / D of the average length L to the average diameter D of the fibrous binder is from 10 to 100,000, and preferably from 20 to 50,000 from the viewpoint that the above effects can be achieved at a higher level. , 30 to 10,000, more preferably 35 to 8,000, and particularly preferably 40 to 2,000.
  • the average diameter D, the average length L, and the ratio L / D may be each independently within the range specified in the present invention. The above ranges or the above ranges of the ratio L / D can be appropriately combined.
  • an average diameter D of 0.1 to 0.5 ⁇ m and an average length L of 10 to 200 ⁇ m, or a ratio L / D of 40 to 2000 ⁇ m is preferable in that the above effects can be achieved at a higher level. preferable.
  • the average diameter D and average length L of the fibrous binder are measured as described below, and the ratio L / D is calculated from the measured values. That is, the average diameter D and the average length L are determined as follows by image processing an electron microscope image or an optical microscope image according to the size of the fibrous binder. This measurement (observation) needs to be performed while the entire fibrous binder is visible. Therefore, in addition to the measurement (observation) using an electron microscope, for example, when the average length L of the fibrous binder exceeds 100 ⁇ m, the measurement (observation) may be performed using an optical microscope or the like.
  • the aggregate of the fibrous binder prepared from the polymer solution described below is observed in any three fields using a scanning electron microscope (SEM, XL30 (trade name), manufactured by PHILIPS) to obtain an SEM image.
  • SEM images of the three fields of view were converted into BMP (bitmap) files, respectively, and 50 fibrous binders were used with “A-image”, an integrated application of IP-1000PC (trade name) manufactured by Asahi Engineering Co., Ltd. Is read, and the fiber width (fiber diameter) and fiber length of each fibrous binder are read in a state where there is no overlap in the image and the entire fibrous binder is visible.
  • the fiber width of the fibrous binder is an average value of the fiber widths at five locations obtained by dividing the fiber length of one fibrous binder into four equal parts.
  • the average value of 40 points excluding the upper and lower 5 points was obtained, This average value is defined as the average diameter D of the fibrous binder.
  • the average value of 40 points excluding the upper and lower 5 points is determined, and this average value is defined as the average length L of the fibrous binder.
  • the average length L thus obtained is divided by the average diameter D to calculate a ratio L / D of the average length L to the average diameter D.
  • the fibrous binder is measured.
  • the method of removing the fibrous binder may be any method (condition) that does not cause a change in the size of the fibrous binder. For example, a method of washing the composition or the constituent layer with a solvent used as a dispersion medium can be applied. At this time, a solvent that does not dissolve the fibrous binder is used.
  • the fibrous binder is formed of a polymer satisfying the following properties (P1) and (P2).
  • a binder made of a resin, an inorganic compound, or the like has been generally used for a solid electrolyte composition used for an all-solid secondary battery.
  • the solid particles It is possible to form a layer in which solid particles are firmly bound by suppressing an increase in interfacial resistance between them, and to manufacture an all-solid-state secondary battery that maintains low resistance and high discharge capacity (discharge capacity density) even after repeated charging and discharging. The effect is obtained.
  • Polymers satisfying the following properties (P1) and (P2) are difficult to fibrillate, and as the binder for the solid particles, a polymer having a rigid structure such as cellulose is used. It is usual to form with. However, in the present invention, on the contrary, it is formed into a fibrous form satisfying the above-mentioned properties (B1) to (B3) by using a binder-forming polymer satisfying the following properties (P1) and (P2).
  • P1 Elastic modulus: 0.1 to 1,000 MPa
  • P2 Elastic deformation rate: 0.01 to 10,000%
  • the elastic modulus of the binder-forming polymer is from 0.1 to 1,000 MPa, and is preferably from 0.5 to 800 MPa, more preferably from 1 to 600 MPa, from the viewpoint that the above effects can be achieved at a higher level. , More preferably from 10 to 500 MPa, particularly preferably from 100 to 400 MPa.
  • the elastic deformation ratio of the binder-forming polymer is from 0.01 to 10,000%, and preferably from 0.1 to 1,000%, and more preferably from 1 to 100%, from the viewpoint that the above effect can be achieved at a higher level. Is more preferably 10 to 80%, particularly preferably 15 to 50%.
  • the elastic modulus and the elastic deformation rate may be each independently within the range specified in the present invention, but the above ranges of the elastic modulus and the above ranges of the elastic deformation ratio may be appropriately combined. Among them, a combination of an elastic modulus of 100 to 400 MPa and an elastic deformation rate of 15 to 50% is preferable.
  • the elastic modulus and the elastic deformation rate of the binder-forming polymer are measured by performing a tensile test using the prepared test piece as follows.
  • a test piece is prepared. That is, a solution of a binder-forming polymer, for example, a solution of a binder-forming polymer obtained by a synthesis method described below is applied onto a Teflon (registered trademark) sheet using a baker-type applicator (manufactured by Paltec Co., Ltd.), and a blow dryer ( (Yamato Scientific Co., Ltd.) and dried at 200 ° C. for 40 hours.
  • a solution of a binder-forming polymer for example, a solution of a binder-forming polymer obtained by a synthesis method described below is applied onto a Teflon (registered trademark) sheet using a baker-type applicator (manufactured by Paltec Co., Ltd.), and a blow dryer ( (Yamato Scientific Co., Ltd.)
  • the polymer film after drying is defined in accordance with JIS K 7127 “Test method for plastic-tensile properties
  • Part 3 Test conditions for film and sheet” using a shopper type sample punch (manufactured by Yasuda Seiki Seisakusho).
  • a standard test piece type 5 to be prepared is produced.
  • a tensile test is performed using a digital force gauge ZTS-5N and a vertical electric measuring stand MX2 series (both trade names, manufactured by Imada).
  • a tensile test is performed using a digital force gauge ZTS-5N and a vertical electric measuring stand MX2 series (both trade names, manufactured by Imada).
  • a tensile test is performed using a digital force gauge ZTS-5N and a vertical electric measuring stand MX2 series (both trade names, manufactured by Imada).
  • a tensile test is performed using a digital force gauge ZTS-5N and a vertical electric measuring stand MX2 series (both trade names, manufactured by Imada).
  • the measurement is performed as follows. That is, according to the above-mentioned method of removing the fibrous binder, after the fibrous binder is removed, the fibrous binder is dissolved in a solvent in which the binder-forming polymer is dissolved, and the measurement can be performed by the above method.
  • the glass transition temperature of the binder-forming polymer is not particularly limited, but is preferably from ⁇ 120 to 80 ° C., more preferably from ⁇ 100 to 60 ° C., from the viewpoint of the shape of the solid particles or the shape corresponding to the surface irregularities. Is more preferable, and the temperature is more preferably ⁇ 80 to 40 ° C.
  • the glass transition temperature (Tg) is measured using a dried sample and a differential scanning calorimeter “X-DSC7000” (trade name, manufactured by SII Nanotechnology Inc.) under the following conditions. The measurement is performed twice on the same sample, and the result of the second measurement is adopted.
  • Atmosphere in the measurement chamber nitrogen (50 mL / min) Heating rate: 5 ° C / min Measurement start temperature: -100 ° C Measurement end temperature: 200 ° C Sample pan: Aluminum pan Mass of measurement sample: 5 mg Calculation of Tg: Tg is calculated by rounding off the decimal point of the intermediate temperature between the descent start point and descent end point of the DSC chart.
  • the glass transition temperature of the binder-forming polymer is, for example, after dispersing the components contained in the composition or the constituent layer in water, and then filtering. The remaining solid is collected and can be measured by the above method.
  • the weight average molecular weight of the binder-forming polymer is not particularly limited, but is preferably 5,000 or more, more preferably 10,000 or more, and particularly preferably 30,000 or more.
  • the upper limit is preferably 1,000,000 or less, more preferably 200,000 or less.
  • the binder-forming polymer is not particularly limited as long as it satisfies the above elastic modulus and elastic deformation rate, and various polymers can be applied.
  • sequential polymerization (polycondensation, polyaddition or addition condensation) -based polymers such as polyurethane, polyurea, polyamide, polyimide, polyester, polyether, and polycarbonate; further, fluoropolymers, hydrocarbon-based thermoplastic resins, and vinyl polymers And (meth) acrylic polymers.
  • the hydrocarbon polymer include natural rubber, polybutadiene, polyisoprene, polystyrene butadiene, and hydrogenated (hydrogenated) polymers thereof.
  • a polymer of a sequential polymerization system is preferable, each polymer of polyurethane, polyurea, polyamide or polyimide is more preferable, polyurethane or polyurea is further preferable, and polyurethane is particularly preferable.
  • the main chain of the polymer refers to a linear molecular chain in which all other molecular chains constituting the polymer can be regarded as branched or pendant to the main chain. Although it depends on the mass average molecular weight of the molecular chain regarded as a pendant, typically, the longest chain among the molecular chains constituting the polymer is the main chain. However, the functional groups of the polymer terminals are not included in the main chain.
  • the side chain of the polymer refers to a molecular chain other than the main chain, and includes a short molecular chain and a long molecular chain.
  • the binder-forming polymer preferably has a component represented by any of the following formulas (1-1) to (1-6), and is selected from the components represented by the following formula according to the type of the polymer. And may have two or more (preferably 2 to 8) constituent components.
  • a preferred combination of the constituent components is not particularly limited, and examples thereof include a combination capable of forming the above-described preferred type of binder-forming polymer.
  • the one kind of constituent in the combination of constituents means the number of kinds of constituents represented by any one of the following formulas, and has two kinds of constituents represented by one of the following formulas. Nor are they interpreted as two components.
  • R 1 and R 2 each represent a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, more preferably 1 to 3), and a specific chain.
  • the substituent having a weight average molecular weight of 50 to 200,000 containing a specific chain is a substituent containing a polyethylene oxide chain, a polypropylene oxide chain, a polycarbonate chain or a polyester chain and having a weight average molecular weight of 50 to 200,000. It is.
  • the mass average molecular weight of this substituent is preferably 500 or more, more preferably 700 or more, and even more preferably 1,000 or more.
  • the upper limit is preferably 100,000 or less, more preferably 10,000 or less.
  • the polycarbonate chain or polyester chain a chain composed of a known polycarbonate or polyester can be used.
  • RN represents a hydrogen atom or an alkyl group (having preferably 1 to 12 carbon atoms, more preferably 1 to 6, and still more preferably 1 to 3).
  • the monovalent substituent having a specific group includes an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfanyl group, a carboxy group, a sulfonic acid group (sulfo group: —SO 3 H), and a phosphate group (phospho group: —OPO (OH 2 )), a nitrile group, an amino group, a zwitterion-containing group, or a monovalent substituent having a group consisting of a metal compound having a hydroxy group or an alkoxide group.
  • the substituent having a specific group may be a substituent consisting of only a specific group or a substituent having a specific group and a linking group.
  • the linking group is not particularly limited, and includes, for example, a group obtained by removing a predetermined number of hydrogen atoms from a substituent T described below.
  • the amino group is represented by -N (R N ) 2 , where R N is as described above.
  • the zwitterion-containing group has a betaine structure (preferably having 1 to 12 carbon atoms, more preferably 1 to 6), and the cation portion includes cations such as quaternary ammonium, sulfonium and phosphonium.
  • the anion part includes each anion such as carboxylate or sulfonate.
  • the group consisting of the metal compound having a hydroxy group is not particularly limited, and examples thereof include a hydroxylsilyl group and a hydroxyltitanyl group.
  • the group consisting of the metal compound having an alkoxide group is not particularly limited, and examples thereof include an alkoxysilyl group (preferably having 1 to 12 carbon atoms, and more preferably 1 to 6) and an alkoxy titanyl group (having 1 to 12 carbon atoms). And more preferably 1 to 6), and more specifically, a trimethoxysilyl group, a methyldimethoxysilyl group, a triethoxysilyl group, a methyldiethoxysilyl group, and a trimethoxytitanyl group.
  • the substituent having an alcoholic hydroxyl group is not particularly limited, and examples thereof include a hydroxyalkyl group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms). Although it does not specifically limit as a substituent which has a phenolic hydroxyl group, For example, a hydroxyphenyl group is mentioned.
  • Examples of the carbon-carbon unsaturated group in the substituent having a carbon-carbon unsaturated group include a carbon-carbon double bond and a carbon-carbon triple bond.
  • Specific examples of the substituent having a carbon-carbon double bond include an acryl group, a methacryl group, a vinyl group, an allyl group, and a maleimide group.
  • Specific examples of the substituent having a carbon-carbon triple bond include an ethynyl group and a propargyl group.
  • R 3 represents a hydrocarbon chain, a linking group containing a specific chain and having a mass average molecular weight of 50 to 200,000, a linking group having a specific group (hetero atom-containing group), or a carbon-carbon unsaturated group. And a linking group having the formula:
  • the hydrocarbon chain that can be taken as R 3 means a hydrocarbon chain composed of a carbon atom and a hydrogen atom (preferably an oligomer or a polymer), and more specifically, a compound composed of a carbon atom and a hydrogen atom Means a structure in which at least two atoms (for example, a hydrogen atom) or a group (for example, a methyl group) are eliminated. Terminal groups that may be present at the terminal of the hydrocarbon chain are not included in the hydrocarbon chain.
  • This hydrocarbon chain is preferably a chain having a structure in which at least two repeating units are connected (including an alkylene group, an alkynylene group, and the like). Further, the hydrocarbon chain is preferably composed of 50 or more carbon atoms.
  • the mass average molecular weight of the hydrocarbon chain is not particularly limited, but is preferably 100 or more and less than 1,000,000, more preferably 300 or more and less than 100,000, and even more preferably 500 or more and less than 10,000.
  • the hydrocarbon chain may have a carbon-carbon unsaturated bond, and may have an aliphatic ring and / or an aromatic ring structure. That is, examples of the hydrocarbon chain include a hydrocarbon chain composed of a hydrocarbon selected from an aliphatic hydrocarbon and an aromatic hydrocarbon, and a hydrocarbon chain composed of an aliphatic hydrocarbon is preferable.
  • the hydrocarbon chain preferably has no ring structure in its main chain, and more preferably a linear or branched aliphatic hydrocarbon chain.
  • the hydrocarbon chain is preferably a chain composed of an elastomer.
  • each chain of a diene-based elastomer having a double bond in the main chain and a non-diene-based elastomer having no double bond in the main chain Is mentioned.
  • the diene elastomer include styrene-butadiene rubber (SBR), styrene-ethylene-butadiene rubber (SEBR), butyl rubber (IIR), butadiene rubber (BR), isoprene rubber (IR), and ethylene-propylene-diene rubber. No.
  • non-diene elastomer examples include olefin elastomers such as ethylene-propylene rubber and styrene-ethylene-butylene rubber, and hydrogen-reduced elastomers of the diene elastomer.
  • the hydrocarbon to be a hydrocarbon chain preferably has a reactive group at its terminal, and more preferably has a terminal reactive group capable of polycondensation.
  • the terminal reactive group capable of polycondensation or polyaddition forms a group bonded to R 3 or R 4 in each of the above formulas by polycondensation or polyaddition.
  • Examples of such a terminal reactive group include an isocyanate group, a hydroxy group, a carboxy group, an amino group, and an acid anhydride. Among them, a hydroxy group is preferable.
  • Examples of the hydrocarbon having a terminal reactive group include, for example, NISSO-PB series (manufactured by Nippon Soda Co., Ltd.), Claysol series (manufactured by Tomoe Kogyo), PolyVEST-HT series (manufactured by Evonik), Poly-bd series (made by Idemitsu Kosan Co., Ltd.), poly-ip series (made by Idemitsu Kosan Co., Ltd.), EPOL (made by Idemitsu Kosan Co., Ltd.), and Polytail series (made by Mitsubishi Chemical Corporation) are preferably used.
  • the specific chain of the linking group having a weight average molecular weight of 50 or more and 200,000 or less, which can be taken as R 3 has a valence of 2 (excluding one more hydrogen atom).
  • the linking group having a specific group which can be taken as R 3 is a substituent having a specific group (hetero atom-containing group) which can be taken as R 1 and R 2 except that the valence is divalent. It has the same meaning, and the preferred range is also the same.
  • the linking group having a carbon-carbon unsaturated group which can be taken as R 3
  • R 3 is a substituent having a carbon-carbon unsaturated group, which can be taken as R 1 and R 2 , except that the valence is divalent. It has the same meaning, and the preferred range is also the same.
  • the component represented by any one of the formulas (1-1) to (1-5) is preferably a component having a long-chain linear group or a long-chain branching group.
  • a component having a specific chain and having a weight average molecular weight of 50 to 200,000 as R 3 is more preferable.
  • the component represented by each of the above formulas may be a component consisting of only the partial structure represented by each of the above formulas, or may be a component containing the partial structure represented by each of the above formulas.
  • the binder-forming polymer is polyurethane or the like, it has a component in which a carbonyl group is bonded to both nitrogen atoms of the partial structure represented by the above formula (1-4) or formula (1-5).
  • R 4 represents an aromatic or aliphatic linking group (tetravalent), and is preferably a linking group represented by any of the following formulas (i) to (ix).
  • X 1 represents a single bond or a divalent linking group.
  • divalent linking group an alkylene group having 1 to 6 carbon atoms (eg, methylene, ethylene, propylene) is preferable.
  • propylene 1,3-hexafluoro-2,2-propanediyl is preferred.
  • L represents —CH 2 CHCH 2 — or —CH 2 —.
  • R X and R Y each represent a hydrogen atom or a substituent.
  • * indicates a binding site to the carbonyl group in formula (1-6).
  • the substituents that can be taken as R X and R Y are not particularly limited, and include the substituents T described below.
  • the alkyl group (having preferably 1 to 12, more preferably 1 to 6, and preferably 1 to 3 carbon atoms) And an aryl group (having preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms).
  • the (total) content of the components represented by the above formula in the binder-forming polymer is not particularly limited, but is preferably 5 to 100% by mass, more preferably 10 to 100% by mass, and is preferably 50 to 100% by mass. More preferably, it is ⁇ 100% by mass.
  • the upper limit of this content may be, for example, 90% by mass or less regardless of the above-mentioned 100% by mass.
  • the binder-forming polymer has a constituent component containing an aliphatic hydrocarbon group having 5 or more carbon atoms, it exhibits hydrophobicity and exhibits high affinity for the solid particles, and the solid particles are dispersed in the solid electrolyte composition. This is preferable in that the properties can be improved.
  • the aliphatic hydrocarbon group a group obtained by removing a hydrogen atom from an alkane (an alkyl group or an alkylene group) or a group obtained by removing a hydrogen atom from an alkene (an alkenyl group or an alkenylene group) is preferable.
  • a group obtained by removing a hydrogen atom from a hydrogen polymer (hydrocarbon polymer chain) is more preferable.
  • the aliphatic hydrocarbon group may be incorporated into the main chain of the binder-forming polymer, or may be incorporated as a side chain.
  • this constituent component is a component derived from a compound having a functional group at an end of an aliphatic hydrocarbon group, and is, for example, a compound represented by the above formulas (1-2) to (1-6). The component represented by any of them is mentioned.
  • the number of carbon atoms of the aliphatic hydrocarbon group may be 5 or more, but is preferably 8 or more, more preferably 10 or more, in view of affinity with solid particles.
  • the upper limit is not particularly limited, and may be, for example, 100,000 or less.
  • the mass average molecular weight is not particularly limited as long as the number of carbon atoms is satisfied.
  • the component containing an aliphatic hydrocarbon group having 5 or more carbon atoms may be different from the component represented by any of formulas (1-1) to (1-6). Those which also correspond to the components represented by any of formulas (1-1) to (1-6) are preferable.
  • As the aliphatic hydrocarbon group having 5 or more carbon atoms a monovalent group obtained by removing one hydrogen atom from the hydrocarbon constituting the hydrocarbon chain that can be taken as R 3 is preferably exemplified.
  • the binder-forming polymer molecule preferably has at least one component containing an aliphatic hydrocarbon group having 5 or more carbon atoms, more preferably has 2 to 1,000, and more preferably has 3 to 1,000. More preferably, the number is 500.
  • the (total) content in the binder-forming polymer is not particularly limited, but is preferably 0 to 80% by mass, more preferably 0.5 to 70% by mass, and more preferably 1 to 60% by mass. Is more preferred.
  • the binder-forming polymer is polyurethane
  • the lower limit of the content can be 30% by mass regardless of the above value. Regardless of the above description, the upper limit of the content may be set to 100% by mass.
  • the binder-forming polymer may have components other than the above-mentioned components.
  • the content in the binder-forming polymer is not particularly limited, but is preferably 80% by mass or less.
  • constituent components other than the above-mentioned constituent components appropriate constituent components capable of forming a polymer according to the polymer type of the binder-forming polymer may be mentioned.
  • a component represented by the following formula (2), each component obtained by changing R 3 in the above formulas (1-2) to (1-5) to R P1 in the following formula (2), etc. Is mentioned.
  • the content of these components in the binder-forming polymer is not particularly limited, and is appropriately determined according to the content of the components represented by the above formulas.
  • the content can be set to 80% by mass or less, preferably 20 to 70% by mass, and set to a content of 100% by mass in total with the contents of the components represented by the above formulas. You can also.
  • R P1 represents a hydrocarbon chain having a molecular weight of 20 or more.
  • the molecular weight of the hydrocarbon chain cannot be unambiguously determined because it depends on the type and the like, but is, for example, preferably 30 or more, more preferably 50 or more, further preferably 100 or more, and particularly preferably 150 or more.
  • the upper limit is not particularly limited and can be set as appropriate, and can be, for example, 10,000 or less.
  • the molecular weight of the hydrocarbon chain is measured on the starting compound before being incorporated into the main chain of the polymer.
  • Hydrocarbon chain which can be taken as R P1 denotes a chain of formed hydrocarbons from carbon and hydrogen atoms, more specifically, at least two atoms of a compound composed of carbon and hydrogen atoms (e.g. A structure in which 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). Terminal groups that may be present at the terminal of the hydrocarbon chain are not included in the hydrocarbon chain.
  • 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 is a chain composed of a normal (non-polymerizable) hydrocarbon group.
  • the hydrocarbon group include an aliphatic or aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group is not particularly limited, and may be, for example, a hydrogen reduced product of an aromatic hydrocarbon group represented by the following formula (M2) or a partial structure of a known aliphatic diisosonate compound (for example, Group).
  • an aromatic hydrocarbon group for example, a phenylene group or a hydrocarbon group represented by the following formula (M2) is preferable.
  • X represents a single bond, —CH 2 —, —C (CH 3 ) 2 —, —SO 2 —, —S—, —CO—, or —O—;
  • —CH 2 — or —O— is preferable, and —CH 2 — is more preferable.
  • the alkylene group and the alkylene group exemplified here may be substituted with a substituent T, preferably a halogen atom (more preferably a fluorine atom).
  • R M2 to R M5 each represent a hydrogen atom or a substituent, and a hydrogen atom is preferable.
  • R M2 to R M5 are not particularly limited, and include, for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, —OR M6 , —N (R M6 ) 2 , —SR M6 (R M6 represents a substituent, preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms), a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom) Is mentioned.
  • R M6 represents a substituent, preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms
  • a halogen atom eg, a fluorine atom, a chlorine atom, a bromine atom
  • —N (R M6 ) 2 is an alkylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 6) or an arylamino group (having preferably 6 to 40 carbon atoms, and 6 to 20 carbon atoms). More preferred).
  • Examples of the component represented by the formula (2) include a component derived from a “diisocyanate compound” described in JP-A-2015-088480, which is incorporated herein.
  • the binder-forming polymer includes the above-mentioned formulas (1-1) to (1-6), a component containing an aliphatic hydrocarbon group having 5 or more carbon atoms, and a component other than these (for example, the following formula (2) )).
  • polyurethane is a component represented by the following formula (2), a component obtained by changing R 3 in the above formula (1-2) to R P1 in the following formula (2), and a component represented by the above formula (1). It appropriately has the constituent components represented by -2).
  • the polyimide has a component represented by the following formula (1-5), a component represented by the following formula (1-6), and the like (provided that 2 One N is excluded).
  • Polycarbonate has a configuration component represented by the above formula (1-2) as a constituent or R 3 is represented by the above formula of introducing oxygen atom at both ends of the R 3 (1-3) Formula ( It has a component represented by 1-3), a component represented by the above formula (1-2), and a component obtained by changing R 3 to R P1 .
  • the polyurethane, polyurea, polyamide, and polyimide polymers that can be taken as the binder-forming polymer are not particularly limited as long as the above properties (P1) and (P2) are satisfied, and examples thereof include those described in JP-A-2015-088480.
  • Examples include a polymer having a urethane bond, a polymer having a urea bond, a polymer having an amide bond (polyamide resin), and a polymer having an imide bond.
  • the binder-forming polymer When the binder-forming polymer has at least one functional group selected from the following functional group (a), the binder-forming polymer exhibits a high binding property to the solid particles and can firmly bind the solid particles to each other. In this respect, it is preferable.
  • This functional group may be contained in the main chain or in the side chain.
  • the functional group (adsorptive functional group on the surface of the inorganic particles) of the binder-forming polymer is chemically or physically interacting with the surface of the inorganic solid electrolyte in the solid electrolyte composition, the active material coexisting as required, or the conductive additive.
  • the interaction is not particularly limited, but includes, for example, hydrogen bonding, acid-base ionic bonding, covalent bonding, aromatic ring ⁇ - ⁇ interaction, or hydrophobic-hydrophobic interaction. And the like.
  • the functional groups interact, the chemical structure of the functional group may or may not change. For example, in the above-mentioned ⁇ - ⁇ interaction or the like, the functional group usually does not change, and the structure is maintained as it is.
  • an anion from which active hydrogen such as a carboxylic acid group or the like is released usually becomes an anion (by changing a functional group) and bonds to a solid electrolyte or the like.
  • This interaction contributes to the adsorption of the fibrous binder to the solid particles during or during the preparation of the solid electrolyte composition.
  • the functional groups also interact with the surface of the current collector.
  • the acidic functional group is not particularly limited, but preferably includes a carboxylic acid group (—COOH), a sulfonic acid group (sulfo group: —SO 3 H), and a phosphoric acid group (phospho group: —OPO (OH) 2 and the like).
  • the acidic functional group may be a salt or an ester thereof.
  • the salt include a sodium salt, a calcium salt and the like.
  • the ester include an alkyl ester and an aryl ester. In the case of an ester, it preferably has 1 to 24 carbon atoms, more preferably has 1 to 12 carbon atoms, and particularly preferably has 1 to 6 carbon atoms.
  • the basic functional group is not particularly limited, but is preferably an amino group.
  • the amino group is not particularly limited, and includes, for example, an amino group having 0 to 20 carbon atoms.
  • the amino group includes an alkylamino group and an arylamino group.
  • the carbon number of the amino group is preferably from 0 to 12, more preferably from 0 to 6, and still more preferably from 0 to 2.
  • Examples of the amino group include amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino and the like.
  • Those capable of forming a salt, such as a hydroxy group and an amino group may be salts.
  • the alkoxysilyl group is not particularly limited, and preferably includes an alkoxysilyl group having 1 to 20 carbon atoms, for example, monomethoxysilyl, dimethoxysilyl, trimethoxysilyl, triethoxysilyl and the like.
  • the aryl group may be a single ring or a condensed ring.
  • the number of carbon atoms is preferably from 6 to 26, and more preferably from 6 to 20.
  • a ring group consisting of paraphenylene, polyparaphenylene or cyclophene is exemplified.
  • the heteroaryl group is not particularly limited, and includes a 5- or 6-membered heteroaryl group having at least one selected from an oxygen atom, a sulfur atom, and a nitrogen atom as a ring-constituting atom.
  • the heteroaryl group may be a single ring or a condensed ring, and preferably has 2 to 20 carbon atoms.
  • a heteroaryl group of the substituent T described later is exemplified.
  • the aliphatic hydrocarbon ring group in which three or more rings are fused is not particularly limited as long as the aliphatic hydrocarbon ring is a ring group in which three or more rings are fused.
  • Examples of the aliphatic hydrocarbon ring to be condensed include a saturated aliphatic hydrocarbon ring and an unsaturated aliphatic hydrocarbon ring.
  • the aliphatic hydrocarbon ring is preferably a 5- or 6-membered ring.
  • the number of condensed rings is not particularly limited, but is preferably 3 to 5 rings, more preferably 3 or 4 rings.
  • the ring group in which three or more saturated aliphatic hydrocarbon rings or unsaturated aliphatic hydrocarbon rings are condensed is not particularly limited, and examples thereof include a ring group composed of a compound having a steroid skeleton.
  • Compounds having a steroid skeleton include, for example, cholesterol, ergosterol, testosterone, estradiol, aldosterone, hydrocortisone, stigmasterol, timosterol, lanosterol, 7-dehydrodesmosterol, 7-dehydrocholesterol, cholanic acid, cholic acid, lithocor Examples include acid, deoxycholic acid, sodium deoxycholate, lithium deoxycholate, hyodeoxycholic acid, chenodeoxycholic acid, ursodeoxycholic acid, dehydrocholic acid, fokecholic acid, hyocholic acid, and compounds containing these skeletons.
  • the functional group selected from the functional group group (a) is appropriately selected.
  • an acidic group is preferably used in view of the binding property with the active material.
  • a functional group, a basic functional group, a hydroxy group, a cyano group or an alkoxysilyl group is preferred, and a carboxylic acid group is more preferred.
  • the solid electrolyte composition contains a negative electrode active material or a conductive auxiliary, an aryl group, a heteroaryl group, or an aliphatic hydrocarbon ring group in which three or more rings are fused is preferable, and an aliphatic ring in which three or more rings are fused is preferred.
  • a group hydrocarbon ring group is more preferred.
  • the functional group is preferably a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or an aryl group, and more preferably a carboxylic acid group, from the viewpoint of exhibiting high binding properties regardless of the active material.
  • the number of functional groups in one molecule of the binder-forming polymer may be one or more, and it is preferable to have a plurality.
  • the number of types of functional groups is not particularly limited as long as it has at least one functional group, and may be one type or two or more types.
  • it can have two or more kinds of functional groups selected from the functional group group (a) separately and appropriately combined.
  • two or more functional groups selected from the functional group group (a) may be appropriately combined to have one composite functional group.
  • the composite functional group includes, for example, an aryl group, a heteroaryl group, or an aliphatic hydrocarbon ring group in which three or more rings are fused, and an acidic functional group, a basic functional group, a hydroxy group, a cyano group, or an alkoxysilyl group. Groups.
  • the binder-forming polymer may have a substituent.
  • substituents include a group selected from the following substituent T.
  • the substituent T is shown below, but is not limited thereto.
  • 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 an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl and the like
  • an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl and the like
  • a cycloalkyl group Preferably a cycloalkyl
  • acylamino groups such as acetylamino and benzoylamino
  • alkylthio groups preferably alkylthio groups having 1 to 20 carbon atoms such as methylthio, ethylthio, isopropylthio and benzylthio
  • arylthio groups preferably Or an arylthio group having 6 to 26 carbon atoms, for example, phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc., a heterocyclic thio group (an -S- group is bonded to the above heterocyclic group) Group), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 20 carbon atoms, for example, methylsulfonyl, ethylsulfonyl and the like), an arylsulfonyl group (preferably an arylsulfon
  • the compound, the substituent, the linking group, and the like include an alkyl group, an alkylene group, an alkenyl group, an alkenylene group, an alkynyl group, and / or an alkynylene group, these may be cyclic or linear, or may be linear or branched. Is also good.
  • the content of the fibrous binder in the solid electrolyte composition is such that a layer excellent in film strength, contact state between solid particles and binding force can be formed, and excellent battery performance is maintained even after repeated charge and discharge.
  • the content is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more based on 100% by mass of the solid components.
  • 20 mass% or less is preferred, 10 mass% or less is more preferred, and 5 mass% or less is still more preferred.
  • the mass ratio of the total mass (total amount) 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) / (mass of the binder)] is , 1,000-1. This ratio is more preferably from 500 to 2, and even more preferably from 100 to 5.
  • the solid electrolyte composition of the present invention may contain one type of fibrous binder alone, or two or more types of fibrous binders.
  • the fibrous binder is a binder-forming polymer that satisfies the above properties (P1) and (P2), and can be produced by forming it into a fibrous form that satisfies the above properties (B1) to (B3).
  • a production method is not particularly limited, and examples thereof include a method of synthesizing a binder-forming polymer and forming the same into a predetermined fibrous shape.
  • the binder-forming polymer is prepared by optionally combining raw material compounds that lead to predetermined constituent components depending on the type of the main chain, and, if necessary, in the presence of a catalyst (including a polymerization initiator, a chain transfer agent, and the like), to undergo sequential polymerization or It can be synthesized by chain polymerization (addition polymerization).
  • a catalyst including a polymerization initiator, a chain transfer agent, and the like
  • the method and conditions for the sequential polymerization or chain polymerization (addition polymerization) are not particularly limited, and known methods and conditions can be appropriately selected.
  • the properties (P1) elastic modulus and (P2) elastic deformation rate of the binder-forming polymer are, respectively, the kind of the binder-forming polymer, the kind, the bonding mode or the content of the constituent component (raw material compound), the molecular weight of the polymer, or the glass. It can be adjusted by the transition temperature and the like.
  • the raw material compound a known compound is appropriately selected according to the type of the binder-forming polymer. For example, there can be mentioned each raw material compound for forming a polymer having a urethane bond, a polymer having a urea bond, a polymer having an amide bond (polyamide resin), a polymer having an imide bond, and the like described in JP-A-2015-088480. .
  • the method for forming the synthesized binder-forming polymer into a predetermined fibrous shape is not particularly limited, and examples thereof include an electrospinning method (electrospinning method).
  • the electrospinning method is a method that utilizes an electrofluid phenomenon that occurs when a high voltage is applied between a spinning nozzle and an electrode provided opposite thereto, and is suitably applied to the production of nanofibers and the like. More specifically, a high voltage is applied to a spinning nozzle, and a polymer or a polymer solution (to which a high voltage is applied) is jetted from the spinning nozzle toward an electrode (a grounded or negatively charged target). And spinning the polymer into a fibrous form.
  • a fibrous polymer is formed on the electrode alone or in a deposited state (non-woven fabric).
  • the electrospinning method can be performed by appropriately selecting a known device and method (condition).
  • the electrospinning method by appropriately setting the solid concentration or the injection amount of the polymer solution to be used, the applied voltage, or the injection distance (the distance from the injection nozzle to the electrode), the average diameter D, average The length L and the ratio L / D can be adjusted, and the binder-forming polymer can be formed into a predetermined fibrous shape.
  • the average diameter D and the average length L of the fiber can be increased by increasing the solid content concentration or the injection amount of the polymer solution or by shortening the injection distance.
  • the average diameter D of the fiber can be increased, while the average length L can be decreased.
  • the solid electrolyte composition of the present invention can also contain an active material.
  • This active material is a material capable of inserting and releasing ions of a metal element belonging to the first or second group of the periodic table. Examples of such an active material include a positive electrode active material and a negative electrode active material.
  • a solid electrolyte composition containing a positive electrode active material (a composition for an electrode) may be referred to as a positive electrode composition
  • a solid electrolyte composition containing a negative electrode active material may be referred to as a negative electrode composition.
  • the positive electrode active material is 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 such as sulfur, which can be combined with Li, or a composite of sulfur and a metal.
  • a transition metal oxide is preferably used as the positive electrode active material, and a transition metal oxide containing a transition metal element M a (at least one element selected from Co, Ni, Fe, Mn, Cu, and V). are more preferred.
  • the transition metal oxide includes an element M b (an element of the first (Ia) group, an element of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si, P or B).
  • the mixing amount is preferably 0 ⁇ 30 mol% relative to the amount of the transition metal element M a (100mol%). That the molar ratio of li / M a was synthesized were mixed so that 0.3 to 2.2, more preferably.
  • transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt structure, (MB) a transition metal oxide having a spinel structure, (MC) a lithium-containing transition metal phosphate compound, (MD) And (ME) lithium-containing transition metal silicate compounds.
  • transition metal oxide having a layered rock salt type structure LiCoO 2 (lithium cobaltate [LCO]), LiNi 2 O 2 (lithium nickelate), LiNi 0.85 Co 0.10 Al 0.1 . 05 O 2 (lithium nickel cobalt aluminum oxide [NCA]), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (lithium nickel manganese cobalt oxide [NMC]) and LiNi 0.5 Mn 0.5 O 2 ( Lithium manganese nickelate).
  • LCO lithium cobaltate
  • NCA lithium nickel cobalt aluminum oxide
  • NMC lithium nickel manganese cobalt oxide
  • LiNi 0.5 Mn 0.5 O 2 Lithium manganese nickelate
  • (MB) As 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 2 NiMn 3 O 8 .
  • Examples of (MC) lithium-containing transition metal phosphate compounds include olivine-type iron phosphates such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , and LiCoPO 4. And monoclinic nasicon-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 And the like, such as cobalt fluorophosphates.
  • Li 2 FePO 4 F such fluorinated phosphorus iron salt
  • Li 2 MnPO 4 hexafluorophosphate manganese salts such as F and Li 2 CoPO 4 F And the like, such as cobalt fluorophosphates.
  • Examples of the lithium-containing transition metal silicate 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 particulate.
  • the average particle size (sphere-converted average particle size) of the positive electrode active material is not particularly limited. For example, it can be 0.1 to 50 ⁇ m.
  • the average particle diameter of the positive electrode active material particles can be measured in the same manner as the above-mentioned average particle diameter of the inorganic solid electrolyte.
  • an ordinary pulverizer or a classifier is used.
  • a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling air jet mill, or a sieve is preferably used.
  • wet pulverization in the presence of water or an organic solvent such as methanol can also be performed if necessary.
  • Classification is preferably performed to obtain a desired particle size.
  • the classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as needed. Classification can be performed both in a dry process and a wet process.
  • 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 may be used alone or in combination of two or more.
  • the mass (mg) (basis weight) of the positive electrode active material per unit area (cm 2 ) of the positive electrode active material layer is not particularly limited. It can be determined appropriately according to the designed battery capacity.
  • the content of the positive electrode active material in the electrode composition is not particularly limited, and is preferably from 10 to 95% by mass, more preferably from 30 to 90% by mass, and still more preferably from 50 to 85% by mass at a solid content of 100% by mass. Preferably, it is particularly preferably 55 to 80% by mass.
  • the negative electrode active material 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 examples thereof include a carbonaceous material, a metal oxide, a metal composite oxide, lithium alone, a lithium alloy, and a negative electrode active material capable of forming an alloy with lithium. .
  • a carbonaceous material, a metal composite oxide or lithium alone is preferably used from the viewpoint of reliability.
  • a negative electrode active material that can be alloyed with lithium is preferable in that the capacity of the all-solid secondary battery can be increased.
  • the solid electrolyte layer formed of the solid electrolyte composition of the present invention maintains a strong binding state and contact state between the solid particles even if a volume change occurs.
  • the material an active material which can be alloyed with lithium, which has a large expansion and contraction due to charge and discharge and has room for improvement in battery life, can be used. As a result, it is possible to increase the capacity of the all-solid 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.
  • various synthetics such as petroleum pitch, 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 used.
  • various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA (polyvinyl alcohol) -based carbon fiber, lignin carbon fiber, glassy carbon fiber, and activated carbon fiber.
  • carbonaceous materials can be classified into non-graphitizable carbonaceous materials (also referred to as hard carbon) and graphite-based carbonaceous materials according to the degree of graphitization.
  • the carbonaceous material preferably has a plane spacing or a density and a crystallite size described in JP-A-62-22066, JP-A-2-6856 and JP-A-3-45473.
  • the carbonaceous material does not need to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, or the like may be used. You can also.
  • hard carbon or graphite is preferably used, and graphite is more preferably used.
  • the oxide of the metal or metalloid element applied as the negative electrode active material is not particularly limited as long as it is an oxide capable of occluding and releasing lithium.
  • An oxide of the metal element metal oxide
  • a composite of the metal element An oxide or a composite oxide of a metal element and a metalloid element (collectively referred to as a metal composite oxide) and an oxide of a metalloid element (metalloid oxide) are given.
  • amorphous oxides are preferable, and chalcogenides, which are reaction products of metal elements with elements of Group 16 of the periodic table, are also preferable.
  • the term “metalloid element” refers to an element having an intermediate property between a metal element and a nonmetalloid element, and usually includes six elements of boron, silicon, germanium, arsenic, antimony, and tellurium, and further includes selenium. , Polonium and astatine.
  • amorphous means an X-ray diffraction method using CuK ⁇ rays having a broad scattering band having an apex in a range of 20 ° to 40 ° in 2 ⁇ value. May have.
  • the strongest intensity of the crystalline diffraction lines observed at 40 ° to 70 ° in the 2 ⁇ value is 100 times or less the intensity of the diffraction line at the apex of the broad scattering band observed at 20 ° to 40 ° in the 2 ⁇ value. Is preferably 5 times or less, and particularly preferably no crystalline diffraction line.
  • an amorphous oxide of a metalloid element or the above-mentioned chalcogenide is more preferable, and an element of group 13 (IIIB) to group 15 (VB) of the periodic table (for example, , Al, Ga, Si, Sn, Ge, Pb, Sb and Bi), a (composite) oxide composed of one or a combination of two or more thereof, or a chalcogenide is particularly preferred.
  • preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , GeO, PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 8 Bi 2 O 3 , Sb 2 O 8 Si 2 O 3 , Sb 2 O 5 , Bi 2 O 3 , Bi 2 O 4 , GeS, PbS, PbS 2 , Sb 2 S 3 or Sb 2 S 5 is a preferred example.
  • Examples of the negative electrode active material that can be used in combination with an amorphous oxide centering on Sn, Si, and Ge include a carbonaceous material that can occlude and / or release lithium ions or lithium metal, simple lithium, a lithium alloy, and lithium. Negative electrode active materials that can be alloyed with are preferably mentioned.
  • An oxide of a metal or metalloid element, particularly a metal (composite) oxide and the above-described chalcogenide preferably contain at least one of titanium and lithium as a component from the viewpoint of high current density charge / discharge characteristics.
  • the lithium-containing metal composite oxide include, for example, a composite oxide of lithium oxide and the metal (composite) oxide or the chalcogenide, more specifically, Li 2 SnO 2.
  • the negative electrode active material for example, a metal oxide also preferably includes a titanium atom (titanium oxide).
  • Li 4 Ti 5 O 12 (lithium titanate [LTO]) is excellent in rapid charge / discharge characteristics due to small volume fluctuation at the time of occlusion and release of lithium ions. This 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 generally used as a negative electrode active material of a secondary battery, and examples thereof include a lithium aluminum alloy.
  • the active material that can be alloyed with lithium is not particularly limited as long as it is commonly used as a negative electrode active material of a secondary battery.
  • the binding state and the contact state of the solid particles are impaired because the expansion and contraction due to charge and discharge are increased, but in the present invention, the binder and the solid state can be maintained by the binder.
  • examples of such an active material include (anode) active materials (alloys and the like) containing a silicon element or a tin element, and metals such as Al and In, and a negative electrode active material containing a silicon element that enables higher battery capacity.
  • a silicon element-containing active material (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 constituent elements is more preferable.
  • a negative electrode containing such a negative electrode active material (a Si negative electrode containing a silicon element-containing active material, a Sn negative electrode containing a tin element-containing active material) is used as a carbon negative electrode (eg, graphite and acetylene black).
  • a carbon negative electrode eg, graphite and acetylene black
  • silicon element-containing active material examples include silicon materials such as Si and SiOx (0 ⁇ x ⁇ 1), and silicon-containing alloys including titanium, vanadium, chromium, manganese, nickel, copper, and lanthanum (for example, LaSi 2 , VSi 2 , La—Si, Gd—Si, Ni—Si), or an organized active material (eg, LaSi 2 / Si), as well as silicon and tin elements such as SnSiO 3 and SnSiS 3 And the like.
  • SiOx itself can be used as a negative electrode active material (semi-metal oxide).
  • a negative electrode active material that can be alloyed with lithium (the Precursor material).
  • the negative electrode active material having a tin element include Sn, SnO, SnO 2 , SnS, SnS 2 , and an active material containing the above silicon element and tin element.
  • a composite oxide with lithium oxide for example, Li 2 SnO 2 can also be used.
  • the above-described negative electrode active material can be used without any particular limitation.However, in terms of battery capacity, a negative electrode active material that can be alloyed with lithium is a preferable embodiment.
  • a negative electrode active material that can be alloyed with lithium is a preferable embodiment.
  • the above-mentioned silicon material or silicon-containing alloy (alloy containing a silicon element) is more preferable, and silicon (Si) or a silicon-containing alloy is further preferable.
  • the shape of the negative electrode active material is not particularly limited, but is preferably in the form of particles.
  • the average particle diameter of the negative electrode active material is preferably from 0.1 to 60 ⁇ m.
  • the average particle size of the negative electrode active material particles can be measured in the same manner as the above-mentioned average particle size of the inorganic solid electrolyte.
  • an ordinary pulverizer or a classifier is used as in the case of the positive electrode active material.
  • the chemical formula of the compound obtained by the above calcination can be calculated from inductively coupled plasma (ICP) emission spectroscopy as a measuring method, and from the mass difference of powder before and after calcination as a simple method.
  • ICP inductively coupled plasma
  • the above-mentioned negative electrode active materials may be used alone or in combination of two or more.
  • the mass (mg) (basis weight) of the negative electrode active material per unit area (cm 2 ) of the negative electrode active material layer is not particularly limited. It can be determined appropriately according to the designed battery capacity.
  • the content of the negative electrode active material in the electrode composition is not particularly limited, and is preferably from 10 to 80% by mass, more preferably from 20 to 80% by mass, based on 100% by mass of the solid content.
  • the negative electrode active material layer when the negative electrode active material layer is formed by charging a 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.
  • the 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 covered with another metal oxide.
  • the surface coating agent include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si or Li. Specific examples include titanate spinel, tantalum-based oxide, niobium-based oxide, lithium niobate-based 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. Further, the surface of the particles of the positive electrode active material or the negative electrode active material may be subjected to a surface treatment with active light or active gas (plasma or the like) before and after the surface coating.
  • the solid electrolyte composition of the present invention can also contain a conductive auxiliary.
  • the conductive assistant is not particularly limited, and those known as general conductive assistants can be used.
  • electron conductive materials such as natural graphite, graphite such as artificial graphite, carbon black such as acetylene black, Ketjen black, furnace black, amorphous carbon such as needle coke, vapor grown carbon fiber or carbon nanotube Carbon fibers such as graphene or fullerene; metal powder such as copper and nickel; metal fibers; and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives. It may be used.
  • ions of a metal belonging to the first or second group of the periodic table when the battery is charged or discharged preferably Li
  • ions of a metal belonging to the first or second group of the periodic table when the battery is charged or discharged preferably Li
  • a material that does not function as an active material without insertion and release of ions is used as a conductive additive. Therefore, among the conductive assistants, those that can function as an active material in the active material layer when the battery is charged and discharged are classified as active materials, not conductive assistants. Whether or not a battery functions as an active material when charged and discharged is not unique and is determined by a combination with the active material.
  • the total content of the conductive assistant in the electrode composition is preferably from 0.1 to 5% by mass, more preferably from 0.5 to 3% by mass, based on 100% by mass of the solid content.
  • the shape of the conductive additive is not particularly limited, but is preferably in the form of particles.
  • the median diameter D50 of the conductive additive is not particularly limited, and is, for example, preferably 0.01 to 1 ⁇ m, and more preferably 0.02 to 0.1 ⁇ m.
  • the solid electrolyte composition of the present invention contains a dispersion medium.
  • a dispersion medium When the solid electrolyte composition contains a dispersion medium, an effect of controlling the cohesiveness of the fibrous binder can be obtained in addition to the usual effects as a dispersion medium (improvement of composition uniformity, improvement of handleability, etc.).
  • the dispersion medium may be any as long as it disperses each component contained in the solid electrolyte composition of the present invention, and preferably, a dispersion medium in which the above-mentioned fibrous binder (the polymer constituting the binder) is dispersed in the form of particles is selected. Is done.
  • Examples of the dispersion medium used in the present invention include various organic solvents.
  • Examples of the organic solvent include alcohol compounds, ether compounds, amide compounds, amine compounds, ketone compounds, aromatic compounds, aliphatic compounds, nitrile compounds, and esters. Each solvent such as a compound is exemplified.
  • Examples of the alcohol compound include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, -Methyl-2,4-pentanediol, 1,3-butanediol and 1,4-butanediol.
  • the ether compound examples include alkylene glycol (diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.), alkylene glycol alkyl ether (ethylene glycol monomethyl ether, monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc., dialkyl ethers (dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, etc.), cyclic ethers (tetrahydrofuran Dioxane (1,2, including 1,3- and 1,4-isomers of), etc.).
  • alkylene glycol diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.
  • amide compound examples include N, N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, ⁇ -caprolactam, formamide, N-methylformamide, acetamide , N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.
  • Examples of the amine compound include triethylamine, diisopropylethylamine, tributylamine and the like.
  • Examples of the ketone compound include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, diisobutyl ketone (DIBK) and the like.
  • Examples of the aromatic compound include an aromatic hydrocarbon compound such as benzene, toluene, and xylene.
  • Examples of the aliphatic compound include aliphatic hydrocarbon compounds such as hexane, heptane, octane, and decane.
  • Examples of the nitrile compound include acetonitrile, propionitrile, isobutyronitrile and the like.
  • Examples of the ester compound include ethyl acetate, butyl acetate, propyl acetate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, butyl pentanate, ethyl isobutyrate, propyl isobutyrate, isopropyl isobutyrate, isobutyl isobutyrate, and pivalic acid Carboxylic esters such as propyl, isopropyl pivalate, butyl pivalate, and isobutyl pivalate, and the like.
  • Examples of the non-aqueous dispersion medium include the above aromatic compounds and aliphatic compounds.
  • the dispersion medium is preferably a ketone compound, an ester compound, an aromatic compound or an aliphatic compound, and more preferably contains at least one selected from ketone compounds, ester compounds, aromatic compounds and aliphatic compounds.
  • the dispersion medium contained in the solid electrolyte composition may be one type, two or more types, and preferably two or more types.
  • the total content of the dispersion medium in the solid electrolyte composition is not particularly limited, but is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass.
  • the solid electrolyte composition of the present invention may further comprise, as desired, other than the above-mentioned components, a lithium salt, an ionic liquid, a thickener, a crosslinking agent (a crosslinking reaction by radical polymerization, condensation polymerization or ring-opening polymerization, etc.). ), A polymerization initiator (such as one that generates an acid or a radical by heat or light), an antifoaming agent, a leveling agent, a dehydrating agent, an antioxidant, and the like.
  • the solid electrolyte composition of the present invention includes both embodiments containing a binder other than the above-mentioned fibrous binder and embodiments not containing the binder.
  • the embodiment containing no binder other than the fibrous binder means that the content of the binder other than the fibrous binder in the solid electrolyte composition is 1% by mass or less based on 100% by mass of the solid content.
  • the binder other than the fibrous binder include those commonly used in solid electrolyte compositions, and include, for example, a particulate or fibrous binder formed of a resin or an inorganic material, and a dispersion medium formed of a resin or an inorganic material. And a binder that dissolves in the binder.
  • the content of the binder in the solid electrolyte composition is 0.02 to 100% by mass in the solid component in total of the fibrous binder and the binder other than the fibrous binder.
  • the content is preferably 30% by mass, more preferably 0.05 to 20% by mass.
  • the content of the fibrous binder is as described above, it is preferably 20 to 100% by mass, and more preferably 30 to 100% by mass of the total content of the fibrous binder and the binder other than the fibrous binder. Is more preferable.
  • the content of the binder other than the fibrous binder is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on 100% by mass of the solid component.
  • the solid electrolyte composition of the present invention can be prepared, preferably as a slurry, by mixing an inorganic solid electrolyte, a fibrous binder, a dispersion medium, and other components as necessary, for example, with various types of mixers generally used. .
  • the mixing method is not particularly limited, and they may be mixed at once or sequentially.
  • the fibrous binder is usually used as a dispersion of the fibrous binder, but is not limited thereto.
  • the mixing environment is not particularly limited, and examples thereof include under dry air or under an inert gas. In producing the solid electrolyte composition of the present invention, the fibrous binder can be used as obtained.
  • the nonwoven fabric may be used in a state in which it is not entangled with other fibrous binders (in a state where the nonwoven fabric is defibrated by a normal defibration method), or may be used in the form of a fibrous film (nonwoven fabric).
  • a fibrous film When used in the form of a fibrous film, it may be defibrated in a dispersion medium by a shearing force or the like in addition to the dispersion medium, and impregnated with a composition containing components other than the fibrous binder into the fibrous film-like fibrous binder. Is also good.
  • the solid electrolyte-containing sheet of the present invention is a sheet-like formed body capable of forming a constituent layer of an all-solid secondary battery, and includes various aspects depending on the 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).
  • the solid electrolyte sheet for an all-solid secondary battery of the present invention may be a sheet having a solid electrolyte layer, and a sheet in which the solid electrolyte layer is formed on a substrate, does not have a substrate, and has a solid electrolyte layer. May be used.
  • 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, and a coat layer.
  • the solid electrolyte sheet for an all-solid secondary battery of the present invention for example, a sheet having, on a substrate, a layer composed of the solid electrolyte composition of the present invention, a normal solid electrolyte layer, and if necessary, a protective layer in this order Is mentioned.
  • the solid electrolyte layer formed by the solid electrolyte composition of the present invention contains an inorganic solid electrolyte and a fibrous binder, and as described above, the contact state between the inorganic solid electrolytes and the binding force between the solid particles and the like. And have been improved in a well-balanced manner.
  • the inorganic solid electrolyte and the fibrous binder may be in a state where the inorganic solid electrolyte is bound with the fibrous binder, for example, the inorganic solid electrolyte and the fibrous binder are interacted or structured, It is a complex.
  • the composite is not particularly limited, and includes the respective embodiments described for the solid electrolyte composition described above.
  • the solid electrolyte layer is the same as the solid electrolyte layer in the all-solid secondary battery described below, and usually does not contain an active material.
  • the solid electrolyte sheet for an all-solid secondary battery can be suitably used as a material constituting a solid electrolyte layer of an all-solid secondary battery.
  • the substrate is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include a sheet (plate-like body) made of a material described below for a current collector, an organic material, an inorganic material, and the like.
  • the organic material include various polymers, and specific examples include polyethylene terephthalate, polypropylene, polyethylene, and cellulose.
  • the inorganic material include glass and ceramic.
  • 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 may be formed on a substrate (current collector).
  • the sheet may be a sheet formed of an active material layer without a substrate.
  • This electrode sheet is usually a sheet having a current collector and an active material layer.
  • 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 electrode sheet of the present invention may have other layers described above.
  • Each layer constituting the electrode sheet of the present invention is the same as each layer described in the all solid state secondary battery described later.
  • the electrode sheet of the present invention is characterized in that when used as a negative electrode active material layer of an all solid state secondary battery, the discharge capacity (discharge capacity density) is further increased while maintaining low resistance and long battery life.
  • a negative electrode sheet for an all-solid secondary battery including an active material that can be alloyed with lithium is used.
  • the active material layer of the electrode sheet is preferably formed of the solid electrolyte composition (electrode composition) of the present invention containing an active material.
  • the negative electrode sheet contains a negative electrode active material that can be alloyed with lithium.
  • the solid electrolyte composition of the present invention is preferably formed.
  • the active material layer of the electrode sheet is a composite of solid particles containing an active material and a conductive auxiliary and a fibrous binder, The contact state between the particles and the binding force between the solid particles are improved in a well-balanced manner.
  • This electrode sheet can be suitably used as a material constituting an active material layer (negative electrode or positive electrode) of an all solid state secondary battery.
  • the method for producing the solid electrolyte-containing sheet is not particularly limited.
  • the solid electrolyte containing sheet can be manufactured using the solid electrolyte composition of the present invention.
  • the solid electrolyte composition of the present invention is prepared as described above, and the obtained solid electrolyte composition is formed (coated and dried) on a substrate (another layer may be interposed). And a method of forming a solid electrolyte layer (coating dried layer) on a substrate.
  • a solid electrolyte-containing sheet having a substrate (current collector) and a coating and drying layer as required can be produced.
  • the coating dry layer is a layer formed by applying the solid electrolyte composition of the present invention and drying the dispersion medium (that is, a layer formed by using the solid electrolyte composition of the present invention, Layer comprising a composition obtained by removing the dispersion medium from the electrolyte composition).
  • This coating and drying layer contains the above-described composite of an inorganic solid electrolyte and a fibrous binder.
  • the dispersion medium may remain in the active material layer and the coating / drying layer as long as the effects of the present invention are not impaired. The remaining amount can be, for example, 3% by mass or less in each layer.
  • the solid electrolyte composition of the present invention is preferably used as a slurry, and if desired, the solid electrolyte composition of the present invention can be slurried by a known method.
  • the steps of applying and drying the solid electrolyte composition of the present invention will be described in the following method for manufacturing an all-solid secondary battery.
  • the coated and dried layer obtained as described above can be pressed.
  • the pressurizing conditions and the like will be described later in a method for manufacturing an all-solid secondary battery.
  • the base material, the protective layer (particularly, the release sheet), and the like can also be peeled off.
  • the all solid state secondary battery of the present invention includes a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer disposed between the positive electrode active material layer and the negative electrode active material layer.
  • the positive electrode active material layer is formed on a positive electrode current collector as necessary, and forms a positive electrode.
  • the negative electrode active material layer is formed on the negative electrode current collector as necessary, and forms a negative electrode.
  • At least one of the solid electrolyte layer, the positive electrode active material layer, and the negative electrode active material layer of the all-solid secondary battery is preferably formed of the solid electrolyte composition of the present invention.
  • the layer is formed of the solid electrolyte composition of the present invention containing the oxidizable active material, including the embodiment in which all the layers are formed of the solid electrolyte composition of the present invention.
  • the all-solid-state secondary battery of the present invention has a low resistance and a large discharge capacity (discharge capacity density), and can maintain a large discharge capacity even after repeated charging and discharging (achieving a long battery life).
  • Each of the positive electrode active material layer and the negative electrode active material layer contains an inorganic solid electrolyte, an active material, an appropriate binder, a conductive auxiliary, and each of the above components.
  • the negative electrode active material layer is not formed of the solid electrolyte composition of the present invention, a layer containing the inorganic solid electrolyte, the active material, and each of the above components as appropriate, a layer made of the metal or alloy described as the negative electrode active material (lithium metal) Layer), and a layer (sheet) made of the carbonaceous material described as the negative electrode active material.
  • the layer made of a metal or an alloy includes, for example, a layer formed by depositing or molding a powder of a metal or an alloy such as lithium, a metal foil or an alloy foil, and a deposition film.
  • the thickness of each of the layer made of a metal or an alloy and the layer made of a carbonaceous material is not particularly limited, and may be, for example, 0.01 to 100 ⁇ m.
  • the solid electrolyte layer contains a solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, an appropriate binder, and the above components.
  • the solid electrolyte composition or the active material layer can be formed of the solid electrolyte composition of the present invention or the above-mentioned solid electrolyte-containing sheet.
  • the solid electrolyte layer and the active material layer to be formed are preferably the same as those in the solid content of the solid electrolyte composition, unless otherwise specified, for the components contained and their contents.
  • the thickness of each of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer is not particularly limited.
  • each layer is preferably from 5 to 1,000 ⁇ m, more preferably from 10 ⁇ m to less than 500 ⁇ m, in consideration of the dimensions of a general all-solid-state secondary battery.
  • it is more preferable that at least one of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer has a thickness of 20 ⁇ m or more and less than 500 ⁇ m.
  • Each of the positive electrode active material layer and the negative electrode active material layer may include a current collector on the side opposite to the solid electrolyte layer.
  • the all-solid-state secondary battery of the present invention may be used as an all-solid-state secondary battery with the above structure depending on the application. Is preferred.
  • the housing may be made of metal or resin (plastic). When using a metallic thing, an aluminum alloy and a thing made of stainless steel can be mentioned, for example. It is preferable that the metallic casing is divided into a casing on the positive electrode side and a casing on the negative electrode side, and electrically connected to the positive electrode current collector and the negative electrode current collector, respectively. It is preferable that the casing on the positive electrode side and the casing on the negative electrode side are joined and integrated via a gasket for preventing short circuit.
  • FIG. 1 is a cross-sectional view schematically illustrating an all solid state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention.
  • the all-solid-state secondary battery 10 of this embodiment includes 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.
  • Each layer is in contact with each other and has a laminated structure.
  • the solid electrolyte composition of the present invention can be preferably used as a material for forming a solid electrolyte layer, a negative electrode active material layer, or a positive electrode active material layer. Further, the solid electrolyte-containing sheet of the present invention is suitable as a solid electrolyte layer, a negative electrode active material layer or a positive electrode active material layer.
  • a positive electrode active material layer (hereinafter, also referred to as a positive electrode layer) and a negative electrode active material layer (hereinafter, also referred to as a negative electrode layer) may be collectively referred to as an electrode layer or an active material layer.
  • the all-solid secondary battery having the layer configuration shown in FIG. 1 When the all-solid secondary battery having the layer configuration shown in FIG. 1 is placed in a 2032 type coin case, the all-solid secondary battery is referred to as an all-solid secondary battery laminate, and the all-solid secondary battery laminate is referred to as an all-solid secondary battery laminate.
  • a battery manufactured in a 2032 type coin case is sometimes referred to as an all solid state secondary battery.
  • one of the solid electrolyte layer and the active material layer is formed using the solid electrolyte composition of the present invention or the solid electrolyte-containing sheet.
  • all the layers are formed using the solid electrolyte composition of the present invention or the solid electrolyte-containing sheet, and in another preferred embodiment, the negative electrode active material layer contains an active material that can be alloyed with lithium. And a negative electrode sheet for an all solid state secondary battery.
  • the negative electrode active material layer is a layer made of a metal or alloy as a negative electrode active material, It can also be formed by using a layer or the like made of a carbonaceous material as a negative electrode active material, and further by depositing a metal belonging to the first or second group of the periodic table on the negative electrode current collector or the like during charging.
  • the components contained in the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 may be the same or different from each other.
  • the positive electrode current collector 5 and the negative electrode current collector 1 are preferably electronic conductors.
  • one or both of the positive electrode current collector and the negative electrode current collector may be simply referred to as a current collector.
  • a material for forming the positive electrode current collector in addition to aluminum, aluminum alloy, stainless steel, nickel and titanium, etc., a material obtained by treating the surface of aluminum or stainless steel with carbon, nickel, titanium or silver (forming a thin film) Are preferred, and among them, aluminum and aluminum alloy are more preferred.
  • materials for forming the negative electrode current collector in addition to aluminum, copper, copper alloy, stainless steel, nickel and titanium, etc., the surface of aluminum, copper, copper alloy or stainless steel is treated with carbon, nickel, titanium or silver.
  • aluminum, copper, copper alloy and stainless steel are more preferred.
  • a film sheet is usually used, but a net, a punched material, a lath, a porous material, a foam, a molded product of a fiber group, and the like can also be used.
  • the thickness of the current collector is not particularly limited, but is preferably 1 to 500 ⁇ m. It is also preferable that the surface of the current collector be provided with irregularities by surface treatment.
  • a functional layer or member is appropriately interposed or provided. May be.
  • Each layer may be composed of a single layer, or may be composed of multiple layers.
  • the all solid state secondary battery of the present invention is not particularly limited, and can be manufactured through (including) the manufacturing method of the solid electrolyte composition of the present invention. Focusing on the raw materials used, it can also be produced using the solid electrolyte composition of the present invention.
  • the all-solid-state secondary battery, the solid electrolyte composition of the present invention is prepared as described above, using the obtained solid electrolyte composition and the like, the solid electrolyte layer of the all-solid-state secondary battery and And / or by forming an active material layer. Thereby, it is possible to manufacture an all-solid secondary battery that maintains a high battery capacity even after repeated charging and discharging.
  • the method for preparing the solid electrolyte composition of the present invention is as described above, and will not be described.
  • the all solid state secondary battery of the present invention includes a step of applying the solid electrolyte composition of the present invention on a base material (for example, a metal foil serving as a current collector) and forming a coating film (forming a film). It can be manufactured via a method.
  • the solid electrolyte composition (electrode composition) of the present invention is applied as a positive electrode composition on a metal foil as a positive electrode current collector to form a positive electrode active material layer, and the positive electrode for an all-solid secondary battery is formed. Make a sheet.
  • the solid electrolyte composition of the present invention for forming a solid electrolyte layer is applied on the positive electrode active material layer to form a solid electrolyte layer.
  • the solid electrolyte composition (electrode composition) of the present invention is applied as a negative electrode composition on the solid electrolyte layer to form a negative electrode active material layer.
  • Obtaining an all-solid secondary battery with a structure in which a solid electrolyte layer is sandwiched between a positive electrode active material layer and a negative electrode active material layer by stacking a negative electrode current collector (metal foil) on the negative electrode active material layer Can be. If necessary, this can be sealed in a housing to obtain a desired all-solid secondary battery.
  • a negative electrode active material layer, a solid electrolyte layer, and a positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collector is stacked to manufacture an all-solid secondary battery. You can also.
  • a positive electrode sheet for an all-solid secondary battery is prepared as described above. Further, the solid electrolyte composition of the present invention is applied as a negative electrode composition on a metal foil as a negative electrode current collector to form a negative electrode active material layer, thereby producing a negative electrode sheet for an all-solid secondary battery. Next, the solid electrolyte layer forming composition of the present invention is applied on one of the active material layers of these sheets as described above to form a solid electrolyte layer. Further, the other of the positive electrode sheet for an all-solid secondary battery and the negative electrode sheet for an all-solid secondary battery is laminated on the solid electrolyte layer such that the solid electrolyte layer and the active material layer are in contact with each other.
  • an all-solid secondary battery can be manufactured.
  • Another method is as follows. That is, a positive electrode sheet for an all-solid secondary battery and a negative electrode sheet for an all-solid secondary battery are prepared as described above. Separately from this, a solid electrolyte composition is applied on a substrate to produce a solid electrolyte sheet for an all-solid secondary battery comprising a solid electrolyte layer. Further, the positive electrode sheet for an all-solid secondary battery and the negative electrode sheet for an all-solid secondary battery are laminated so as to sandwich the solid electrolyte layer peeled off from the base material. Thus, an all-solid secondary battery can be manufactured.
  • Each of the above manufacturing methods is a method of forming a solid electrolyte layer, a negative electrode active material layer and a positive electrode active material layer with the solid electrolyte composition of the present invention, but in the method of manufacturing an all solid secondary battery of the present invention.
  • the solid electrolyte layer is formed of a composition other than the solid electrolyte composition of the present invention, examples of the material include a commonly used solid electrolyte composition.
  • the negative electrode active material layer is formed of a material other than the solid electrolyte composition of the present invention, a known negative electrode active material composition, a metal or alloy (metal layer) as the negative electrode active material, or a carbonaceous material as the negative electrode active material ( Carbonaceous material layer).
  • a known negative electrode active material composition a metal or alloy (metal layer) as the negative electrode active material, or a carbonaceous material as the negative electrode active material ( Carbonaceous material layer).
  • 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 solid electrolyte layer or the like can also be formed by, for example, pressure-forming a solid electrolyte composition or the like on a substrate or an active material layer under a pressure condition described later.
  • the method of applying the composition used for manufacturing the all-solid secondary battery is not particularly limited and can be appropriately selected. Examples include coating (preferably wet coating), spray coating, spin coating, dip coating, slit coating, stripe coating, and bar coating.
  • the composition may be subjected to a drying treatment after each application, or may be subjected to a drying treatment after multi-layer application.
  • the drying temperature is not particularly limited.
  • the lower limit is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, even more preferably 80 ° C. or higher.
  • the upper limit is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 200 ° C. or lower. By heating in such a temperature range, the dispersion medium can be removed and a solid state (coated dry layer) can be obtained. Further, it is preferable because the temperature is not too high and each member of the all solid state secondary battery is not damaged.
  • the solid electrolyte composition of the present invention when applied and dried, the above-described complex with the inorganic solid electrolyte and the fibrous binder, and furthermore, the active material or the conductive auxiliary can be formed, and the solid particles and the like are strongly bonded.
  • the solid particles and the like are strongly bonded.
  • a pressurizing method a hydraulic cylinder press or the like can be used.
  • the pressure is not particularly limited, and is generally preferably 10 MPa or more, for example, in the range of 50 to 1500 MPa.
  • the applied composition may be heated simultaneously with the application of pressure.
  • the heating temperature is not particularly limited, and is generally in the range of 30 to 300 ° C. Pressing can be performed at a temperature higher than the glass transition temperature of the inorganic solid electrolyte.
  • Pressurization may be performed in a state where the coating solvent or the dispersion medium is dried in advance, or may be performed in a state where the coating solvent or the dispersion medium remains.
  • each composition may be applied simultaneously, 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 pressurization is not particularly limited, and may be any of air, dry air (dew point ⁇ 20 ° C. or lower), and inert gas (eg, argon gas, helium gas, and nitrogen gas). Since the inorganic solid electrolyte reacts with moisture, the atmosphere during pressurization is preferably under dry air or in an inert gas.
  • a high pressure may be applied in a short time (for example, within several hours), or a medium pressure may be applied for a long time (one day or more).
  • an all-solid secondary battery restraint (such as a screw tightening pressure) can be used.
  • the pressing pressure may be uniform or different with respect to a pressure-receiving portion such as a sheet surface.
  • the pressing pressure can be changed according to the area and the film thickness of the portion to be pressed. The same part can be changed stepwise with different pressures.
  • the press surface may be smooth or rough.
  • the all-solid secondary battery manufactured as described above be initialized after manufacturing or before use.
  • the initialization is not particularly limited.
  • the initialization can be performed by performing initial charge / discharge in a state where the press pressure is increased, and then releasing the pressure until the general use pressure of the all solid state secondary battery is reached.
  • the all solid state secondary battery of the present invention can be applied to various uses. Although there is no particular limitation on the application mode, for example, when mounted on an electronic device, a notebook computer, pen input computer, mobile computer, electronic book player, mobile phone, cordless phone handset, pager, handy terminal, mobile fax, mobile phone Copy, portable printer, headphone stereo, video movie, liquid crystal television, handy cleaner, portable CD, mini disk, electric shaver, transceiver, electronic notebook, calculator, portable tape recorder, radio, backup power supply, memory card, and the like.
  • Other consumer products include automobiles (electric vehicles, etc.), electric vehicles, motors, lighting fixtures, toys, game machines, road conditioners, watches, strobes, cameras, medical equipment (pacemakers, hearing aids, shoulder massagers, etc.). . Furthermore, it can be used for various types of military use and space use. Further, it can be combined with a solar cell.
  • Neostan U-600 (trade name, manufactured by Nitto Kasei) was added to this solution, and the mixture was stirred at 80 ° C. for 4 hours. 1 g of methanol was added to this solution, and stirring was continued at 80 ° C. for 30 minutes to synthesize a binder-forming polymer B-1 to obtain a polymer solution B-1.
  • the polymer B-5 is a polyimide polymer having an aryl group (phenyl group) of a functional group included in the functional group group (a) in a main chain.
  • Binder-Forming Polymer B-6 (Preparation of Polymer Solution B-6)> Hydrogenated styrene butadiene rubber (DYNARON1321P (trade name), manufactured by JSR Corporation) was dissolved in toluene as polymer B-6 to prepare polymer solution B-6.
  • the polymer B-6 is a hydrocarbon polymer having an aryl group (phenyl group) of a functional group included in the functional group group (a) on a side chain.
  • HMDI 4,4'-dicyclohexylmethane diisocyanate (Fujifilm Wako Pure Chemical Industries, Ltd.) MDI: diphenylmethane diisocyanate (Fujifilm Wako Pure Chemical Industries, Ltd.)
  • DPTCA diphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride (Tokyo Kasei Co., Ltd.)
  • DMBA 2,2-bis (hydroxymethyl) butyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • ED-600 Polyetheramine (Jeffamine ED-600 (trade name), manufactured by Huntsman, Mw600)
  • T5650J Polycarbonate diol (Duranol T5650J (trade name), manufactured by Asahi Kasei Corporation, Mw 2,000)
  • G3450J polycarbonate diol (Duranol G3450J (trade name), Mw800, manufactured by Asa
  • the component represented by any of the above formulas (1-1) to (1-6) are DPTCA, DMBA, PPG400, ED-600, EDA, T5650J, G3450J, GI-1000, EPOL, BD Is a constituent component derived from each starting compound.
  • the component represented by the above formula (2) is a component derived from each raw material compound of HMDI and MDI.
  • fibrous binders F-1 to F-15, CF-1, CF-3 and CF-4 were prepared by electrospinning into fibers of each polymer. Specifically, in the electrospinning method, using the polymer solutions shown in Table 1, the solid content concentration (0.5 to 30% by mass) of this polymer solution, the applied voltage (2 to 50 kV), and the spinning section (spinning section) Each fibrous binder was obtained by controlling the injection distance (10 to 300 mm) from the nozzle) to the electrode (within the range described in parentheses).
  • Li 2 S lithium sulfide
  • P 2 S 5 diphosphorus pentasulfide
  • Example 1 Using the obtained binder-forming polymer, a solid electrolyte composition, an electrode sheet for an all-solid secondary battery and an all-solid secondary battery are respectively manufactured, and the electrode sheet for an all-solid secondary battery and the all-solid secondary battery are manufactured. The following characteristics were evaluated. Table 5 shows the results.
  • ⁇ Preparation of solid electrolyte composition 180 zirconia beads having a diameter of 5 mm were put into a 45-mL zirconia container (manufactured by Fritsch), and 4.85 g of the Li-PS-based glass synthesized in Synthesis Example 7 above was used.
  • the binder CF-2 0.15 g (in terms of solid content mass) and 8.0 g of heptane as a dispersion medium were added. Thereafter, the container was set on a planetary ball mill P-7 (trade name) manufactured by Fritsch Co., and mixing was continued at a temperature of 25 ° C. and a rotation speed of 250 rpm for 60 minutes to obtain solid electrolyte compositions S-1 to S-3, respectively.
  • the solid electrolyte composition S-3 is a solid electrolyte composition for comparison.
  • the negative electrode sheets A-1 to A-24 for all-solid-state secondary batteries having the above were prepared respectively.
  • the negative electrode sheets A-17 to A-21 and A-24 for an all solid state secondary battery are negative electrode sheets for comparison.
  • the positive electrode sheets C-1 to C-5 for all-solid-state secondary batteries having the above were respectively produced.
  • the positive electrode sheet C-5 for an all-solid secondary battery is a positive electrode sheet for comparison.
  • Si Silicon Sn: Tin SiO: silicon monoxide
  • C Graphite NMC: LiNi 1/3 Co 1/3 Mn 1/3 O 2
  • LCO LiCoO 2
  • LPS sulfide-based inorganic solid electrolyte synthesized in Synthesis
  • LLZ Li 7 La 3 Zr 2 O 12
  • AB acetylene black
  • PTFE polytetrafluoroethylene
  • ⁇ Manufacture of all-solid secondary batteries> (Preparation of electrode sheet) An all-solid secondary battery was manufactured using the electrode sheet subjected to the following bending test. In the bending test, the diameter of the prepared negative electrode sheet for all-solid-state secondary battery and the positive electrode sheet for all-solid-state secondary battery was determined in ⁇ Evaluation 1: Film strength test of negative-electrode sheet for all-solid-state secondary battery> described below. The evaluation was performed in the same manner as in ⁇ Evaluation 1: Membrane strength test of negative electrode sheet for all-solid-state secondary battery>, except that bending was repeated three times using a 10-mm mandrel.
  • the above-prepared solid electrolyte composition S-1 was applied on the negative electrode active material layer of each negative electrode sheet for an all-solid secondary battery subjected to the bending test by an applicator so as to have a basis weight shown in Table 5. Then, after heating at 80 ° C. for 1 hour, it was further dried at 110 ° C. for 6 hours.
  • the sheet in which the coating and drying layer was formed on the negative electrode active material layer was pressurized (30 MPa, 1 minute) while heating (120 ° C.) using a heat press machine, and the solid electrolyte layer, the negative electrode active material layer, and the stainless steel were pressed.
  • a sheet having a structure in which a foil and a foil were laminated in this order was prepared and cut into a disk shape having a diameter of 15 mm (referred to as a disk-shaped negative electrode sheet).
  • the positive electrode sheet for an all solid state secondary battery shown in Table 5 where the bending test was performed was cut out into a disk shape having a diameter of 13 mm.
  • a laminated body for an all-solid secondary battery having a laminated structure shown in FIG. 1, that is, a structure in which an aluminum foil, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a SUS foil were laminated in this order was produced.
  • Table 5 shows the thickness of each layer.
  • the all-solid-state rechargeable battery laminate 12 thus prepared is placed in a stainless steel 2032 type coin case 11 in which a spacer and a washer (not shown in FIG. 2) are incorporated. By caulking the coin case 11, All-solid secondary batteries 13 of 101 to 123 and c01 to c06 were produced.
  • ⁇ Evaluation 1 Film strength test of negative electrode sheet for all solid state secondary battery> The film strength of the negative electrode active material layers in the negative electrode sheets A-1 to A-24 for all solid state secondary batteries was evaluated by a bending resistance test (based on JIS K5600-5-1) using a mandrel tester. The results are shown in the “film strength” column of Table 5. Specifically, the negative electrode active material layer is opposite to the mandrel (SUS foil on the mandrel side) using a test piece cut out from the negative electrode sheet for an all-solid secondary battery into a strip having a width of 50 mm and a length of 100 mm.
  • the test piece is set so that its width direction is parallel to the axis of the mandrel, and is bent 180 ° (once) along the outer peripheral surface of the mandrel. Was visually observed.
  • This bending test is first performed using a mandrel having a diameter of 32 mm, and when no cracks or cracks occur, the diameter (mm) of the mandrel is set to 25, 20, 16, 12, 10, 8, 6, 5, The diameter was gradually reduced to 4, 3, and 2, and the diameter of the mandrel where the first crack or crack occurred was recorded.
  • the diameter (defect occurrence diameter) of the mandrel in which the crack or crack separation first occurred was evaluated according to which of the following evaluation criteria was included.
  • the film strength of the positive electrode sheets C-1 to C-5 for an all-solid secondary battery was evaluated in the same manner as in ⁇ Evaluation 1: Film strength test of negative electrode sheet for an all-solid secondary battery>.
  • the positive electrode sheets for battery C-1 to C-4 were evaluated as A, and the positive electrode sheet for all-solid secondary battery C-5 was evaluated as E.
  • ⁇ Evaluation 2 Battery performance test (discharge capacity) of all solid state secondary battery>
  • the discharge capacity of the all-solid-state secondary battery manufactured as described above was measured by a charge / discharge evaluation device “TOSCAT-3000” (trade name, manufactured by Toyo System Co., Ltd.). Specifically, the all-solid-state secondary battery was charged at a current value of 0.2 mA until the battery voltage reached 4.2 V, and then discharged at a current value of 0.2 mA until the battery voltage reached 3.0 V.
  • One charge and one discharge were defined as a charge / discharge cycle, and the charge / discharge was repeated three cycles. The discharge capacity at the third cycle was determined.
  • This discharge capacity was converted into the surface area of the positive electrode active material layer per 100 cm 2 , and evaluated as one of the following evaluation criteria as the discharge capacity of the all-solid secondary battery.
  • the evaluation criterion C or higher is a pass level.
  • ⁇ Evaluation 4 Resistance measurement of all solid state secondary battery> The resistance of each of the all-solid-state secondary batteries manufactured as described above was measured by a charge / discharge evaluation device “TOSCAT-3000” (trade name, manufactured by Toyo System Co., Ltd.). Specifically, the all-solid-state secondary battery was charged at a current value of 0.2 mA until the battery voltage reached 4.2 V, and then discharged at a current value of 2.0 mA until the battery voltage reached 3.0 V. The battery voltage 10 seconds after the start of discharging was read and evaluated according to any of the following evaluation criteria. In this test, the higher the battery voltage, the lower the resistance of the all-solid-state secondary battery, indicating that an evaluation criterion C or higher is a pass level.
  • ⁇ Evaluation 5 Evaluation of battery life of all solid state secondary battery>
  • Each sample No. 10 samples of all solid-state rechargeable batteries are manufactured, and the discharge capacity of the 10 samples of all solid-state rechargeable batteries is measured by a charge / discharge evaluation device “TOSCAT-3000” (trade name, manufactured by Toyo System Co., Ltd.). The life was evaluated. Specifically, each all-solid-state secondary battery was charged at a current value of 0.2 mA until the battery voltage reached 4.2 V, and then discharged at a current value of 2.0 mA until the battery voltage reached 3.0 V. did. One charge and one discharge were defined as one charge / discharge cycle, and charge / discharge was repeated 100 cycles under the same conditions.
  • the discharge capacity at the fifth charge / discharge cycle and the discharge capacity at the 100th charge / discharge cycle were determined as follows.
  • the average value of the discharge capacity at the 5th cycle and the 100th cycle was calculated for all the solid-state rechargeable batteries of 6 samples excluding the upper and lower two samples of the performance among the 10 sample batteries.
  • the ratio of the average discharge capacity at the 100th cycle to (the average discharge capacity at the 100th cycle / the average discharge capacity at the 5th cycle) ⁇ 100 (%) was calculated. An evaluation was made depending on which of the following evaluation criteria this ratio was included in.
  • the evaluation criterion C or higher is a pass level. -Evaluation criteria- A: 85% or more B: 75% or more, less than 85% C: 65% or more, less than 75% D: 55% or more, less than 65% E: less than 55%
  • Each of the electrode sheets A-17 to A-21, A-24 and C-5 formed of the solid electrolyte composition (composition for electrode) containing no fibrous binder specified in the present invention has sufficient film strength. Does not demonstrate.
  • all-solid secondary batteries c01 to c06 each including a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer formed of a solid electrolyte composition or a composition for an electrode containing no fibrous binder specified in the present invention. All have insufficient discharge capacity, discharge capacity density and resistance, and are inferior in battery life.
  • electrode sheets A-1 to A-16, A-22 and A23 and C-1 to C formed from a solid electrolyte composition (composition for an electrode) containing the fibrous binder specified in the present invention.
  • All of -4 indicate sufficient film strength.
  • Each of the batteries 123 is excellent in discharge capacity, discharge capacity density and resistance, and shows a long battery life.
  • the solid electrolyte composition containing the fibrous binder specified in the present invention suppresses the increase in the interfacial resistance between the solid particles in the all-solid secondary battery, firmly binds the solid particles, and has a small resistance. And excellent discharge capacity and discharge capacity density can be maintained even when charge and discharge are repeated.
  • All of the solid-state secondary batteries 106 and 109 to 112 using Si, Sn, or SiO as the negative electrode active material have a discharge capacity that is smaller than that of the all-solid-state secondary battery 116 using graphite as the negative electrode active material layer. Density is increasing. In addition, these all-solid-state secondary batteries maintain strong film strength and long battery life despite a large change in the volume of the negative electrode active material layer. As described above, according to the preferred embodiment of the present invention, it is possible to solve the problems (binding property of solid particles and battery life) peculiar to the negative electrode active material layer having a large volume change.
  • the all-solid secondary battery c06 using a fluororesin as a binder, and the all-solid secondary batteries c02 and c05 using a particulate binder or a solution binder both have binding properties of solid particles and It turns out that the problem peculiar to the negative electrode active material layer which is inferior in battery life and whose volume change is large cannot be solved.

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Abstract

L'invention concerne : une composition d'électrolyte solide comprenant un électrolyte solide inorganique, un milieu de dispersion, et un liant fibreux comprenant un polymère ayant un module d'élasticité de 0,1 à 1000 MPa et une déformation élastique de 0,01 à 10 000 %, le liant ayant un diamètre moyen D de 0 001 à 10 µm et une longueur moyenne L de 0,1 µm à 1000 mm, et le rapport de la longueur moyenne L au diamètre moyen D étant de 10 à 100 000 ; une feuille contenant un électrolyte solide qui a une couche comprenant cette composition ; une feuille d'électrode pour une batterie secondaire entièrement solide ; et une batterie secondaire entièrement solide.
PCT/JP2019/029610 2018-08-13 2019-07-29 Composition d'électrolyte solide, feuille contenant un électrolyte solide, feuille d'électrode pour batteries secondaires entièrement solides, et batterie secondaire entièrement solide Ceased WO2020036055A1 (fr)

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