WO2017130832A1 - Composition d'électrolyte solide, feuille contenant un électrolyte solide, accumulateur tout solide, procédé de production de feuille contenant un électrolyte solide, et procédé de fabrication d'accumulateur tout solide - Google Patents

Composition d'électrolyte solide, feuille contenant un électrolyte solide, accumulateur tout solide, procédé de production de feuille contenant un électrolyte solide, et procédé de fabrication d'accumulateur tout solide Download PDF

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WO2017130832A1
WO2017130832A1 PCT/JP2017/001739 JP2017001739W WO2017130832A1 WO 2017130832 A1 WO2017130832 A1 WO 2017130832A1 JP 2017001739 W JP2017001739 W JP 2017001739W WO 2017130832 A1 WO2017130832 A1 WO 2017130832A1
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group
solid electrolyte
solid
compound
active material
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PCT/JP2017/001739
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Japanese (ja)
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雅臣 牧野
智則 三村
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富士フイルム株式会社
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solid electrolyte composition, a solid electrolyte-containing sheet and an all-solid secondary battery, and a method for producing a solid electrolyte-containing sheet and an all-solid secondary battery.
  • a lithium ion secondary battery is a storage battery that has a negative electrode, a positive electrode, and an electrolyte sandwiched between the negative electrode and the positive electrode, and can be charged and discharged by reciprocating lithium ions between the two electrodes.
  • an organic electrolytic solution has been used as an electrolyte in a lithium ion secondary battery.
  • the organic electrolyte is liable to leak, and there is a possibility that a short circuit occurs inside the battery due to overcharge and overdischarge, resulting in ignition, and further improvements in reliability and safety are required. Under such circumstances, an all-solid secondary battery using an inorganic solid electrolyte instead of an organic electrolyte has been attracting attention.
  • the all-solid-state secondary battery consists of a solid negative electrode, electrolyte, and positive electrode, which can greatly improve safety and reliability, which is a problem of batteries using organic electrolytes, and can extend the service life. It will be. Furthermore, the all-solid-state secondary battery can have a structure in which electrodes and an electrolyte are directly arranged in series. Therefore, it is possible to increase the energy density as compared with a secondary battery using an organic electrolytic solution, and application to electric vehicles, large-sized storage batteries, and the like is expected.
  • any one of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer is formed of an inorganic solid electrolyte and / or an active material and a binder particle such as a specific polymer compound. It has been proposed to form a material containing (binder).
  • Patent Document 1 discloses a solid electrolyte composition containing 99% or more of a carbon-carbon double bond that is hydrogenated and containing a crystalline norbornene-based ring-opening polymer hydride having a specific melting point as a binder, and An all-solid secondary battery is described.
  • Patent Document 2 includes a solid electrolyte material obtained by applying a monomer or oligomer having a double bond and a composition containing a radical polymerization initiator as a binder composition, radical polymerization, and curing. Sheets and solid state batteries are described.
  • the solid electrolyte composition according to (1) or (2), wherein the compound having a non-aromatic carbon-carbon unsaturated bond has at least one functional group selected from the following functional group group.
  • ⁇ Functional group group > Hydroxy group, mercapto group, carboxy group, sulfonic acid group, phosphoric acid group, amino group, cyano group, isocyanate group, acid anhydride group, epoxy group, oxetanyl group, alkoxy group, carbonyl group, three or more ring structures Group having, amide bond, urea bond, urethane bond, imide bond, isocyanurate bond.
  • the compound having a non-aromatic carbon-carbon unsaturated bond is any one of (1) to (3) having two or more non-aromatic carbon-carbon unsaturated bonds in one molecule.
  • the compound having a non-aromatic carbon-carbon unsaturated bond has any one of a star type, a hyperbranch type, and a dendrimer type, according to any one of (1) to (4) Solid electrolyte composition.
  • the solid electrolyte composition according to (1), wherein the compound having a non-aromatic carbon-carbon unsaturated bond is represented by the following general formula (1a) or (2a).
  • R 11 to R 13 , R 14 , R 21 to R 23 and R 24 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group
  • R 31 and R 34 represent a hydrogen atom or an alkyl group.
  • L 11 , L 21 and L 31 represent a single bond or a divalent linking group.
  • n and m are integers of 1 to 20, and l is an integer of 0 to 20.
  • X represents an n + m + 1 valent organic group.
  • a step (1a) of obtaining a coated sheet by applying the solid electrolyte composition according to any one of (1) to (14) on a substrate A process for producing a solid electrolyte-containing sheet, comprising a step (2a) of heating the coating sheet to 50 ° C. or more and crosslinking and curing it by a metathesis reaction of a compound having a non-aromatic carbon-carbon unsaturated bond.
  • a process for producing a solid electrolyte-containing sheet comprising a step (2a) of heating the coating sheet to 50 ° C. or more and crosslinking and curing it by a metathesis reaction of a compound having a non-aromatic carbon-carbon unsaturated bond.
  • Conditions for initiating metathesis reaction of a compound having a non-aromatic carbon-carbon unsaturated bond by heating the solid electrolyte composition according to any one of (1) to (14) to 50 ° C.
  • seat including the process (2b) which apply
  • Z 1 represents the following general formula (3-1)
  • Z 2 represents the following general formula (3-2).
  • R 3 represents a hydrogen atom, an alkyl group or an aryl group.
  • L 3 represents a single bond or a divalent linking group.
  • n and m are integers of 1 to 20, and l is an integer of 0 to 20.
  • X represents an n + m + 1 valent organic group.
  • R 1 and R 2 represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.
  • L 1 and L 2 represent a single bond or a divalent linking group. * Indicates a binding site with X.
  • An all-solid secondary battery comprising a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order, An all-solid-state secondary battery in which at least one of a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer comprises the solid electrolyte-containing sheet according to (17) or (18).
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • acryl or “(meth) acryl” is simply described, it means methacryl and / or acryl.
  • substituents, etc. when there are a plurality of substituents, linking groups, etc. (hereinafter referred to as substituents, etc.) indicated by specific symbols, or when a plurality of substituents etc. are specified simultaneously or alternatively, It means that a substituent etc. may mutually be same or different. The same applies to the definition of the number of substituents and the like.
  • the mass average molecular weight can be measured as a molecular weight in terms of polystyrene by GPC, unless otherwise specified.
  • GPC device HLC-8220 manufactured by Tosoh Corporation
  • G3000HXL + G2000HXL is used as the column
  • the flow rate is 1 mL / min at 23 ° C.
  • detection is performed by RI.
  • the eluent can be selected from THF (tetrahydrofuran), chloroform, NMP (N-methyl-2-pyrrolidone), m-cresol / chloroform (manufactured by Shonan Wako Pure Chemical Industries, Ltd.) and dissolves. If present, use THF.
  • the solid electrolyte composition of the present invention When used as a material for a solid electrolyte layer and / or an active material layer of an all-solid-state secondary battery, the solid electrolyte composition enhances the binding between solid particles and is a solid resulting from repeated charge and discharge. It has an excellent effect of suppressing an increase in interfacial resistance between particles and improving cycle characteristics.
  • the solid electrolyte-containing sheet and the all-solid secondary battery of the present invention utilize the solid electrolyte composition that exhibits the above-described excellent effects and exhibit excellent performance.
  • seat and all-solid-state secondary battery of this invention can each be manufactured suitably.
  • 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 an all-solid secondary battery (coin battery) produced in the example.
  • the solid electrolyte composition of the present invention comprises an inorganic solid electrolyte (A) having conductivity of ions of metals belonging to Group 1 or Group 2 of the periodic table, and a compound having a non-aromatic carbon-carbon unsaturated bond (B) and a metathesis catalyst (C) are contained.
  • A inorganic solid electrolyte
  • B non-aromatic carbon-carbon unsaturated bond
  • C metathesis catalyst
  • the solid electrolyte composition of the present invention contains an inorganic solid electrolyte.
  • the solid electrolyte of the inorganic solid electrolyte is a solid electrolyte that can move ions inside. Since it does not contain organic substances as the main ionic conductivity material, organic solid electrolytes (polymer electrolytes typified by polyethylene oxide (PEO) etc., organics typified by lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) etc. It is clearly distinguished from the electrolyte salt). Further, since the inorganic solid electrolyte is solid in a steady state, it is not dissociated or released into cations and anions.
  • PEO polyethylene oxide
  • LiTFSI lithium bis (trifluoromethanesulfonyl) imide
  • the electrolyte solution and inorganic electrolyte salts LiPF 6 , LiBF 4 , lithium bis (fluorosulfonyl) imide (LiFSI), LiCl, etc.
  • the inorganic solid electrolyte is not particularly limited as long as it has conductivity of ions of metal elements belonging to Group 1 or Group 2 of the periodic table, and generally does not have electron conductivity.
  • the inorganic solid electrolyte preferably has an ionic conductivity of lithium ions.
  • inorganic solid electrolyte a solid electrolyte material usually used for an all-solid secondary battery can be appropriately selected and used.
  • Typical examples of inorganic solid electrolytes include (i) sulfide-based inorganic solid electrolytes and (ii) oxide-based inorganic solid electrolytes.
  • a sulfide-based inorganic solid electrolyte is preferably used from the viewpoint that a better interface can be formed between the active material and the inorganic solid electrolyte.
  • the sulfide-based inorganic solid electrolyte contains a sulfur atom (S) and has ionic conductivity of a metal element belonging to Group 1 or Group 2 of the periodic table, And what has electronic insulation is preferable.
  • the sulfide-based inorganic solid electrolyte preferably contains at least Li, S, and P as elements and has lithium ion conductivity. However, depending on the purpose or the case, other than Li, S, and P may be used. An element may be included. For example, a lithium ion conductivity inorganic solid electrolyte satisfying the composition represented by the following formula (1) can be mentioned and is preferable.
  • L represents an element selected from Li, Na and K, and Li is preferred.
  • M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge. Among these, B, Sn, Si, Al, or Ge is preferable, and Sn, Al, or Ge is more preferable.
  • A represents I, Br, Cl or F, preferably I or Br, and particularly preferably I.
  • L, M, and A can each be one or more of the above elements.
  • a1 to e1 indicate the composition ratio of each element, and a1: b1: c1: d1: e1 satisfies 1 to 12: 0 to 1: 1: 2 to 12: 0 to 5.
  • a1 is further preferably 1 to 9, and more preferably 1.5 to 4.
  • b1 is preferably 0 to 0.5.
  • d1 is preferably 3 to 7, and more preferably 3.25 to 4.5.
  • e1 is preferably 0 to 3, more preferably 0 to 1.
  • the composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based inorganic solid electrolyte.
  • the sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass ceramic), or only a part may be crystallized.
  • glass glass
  • glass ceramic glass ceramic
  • Li—PS system glass containing Li, P, and S or Li—PS system glass ceramics containing Li, P, and S can be used.
  • the sulfide-based inorganic solid electrolyte includes [1] lithium sulfide (Li 2 S) and phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), [2] lithium sulfide and at least one of simple phosphorus and simple sulfur, Or [3] It can be produced by the reaction of lithium sulfide, phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), at least one of elemental phosphorus and elemental sulfur.
  • the ratio of Li 2 S to P 2 S 5 in the Li—PS system glass and Li—PS system glass ceramic is a molar ratio of Li 2 S: P 2 S 5 , preferably 65:35 to 85:15, more preferably 68:32 to 77:23.
  • the lithium ion conductivity can be further increased.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 ⁇ 4 S / cm or more, more preferably 1 ⁇ 10 ⁇ 3 S / cm or more. Although there is no particular upper limit, it is practical that it is 1 ⁇ 10 ⁇ 1 S / cm or less.
  • the sulfide-based inorganic solid electrolyte include, for example, those using a raw material composition containing Li 2 S and a sulfide of an element belonging to Group 13 to Group 15. it can. More specifically, Li 2 S—P 2 S 5 , Li 2 S—LiI—P 2 S 5 , Li 2 S—LiI—Li 2 O—P 2 S 5 , Li 2 S—LiBr—P 2 S 5 , Li 2 S—Li 2 O—P 2 S 5 , Li 2 S—Li 3 PO 4 —P 2 S 5 , Li 2 S—P 2 S 5 —P 2 O 5 , Li 2 S—P 2 S 5- SiS 2 , Li 2 S—P 2 S 5 —SnS, Li 2 S—P 2 S 5 —Al 2 S 3 , Li 2 S—GeS 2 , Li 2 S—GeS 2 —ZnS, Li 2 S— Ga 2 S 3 , Li 2 S—GeS 2 —G
  • Examples of a method for synthesizing a sulfide-based inorganic solid electrolyte material using such a raw material composition include an amorphization method.
  • Examples of the amorphization method include a mechanical milling method and a melt quenching method, and among them, the mechanical milling method is preferable. This is because processing at room temperature is possible, and the manufacturing process can be simplified. Among them, Li 2 S-P 2 S 5, LGPS (Li 10 GeP 2 S 12), Li 2 S-P 2 S 5 -SiS 2 and the like are preferable.
  • the oxide-based inorganic solid electrolyte contains an oxygen atom (O) and has ionic conductivity of a metal element belonging to Group 1 or Group 2 of the periodic table, And what has electronic insulation is preferable.
  • the oxide-based inorganic solid electrolyte preferably has an ionic conductivity of 1 ⁇ 10 ⁇ 6 S / cm or more, more preferably 5 ⁇ 10 ⁇ 6 S / cm or more, and 1 ⁇ 10 ⁇ 5 S. / Cm or more is particularly preferable.
  • the upper limit is not particularly limited, but it is practical that it is 1 ⁇ 10 ⁇ 1 S / cm or less.
  • Li xa La ya TiO 3 [xa satisfies 0.3 ⁇ xa ⁇ 0.7, and ya satisfies 0.3 ⁇ ya ⁇ 0.7.
  • LLT Li xb La yb Zr zb M bb mb Onb
  • M bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In and Sn
  • Xb satisfies 5 ⁇ xb ⁇ 10
  • yb satisfies 1 ⁇ yb ⁇ 4
  • zb satisfies 1 ⁇ zb ⁇ 4
  • mb satisfies 0 ⁇ mb ⁇ 2
  • nb satisfies 5 ⁇ nb ⁇ 20.
  • Li xc B yc M cc zc Onc (M cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In and Sn.
  • Xc is 0 ⁇ xc ⁇ 5
  • Yc satisfies 0 ⁇ yc ⁇ 1,
  • zc satisfies 0 ⁇ zc ⁇ 1,
  • nc satisfies 0 ⁇ nc ⁇ 6
  • Li xd (Al, Ga) yd (Ti, Ge) zd Si ad P md Ond (xd satisfies 1 ⁇ xd ⁇ 3, yd Satisfies 0 ⁇ yd ⁇ 1, zd satisfies 0 ⁇ zd ⁇ 2, ad satisfies 0 ⁇ ad ⁇ 1, md satisfies 1 ⁇ md ⁇ 7, and nd satisfies 3 ⁇
  • Li, P and O Phosphorus compounds containing Li, P and O are also desirable.
  • lithium phosphate Li 3 PO 4
  • LiPON obtained by substituting a part of oxygen of lithium phosphate with nitrogen
  • LiPOD 1 (D 1 is preferably Ti, V, Cr, Mn, Fe, Co, Ni, And at least one element selected from Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt, and Au.
  • LiA 1 ON (A 1 is one or more elements selected from Si, B, Ge, Al, C, and Ga) can be preferably used.
  • LLT Li xb La yb Zr zb M bb mb O nb
  • LLZ Li 3 BO 3, Li 3 BO 3 -Li 2 SO 4, Li xd (Al , Ga) yd (Ti, Ge) zd Si ad P md O nd (xd, yd, zd, ad, md and nd are as defined above.) is preferred, LLZ, LLT LAGP (Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 ) or LATP ([Li 1.4 Ti 2 Si 0.4 P 2.6 O 12 ] —AlPO 4 ) is more preferable.
  • the inorganic solid electrolyte is preferably a particle.
  • the volume average particle diameter of the particulate inorganic solid electrolyte is not particularly limited, but is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more. As an upper limit, it is preferable that it is 100 micrometers or less, and it is more preferable that it is 50 micrometers or less.
  • the measurement of the volume average particle diameter of an inorganic solid electrolyte is performed in the following procedures.
  • the inorganic solid electrolyte particles are prepared by diluting a 1 mass% dispersion in a 20 mL sample bottle using water (heptane in the case of a substance unstable to water).
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes and used immediately after that.
  • a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA)
  • data was acquired 50 times using a quartz cell for measurement at a temperature of 25 ° C., Obtain the volume average particle size.
  • JISZ8828 2013 “Particle Size Analysis—Dynamic Light Scattering Method” is referred to as necessary. Five samples are prepared for each level, and the average value is adopted.
  • the content of the inorganic solid electrolyte in the solid electrolyte composition is preferably 5% by mass or more at a solid content of 100% by mass considering the balance between battery performance, reduction in interface resistance, and maintenance effect. % Or more is more preferable, and 20% by mass or more is particularly preferable. As an upper limit, it is preferable that it is 99.9 mass% or less from the same viewpoint, It is more preferable that it is 99.5 mass% or less, It is especially preferable that it is 99 mass% or less.
  • the content of the inorganic solid electrolyte in the solid electrolyte composition is such that the total content of the positive electrode active material or the negative electrode active material and the inorganic solid electrolyte is within the above range.
  • the solid content means the inorganic solid electrolyte (A), the compound (B) having a non-aromatic carbon-carbon unsaturated bond, the metathesis catalyst (C), and drying at 170 ° C. for 6 hours in a nitrogen atmosphere.
  • An inorganic solid electrolyte may be used individually by 1 type, or may be used in combination of 2 or more type.
  • Compound having non-aromatic carbon-carbon unsaturated bond (B) A compound having a non-aromatic carbon-carbon unsaturated bond (hereinafter also simply referred to as compound (B)) is a non-aromatic carbon-carbon unsaturated bond (hereinafter also simply referred to as non-aromatic unsaturated bond). If it is a compound which has.), It will not specifically limit. Non-aromatic means that it does not have aromaticity.
  • Non-aromatic unsaturated bonds include, for example, carbon-carbon double bonds and carbon-carbon triple bonds that do not have aromaticity, and are preferable.
  • the non-aromatic unsaturated bond may be present at any position in the molecule of the compound (B), and a group having a non-aromatic unsaturated bond (hereinafter simply referred to as a non-aromatic unsaturated group). ) May be chain-like or branched, or may further form a ring.
  • the non-aromatic unsaturated group is a group in which at least one hydrogen atom or alkyl group of the compound represented by the following general formula (1) or (2) is replaced with a bond “—” (hereinafter, represented by the general formula (1) Or a group represented by (2)) is preferred.
  • R 1a to R 4a , R 5a and R 6a are a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group Or a carbamoyl group.
  • R 1a to R 4a may form a ring structure with any organic group.
  • R 5a and R 6a may form a ring structure with an arbitrary organic group.
  • at least one of R 1a to R 4a represents a hydrogen atom or a group having an alkyl group.
  • at least one of R 5a and R 6a is a hydrogen atom or a group having an alkyl group.
  • R 1a is a hydrogen atom
  • R 1a is a substituent in which the hydrogen atom in R 1a is replaced with a bond “—”
  • R 1a is alkoxycarbonyl
  • R 1a is alkoxycarbonyl
  • alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group and carbamoyl group in R 1a to R 4a , R 5a and R 6a are substituted as described below.
  • the preferred description of the group Z can be applied.
  • R 1a and R 2a are hydrogen atoms
  • R 3a is a hydrogen atom or an alkyl group
  • R 4a is a hydrogen atom, an alkyl group, an alkoxycarbonyl group or an aryloxy group. a carbonyl group, a hydrogen atom or an alkyl group bond in R 3a or R 4a "-" group is replaced with are preferred.
  • a R 5a is a hydrogen atom
  • a R 6a is a hydrogen atom or an alkyl group
  • a bond hydrogen atoms in R 6a "-" group is replaced with are preferred.
  • the specific non-aromatic unsaturated group is preferably any one selected from a terminal vinyl group, an allyl group, a (meth) acryloyl group, and a terminal ethynyl group.
  • the compound (B) has a non-aromatic unsaturated bond at the molecular end, the reactivity of the metathesis reaction described later is further increased, and the compound (B) can be crosslinked at a low temperature. Moreover, the binding property between solid particles improves because crosslinking efficiency increases more. From these viewpoints, the non-aromatic unsaturated group is more preferably a terminal vinyl group or a terminal ethynyl group.
  • the compound (B) preferably has two or more non-aromatic unsaturated groups, and more preferably three or more.
  • the compound (B) has at least one functional group selected from the following functional group group, and the interaction between the compound (B) and the inorganic solid electrolyte, or the compound (B), the inorganic solid electrolyte, and the active material It is preferable from the viewpoint of enhancing the interaction and enhancing the binding property.
  • An acid anhydride group means a group obtained from an acid anhydride of a dicarboxylic acid (a group in which at least one hydrogen atom is replaced with a bond “—”).
  • the amino group preferably has 0 to 12 carbon atoms, more preferably 0 to 6, and particularly preferably 0 to 2.
  • the sulfonic acid group may be its ester or salt.
  • the number of carbon atoms is preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 6.
  • the phosphate group may be its ester or salt.
  • the number of carbon atoms is preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 6.
  • the said functional group may exist as a substituent or may exist as a coupling group.
  • the amino group may exist as a divalent imino group or a trivalent nitrogen atom.
  • a polar group is preferably used from the viewpoint of affinity for the inorganic solid electrolyte and / or the positive electrode active material.
  • a hydroxy group, a mercapto group, a carboxy group, a sulfonic acid group, a phosphoric acid group and an amino group are preferable, and a carboxy group is more preferable.
  • a nonpolar group is preferably used from the viewpoint of affinity for the negative electrode active material and / or the conductive auxiliary agent.
  • a group having 3 or more ring structures is preferable.
  • At least one hydrogen atom of the aromatic hydrocarbon, aliphatic hydrocarbon or unsaturated hydrocarbon represented by the following general formula (A) is replaced with a bond “-”
  • at least one kind of a group in which at least one hydrogen atom of the aliphatic hydrocarbon represented by the general formula (B) described later is replaced with a bond “—”.
  • An aromatic hydrocarbon, an unsaturated hydrocarbon or an aliphatic hydrocarbon represented by the following general formula (A), and an aliphatic hydrocarbon represented by the following general formula (B) are carbonaceous materials that are negative electrode active materials. Excellent affinity with materials.
  • the dispersion stability of the compound (B) having a group in which at least one hydrogen atom of these compounds is replaced with a bond “—” in the solid electrolyte composition is further improved, and the solid electrolyte-containing sheet
  • the binding property can be improved.
  • improvement in dispersion stability and binding property it is possible to improve cycle characteristics of an all-solid secondary battery produced using this solid electrolyte composition.
  • CHC represents a benzene ring, a cyclohexane ring, a cyclohexene ring, or a cyclohexadiene ring.
  • n A represents an integer of 0 to 8.
  • R A1 ⁇ R A6 each independently represent a hydrogen atom or a substituent.
  • the ring structure may have a hydrogen atom in addition to R A1 to R A6 .
  • X A1 and X A2 each independently represent a hydrogen atom or a substituent.
  • R A1 to R A6 groups adjacent to each other may be bonded to form a 5- or 6-membered ring.
  • n A any one substituent of R A1 to R A6 is — (CHC 1 ) m A —R Ax , or any two of R A1 to R A6 are bonded to each other To form — (CHC 1 ) m A —.
  • CHC 1 represents a phenylene group, a cycloalkylene group, a cycloalkenylene group
  • m A represents an integer of 2 or more
  • R Ax represents a hydrogen atom or a substituent.
  • n A is 1, at least two of R A1 to R A6 , X A1 and X A2 are adjacent to each other to form a benzene ring, a cyclohexane ring, a cyclohexene ring or a cyclohexadiene ring.
  • Examples of the substituent represented by R A1 to R A6 include an alkyl group, aryl group, heteroaryl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, Acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, hydroxy group, carboxy group or salt thereof, sulfo group or salt thereof, amino group, mercapto group, amide group, formyl Group, cyano group, halogen atom, (meth) acryl group, (meth) acryloyloxy group, (meth) acrylamide group, epoxy group, oxetanyl group and the like.
  • n A is more preferably an integer of 0 to 6, and particularly preferably an integer of 1 to 4.
  • the aromatic hydrocarbon represented by the general formula (A) is preferably a compound represented by the following general formula (A-1) or (A-2).
  • Ar is a benzene ring.
  • R A1 ⁇ R A6, X A1 and X A2 has the same meaning as R A1 ⁇ R A6, X A1 and X A2 in general formula (A), the preferred range is also the same.
  • n A 1 represents an integer of 1 or more. However, when n A 1 is 1, in R A1 to R A6 , X A1 and X A2 , at least two adjacent to each other are bonded to form a benzene ring.
  • R Ax has the same meaning as R Ax in general formula (A), and the preferred range is also the same.
  • R A10 represents a substituent, and n A x represents an integer of 0 to 4.
  • m A 1 represents an integer of 3 or more.
  • R Ay represents a hydrogen atom or a substituent. Here, R Ax and R Ay may be combined.
  • n A 1 is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2.
  • m A 1 is preferably an integer of 3 to 10, more preferably an integer of 3 to 8, and particularly preferably an integer of 3 to 5.
  • aromatic hydrocarbon represented by the general formula (A) examples include naphthalene, anthracene, phenanthracene, pyrene, tetracene, tetraphen, chrysene, triphenylene, pentacene, pentaphen, perylene, pyrene, benzo [a] pyrene. , Coronene, anthanthrene, corannulene, obalene, graphene, cycloparaphenylene, polyparaphenylene, or a compound containing a cyclophene structure. However, the present invention is not limited to these.
  • Y B1 and Y B2 each independently represent a hydrogen atom, a methyl group or a formyl group.
  • R B1 , R B2 , R B3 and R B4 each independently represent a substituent, and a B , b B , c B and d B each represent an integer of 0 to 4.
  • the A ring may be a saturated ring, an unsaturated ring having 1 or 2 double bonds, or an aromatic ring, and the B ring and the C ring are unsaturated rings having 1 or 2 double bonds. It may be.
  • substituents adjacent to each other may be bonded to form a ring.
  • the aliphatic hydrocarbon represented by the general formula (B) is a compound having a steroid skeleton.
  • the carbon numbers of the steroid skeleton are as follows.
  • the substituent in R B1 , R B2 , R B3 and R B4 may be any substituent, but an alkyl group, an alkenyl group, a hydroxy group, a formyl group, an acyl group, a carboxy group or a salt thereof, (meth) An acryl group, a (meth) acryloyloxy group, a (meth) acrylamide group, an epoxy group, and an oxetanyl group are preferable, and a ⁇ O group formed by jointly forming two substituents on the same carbon atom is preferable.
  • the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms and may have a substituent.
  • Such a substituent may be any substituent, and examples thereof include an alkyl group, an alkenyl group, a hydroxy group, a formyl group, an acyl group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, and a sulfo group.
  • the alkyl group further preferably contains a double bond or triple bond unsaturated carbon bond inside.
  • the alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms and may have a substituent.
  • Such a substituent may be any substituent, and examples thereof include an alkyl group, an alkenyl group, a hydroxy group, a formyl group, an acyl group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, and a sulfo group.
  • R B1 is preferably substituted with carbon number 3
  • R B2 is preferably substituted with carbon number 6 or 7
  • R B3 is preferably substituted with carbon number 11 or 12
  • R B4 is carbon Substitution with number 17 is preferred.
  • Y B1 and Y B2 are preferably a hydrogen atom or a methyl group.
  • a B , b B , c B , and d B are preferably integers of 0 to 2.
  • the double bond is preferably a bond of carbon numbers 4 and 5
  • the double bond is a bond of carbon numbers 5 and 6 or 6 and 7
  • the double bond is preferably a bond having carbon numbers 8 and 9.
  • the compound represented by the general formula (B) includes all stereoisomers.
  • the bonding direction of the substituent is represented by ⁇ in the downward direction on the paper and ⁇ in the upward direction on the paper, it may be either ⁇ or ⁇ , or a mixture thereof.
  • the arrangement of the A / B ring, the arrangement of the B / C ring, and the arrangement of the C / D ring may be either a trans arrangement or a cis arrangement, or a mixed arrangement thereof. Absent.
  • the sum of a B to d B is 1 or more, and any of R B1 , R B2 , R B3 and R B4 is preferably a hydroxy group or an alkyl group having a substituent.
  • aliphatic hydrocarbon represented by the general formula (B) examples include cholesterol, ergosterol, testosterone, estradiol, aldosterol, aldosterone, hydrocortisone, stigmasterol, timosterol, lanosterol, 7-dehydrodesmosterol, 7 -Of dehydrocholesterol, colanic acid, cholic acid, lithocholic acid, deoxycholic acid, sodium deoxycholate, lithium deoxycholate, hyodeoxycholic acid, chenodeoxycholic acid, ursodeoxycholic acid, dehydrocholic acid, hookecholic acid or hyocholic acid
  • Examples include compounds containing a structure. However, the present invention is not limited to these.
  • the group having 3 or more ring structures is particularly preferably a group having a cholesterol ring structure or a structure in which 3 or more aromatic groups are condensed, and most preferably a deoxycholic acid residue or a pyrenyl group.
  • the compound (B) may be a monomer, an oligomer, or a polymer, and the property at room temperature may be a gas or a liquid. It may be solid.
  • the molecular weight is not particularly limited, but the molecular weight or mass average molecular weight (Mw) is preferably less than 10,000, and more preferably less than 1000.
  • the lower limit is not particularly limited, but is preferably 20 or more.
  • the compound name is ethylene for a double bond and acetylene for a triple bond.
  • the above molecular weight means the molecular weight of the core part.
  • the non-aromatic unsaturated bond may be in the main chain or in the side chain, but is preferably in the side chain. It is preferable that the compound (B) has a structure of any one of a star type, a hyperbranch type, and a dendrimer type in that the crosslinking density of the compound (B2) formed by the metathesis reaction can be increased.
  • the star type is a structure of a multi-branched polymer, and includes a core portion and at least three arm portions coupled to the core portion.
  • the core part is preferably an atomic group having a molecular weight of 200 or more, and more preferably an atomic group having a molecular weight of 300 or more.
  • the upper limit is preferably 5,000 or less, more preferably 4,000 or less, and particularly preferably 3,000 or less.
  • This core is preferably not only tetravalent carbon atoms.
  • the core part is preferably an organic group X in the following general formula (1a) or (2a).
  • the molecular weight of the arm part is preferably 500 or more, and more preferably 1,000 or more.
  • an upper limit it is preferable that it is 1,000,000 or less, and it is more preferable that it is 500,000 or less.
  • a monomer capable of forming an arm part Polymer Handbook 2nd ed. , J .; Brandrup, Wiley lnterscience (1975) Chapter 2 Pages 1-483 can be used.
  • the hyperbranched type and the dendrimer type are also one structure of a multi-branched polymer, and have a branched structure in the arm part.
  • the dendrimer refers to a polymer having a symmetrical and regular branched structure spreading three-dimensionally from the core portion. In dendrimers, a certain chemical bond called a dendron is repeated between branches. It is different from hyperbranched polymers and other polymers in that the branching has a regular and well-defined structure and no molecular weight distribution, that is, a single molecular weight.
  • the hyperbranched polymer has a structure in which a repeating unit corresponding to the arm portion branches and extends from the core portion. Branching of repeating units occurs randomly and has a molecular weight distribution.
  • Compound (B) preferably has a non-aromatic unsaturated bond at the arm part in the star-type, hyperbranch-type and dendrimer-type structures, and more preferably at the end of the arm part.
  • the compound (B) preferably has two or more non-aromatic unsaturated bonds in one molecule, and the compound (B) is more preferably represented by the following general formula (1a) or (2a). .
  • R 11 to R 13 , R 14 , R 21 to R 23 and R 24 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group
  • R 31 and R 34 represent a hydrogen atom or an alkyl group.
  • L 11 , L 21 and L 31 represent a single bond or a divalent linking group.
  • n and m are integers of 1 to 20, and l is an integer of 0 to 20.
  • X represents an n + m + 1 valent organic group.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and specifically, methyl, ethyl or octyl is preferable.
  • the alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and specifically, ethenyl, 2-octenyl, 2,5-heptadienyl, 2,5-octadienyl, or 9-decenyl is preferable.
  • the alkynyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and specifically ethynyl is preferable.
  • the aryl group preferably has 6 to 18 carbon atoms, specifically phenyl.
  • R 11 , R 12 , R 21 and R 22 are preferably all hydrogen atoms
  • the compound represented by the general formula (2a) is represented by R 14 and R Both 24 are preferably hydrogen atoms.
  • R 31 and R 34 For the alkyl group, alkenyl group, alkynyl group and aryl group in R 31 and R 34, preferred descriptions in R 11 to R 13 , R 14 , R 21 to R 23 and R 24 can be applied.
  • R 31 and R 34 also preferably have a functional group selected from the functional group group described above (hereinafter also referred to as a specific functional group).
  • L 11 and L 21 link X to the non-aromatic unsaturated group (for example, —C (R 13 ) ⁇ C (R 11 ) (R 12 )) in the general formulas (1a) and (2a). Any group may be used as long as it does not affect the reaction between the non-aromatic unsaturated group and the metathesis catalyst.
  • L 31 is a group linking R 31 and X in the general formula (1a) and R 34 and X in the general formula (2a), and affects the reaction between the non-aromatic unsaturated group and the metathesis catalyst. Any group may be used as long as it is not given. That is, L 11 , L 21 and L 31 are linking groups having no non-aromatic unsaturated bond.
  • the divalent linking group in L 11 , L 21 and L 31 is an alkylene group (the carbon number is preferably 1-18, more preferably 1-10), an arylene group (the carbon number is preferably 6-18).
  • a heteroarylene group (a 5- or 6-membered heteroarylene group having at least one of an oxygen atom, a sulfur atom and a nitrogen atom as a ring-constituting atom is more preferable.
  • the ring to be ring is preferably a benzene ring or an alicyclic ring, and the number of carbon atoms constituting the heteroarylene group is preferably 2 to 20.
  • the heteroaryl ring in the heteroarylene group includes an aromatic ring and an aliphatic ring.
  • RN represents a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms) or an aryl group (preferably having 6 to 12 carbon atoms).
  • L 11 , L 21 and L 31 are a single bond, an alkylene group, —C ( ⁇ O) —O—, —C ( ⁇ O) -alkylene, —O-alkylene, —C ( ⁇ O) —O-alkylene. Or, —O—C ( ⁇ O) -alkylene is more preferable.
  • L 11 , L 21 and L 31 may be bonded to X on either side.
  • X may be bonded to X with an oxygen atom or may be bonded to X with a carbonyl group.
  • L 11 , L 21 and L 31 also preferably have a specific functional group.
  • n and m are preferably integers of 1 to 10.
  • l is preferably an integer of 1 to 10, more preferably an integer of 2 to 5.
  • n + m is preferably an integer of 2 to 40, more preferably an integer of 3 to 8.
  • X is preferably a 2 to 60 valent organic group, more preferably a 3 to 12 valent organic group.
  • the m + n + 1 valent organic group in X is, for example, a polycyclic organic group represented by any one of the following general formulas (Q-1) to (Q-19), and the following general formulas (Q-20) to (Q-36)
  • Preferred examples thereof include a cyclic siloxane residue and a silsesquioxane residue represented by any one of the following general formulas (P-1) to (P-8).
  • the compound (B) is a sol-gel body of trialkoxysilane having a non-aromatic unsaturated bond with the compound represented by the general formula (1a) or (2a) And a mixture thereof.
  • the content of the compound represented by the general formula (1a) or (2a) in the compound (B) as a mixture is preferably 10 to 99% by mass, and more preferably 50 to 95% by mass.
  • Y in the following general formulas (Q-1) to (Q-36) and (H-1) to (H-3) and R in the following general formulas (P-1) to (P-8) are arbitrary. And represents a binding site with L 11 , L 21 or L 31 .
  • the arbitrary linking group is, for example, a single bond, an alkylene group (the number of carbon atoms is preferably 1-18, more preferably 1-10), —O—, —C ( ⁇ O) —, —C ( ⁇ O ) O—, —C ( ⁇ O) NR—, —S— and —NR— (wherein R represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom), a single bond, an alkylene group, -O-, -S- or -NR- is preferred. It may be bonded to X on either side.
  • a to f represent the number of repetitions, preferably 2 to 20, and more preferably 3 to 10.
  • the compound (B) represented by the general formula (1a) or (2a) can be synthesized by the following method. That is, a compound in which the terminal portion in X which is a mother nucleus of a multi-branched skeleton (star type, hyperbranch type and dendrimer type) is a nucleophilic functional group such as hydroxy group, carboxy group, amino group and mercapto group, Alternatively, for a compound having a leaving group such as a halogen atom (Cl, Br, I), —OTs, and —OMs, a non-aromatic unsaturated bond and a reactive functional group (hydroxy group, carboxy group, amino group) And a compound having a mercapto group or the like).
  • a compound having a leaving group such as a halogen atom (Cl, Br, I), —OTs, and —OMs
  • Ts represents a tosyl group and Ms represents a mesyl group.
  • the compound (B) is obtained by forming an ester bond from the reaction of a hydroxy group and a carboxy group, an amide bond from a reaction of an amino group and a carboxy group, and a thioester bond from a reaction of a mercapto group and a carboxy group.
  • leaving groups such as halogen atoms (Cl, Br, I), -OTs and -OMs, a hydroxyl group, an amino group and a mercapto group are reacted to form an ether bond, an amide bond and a thioether bond, respectively.
  • Compound (B) is obtained.
  • Examples of the compound (B) include those described below, but the present invention is not limited thereto.
  • Y or R in X is described in the column of the bracket structure with n, m, or l to be bonded (for example, the structure of () n ).
  • L 11 and L 21 are bonded to Y or R by the left bond described below (for example, carbonyl bond in b-1).
  • the number of subscripts in () or [] represents mol%. However, the number in parentheses in [] indicates the number of repeating units.
  • Compound (B) may be used alone or in combination of two or more.
  • the content of the compound (B) in the solid electrolyte composition is 0.05% by mass to 30% by mass when the solid content is 100% by mass considering the balance between battery performance, reduction in interface resistance and maintenance effect. It is preferably 0.1% by mass to 20% by mass, more preferably 1% by mass to 10% by mass.
  • the mass ratio of the total mass (total amount) of the inorganic solid electrolyte and, if necessary, the electrode active material to be included relative to the mass of the compound (B) [(mass of inorganic solid electrolyte + mass of electrode active material) / compound (B ))] is preferably in the range of 1,000 to 1. This ratio is more preferably 500 to 2, and further preferably 100 to 10.
  • Metal catalyst (C) As the metathesis catalyst, atoms of Group 5, Group 6, and Group 8 (long period periodic table, the same applies hereinafter) are used as transition metal atoms.
  • the atoms of each group are not particularly limited, but the preferred Group 5 atom is tantalum, the preferred Group 6 atom is molybdenum and tungsten, and the preferred Group 8 atom is ruthenium and osmium.
  • the metathesis catalyst is preferably a ruthenium catalyst (that is, a ruthenium-containing catalyst).
  • a Schrock-type polymerization catalyst Japanese Patent Laid-Open No. 7-179575, Schrock, which is a general metathesis polymerization catalyst consisting essentially of (a) a transition metal compound catalyst component and (b) a metal compound promoter component. et al., J. Am. Chem. Soc., 1990, 112, 3875 et al.) and Grubbs type polymerization catalyst (Fu et al., J. Am. Chem. Soc., 1993, 115). Nguyen et al., J. Am. Chem. Soc., 1992, 114, 3974-;
  • the metathesis catalyst (C) used in the present invention is preferably a Grubbs type polymerization catalyst, and more preferably a ruthenium carbene complex.
  • the following catalysts can be preferably used, and products described in the catalog made by Aldrich, the catalog made by Wako Pure Chemical Industries, etc. are available. Typical examples include the following catalysts.
  • the metathesis catalyst (C) is more preferably a catalyst in which an oxygen atom or a nitrogen atom is coordinated or bonded to a ruthenium atom.
  • the content of the metathesis catalyst (C) in the solid electrolyte composition is 0.001% by mass to 5% by mass when the solid content is 100% by mass in consideration of both battery performance, reduction in interface resistance and maintenance effect. %, More preferably 0.01% by mass to 2% by mass, and still more preferably 0.1% by mass to 1% by mass.
  • the solid electrolyte composition of the present invention may not contain a dispersion medium.
  • a substituent that does not specify substitution or non-substitution means that the group may have an appropriate substituent. This is also the same for compounds that do not specify substitution or non-substitution.
  • Preferred substituents include the following substituent Z. Examples of the substituent Z include the following.
  • alkyl group preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • alkenyl A group 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 group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc., but in this specification,
  • a 5- or 6-membered heterocyclic group having at least one selected from an atom, a sulfur atom and a nitrogen atom is preferred, and examples thereof include tetrahydropyranyl, tetrahydrofuranyl, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2 -Benzimidazolyl, 2-thiazolyl, 2-oxazolyl, pyrrolidone group, etc.), alcohol Si group (preferably an alkoxy group having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropyloxy, benzyloxy and the like), an aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy and the like, but the term “alkoxy group” in this specification usually includes an aryloyl group), an alkoxycarbonyl group (preferably an alkoxy having 2 to 20 carbon
  • an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy), an aryloyloxy group (preferably an aryloyloxy group having 7 to 23 carbon atoms, such as benzoyloxy, etc., provided that In this specification, an acyloxy group usually means an aryloyloxy group), a carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.
  • An acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, benzoylamino, etc.), an alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, such as methylthio, ethylthio, isopropylthio) , Benzylthio, etc.), Ally A thio group (preferably an arylthio group having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), an alkylsulfonyl group (preferably having 1 to 20 carbon atoms) Alkylsulfonyl groups such as methylsulfonyl and ethylsulfonyl), arylsulfonyl groups (preferably arylsulfonyl groups having 6 to 22 carbon
  • each of the groups listed as the substituent Z may be further substituted by the above-described substituent Z.
  • a compound or a substituent / linking group includes an alkyl group / alkylene group, an alkenyl group / alkenylene group, an alkynyl group / alkynylene group, etc., these may be cyclic or linear, and may be linear or branched These may be substituted as described above or may be unsubstituted.
  • the solid electrolyte composition for an all-solid secondary battery of the present invention preferably contains a binder.
  • the binder used in the present invention is not particularly limited as long as it is an organic polymer.
  • the binder that can be used in the present invention is preferably a binder that is usually used as a binder for a positive electrode or a negative electrode of a battery material, and is not particularly limited.
  • a binder made of a resin described below is preferable.
  • fluorine-containing resin examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), a copolymer of polyvinylidene fluoride and hexafluoropropylene (PVdF-HFP), and the like.
  • hydrocarbon-based thermoplastic resin examples include polyethylene, polypropylene, styrene butadiene rubber (SBR), hydrogenated styrene butadiene rubber (HSBR), butylene rubber, acrylonitrile butadiene rubber, polybutadiene, and polyisoprene.
  • acrylic resin examples include poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate isopropyl, poly (meth) acrylate isobutyl, poly (meth) butyl acrylate, poly (meth) ) Hexyl acrylate, poly (meth) acrylate octyl, poly (meth) acrylate dodecyl, poly (meth) acrylate stearyl, poly (meth) acrylate 2-hydroxyethyl, poly (meth) acrylic acid, poly (meth) ) Benzyl acrylate, poly (meth) acrylate glycidyl, poly (meth) acrylate dimethylaminopropyl, and copolymers of monomers constituting these resins.
  • copolymers with other vinyl monomers are also preferably used.
  • examples thereof include poly (meth) acrylate methyl-polystyrene copolymer, poly (meth) acrylate methyl-acrylonitrile copolymer, poly (meth) acrylate butyl-acrylonitrile-styrene copolymer, and the like.
  • a polycondensation polymer can also be used.
  • the polycondensation polymer for example, urethane resin, urea resin, amide resin, imide resin, polyester resin, and the like can be suitably used.
  • the polycondensation polymer preferably has a hard segment part and a soft segment part.
  • the hard segment site indicates a site capable of forming an intermolecular hydrogen bond
  • the soft segment site generally indicates a flexible site having a glass transition temperature (Tg) of room temperature (25 ⁇ 5 ° C.) or lower and a molecular weight of 400 or higher. These may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the upper limit of the glass transition temperature of the binder is preferably 50 ° C. or lower, more preferably 0 ° C. or lower, and most preferably ⁇ 20 ° C. or lower.
  • the lower limit is preferably ⁇ 100 ° C. or higher, more preferably ⁇ 70 ° C. or higher, and particularly preferably ⁇ 50 ° C. or higher.
  • the glass transition temperature (Tg) is measured under the following conditions using a dry sample and a differential scanning calorimeter “X-DSC7000” (trade name, manufactured by SII Nanotechnology Co., Ltd.). The measurement is performed twice on the same sample, and the second measurement result is adopted.
  • Measurement chamber atmosphere Nitrogen (50 mL / min) Temperature increase rate: 5 ° C / min Measurement start temperature: -100 ° C Measurement end temperature: 200 ° C
  • Sample pan Aluminum pan Mass of measurement sample: 5 mg Calculation of Tg: Tg is calculated by rounding off the decimal point of the intermediate temperature between the lowering start point and the lowering end point of the DSC chart.
  • the water concentration of the polymer constituting the binder used in the present invention is preferably 100 ppm (mass basis) or less, and Tg is preferably 100 ° C. or less.
  • the solvent used for the polymerization reaction of the polymer is not particularly limited. It is desirable to use a solvent that does not react with the inorganic solid electrolyte and the active material and that does not decompose them.
  • a solvent that does not react with the inorganic solid electrolyte and the active material and that does not decompose them.
  • hydrocarbon solvents toluene, heptane, xylene
  • ester solvents ethyl acetate, propylene glycol monomethyl ether acetate
  • ether solvents tetrahydrofuran, dioxane, 1,2-diethoxyethane
  • ketone solvents acetone
  • Methyl ethyl ketone Methyl ethyl ketone, cyclohexanone
  • nitrile solvents acetonitrile, propionitrile, butyronitrile, isobutyronitrile
  • halogen solvents dichloromethane
  • the polymer constituting the binder used in the present invention preferably has a mass average molecular weight of 10,000 or more, more preferably 20,000 or more, and even more preferably 50,000 or more. As an upper limit, 1,000,000 or less is preferable, 200,000 or less is more preferable, and 100,000 or less is more preferable. In the present invention, the molecular weight of the polymer means a mass average molecular weight unless otherwise specified.
  • the content of the binder in the solid electrolyte composition for an all-solid-state secondary battery is 100% by mass of the solid component in consideration of a good interfacial resistance reduction property and its maintainability when used in an all-solid-state secondary battery. 0.01% by mass or more is preferable, 0.1% by mass or more is more preferable, and 1% by mass or more is more preferable. As an upper limit, from a viewpoint of a battery characteristic, 20 mass% or less is preferable, 10 mass% or less is more preferable, and 10 mass% or less is further more preferable.
  • the mass ratio [(mass of inorganic solid electrolyte + mass of electrode active material) / mass of binder] of the total mass (total amount) of the inorganic solid electrolyte and the electrode active material to be included if necessary with respect to the mass of the binder is: A range of 1,000 to 1 is preferred. This ratio is more preferably 500 to 2, and further preferably 100 to 10.
  • the binder used in the present invention is a polymer particle that retains the particle shape.
  • PMMA poly (meth) methyl acrylate
  • PMMA-PMA poly (methyl methacrylate-methacrylic acid) copolymer
  • PMMA-PHM poly (methyl methacrylate-ethyl methacrylate phosphate) copolymer
  • -PHM poly (meth) methyl acrylate
  • the “polymer particles” refer to particles that do not completely dissolve even when added to the dispersion medium described later, and are dispersed in the dispersion medium in the form of particles and exhibit an average particle diameter of more than 0.01 ⁇ m.
  • the shape of the polymer particles is not limited as long as they are solid.
  • the polymer particles may be monodispersed or polydispersed.
  • the polymer particles may be spherical or flat and may be amorphous.
  • the surface of the polymer particles may be smooth or may have an uneven shape.
  • the polymer particles may have a core-shell structure, and the core (inner core) and the shell (outer shell) may be made of the same material or different materials. Moreover, it may be hollow and the hollow ratio is not limited.
  • the polymer particles can be synthesized by a method of polymerizing in the presence of a surfactant, an emulsifier or a dispersant, or a method of depositing in a crystalline form as the molecular weight increases. Moreover, you may use the method of crushing the existing polymer mechanically, or the method of making a polymer liquid fine particle by reprecipitation.
  • the average particle diameter of the polymer particles is preferably 0.01 ⁇ m to 100 ⁇ m, more preferably 0.05 ⁇ m to 50 ⁇ m, further preferably 0.1 ⁇ m to 20 ⁇ m, and particularly preferably 0.2 ⁇ m to 10 ⁇ m.
  • the average particle diameter of the polymer particles used in the present invention is based on the measurement conditions and definitions described below.
  • the polymer particles are diluted and prepared in a 20 ml sample bottle using an arbitrary solvent (dispersion medium used for preparation of the solid electrolyte composition for an all-solid-state secondary battery, for example, heptane).
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes and used immediately after that.
  • the measurement from the produced all-solid-state secondary battery is performed, for example, after disassembling the battery and peeling off the electrode, then measuring the electrode material according to the method for measuring the average particle diameter of the polymer particles, This can be done by eliminating the measured value of the average particle diameter of the particles other than the polymer particles that have been measured.
  • a commercial item can be used for the binder used for this invention. Moreover, it can also prepare by a conventional method.
  • the solid electrolyte composition of the present invention preferably contains a dispersion medium.
  • the dispersion medium only needs to disperse each of the above components, and examples thereof include various organic solvents, and those that dissolve the metathesis catalyst (C) are preferable. Specific examples of the dispersion medium include the following.
  • Examples of the alcohol compound solvent include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, Examples include 2-methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-butanediol.
  • ether compound solvents examples include alkylene glycol alkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene.
  • alkylene glycol alkyl ethers ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, 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.), alkyl aryl ethers (anisole, etc.) , Cyclic ethers (tetrahydrofuran, dioxane (1,2, including 1,3- and 1,4-isomers of), etc.).
  • Examples of the amide compound solvent include N, N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ⁇ -caprolactam, formamide, N -Methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.
  • Examples of the amino compound solvent include triethylamine, diisopropylethylamine, tributylamine and the like.
  • Examples of the ketone compound solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • Examples of the aromatic compound solvent include benzene, toluene, xylene, mesitylene and the like.
  • Examples of the aliphatic compound solvent include hexane, heptane, octane, decane, and the like.
  • Examples of the nitrile compound solvent include acetonitrile, propyronitrile, isobutyronitrile, and the like.
  • ester compound solvent examples include ethyl acetate, butyl acetate, propyl acetate, butyl butyrate, and butyl pentanoate.
  • non-aqueous dispersion medium examples include the above aromatic compound solvents and aliphatic compound solvents.
  • amino compound solvents, ether compound solvents, ketone compound solvents, aromatic compound solvents, and aliphatic compound solvents are preferable, and ether compound solvents, aromatic compound solvents, and aliphatic compound solvents are more preferable.
  • the functional group active for the sulfide-based inorganic solid electrolyte is not included, so that the sulfide-based inorganic solid electrolyte can be handled stably, which is preferable.
  • a combination of a sulfide-based inorganic solid electrolyte and an aliphatic compound solvent is preferable.
  • the dispersion medium preferably has a boiling point of 50 ° C. or higher, more preferably 70 ° C. or higher, at normal pressure (1 atm).
  • the upper limit is preferably 250 ° C. or lower, and more preferably 220 ° C. or lower.
  • the said dispersion medium may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the content of the dispersion medium in the solid electrolyte composition can be appropriately set in consideration of the balance between the viscosity of the solid electrolyte composition and the drying load. Generally, it is preferably 20 to 99% by mass, more preferably 25 to 70% by mass, and particularly preferably 30 to 60% by mass in the solid electrolyte composition.
  • the solid electrolyte composition of the present invention may contain an active material capable of inserting and releasing ions of metal elements belonging to Group 1 or Group 2 of the Periodic Table.
  • the active material includes a positive electrode active material and a negative electrode active material, and a transition metal oxide that is a positive electrode active material or a metal oxide that is a negative electrode active material is preferable.
  • a solid electrolyte composition containing an active material positive electrode active material, negative electrode active material
  • an electrode layer composition positive electrode layer composition, negative electrode layer composition.
  • the positive electrode active material that may be contained in the solid electrolyte composition of the present invention is preferably one that can reversibly insert and release lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, and may be a transition metal oxide or an element that can be complexed with Li such as sulfur.
  • the positive electrode active material it is preferable to use a transition metal oxide, and a transition metal oxide having a transition metal element M a (one or more elements selected from Co, Ni, Fe, Mn, Cu, and V). More preferred.
  • this transition metal oxide includes an element M b (an element of the first (Ia) group of the metal periodic table other than lithium, an element of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Elements such as Sb, Bi, Si, P, and B) may be mixed.
  • the mixing amount is preferably 0 ⁇ 30 mol% relative to the amount of the transition metal element M a (100mol%). Those synthesized by mixing so that the molar ratio of Li / Ma is 0.3 to 2.2 are more preferable.
  • transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt structure, (MB) a transition metal oxide having a spinel structure, (MC) a lithium-containing transition metal phosphate compound, (MD And lithium-containing transition metal halide phosphate compounds, (ME) lithium-containing transition metal silicate compounds, and the like.
  • transition metal oxide having a layered rock salt structure LiCoO 2 (lithium cobaltate [LCO]), LiNi 2 O 2 (lithium nickelate) LiNi 0.85 Co 0.10 Al 0.05 O 2 (nickel cobalt lithium aluminum oxide [NCA]), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (nickel manganese lithium cobalt oxide [NMC]), LiNi 0.5 Mn 0.5 O 2 (manganese) Lithium nickelate).
  • transition metal oxide having an (MB) spinel structure include LiCoMnO 4, Li 2 FeMn 3 O 8 , Li 2 CuMn 3 O 8 , Li 2 CrMn 3 O 8, and Li 2 NiMn 3 O 8. .
  • Examples of (MC) lithium-containing transition metal phosphate compounds include olivine-type iron phosphate salts such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , LiCoPO 4 and the like. And monoclinic Nasicon type vanadium phosphate salts such as Li 3 V 2 (PO 4 ) 3 (vanadium lithium phosphate).
  • the (MD) lithium-containing transition metal halogenated phosphate compound for example, Li 2 FePO 4 F such fluorinated phosphorus iron salt, Li 2 MnPO 4 hexafluorophosphate manganese salts such as F, Li 2 CoPO 4 F Cobalt fluorophosphates such as
  • Examples of the (ME) lithium-containing transition metal silicate compound include Li 2 FeSiO 4 , Li 2 MnSiO 4 , Li 2 CoSiO 4, and the like.
  • a transition metal oxide having a (MA) layered rock salt structure is preferable, and LCO or NMC is more preferable.
  • the shape of the positive electrode active material is not particularly limited, but is preferably particulate.
  • the volume average particle diameter (sphere conversion average particle diameter) of the positive electrode active material is not particularly limited.
  • the thickness can be 0.1 to 50 ⁇ m.
  • an ordinary pulverizer and / or classifier may be used.
  • the positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
  • the volume average particle diameter (sphere-converted average particle diameter) of the positive electrode active material particles can be measured using a laser diffraction / scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA).
  • the positive electrode active materials may be used alone or in combination of two or more.
  • the mass (mg) (weight per unit area) of the positive electrode active material per unit area (cm 2 ) of the positive electrode active material layer is not particularly limited. This can be determined as appropriate according to the designed battery capacity.
  • the content of the positive electrode active material in the solid electrolyte composition is not particularly limited, and is preferably 10 to 95% by mass, more preferably 30 to 90% by mass, and even more preferably 50 to 85% by mass at 100% by mass. 70 to 80% by mass is preferable.
  • the negative electrode active material that may be contained in the solid electrolyte composition of the present invention is preferably one that can reversibly insert and release lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, and is a carbonaceous material, a metal oxide such as tin oxide and silicon oxide, a metal composite oxide, a lithium simple substance and a lithium alloy such as a lithium aluminum alloy, and Sn. And metals that can form an alloy with lithium, such as Si and In.
  • a carbonaceous material or a lithium composite oxide is preferably used from the viewpoint of reliability.
  • the metal composite oxide is preferably capable of inserting and extracting lithium.
  • the material is not particularly limited, but preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
  • the carbonaceous material used as the negative electrode active material is a material substantially made of carbon.
  • various synthetic resins such as petroleum pitch, carbon black such as acetylene black (AB), graphite (artificial graphite such as natural graphite and vapor-grown graphite), PAN (polyacrylonitrile) resin and furfuryl alcohol resin
  • carbonaceous material which baked can be mentioned.
  • various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA (polyvinyl alcohol) -based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber, etc.
  • Other examples include mesophase microspheres, graphite whiskers, and flat graphite.
  • an amorphous oxide is particularly preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used. It is done.
  • amorphous as used herein means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering band having a peak in the region of 20 ° to 40 ° in terms of 2 ⁇ , and is a crystalline diffraction line. You may have.
  • the strongest intensity of crystalline diffraction lines seen from 2 ° to 40 ° to 70 ° is 100 times the diffraction line intensity at the peak of the broad scattering band seen from 2 ° to 20 °. It is preferable that it is 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.
  • the amorphous oxide of the metalloid element and the chalcogenide are more preferable, and elements of Groups 13 (IIIB) to 15 (VB) of the periodic table, Al , Ga, Si, Sn, Ge, Pb, Sb, Bi alone or in combination of two or more thereof, and chalcogenide are particularly preferable.
  • preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , SiO, GeO, SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 8 Bi 2 O 3 , Sb 2 O 8 Si 2 O 3 , Bi 2 O 4 , SnSiO 3 , GeS, SnS, SnS 2 , PbS, PbS 2 , Sb 2 S 3 , Sb 2 S 5 and SnSiS 3 are preferred. Moreover, these may be a complex oxide with lithium oxide, for example, Li 2 SnO 2 .
  • the negative electrode active material contains a titanium atom. More specifically, Li 4 Ti 5 O 12 (lithium titanate [LTO]) is excellent in rapid charge / discharge characteristics due to small volume fluctuations during occlusion and release of lithium ions, and the deterioration of the electrode is suppressed, and the lithium ion secondary This is preferable in that the battery life can be improved.
  • Li 4 Ti 5 O 12 lithium titanate [LTO]
  • hard carbon or graphite is preferably used, and graphite is more preferably used.
  • the carbonaceous materials may be used singly or in combination of two or more.
  • the shape of the negative electrode active material is not particularly limited, but is preferably particulate.
  • the average particle size of the negative electrode active material is preferably 0.1 to 60 ⁇ m.
  • a normal pulverizer and / or classifier is used.
  • a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill, and a sieve are preferably used.
  • pulverizing wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary.
  • classification is preferably performed.
  • the classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be used both dry and wet.
  • the average particle diameter of the negative electrode active material particles can be measured by the same method as the above-described method for measuring the volume average particle diameter of the positive electrode active material.
  • the chemical formula of the compound obtained by the above firing method can be calculated from an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method, and from a mass difference between powders before and after firing as a simple method.
  • ICP inductively coupled plasma
  • Examples of the negative electrode active material that can be used in combination with the amorphous oxide negative electrode active material centering on Sn, Si, or Ge include carbon materials that can occlude and release lithium ions or lithium metal, lithium, lithium alloys, and lithium. An alloyable metal is preferable.
  • a Si-based negative electrode it is also preferable to apply a Si-based negative electrode.
  • a Si negative electrode can occlude more Li ions than a carbon negative electrode (graphite, acetylene black, etc.). That is, the amount of Li ion occlusion per unit weight increases. Therefore, the battery capacity can be increased. As a result, there is an advantage that the battery driving time can be extended.
  • the said negative electrode active material may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the mass (mg) (weight per unit area) of the negative electrode active material per unit area (cm 2 ) of the negative electrode active material layer is not particularly limited. This can be determined as appropriate according to the designed battery capacity.
  • the content of the negative electrode active material in the solid electrolyte composition is not particularly limited, and is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, and more preferably 30 to 80% at a solid content of 100% by mass. More preferably, it is 40% by weight, and still more preferably 40-75% by weight.
  • the solid electrolyte composition of the present invention may appropriately contain a conductive aid used for improving the electronic conductivity of the active material, as necessary.
  • a conductive aid used for improving the electronic conductivity of the active material
  • a general conductive auxiliary agent can be used.
  • graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black, and furnace black, amorphous carbon such as needle coke, vapor grown carbon fiber, and carbon nanotube, which are electron conductive materials
  • Carbon fibers such as graphene, carbonaceous materials such as graphene and fullerene, metal powders such as copper and nickel, metal fibers may be used, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives May be used.
  • 1 type of these may be used and 2 or more types may be used.
  • the solid electrolyte composition of the present invention preferably contains a lithium salt (supporting electrolyte).
  • the lithium salt is preferably a lithium salt that is usually used in this type of product, and is not particularly limited. This lithium salt is not included in the binder particles (the polymer forming the binder particles) (for example, it is present alone in the solid electrolyte layer composition), and the lithium salt is included in the binder particles. Is different.
  • the content of the lithium salt is preferably 0 part by mass or more and more preferably 5 parts by mass or more with respect to 100 parts by mass of the solid electrolyte. As an upper limit, 50 mass parts or less are preferable, and 20 mass parts or less are more preferable.
  • the solid electrolyte composition of the present invention may contain a dispersant.
  • a dispersant By adding a dispersant, even when the concentration of either the electrode active material or the inorganic solid electrolyte is high, the aggregation can be suppressed, and a uniform active material layer and solid electrolyte layer can be formed.
  • the dispersant those usually used for all-solid secondary batteries can be appropriately selected and used. For example, it consists of a low molecule or oligomer having a molecular weight of 200 or more and less than 3000, and contains the functional group represented by the functional group (I) and an alkyl group having 8 or more carbon atoms or an aryl group having 10 or more carbon atoms in the same molecule. Those are preferred.
  • the content of the dispersant in the layer is preferably 0.2 to 10% by mass.
  • the solid electrolyte composition of the present invention is obtained by mixing or adding the inorganic solid electrolyte (A), the compound (B) and the metathesis catalyst (C), and other components such as an active material and a dispersion medium, if necessary.
  • it can manufacture by mixing the said component using various mixers.
  • the mixing conditions are not particularly limited, and examples thereof include a ball mill, a bead mill, a planetary mixer, a blade mixer, a roll mill, a kneader, and a disk mill.
  • the timing of adding the metathesis catalyst may be before mixing (for example, ball mill) or at the time of slurry preparation after mixing (for example, ball mill).
  • the compound (B) having a non-aromatic carbon-carbon unsaturated bond is polymerized by a metathesis reaction proceeding in the presence of the metathesis catalyst (C).
  • the cross-metathesis reaction proceeds, so that between the non-aromatic unsaturated bonds of the compound (B) A new non-aromatic unsaturated bond is formed.
  • the solid electrolyte composition of the present invention is presumed to cure when the cross-metathesis reaction (crosslinking) proceeds to form a network polymer and gel, and the cross-metathesis reaction (crosslinking) is completed. .
  • Z 1 represents the following general formula (3-1)
  • Z 2 represents the following general formula (3-2).
  • R 3 represents a hydrogen atom, an alkyl group or an aryl group.
  • L 3 represents a single bond or a divalent linking group.
  • n and m are integers of 1 to 20, and l is an integer of 0 to 20.
  • X represents an n + m + 1 valent organic group.
  • R 1 and R 2 represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.
  • L 1 and L 2 represent a single bond or a divalent linking group. * Indicates a binding site with X.
  • the alkyl group, alkenyl group and aryl group in R 1 and R 2 in the general formula (3) and the alkyl group and aryl group in R 3 are the alkyl groups in R 13 and R 23 in the general formula (1a).
  • L 1 , L 2 and L 3 , n, m and l and X are L 11 , L 21 and L 31 in the above general formula (1a), n, m and It is synonymous with l and X.
  • the metathesis reaction may occur in any of a grinding process using a ball mill when preparing the composition, a heating process different from the composition preparation, and a process of heating the sheet coated with the composition.
  • the reaction is preferably completed in the state of the solid electrolyte-containing sheet prepared by coating.
  • the reaction conditions of the compound (B) using the metathesis catalyst (C) a conventional method in the metathesis reaction is used.
  • the reaction temperature is preferably 50 ° C. to 180 ° C.
  • the reaction time is preferably from 0.1 to 2 hours, more preferably from 0.5 to 1 hour.
  • the unsaturated bond ratio of the compound (B2) calculated by the following formula (5) preferably satisfies the following formula (6).
  • the number of non-aromatic carbon-carbon unsaturated bonds in compound (B2) is 1 for double bonds and 2 for triple bonds, and the unsaturated bond ratio is calculated by the following formula (5).
  • Unsaturated bond ratio (total number of non-aromatic carbon-carbon unsaturated bonds in compound (B2)) / (total number of all carbon-carbon bonds in compound (B2)) ⁇ 100 formula ( 5) 1% ⁇ Unsaturated bond ratio ⁇ 90% Formula (6)
  • the unsaturated bond ratio of the compound (B2) is more preferably 2% ⁇ unsaturated bond ⁇ 50%, and more preferably 3% ⁇ unsaturated bond ⁇ 20%.
  • the structural unit represented by the general formula (3) in the compound (B2) include the following structural units, but the present invention is not construed as being limited thereto.
  • the part marked with “**” corresponds to the terminal site in the structural unit represented by the general formula (3-1) or (3-2).
  • the number of subscripts in () or [] represents mol%. However, the number in () in [] indicates the number of repeating units.
  • the solid electrolyte-containing sheet of the present invention includes an inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table, and the general formula ( 3) the compound (B2) having a structural unit having a non-aromatic carbon-carbon unsaturated bond and a metathesis catalyst (C) residue of Ru, Mo and / or W metal of 10 ppm or more ( Preferably, it is 10,000 ppm or less.
  • Examples of the method for detecting the amount of catalyst before metathesis crosslinking and the amount of catalyst residue after metathesis crosslinking include a method of determining from the amount of elements contained in Ru, Mo and W metals.
  • the amount of elements contained in the Ru, Mo, W metal is, for example, X-ray photoelectron spectroscopy, Auger electron spectroscopy, ICP (Inductively Coupled Plasma) -mass spectrometry, ICP-luminescence analysis, atomic absorption analysis, X-ray fluorescence It can be measured by analytical methods, neutron activation analysis methods, and the like.
  • the metathesis catalyst (C) residue means a compound or partial structure containing a metal element derived from the metathesis catalyst (C).
  • the metathesis catalyst (C) residue may be present in any structure as long as it contains a metal element (Ru, Mo and / or W metal).
  • the metathesis catalyst (C) residue may be incorporated into the compound (B2). It is assumed that it exists as a carbene metal complex.
  • Compound (B2) may be contained alone or in combination of two or more.
  • the content of the compound (B2) in the solid electrolyte-containing sheet is 0.05% by mass to 30% by mass in terms of 100% by mass of the total solid components, considering both battery performance, reduction in interface resistance, and maintenance effect. %, More preferably 0.1% by mass to 20% by mass, and even more preferably 1% by mass to 10% by mass.
  • the solid electrolyte-containing sheet of the present invention can be suitably used for an all-solid-state secondary battery, and includes various modes depending on the application.
  • a sheet preferably used for a solid electrolyte layer also referred to as a solid electrolyte sheet for an all-solid secondary battery
  • a sheet preferably used for an electrode or a laminate of an electrode and a solid electrolyte layer an electrode sheet for an all-solid secondary battery Etc.
  • these various sheets may be collectively referred to as an all-solid secondary battery sheet.
  • the all-solid-state secondary battery sheet is a sheet having a solid electrolyte layer or an active material layer (electrode layer) on a base material.
  • the all-solid-state secondary battery sheet may have other layers as long as it has a substrate and a solid electrolyte layer or an active material layer. It classifies into a secondary battery electrode sheet. Examples of the other layer include a protective layer, a current collector, a coat layer (current collector, solid electrolyte layer, active material) and the like.
  • a solid electrolyte sheet for an all-solid secondary battery for example, a solid electrolyte layer and, if necessary, a protective layer in this order on a substrate for forming the solid electrolyte layer of the all-solid secondary battery of the present invention.
  • seat which has is mentioned.
  • the substrate is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include the materials described in the above current collector, sheet materials (plate bodies) such as organic materials and inorganic materials.
  • sheet materials such as organic materials and inorganic materials.
  • the organic material include various polymers, and specific examples include polyethylene terephthalate, polypropylene, polyethylene, and cellulose.
  • the inorganic material include glass and ceramic.
  • the configuration and layer thickness of the solid electrolyte layer of the all-solid-state secondary battery sheet are the same as the configuration and layer thickness of the solid electrolyte layer described later in the all-solid-state secondary battery of the present invention.
  • This sheet is obtained by forming (coating and drying) the solid electrolyte composition of the present invention on a base material (which may be via another layer) to form a solid electrolyte layer on the base material. It is done.
  • the solid electrolyte composition of the present invention can be prepared by the above-described method.
  • the electrode sheet for an all-solid secondary battery of the present invention is a metal as a current collector for forming the active material layer of the all-solid-state secondary battery of the present invention.
  • This electrode sheet is usually a sheet having a current collector and an active material layer, but an embodiment having a current collector, an active material layer, and a solid electrolyte layer in this order, and a current collector, an active material layer, and a solid electrolyte The aspect which has a layer and an active material layer in this order is also included.
  • the configuration and the layer thickness of each layer constituting the electrode sheet are the same as the configuration and the layer thickness of each layer described later in the all-solid secondary battery of the present invention.
  • the electrode sheet is obtained by forming (coating and drying) the solid electrolyte composition containing the active material of the present invention on a metal foil to form an active material layer on the metal foil.
  • the method for preparing the solid electrolyte composition containing the active material is the same as the method for preparing the solid electrolyte composition except that the active material is used.
  • the active material layer and / or the solid electrolyte layer formed with the solid electrolyte composition of the present invention is preferably a component (B) that is replaced with the compound (B2) with respect to the component species and the content ratio thereof. This is the same as that in the solid content of the solid electrolyte composition.
  • the all solid state secondary battery of the present invention has a positive electrode, a negative electrode facing the positive electrode, and a solid electrolyte layer between the positive electrode and the negative electrode.
  • the positive electrode has a positive electrode active material layer on a positive electrode current collector.
  • the negative electrode has a negative electrode active material layer on a negative electrode current collector.
  • At least one of the negative electrode active material layer, the positive electrode active material layer, and the solid electrolyte layer is preferably formed of the solid electrolyte composition of the present invention. Among them, all the layers are formed of the solid electrolyte composition of the present invention. More preferably.
  • the active material layer or the solid electrolyte layer formed of the solid electrolyte composition is preferably the same as that in the sheet for the all-solid secondary battery with respect to the component types to be contained and the content ratio thereof.
  • preferred embodiments of the present invention will be described, but the present invention is not limited thereto.
  • FIG. 1 is a cross-sectional view schematically showing an all solid state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention.
  • the all-solid-state secondary battery 10 according to 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 stacked in this order as viewed from the negative electrode side.
  • the adjacent layers are in direct contact with each other.
  • lithium ions (Li + ) accumulated in the negative electrode are returned to the positive electrode side, and electrons can be supplied to the working part 6.
  • a light bulb is adopted as a model for the operation site 6 and is lit by discharge.
  • any of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is formed of the solid electrolyte composition of the present invention. That is, when the solid electrolyte layer 3 is formed of the solid electrolyte composition of the present invention, the solid electrolyte layer 3 includes an inorganic solid electrolyte, a compound (B2), and a metathesis catalyst residue.
  • the solid electrolyte layer usually does not contain a positive electrode active material and / or a negative electrode active material.
  • the compound (B2) is present between solid particles such as an inorganic solid electrolyte and an active material contained in an adjacent active material layer, thereby reducing the interfacial resistance between the solid particles.
  • the binding property is high.
  • the positive electrode active material layer 4 and / or the negative electrode active material layer 2 are formed of the solid electrolyte composition of the present invention, the positive electrode active material layer 4 and the negative electrode active material layer 2 are respectively a positive electrode active material or a negative electrode active material.
  • an inorganic solid electrolyte, a compound (B2), and a metathesis catalyst residue When the active material layer contains an inorganic solid electrolyte, the ionic conductivity can be improved.
  • the compound (B2) is present between solid particles and the like, whereby the interfacial resistance is reduced and the binding property is increased.
  • the inorganic solid electrolyte contained in the positive electrode active material layer 4, the solid electrolyte layer 3 and the negative electrode active material layer 2, the compound (B2) which may be contained, and the metathesis catalyst residue may be the same or different from each other. May be.
  • either or both of the positive electrode active material layer and the negative electrode active material layer may be simply referred to as an active material layer or an electrode active material layer.
  • One or both of the positive electrode active material and the negative electrode active material may be simply referred to as an active material or an electrode active material.
  • a solid electrolyte composition containing the compound (B), a metathesis catalyst, and solid particles such as an inorganic solid electrolyte and an active material Each of the layers can improve the binding property between the solid particles, and as a result, good cycle characteristics in the all-solid secondary battery can also be realized.
  • the above compound (B) and a metathesis catalyst are heat-cured (metathesis reaction) in a state where solid particles such as an inorganic solid electrolyte are dispersed, whereby a three-dimensionally crosslinked polymer (B) (B2) is formed.
  • the thicknesses of the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 are not particularly limited. Considering general battery dimensions, the thickness of each of the above layers is preferably 10 to 1,000 ⁇ m, more preferably 20 ⁇ m or more and less than 500 ⁇ m. In the all solid state secondary battery of the present invention, it is more preferable that the thickness of at least one of the positive electrode active material layer 4, the solid electrolyte layer 3 and the negative electrode active material layer 2 is 50 ⁇ m or more and less than 500 ⁇ m.
  • the positive electrode current collector 5 and the negative electrode current collector 1 are preferably electronic conductors. In the present invention, either or both of the positive electrode current collector and the negative electrode current collector may be simply referred to as a current collector.
  • Materials for forming the positive electrode current collector include aluminum, aluminum alloy, stainless steel (SUS), nickel, titanium, etc., as well as the surface of aluminum or stainless steel treated with carbon, nickel, titanium, or silver ( Those having a thin film formed thereon are preferred, and among these, aluminum and aluminum alloys are more preferred.
  • the negative electrode current collector in addition to aluminum, copper, copper alloy, stainless steel (SUS), nickel, titanium, etc., the surface of aluminum, copper, copper alloy, stainless steel, carbon, nickel, titanium or What processed silver is preferable and aluminum, copper, a copper alloy, and stainless steel are more preferable.
  • the current collector is usually in the form of a film sheet, but a net, a punched one, a lath, a porous body, a foam, a fiber group molded body, or the like can also be used.
  • the thickness of the current collector is not particularly limited, but is preferably 1 to 500 ⁇ m.
  • the current collector surface is roughened by surface treatment.
  • a functional layer, a member, or the like is appropriately interposed or disposed between or outside each of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector. May be.
  • Each layer may be composed of a single layer or a plurality of layers.
  • the basic structure of the all-solid-state secondary battery can be manufactured by arranging each of the above layers. Depending on the application, it may be used as an all-solid secondary battery as it is, but in order to form a dry battery, it is further enclosed in a suitable housing.
  • the housing may be metallic or made of resin (plastic). In the case of using a metallic material, for example, an aluminum alloy or a stainless steel material can be used.
  • the metallic housing is preferably divided into a positive-side housing and a negative-side housing, and electrically connected to the positive current collector and the negative current collector, respectively.
  • the casing on the positive electrode side and the casing on the negative electrode side are preferably joined and integrated through a gasket for preventing a short circuit.
  • the sheet coated with the solid electrolyte composition containing the compound (B) having a non-aromatic carbon-carbon unsaturated bond and the metathesis catalyst (C) is heated to be non-aromatic.
  • the compound having a carbon-carbon unsaturated bond undergoes a metathesis reaction to form a solid electrolyte-containing sheet containing the compound (B2) having a non-aromatic carbon-carbon unsaturated bond and the metathesis catalyst residue. It is preferable to form a structure in which solid particles such as a solid electrolyte and an active material are entangled in the network-like crosslinked body formed by the compound (B2), and finally cured.
  • the first aspect and the second aspect are preferably exemplified below.
  • 1st aspect (1a) which obtains a coating sheet by apply
  • a process for producing a solid electrolyte-containing sheet comprising a step (2a) of heating the coated sheet to 50 ° C. or higher and crosslinking and curing it by a metathesis reaction of the compound (B) having a non-aromatic carbon-carbon unsaturated bond.
  • Second aspect A step (1b) in which the solid electrolyte composition of the present invention is heated to 50 ° C.
  • seat including the process (2b) which apply
  • the steps (2a) and (1b) heating to 50 ° C. or higher results in the conditions for initiating the metathesis reaction of the compound (B). Thereafter, as the metathesis reaction (crosslinking) proceeds, the solid electrolyte composition of the present invention becomes a gel. Further, the crosslinking (curing) is progressed by the reaction (crosslinking).
  • the metathesis reaction initiating condition means a condition in which the metathesis reaction can be initiated.
  • crosslinking curing means that the metathesis reaction (crosslinking) proceeds sufficiently to cure from a gel to a cured product.
  • step (1b) the solid electrolyte composition of the present invention is subjected to a metathesis reaction initiation condition, and the composition is thickened as the metathesis reaction proceeds. Therefore, it is also possible to facilitate the coating process of the composition on the substrate by adjusting the time for applying the composition obtained in the process (1b) to the process (2b).
  • the heating conditions in the step (2a) are preferably 50 ° C. to 180 ° C., more preferably 80 ° C. to 160 ° C., and the heating time is preferably 0.1 hours to 2 hours, 0.5 hours. ⁇ 1 hour is more preferred.
  • the heating conditions in the step (1b) are preferably a temperature of 50 ° C. to 100 ° C., more preferably 50 ° C. to 80 ° C., and a heating time of 0.1 hour to 1 hour, preferably 0.1 hour to 0 .5 hours is more preferred.
  • the reaction is promoted and cured by heating after coating on the substrate.
  • the heating conditions at this time are preferably 50 ° C. to 180 ° C., more preferably 80 ° C. to 160 ° C., and the heating time is preferably 0.1 hours to 2 hours, more preferably 0.5 hours to 1 hour. .
  • a solid electrolyte sheet for an all-solid secondary battery which is a sheet containing a base material and a solid electrolyte layer, can be produced.
  • the all-solid-state secondary battery electrode sheet can be produced by the above-described method for producing a solid electrolyte-containing sheet. That is, when the solid electrolyte composition of the present invention contains an active material, it is preferably applied on the current collector instead of the base material in the step (1a) and the step (2b). In this case, an electrode sheet for an all-solid secondary battery, which is a sheet containing a solid electrolyte layer and an active material layer, can be produced.
  • the all-solid-state secondary battery can be produced by a conventional method except that the production method for the solid electrolyte-containing sheet is included.
  • the all-solid-state secondary battery and the electrode sheet for the all-solid-state secondary battery can be manufactured by forming each of the above layers using the solid electrolyte composition of the present invention.
  • any one of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer may be produced by the above-described method for producing a solid electrolyte-containing sheet, and the other layers are solid electrolyte compositions that are not the present invention. And may be prepared by conventional methods. This will be described in detail below.
  • the all-solid-state secondary battery of the present invention includes (intervenes) a method in which the solid electrolyte composition of the present invention is applied onto a metal foil serving as a current collector and a coating film is formed (film formation).
  • a positive electrode active material layer is formed by applying a solid electrolyte composition containing a positive electrode active material as a positive electrode material (positive electrode layer composition) on a metal foil that is a positive electrode current collector.
  • a positive electrode sheet for a secondary battery is prepared.
  • a solid electrolyte composition for forming a solid electrolyte layer is applied on the positive electrode active material layer to form a solid electrolyte layer.
  • a solid electrolyte composition containing a negative electrode active material is applied as a negative electrode material (negative electrode layer composition) on the solid electrolyte layer to form a negative electrode active material layer.
  • An all-solid secondary battery having a structure in which a solid electrolyte layer is sandwiched between a positive electrode active material layer and a negative electrode active material layer is obtained by stacking a negative electrode current collector (metal foil) on the negative electrode active material layer. Can do. If necessary, this can be enclosed in a housing to obtain a desired all-solid secondary battery.
  • each layer is reversed, and 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.
  • Another method includes the following method. That is, a positive electrode sheet for an all-solid secondary battery is produced as described above. In addition, a solid electrolyte composition containing a negative electrode active material is applied as a negative electrode material (a composition for a negative electrode layer) on a metal foil that is a negative electrode current collector to form a negative electrode active material layer. A negative electrode sheet for a secondary battery is prepared. Next, a solid electrolyte layer is formed on one of the active material layers of these sheets as described above. Furthermore, 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 so that the solid electrolyte layer and the active material layer are in contact with each other.
  • Another method includes the following method. That is, as described above, a positive electrode sheet for an all-solid secondary battery and a negative electrode sheet for an all-solid secondary battery are produced. 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. Furthermore, it laminates
  • An all-solid-state secondary battery can also be manufactured by a combination of the above forming methods. For example, as described above, a positive electrode sheet for an all-solid secondary battery, a negative electrode sheet for an all-solid secondary battery, and a solid electrolyte sheet for an all-solid secondary battery are produced. Then, after laminating the solid electrolyte layer peeled off from the base material on the negative electrode sheet for an all solid secondary battery, an all solid secondary battery can be produced by pasting the positive electrode sheet for the all solid secondary battery. it can. In this method, the solid electrolyte layer can be laminated on the positive electrode sheet for an all-solid secondary battery, and bonded to the negative electrode sheet for an all-solid secondary battery.
  • the method for applying the solid electrolyte composition is not particularly limited, and can be appropriately selected. Examples thereof include coating (preferably wet coating), spray coating, spin coating coating, dip coating, slit coating, stripe coating, and bar coating coating. At this time, the solid electrolyte composition may be dried after being applied, or may be dried after being applied in multiple layers.
  • the drying temperature is not particularly limited.
  • the lower limit is preferably 30 ° C or higher, more preferably 60 ° C or higher, and still 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.
  • a dispersion medium By heating in such a temperature range, a dispersion medium can be removed and it can be set as a solid state. Moreover, it is preferable because the temperature is not excessively raised and each member of the all-solid-state secondary battery is not damaged. Thereby, in the all-solid-state secondary battery, excellent overall performance is exhibited, and good binding properties and good ionic conductivity can be obtained even without pressure.
  • the pressurizing method is a hydraulic cylinder press.
  • the applied pressure is not particularly limited and is generally preferably in the range of 50 to 1500 MPa.
  • the heating temperature is not particularly limited, and is generally in the range of 30 to 300 ° C. It is also possible to press at a temperature higher than the glass transition temperature of the inorganic solid electrolyte.
  • the pressurization may be performed in a state where the coating solvent or the dispersion medium is previously dried, or may be performed in a state where the solvent or the dispersion medium remains.
  • the atmosphere during pressurization is not particularly limited, and may be any of the following: air, dry air (dew point of ⁇ 20 ° C. or lower), inert gas (for example, argon gas, helium gas, nitrogen gas).
  • the pressing time may be a high pressure in a short time (for example, within several hours), or a medium pressure may be applied for a long time (1 day or more).
  • a restraining tool screw tightening pressure or the like
  • the pressing pressure may be uniform or different with respect to the pressed part such as the sheet surface.
  • the pressing pressure can be changed according to the area and film thickness of the pressed part. Also, the same part can be changed stepwise with different pressures.
  • the press surface may be smooth or roughened.
  • the all solid state secondary battery manufactured as described above is preferably initialized after manufacture or before use.
  • the initialization is not particularly limited, and can be performed, for example, by performing initial charging / discharging in a state where the press pressure is increased, and then releasing the pressure until the general use pressure of the all-solid 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 installed in an electronic device, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a mobile phone, a cordless phone, a pager, a handy terminal, a mobile fax machine, a mobile phone Copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, minidisc, electric shaver, transceiver, electronic notebook, calculator, memory card, portable tape recorder, radio, backup power supply, memory card, etc. It is done.
  • Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military purposes and space. Moreover, it can also combine with a solar cell.
  • An all-solid secondary battery is a secondary battery in which the positive electrode, the negative electrode, and the electrolyte are all solid. In other words, it is distinguished from an electrolyte type secondary battery using a carbonate-based solvent as an electrolyte.
  • this invention presupposes an inorganic all-solid-state secondary battery.
  • the all-solid-state secondary battery includes an organic (polymer) all-solid-state secondary battery using a polymer compound such as polyethylene oxide as an electrolyte, and an inorganic all-solid-state secondary battery using the above-described Li-PS, LLT, LLZ, or the like. It is divided into batteries.
  • the application of the polymer compound to the inorganic all-solid secondary battery is not hindered, and the polymer compound can be applied as a binder particle for the positive electrode active material, the negative electrode active material, and the inorganic solid electrolyte particle.
  • the inorganic solid electrolyte is distinguished from the above-described electrolyte (polymer electrolyte) using a polymer compound such as polyethylene oxide as an ion conductive medium, and the inorganic compound serves as an ion conductive medium. Specific examples include the above-described Li—PS, LLT, and LLZ.
  • the inorganic solid electrolyte itself does not release cations (Li ions) but exhibits an ion transport function.
  • a material that is added to the electrolytic solution or the solid electrolyte layer and serves as a source of ions that release cations is sometimes called an electrolyte, but it is distinguished from the electrolyte as the ion transport material.
  • electrolyte salt or “supporting electrolyte”.
  • the electrolyte salt include LiTFSI (lithium bistrifluoromethanesulfonylimide).
  • composition means a mixture in which two or more components are uniformly mixed. However, as long as the uniformity is substantially maintained, aggregation or uneven distribution may partially occur within a range in which a desired effect is achieved.
  • a solid electrolyte composition when it is referred to as a solid electrolyte composition, it basically refers to a composition (typically a paste) that is a material for forming a solid electrolyte layer or the like, and an electrolyte layer or the like formed by curing the composition. Shall not be included in this.
  • Example 1 ⁇ Preparation example of solid electrolyte composition> Into a 45 mL zirconia container (manufactured by Fritsch), 180 zirconia beads having a diameter of 5 mm are charged, 9.0 g of inorganic solid electrolyte, 0.9 g of compound (B), and 18 g of dispersion medium are added. A container was set in P-7 and mixed for 2 hours at a rotation speed of 300 rpm. 0.18 g of the catalyst was added thereto, and mixing was further continued at 150 rpm for 5 minutes to prepare solid electrolyte compositions S-1 to S-10, T-1 and T-2. When the solid electrolyte composition contained an active material, the active material was added and mixed at the same timing as the addition of the metathesis catalyst to prepare a solid electrolyte composition.
  • Table 1 shows the components and blending mass ratios of each solid electrolyte composition.
  • LLT Li 0.5 La 0.5 TiO 3 (manufactured by Toshima Seisakusho)
  • LPS Li—PS system glass LLZ synthesized above: Li 7 La 3 Zr 2 O 12
  • B-1 Polyallyl methacrylate (Mw3200)
  • B-2 Sol-gel body of allyltriethoxysilane (containing 50% by mass of octaallylsilsesquioxane) (Mw2100)
  • B-3 3 modified form of succinic acid and linolenic acid of dipentaerythritol (Mw3500)
  • B-4 2: 4 modified form of dipentaerythritol deoxycholic acid and undecenoic acid (Mw2890)
  • B-5 Octamethacryloyl-substituted silsesquioxane (product number MA0735, Mw2560 manufactured by Hybrid Plastics Co., Ltd.)
  • Cycloolefin polymer Zeonex 330
  • Unsaturated bond rate (total number of non-aromatic carbon-carbon unsaturated bonds in compound after curing) / (total number of all carbon-carbon bonds in compound after curing) ⁇ 100 compound (formula ( 5)
  • Binding Test A 180 ° peel strength test (JIS Z0237-2009) was performed on the obtained solid electrolyte-containing sheet.
  • An adhesive tape (width 24 mm, length 300 mm) (trade name: Cellotape (registered trademark) CT-24, manufactured by Nichiban Co., Ltd.) was attached to the surface of the solid electrolyte-containing sheet on which the solid electrolyte composition was cured.
  • the adhesive tape was fixed to the upper jig.
  • the test was carried out at a load speed of 300 mm / min. After peeling off the 25 mm adhesive tape after the start of measurement, the 50 mm adhesive tape peeled off from the solid electrolyte-containing sheet was averaged for the measured adhesive strength every 0.05 mm in length, and the peel adhesive value ( Average peel strength (N)). The average peel strength was evaluated according to the following evaluation criteria.
  • a solid produced using the solid electrolyte composition of the present invention comprising a specific compound (B) having a non-aromatic unsaturated bond, an inorganic solid electrolyte (A), and a metathesis catalyst (C).
  • the electrolyte-containing sheet had high adhesion and excellent binding properties.
  • a solid electrolyte-containing sheet prepared using a comparative solid electrolyte composition T-1 containing a cycloolefin polymer and a comparative solid electrolyte composition T-2 containing a radical polymerization initiator is In either case, the adhesion was low and the binding property was not sufficient.
  • Each all-solid secondary battery after initialization was charged at a current density of 0.2 mA / cm 2 until the battery voltage reached 4.2 V, then the battery voltage at a current density of 0.2 mA / cm 2 2.5V Discharged until reached. Charging / discharging was repeated with this charging / discharging as one cycle. In this charge / discharge cycle, the number of cycles when the discharge capacity reached less than 80 when the discharge capacity in the first cycle after initialization was set to 100 was evaluated according to the following criteria. In addition, evaluation "C" or more is a pass level of this test.
  • the electrode layer was formed using the solid electrolyte composition of the present invention containing the specific compound (B) having a non-aromatic unsaturated bond, the inorganic solid electrolyte (A), and the metathesis catalyst (C).
  • the formed all-solid-state secondary battery was excellent in cycle characteristics.
  • the solid electrolyte composition of the present invention was able to produce an all-solid secondary battery having high binding properties and excellent cycle characteristics.
  • a solid electrolyte composition T-1 containing a cycloolefin polymer for comparison and a solid electrolyte composition T-2 for comparison containing a radical polymerization initiator were used to form an all-solid-state electrode layer. None of the secondary batteries had sufficient cycle characteristics.

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Abstract

L'invention concerne une composition d'électrolyte solide qui contient un électrolyte solide inorganique possédant de la conductivité d'ions d'un métal du groupe 1 ou du groupe 2 du tableau périodique, un composé comprenant une liaison insaturée carbone-carbone non aromatique, et un catalyseur de métathèse ; une feuille contenant un électrolyte solide ; un accumulateur tout solide ; un procédé de production d'une feuille contenant un électrolyte solide ; et un procédé de fabrication d'un accumulateur tout solide.
PCT/JP2017/001739 2016-01-28 2017-01-19 Composition d'électrolyte solide, feuille contenant un électrolyte solide, accumulateur tout solide, procédé de production de feuille contenant un électrolyte solide, et procédé de fabrication d'accumulateur tout solide WO2017130832A1 (fr)

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CN113782751A (zh) * 2021-09-17 2021-12-10 宁波信远炭材料股份有限公司 高柔韧性的碳素/树脂复合材料的制备方法

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