WO2021060542A1 - 無機固体電解質含有組成物、全固体二次電池用シート、全固体二次電池用電極シート及び全固体二次電池、並びに、全固体二次電池用シート及び全固体二次電池の製造方法 - Google Patents

無機固体電解質含有組成物、全固体二次電池用シート、全固体二次電池用電極シート及び全固体二次電池、並びに、全固体二次電池用シート及び全固体二次電池の製造方法 Download PDF

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WO2021060542A1
WO2021060542A1 PCT/JP2020/036473 JP2020036473W WO2021060542A1 WO 2021060542 A1 WO2021060542 A1 WO 2021060542A1 JP 2020036473 W JP2020036473 W JP 2020036473W WO 2021060542 A1 WO2021060542 A1 WO 2021060542A1
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group
solid electrolyte
inorganic solid
solid
secondary battery
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French (fr)
Japanese (ja)
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安田　浩司
裕介 飯塚
宏顕 望月
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Fujifilm Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • ⁇ 12> The inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 11>, which contains a dispersion medium.
  • ⁇ 13> The inorganic solid electrolyte-containing composition according to claim 12, wherein the dispersion medium is selected from a ketone compound, an aliphatic compound and an ester compound.
  • ⁇ 14> An all-solid-state secondary battery sheet having a layer composed of the inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 13> above.
  • ⁇ 15> An electrode sheet for an all-solid secondary battery having an active material layer composed of the inorganic solid electrolyte-containing composition according to ⁇ 9> or ⁇ 10> above.
  • the inorganic solid electrolyte-containing composition of the present invention comprises an inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table, and a compound (LB) represented by the formula (1) described later. Contains.
  • the content state of the inorganic solid electrolyte and the compound (LB) is not particularly limited, and the solid particles such as the inorganic solid electrolyte and the compound (LB) are independently present (dispersed). May be. That is, the compound (LB) may or may not be adsorbed or adhered to the surface of the solid particles. In the present invention, the compound (LB) is preferably adsorbed or adhered to the surface of solid particles.
  • the composition containing an inorganic solid electrolyte of the present invention can form a constituent layer capable of maintaining a strong binding state (bonding property) between solid particles even when the all-solid secondary battery is repeatedly charged and discharged, and can be charged and discharged. Even for the active material layer that expands and contracts, particularly the negative electrode active material layer that expands and contracts greatly, it is possible to suppress a decrease in the binding state (peeling, separation, etc.) and maintain a strong binding state between the solid particles.
  • the all-solid-state secondary battery provided with such a constituent layer can reduce the resistance and improve the cycle characteristics by using the composition containing the inorganic solid electrolyte of the present invention as the constituent layer-forming material of the all-solid-state secondary battery. realizable.
  • the compound (LB) adsorbed on the solid particles by one of the functional groups contains a rigid cyclic structure in the molecular structure represented by the formula (1), so that the compound (LB) has a rigid cyclic structure with respect to the solid particles. It is thought that it will be in a radially extending state (it will be in an upright state on solid particles).
  • the compound (LB) is a low molecular weight compound (not a polymer), it tends to be easily adsorbed radially.
  • other functional groups of the compound (LB) adsorbed on the solid particles are easily adsorbed on the other solid particles, and a network (adsorption state) between the plurality of solid particles via the compound (LB) is formed. Will be done.
  • the composition containing an inorganic solid electrolyte of the present invention also includes an embodiment containing an active material, a conductive additive, and the like in addition to the inorganic solid electrolyte (the composition of this embodiment is referred to as an electrode composition).
  • the composition of this embodiment is referred to as an electrode composition.
  • composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based inorganic solid electrolyte as described below.
  • the sulfide-based inorganic solid electrolyte may be non-crystal (glass) or crystallized (glass-ceramic), or only a part thereof may be crystallized.
  • Li-PS-based glass containing Li, P and S, or Li-PS-based glass ceramics containing Li, P and S can be used.
  • Sulfide-based inorganic solid electrolytes include, for example, lithium sulfide (Li 2 S), phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), simple phosphorus, simple sulfur, sodium sulfide, hydrogen sulfide, and lithium halide (for example). It can be produced by the reaction of at least two or more raw materials in sulfides of LiI, LiBr, LiCl) and the element represented by M (for example, SiS 2 , SnS, GeS 2).
  • the mixing ratio of each raw material does not matter.
  • an amorphization method can be mentioned.
  • the amorphization method include a mechanical milling method, a solution method and a melt quenching method. This is because processing at room temperature is possible and the manufacturing process can be simplified.
  • the oxide-based inorganic solid electrolyte contains an oxygen atom, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. Those having sex are preferable.
  • the oxide-based inorganic solid electrolyte preferably has an ionic conductivity of 1 ⁇ 10 -6 S / cm or more, more preferably 5 ⁇ 10 -6 S / cm or more, and 1 ⁇ 10 -5 S / cm or more. It is particularly preferable that it is / cm or more.
  • the upper limit is not particularly limited, but it is practical that it is 1 ⁇ 10 -1 S / cm or less.
  • Li xa La ya TiO 3 [xa satisfies 0.3 ⁇ xa ⁇ 0.7, and ya satisfies 0.3 ⁇ ya ⁇ 0.7.
  • LLT Li xb Layb Zr zb M bb mb Onb
  • M bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In and Sn.
  • Xb satisfies 5 ⁇ xb ⁇ 10, yb satisfies 1 ⁇ yb ⁇ 4, zb satisfies 1 ⁇ zb ⁇ 4, mb satisfies 0 ⁇ mb ⁇ 2, and nb satisfies 5 ⁇ nb ⁇ 20. Satisfy.); Li xc Byc M cc zc Onc (M cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In and Sn.
  • Li 7 La 3 Zr 2 O 12 (LLZ) having a garnet-type crystal structure.
  • Phosphorus compounds containing Li, P and O are also desirable.
  • lithium phosphate Li 3 PO 4
  • LiPON in which a part of oxygen of lithium phosphate is replaced with nitrogen
  • LiPOD 1 (D 1 is preferably Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and one or more elements selected from Au) and the like.
  • LiA 1 ON (A 1 is one or more elements selected from Si, B, Ge, Al, C and Ga) and the like can also be preferably used.
  • the halide-based inorganic solid electrolyte contains a halogen atom, has the conductivity of an ion of a metal belonging to Group 1 or Group 2 of the Periodic Table, and has electrons. Insulating compounds are preferred.
  • the halide-based inorganic solid electrolyte is not particularly limited, and examples thereof include compounds such as Li 3 YBr 6 and Li 3 YCl 6 described in LiCl, LiBr, LiI, ADVANCED MATERIALS, 2018, 30, 1803075. Of these, Li 3 YBr 6 and Li 3 YCl 6 are preferable.
  • the hydride-based inorganic solid electrolyte contains a hydrogen atom, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. A compound having a property is preferable.
  • the hydride-based inorganic solid electrolyte is not particularly limited, and examples thereof include LiBH 4 , Li 4 (BH 4 ) 3 I, and 3 LiBH 4- LiCl.
  • the inorganic solid electrolyte is preferably particles.
  • the particle size (volume average particle size) of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more.
  • the upper limit is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • the particle size of the inorganic solid electrolyte is measured by the following procedure. Inorganic solid electrolyte particles are prepared by diluting 1% by mass of a dispersion in a 20 mL sample bottle with water (heptane in the case of a water-unstable substance).
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes, and immediately after that, it is used for the test.
  • data was captured 50 times using a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA) using a measuring quartz cell at a temperature of 25 ° C. Obtain the volume average particle size.
  • JIS Japanese Industrial Standards
  • Z 8828 2013 "Particle size analysis-Dynamic light scattering method” as necessary. Five samples are prepared for each level and the average value is adopted.
  • the inorganic solid electrolyte may contain one kind or two or more kinds.
  • the mass (mg) (grain amount) of the inorganic solid electrolyte per unit area (cm 2) of the solid electrolyte layer is not particularly limited. It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm 2 .
  • the amount of the inorganic solid electrolyte is preferably such that the total amount of the active material and the inorganic solid electrolyte is in the above range.
  • the content of the inorganic solid electrolyte in the composition containing the inorganic solid electrolyte is not particularly limited, but in terms of binding property (strong binding state) and dispersibility, the solid content is 100% by mass. It is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more. From the same viewpoint, the upper limit is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less.
  • the inorganic solid electrolyte-containing composition of the present invention contains a compound (LB) represented by the following formula (1). As described above, this compound (LB) has a function of improving the binding state of solid particles in the constituent layer.
  • the inorganic solid electrolyte-containing composition of the present invention may contain one or more of the above compounds (LB), and may contain, for example, 1 to 3 types.
  • This interaction is not particularly limited, but is, for example, due to a hydrogen bond, an acid-base ionic bond, a covalent bond, a ⁇ - ⁇ interaction due to an aromatic ring, or a hydrophobic-hydrophobic interaction. Things etc. can be mentioned.
  • the chemical structure of the functional groups may or may not change.
  • the functional group usually does not change and the structure as it is is maintained.
  • an active hydrogen such as a carboxylic acid group is usually released as an anion (the functional group is changed) to bond with the solid particle.
  • -NHCOOR 18 and -OCONHR 21 represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms.
  • Etc. are more preferable, and -NHCOOR 18 and -OCONHR 21 (where R 18 and R 21 represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms). Etc. are particularly preferable.
  • the amide group is not particularly limited, but includes, for example, a carbonyl group and an amino group or an imino group such as -CONR 16 R 17 and -NR 15- COR 18 (R 15 to R 18 are as described above).
  • a group containing the above is given as a preferable example.
  • Examples of the amide group is preferably an -NR 15 -COR 18, -NHCOR 18 is more preferable.
  • the alkoxysilyl group is not particularly limited, and examples thereof include mono-, di-, and tri-alkoxysilyl groups, preferably an alkoxysilyl group having 1 to 20 carbon atoms, and more preferably an alkoxysilyl group having 1 to 6 carbon atoms. ..
  • methoxysilyl, ethoxysilyl, t-butoxysilyl, cyclohexylsilyl, and each group exemplified by Substituent Z described later can be mentioned.
  • Examples of the (meth) acryloyloxy group include acryloyloxy and methacryloyloxy.
  • the acidic group or the like may form a salt in the inorganic solid electrolyte-containing composition and the constituent layer, but it is preferable that no salt is formed at least when used in the preparation of the inorganic solid electrolyte-containing composition.
  • the functional group contained in the compound (LB) is preferably an acidic group, an amide group, a urea group or a urethane group, and more preferably an acidic group.
  • the compound (LB) has, as an arbitrary substituent, a group having a basic nitrogen atom, an epoxy group, an isocyanate group or a hydroxyl group (phenolic hydroxyl group) in addition to the functional groups represented by X 1 and X 2 of the formula (1). It may have (including), but it is preferable that it does not have these substituents other than the above functional groups.
  • the amino group is synonymous with the amino group of the substituent Z described later, but an unsubstituted amino group or an alkylamino group is preferable.
  • Each of the three Rs of the amidine group indicates a hydrogen atom or a substituent (for example, a group selected from the substituent Z described later).
  • B represents a cyclic linking group or acyclic linking group having no single bond or condensed ring structure, and a cyclic linking group or acyclic linking group (collectively referred to as a linking group) is preferable. Since the linking group that can be taken as B does not have a fused ring structure, the interaction with the inorganic solid electrolyte is increased, the film strength of the inorganic solid electrolyte layer is improved, and the cycle characteristics are improved.
  • the linking group (cyclic linking group and non-cyclic linking group) that can be taken as B is not particularly limited as long as it does not have a condensed ring structure as a substituent in its molecular structure.
  • having no condensed ring structure in the molecular structure means that the molecular structure does not contain the condensed ring structure in all or part of the molecular structure, and it is necessary that the molecular structure does not have the condensed ring structure as a substituent.
  • the condensed ring structure means a structure formed by combining a plurality of rings, and includes an aromatic or aliphatic condensed ring structure.
  • Atomic, sulfur atom, imino group (-NR N- ), carbonyl group, sulfonyl group (-SO 2- ), phosphate linking group (-OP (OH) (O) -O-), phosphonic acid linking group (-P (OH) (O) -O-), or a group related to a combination thereof and the like can be mentioned.
  • the alkylene group and the alkenylene group that can be used as the linking group may be linear, branched or cyclic, respectively.
  • Examples of the cyclic alkylene group include a group obtained by further removing one or two hydrogen atoms from the cycloalkyl group in the substituent Z depending on the valence, and examples thereof include a monocyclic alkylene group.
  • Examples of the monocyclic heterocyclic group include a group obtained by removing one or two hydrogen atoms from the heterocyclic group in the substituent Z depending on the valence.
  • (iso) ) A group consisting of cyanuric acid can be mentioned.
  • a group consisting of a combination of an alkylene group, an alkenylene group, a carbonyl group, an oxygen atom, a sulfur atom, a sulfonyl group and an imino group is preferable, and for example, an alkylene group and an oxygen atom are combined.
  • Examples include an alkylenedioxy group.
  • the total number of atoms constituting the linking group is preferably 1 to 36, more preferably 1 to 24, and even more preferably 1 to 12.
  • the number of connecting atoms of the linking group is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.
  • the lower limit is 1 or more.
  • the number of connected atoms is the minimum number of atoms connecting A 1 and A 2, etc. in the formula (1).
  • the compound A-11 used in the examples is a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group (alkylene group having 3 carbon atoms), it constitutes a linking group.
  • the number of atoms to be used is 9, but the number of connected atoms is 1.
  • the linking group that can be taken as B is preferably a monocyclic linking group or a non-cyclic (linear or branched) linking group, for example, a cycloalkylene group, a monocyclic arylene group, a monocyclic heterocyclic group and the like.
  • Single ring linking group alkylene group (linear or branched) (eg -CH 2- , -C (CH 3 ) 2- ), oxygen atom, carbonyl group, sulfonyl group or alkylenedioxy group
  • alkylene group linear or branched
  • oxygen atom oxygen atom
  • carbonyl group sulfonyl group or alkylenedioxy group
  • an alkylene group, a carbonyl group or a sulfonyl group is further preferable
  • an alkylene group having 1 to 3 carbon atoms is particularly preferable from the viewpoint of enhancing the binding property.
  • the monocyclic linking group a monocyclic arylene group is preferable.
  • the linking group that can be adopted as B is appropriately determined within the range that satisfies the definition of the formula (1), but as much as possible, it is preferable that the linking group is not the group related to the combination but the above-mentioned single group.
  • the compound A-03 used in the examples has a monocyclic arylene group (-C 6 H 4 ) with the -C (CH 3 ) 2 CH 2 C 6 H 4 CH 2 C (CH 3 ) -group as a whole.
  • two alkylene groups (-CH 2 C (CH 3 )-) can be interpreted as a group, but in the present invention, a monocyclic arylene group is interpreted as B and two.
  • the alkylene group is interpreted as Y 1 and Y 2.
  • the linking group that can be taken as B may have a substituent.
  • the substituent that B may have include Substituent Z, which is preferably a substituent other than the functional group selected from the above-mentioned functional group group (I), and more preferably an alkyl group or a halogen atom. And so on.
  • the alkylene group is preferably substituted with a halogen atom, and more preferably substituted with a fluorine atom.
  • the linking group that can be taken as B has a substituent, it is interpreted as one group as much as possible.
  • the 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group of compound A-11 used in the examples has all hydrogen atoms substituted with fluorine atoms and has a carbon number of carbons. It is interpreted as a branched alkylene group of 3 and not as a methylene group substituted with two trifluoromethyl groups.
  • a 1 and A 2 in the formula (1) represent a linking group having a cyclic structure.
  • the valence of this linking group is not particularly limited, but is usually 2 to 6 valences, preferably divalent or trivalent, and more preferably divalent.
  • the fact that the linking group has a cyclic structure means that the chemical structure forming the linking group contains a cyclic structure, and includes an embodiment in which the linking group itself has a cyclic structure.
  • the ring forming the cyclic structure contained in A 1 and A 2 may be a saturated, unsaturated (excluding aromatic ring) or aromatic ring, and may be a hydrocarbon ring or a hetero ring.
  • a group composed of a cycloalkyl group (preferably a cyclohexyl group), an aryl group or a heterocyclic group is preferable, a group composed of an aryl group (aromatic hydrocarbon ring group) is more preferable, and a group composed of a phenyl group is more preferable.
  • the linking group containing a cyclic structure in the chemical structure may include any of the groups listed in the linking groups in which the linking group itself has a cyclic structure, and each of these groups and the above-mentioned linking group. Examples of the group related to the combination with each group listed as the linking group that can be taken as B can be mentioned.
  • Alkenylene group (preferably 2 to 10 carbon atoms, more preferably 2 to 3 carbon atoms), arylene group (preferably 6 to 24 carbon atoms, more preferably 6 to 10 carbon atoms), hetero Examples thereof include a ring group, an oxygen atom, a sulfur atom, an imino group (-NR N- ), a carbonyl group, a sulfonyl group, a phosphate linking group, a phosphonic acid linking group, or a group related to a combination thereof.
  • the alkylene group and the alkenylene group that can be used as the linking group may be linear, branched or cyclic, respectively.
  • the linking groups that can be taken as Y 1 and Y 2 are preferably a monocyclic linking group or a non-cyclic (linear or branched chain) linking group, and more preferably, for example, an alkylene group, an alkyleneoxy group or an aryleneoxy group. ..
  • the linking group that can be taken as Y 1 and Y 2 may have a substituent. Examples of the substituent that B may have include Substituent Z, and preferably, Substituents other than the functional group selected from the above-mentioned functional group group (I) can be mentioned.
  • the cyclic linking group present in the compound (LB) can be attributed to any of B, A 1 or Y 1 in the formula (1), within the range satisfying the definition of the formula (1). it may be appropriately interpreted, but preferably belonging to cyclic structures preferentially a 1.
  • a phenylene group in the compound A-11 was used in the examples, B (group of the combination of the arylene group in the alkylene group and monocyclic), but can be interpreted in any of A 1 and Y 1, the present invention in interprets the a 1, an alkylene group alone B, and Y 1 is interpreted as a single bond.
  • a 2 and Y 2 in the formula (1) is interpreted as a single bond.
  • X 1 and X 2 in the formula (1) represent functional groups included in the functional group group (I).
  • the functional groups that can be taken as X 1 and X 2 are as described above.
  • a is 0 or 1 and b is 1 or 2.
  • At least one of B, A 1 , A 2 , Y 1 and Y 2 comprises a cyclic structure. That is, compound (LB) contains a rigid cyclic structure in all or part of the chemical structure connecting X 1 and X 2. As a result, the rigidity of the compound (LB) represented by the formula (1) is also increased, and a strong binding state can be realized.
  • the number of cyclic structures contained in the compound (LB) is not particularly limited, but is preferably 1 to 6, more preferably 1 to 4, and further preferably 1 or 2. preferable.
  • Examples of the mode in which the compound (LB) contains a cyclic structure include a mode in which B, Y 1 and Y 2 are all single bonds, a mode in which all a are 1, or a mode in which all a are 0. , B, and one of Y 1 and Y 2 is a linking group containing a cyclic structure. Among them, it is preferable that at least one of B, A 1 and Y 1 and at least one of B, A 2 and Y 2 each contain a cyclic structure.
  • the compound (LB) represented by the formula (1) preferably has a symmetrical structure centered on B in the formula.
  • the symmetric structure that can be taken as the compound (LB) is not a geometrically symmetric structure, but a mode in which the presence or absence of a partial structure represented by the same or corresponding reference numeral is the same when expressed by the above formula (1). Further, it includes an embodiment in which the presence or absence of a partial structure is the same and the chemical structure thereof is also the same.
  • the combination a represented by the following equation (1-3) is 1, Y 1 and Y 2
  • B is preferably a linking group.
  • the formula (1-3) or the formula (1-4) b is preferably 1 and in the combination represented by the formula (1-5), b is preferably 2.
  • B is preferably a non-cyclic linking group, and A 1 and A 2 are preferably aromatic hydrocarbon ring groups.
  • the combination of B and A 1 or A 2 is not particularly limited and can be appropriately combined, but a preferable one that can be taken as B and A 1 or A are preferable.
  • a combination with a preferable one that can be taken as 2 is preferable.
  • a more preferable combination of A 2 , B and A 1 is a combination of (A 2 ) a phenylene group, (B) an alkylene group, a carbonyl group or a sulfonyl group, and (A 1 ) a phenylene group.
  • the compound (LB) represented by the formula (1) may have a substituent.
  • the substituent is not particularly limited as long as the effect of the present invention is not impaired, and examples thereof include a substituent Z described later, and a group other than the functional group contained in the functional group group (I) is preferable.
  • an alkyl group and an alkoxycarbonyl group which may be substituted with a halogen atom (preferably a fluorine atom) can be mentioned.
  • the alkyl group constituting the alkoxycarbonyl group is not particularly limited, and the alkyl group in the following substituent Z can be applied. Examples of the alkoxycarbonyl group substituted with a fluorine atom include groups contained in compounds A-17 to A-20 used in Examples.
  • the compound (LB) is preferably a low molecular weight compound, and its molecular weight is appropriately determined.
  • the molecular weight can be, for example, 150 to 3000.
  • Specific examples of the compound (LB) include compounds A-01 to A-23 used in Examples, but the present invention is not limited thereto.
  • a compound in which the carboxy group of the compounds A-01 to A-23 is changed to the other functional group described above can be mentioned.
  • -Substituent Z- Alkyl groups preferably alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • alkenyl groups preferably alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • an alkenyl group having 2 to 20 carbon atoms for example, vinyl, allyl, oleyl, etc.
  • an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms, for example, ethynyl, butadynyl, phenylethynyl, etc.
  • a cycloalkyl group having 3 to 20 carbon atoms for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc., is usually used in the present specification to include a cycloalkyl group.
  • An aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), an aralkyl group (preferably having 7 carbon atoms).
  • Heterocyclic groups include aromatic heterocyclic groups and aliphatic heterocyclic groups. Including groups. For example, tetrahydropyran ring group, tetrahydrofuran ring group, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzoimidazolyl, 2-thiazolyl, 2-oxazolyl, pyrrolidone group, etc.), alkoxy group (preferably carbon). Alkyl groups of number 1 to 20, such as methoxy, ethoxy, isopropyloxy, benzyloxy, etc., aryloxy groups (preferably aryloxy groups of 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methyl).
  • aryloxy groups such as phenoxy and 4-methoxyphenoxy mean including an aryloxy group), heterocyclic oxy groups (groups in which an —O— group is bonded to the heterocyclic group), and alkoxy.
  • a carbonyl group preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, for example, ethoxycarbonyl, 2-ethylhexyloxycarbonyl, dodecyloxycarbonyl, etc.
  • an aryloxycarbonyl group preferably 6 to 26 carbon atoms.
  • a reeloxycarbonyl group such as phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-methylphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc., a heterocyclic oxycarbonyl group (-O-CO- group bonded to the heterocyclic group).
  • Group amino group (preferably containing 0 to 20 carbon atoms, alkylamino group, arylamino group, for example, amino (-NH 2 ), N, N-dimethylamino, N, N-diethylamino, N.
  • sulfamoyl group (preferably 0 to 20 carbon number sulfamoyl group, for example, N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.), acyl group (alkylcarbonyl group, alkenyl, etc.) It contains a carbonyl group, an alkynylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, preferably an acyl group having 1 to 20 carbon atoms, for example, acetyl, propionyl, butyryl, octanoyl, hexadecanoyl, acryloyl, methacryloyl, crotonoyl, benzoyl.
  • acyloxy groups alkylcarbonyloxy groups, alkenylcarbonyloxy groups, alkynylcarbonyloxy groups, arylcarbonyloxy groups, heterocyclic carbonyloxy groups, preferably acyloxy groups having 1 to 20 carbon atoms, for example.
  • an arylthio group having 6 to 26 carbon atoms for example, phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc., or a heterocyclic thio group (—S— group is bonded to the heterocyclic group).
  • Alkyl sul Honyl groups preferably alkylsulfonyl groups having 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, etc.
  • arylsulfonyl groups preferably arylsulfonyl groups having 6 to 22 carbon atoms, such as benzenesulfonyl groups, etc.
  • alkylsilyls preferably alkylsulfonyl groups having 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, etc.
  • alkylsul Honyl groups preferably alkylsulfonyl groups having 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, etc.
  • arylsulfonyl groups preferably arylsulfonyl groups having 6 to 22 carbon atoms, such as benz
  • Groups preferably alkylsilyl groups having 1 to 20 carbon atoms, such as monomethylsilyl, dimethylsilyl, trimethylsilyl, triethylsilyl, etc.
  • arylsilyl groups preferably arylsilyl groups having 6 to 42 carbon atoms, such as triphenylsilyl.
  • Etc. alkoxysilyl group (preferably alkoxysilyl group having 1 to 20 carbon atoms, for example, monomethoxysilyl, dimethoxysilyl, trimethoxysilyl, triethoxysilyl, etc.), aryloxysilyl group (preferably 6 to 42 carbon atoms).
  • aryloxy silyl group for example, triphenyl oxysilyl etc.
  • a phosphinyl group preferably a phosphinyl group having 0 to 20 carbon atoms, for example, -P (R P) 2)
  • phosphonic Acid groups preferably phosphonic acid groups having 0 to 20 carbon atoms, for example, -PO (OR P ) 2
  • sulfo groups sulfonic acid groups
  • carboxy groups preferably phosphonic acid groups having 0 to 20 carbon atoms, for example, -PO (OR P ) 2
  • sulfo groups sulfonic acid groups
  • carboxy groups
  • RP is a hydrogen atom or a substituent (preferably a group selected from the substituent Z). Further, each group listed in these substituents Z may be further substituted with the above-mentioned substituent Z.
  • the alkyl group, alkylene group, alkenyl group, alkenylene group, alkynyl group, alkynylene group and the like may be cyclic, chain-like, or linearly branched. May be.
  • the content of the compound (LB) in the inorganic solid electrolyte-containing composition is not particularly limited, but is 0.05% by mass or more at 100% by mass of the solid content in terms of strengthening the bound state of the solid particles. It is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more.
  • the upper limit can be, for example, 15% by mass or less, but in terms of reducing battery resistance, it is preferably 10% by mass or less, more preferably 4% by mass or less, and 2.5% by mass. It is more preferably% or less, and particularly preferably 1.2% by mass or less.
  • the ratio of the content of the inorganic solid electrolyte [SE] to the total content of the compound (LB) [LB] in 100% by mass of the solid content: [LB] / [SE]. ] Is not particularly limited and can be 0.001 to 0.2, but in terms of strengthening the bound state of the solid particles (improving the strength of the constituent layer), lowering the resistance and the cycle characteristics, It is preferably 002 to 0.1, and is 0.003 to 0.05 in that the bound state of the solid particles can be further strengthened, the resistance can be lowered, and the cycle characteristics can be improved at a high level. More preferred.
  • composition containing an inorganic solid electrolyte does not contain an active material, it is more preferably 0.007 to 0.03, and particularly preferably 0.007 to 0.01.
  • inorganic solid electrolyte-containing composition contains the (negative electrode) active material, it is more preferably 0.003 to 0.03, and particularly preferably 0.003 to 0.01.
  • the inorganic solid electrolyte-containing composition of the present invention contains the following polymer binder
  • the total content of the polymer binder content [BR] and the compound (LB) in 100% by mass of the solid content of the inorganic solid electrolyte-containing composition is contained.
  • the ratio with the amount [LB]: [BR] / [LB] is not particularly limited, but is preferably 0.05 to 15 in terms of reducing the frictional resistance of the solid particles, lowering the resistance, and the cycle characteristics. , 0.1 to 10 is more preferable, and 0.2 to 5 is further preferable, in that the frictional resistance of the solid particles can be further reduced, and the resistance can be lowered and the cycle characteristics can be improved at a high level. It is preferably 0.8 to 5, and particularly preferably 0.8 to 5.
  • the inorganic solid electrolyte-containing composition of the present invention preferably contains a polymer binder.
  • a polymer binder By containing the polymer binder, the binding property of the solid particles can be improved, which contributes to the improvement of the cycle characteristics and the like.
  • the polymer forming the polymer binder is not particularly limited, and examples thereof include various polymers usually used for the constituent layers of the all-solid-state secondary battery. For example, sequential polymerization (polycondensation, polyaddition or addition condensation) polymer such as polyurethane, polyurea, polyamide, polyimide, polyester, polyether, polycarbonate, etc., and further, fluoropolymer (fluorine-containing polymer), hydrocarbon polymer, etc. Examples thereof include chain polymerization polymers such as vinyl polymers and (meth) acrylic polymers.
  • polyurethane, polyurea, polyamide, and polyimide polymers that can be taken as sequential polymerization polymers include polymers having a hard segment and a soft segment described in JP-A-2015-08480 (polymer binder (B), Polymers that form a binder having at least one component represented by a specific formula, which are described in International Publication No. 2018/147051, and each of those described in International Publication No. 2018/20827 and International Publication No. 2015/046313. Polymers and the like can be mentioned.
  • fluoropolymer examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), a copolymer of polyvinylidene fluoride and hexafluoropropylene (PVdF-HFP), polyvinylidene fluoride and hexa.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • PVdF-HFP a copolymer of polyvinylidene fluoride and hexafluoropropylene
  • PVdF-HFP-TFE tetrafluoroethylene
  • the copolymerization ratio [PVdF: HFP] (mass ratio) of PVdF and HFP is not particularly limited, but is preferably 9: 1 to 5: 5, and more preferably 9: 1 to 7: 3.
  • the copolymerization ratio [PVdF: HFP: TFE] (mass ratio) of PVdF, HFP, and TFE is not particularly limited, but may be 20 to 60:10 to 40: 5 to 30. preferable.
  • hydrocarbon polymer examples include polyethylene, polypropylene, natural rubber, polybutadiene, polyisoprene, polystyrene, polystyrene butadiene copolymer, styrene-based thermoplastic elastomer, polybutylene, acrylonitrile butadiene copolymer, or hydrogenation thereof (hydrogenation). Chemistry) Polymers can be mentioned.
  • the styrene-based thermoplastic elastomer or its hydride is not particularly limited, and for example, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), styrene-isobutylene.
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • styrene-isobutylene styrene-isobutylene.
  • SIBS styrene block copolymer
  • SIBS hydrogenated SIS
  • SBS styrene-butadiene-styrene block copolymer
  • SEEPS hydrogenated SBS
  • SEPS styrene-ethylene-ethylene-propylene-styrene block copolymer
  • SEPS ethylene-propylene-styrene block copolymer
  • SBR styrene-butadiene rubber
  • HSBR hydride styrene-butadiene rubber
  • the hydrocarbon polymer having no unsaturated group (for example, 1,2-butadiene constituent) bonded to the main chain is preferable in that the formation of chemical crosslinks can be suppressed.
  • the vinyl-based polymer include polymers containing, for example, 50 mol% or more of vinyl-based monomers other than the (meth) acrylic compound (M1).
  • the vinyl-based monomer include vinyl compounds described later.
  • Specific examples of the vinyl polymer include polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, and a copolymer containing these.
  • this vinyl-based polymer is a constituent component derived from the (meth) acrylic compound (M1) that forms the (meth) acrylic polymer described later, and further a constituent component derived from the macromonomer described later. It is preferable to have (MM).
  • the content of the constituent component derived from the vinyl-based monomer is preferably the same as the content of the constituent component derived from the (meth) acrylic compound (M1) in the (meth) acrylic polymer.
  • the content of the constituent component derived from the (meth) acrylic compound (M1) is not particularly limited as long as it is less than 50 mol% in the polymer, but is preferably 0 to 40 mol%, and is preferably 5 to 35 mol%. Is more preferable.
  • the content of the component (MM) is preferably the same as the content in the (meth) acrylic polymer.
  • the (meth) acrylic polymer is at least one (meth) acrylic compound (M1) selected from a (meth) acrylic acid compound, a (meth) acrylic acid ester compound, a (meth) acrylamide compound and a (meth) acrylonitrile compound. ) Is (co) polymerized to obtain a polymer. Further, a (meth) acrylic polymer composed of a copolymer of the (meth) acrylic compound (M1) and another polymerizable compound (M2) is also preferable.
  • M1 selected from a (meth) acrylic acid compound, a (meth) acrylic acid ester compound, a (meth) acrylamide compound and a (meth) acrylonitrile compound.
  • the other polymerizable compound (M2) is not particularly limited, and examples thereof include vinyl compounds such as styrene compounds, vinylnaphthalene compounds, vinylcarbazole compounds, allyl compounds, vinyl ether compounds, vinyl ester compounds, and dialkyl itaconate compounds.
  • vinyl compound examples include "vinyl-based monomers” described in JP-A-2015-88486.
  • a (meth) acrylic polymer having a component (MM) derived from a macromonomer is also preferable.
  • a (meth) acrylic polymer for example, a macromonomer having a mass average molecular weight of 1,000 or more is incorporated as a side chain component described in International Publication No.
  • the content of the constituent component derived from the (meth) acrylic compound (M1) is preferably 50 mol% or more, and the content of the other polymerizable compound (M2) is not particularly limited. However, for example, it can be 50 mol% or less, and preferably less than 50 mol%.
  • the content of the component (MM) is preferably 1 to 70% by mass.
  • polyurethane, fluorine-based polymer or hydrocarbon-based polymer is preferable, polyurethane, PVdF-HFP, SEBS, SBS, SBR or HSBR is more preferable, polyurethane, PVdF-HFP or SEBS is more preferable, and polyurethane or PVdF- HFP is particularly preferred.
  • n1 and n2 indicate the degree of polymerization, respectively, n1 is a number of 2 or more, n2 is a number of 0 or more than 1, and can be a number of 2 or more.
  • the component represented by the formula (I-7) is a component containing a single polyalkyleneoxy chain.
  • the main chain of polyurethane has at least two different constituents represented by the above formula (I-7), preferably two or three types, and more preferably two types.
  • the constituent component represented by the formula (I-7) is preferably a constituent component derived from at least two kinds selected from polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol.
  • the (number average) molecular weight of two or more different constituents represented by the formula (I-7) and the (number average) molecular weight of each constituent are the above-mentioned at least two types of polyether structures, respectively. It is synonymous with the (number average) molecular weight of, and the preferred range is also the same.
  • n1 in two or more different constituents represented by the formula (I-7) is appropriately set within a range satisfying the (number average) molecular weight, and has the same meaning as the degree of polymerization of the above-mentioned polyether structure. And the preferred range is the same.
  • the constituent component represented by the formula (I-7) is a constituent component containing a copolymer of two types of polyalkyleneoxy chains.
  • the bonding mode of the two polyalkyleneoxy chains in the copolymer is not particularly limited, and may be a random bond, a block bond, or an alternating bond.
  • the main chain of polyurethane may have at least one kind of constituent component represented by the above formula (I-7), and preferably one kind.
  • examples of the constituent component represented by the formula (I-7) include a constituent component composed of a polyethylene oxy chain and a copolymer of a polypropylene oxy chain.
  • n1 and n2 are appropriately set within a range satisfying the (number average) molecular weight, respectively, and have the same meaning as the degree of polymerization of the above-mentioned polyether structure, and the preferable range is also the same.
  • Polyurethane may have components other than the components represented by the above formulas.
  • a constituent component is not particularly limited as long as it can be sequentially polymerized with the raw material compound that derives the constituent component represented by each of the above formulas.
  • the (total) content of the components represented by the above formulas (1-1) to (I-7) in the polyurethane is not particularly limited, but is preferably 5 to 100% by mass, and 10 to 10 to 100% by mass. It is more preferably 100% by mass, further preferably 50 to 100% by mass, and even more preferably 80 to 100% by mass.
  • the upper limit of this content may be, for example, 90% by mass or less regardless of the above 100% by mass.
  • the content of the constituent components other than the constituent components represented by the above formulas in the polyurethane is not particularly limited, but is preferably 50% by mass or less.
  • the component in which RP2 is a chain composed of a low molecular weight hydrocarbon group (for example, represented by the above formula (I-3A)).
  • the content of the constituent components in the polyurethane is not particularly limited, but is, for example, preferably 0 to 50 mol%, more preferably 1 to 30 mol%, and 2 to 20 mol%. More preferably, it is more preferably 4 to 10 mol%.
  • the component in which RP2 is the polyalkyleneoxy chain as a molecular chain for example, represented by the above formula (I-3B)).
  • the content of the component) in the polyurethane is not particularly limited, but is preferably, for example, 0 to 50 mol%, more preferably 0 to 45 mol%, and 0 to 43 mol%. Is more preferable.
  • the component in which RP2 is the hydrocarbon polymer chain as a molecular chain for example, represented by the above formula (I-3C)
  • the content of the component) in the polyurethane is not particularly limited, but is, for example, preferably 0 to 50 mol%, more preferably 1 to 45 mol%, and 3 to 40 mol%. Is even more preferable, 3 to 30 mol% is further preferable, 3 to 20 mol% is particularly preferable, and 3 to 10 mol% is most preferable.
  • the content of the other component is preferably, for example, 10 to 50 mol%, preferably 15 to 40 mol%. It is more preferably present, and further preferably 20 to 30 mol%.
  • the ratio of the content of one component to the other component [one component: the other component] is not particularly limited, but is preferably, for example, 10:90 to 80:20. It is more preferably 20:80 to 70:30.
  • polyurethane has three or more different constituents represented by the formula (I-7)
  • a constituent having a polyether structure formed of an alkyleneoxy group having the smallest molecular weight is used as the other constituent.
  • the other constituents are one of the above constituents.
  • the component represented by the formula (I-7) also corresponds to the component represented by the formula (I-3B)
  • the content of the component represented by the formula (I-7) is Regardless of the content of the component represented by the formula (I-3B), the content described by the component represented by the formula (I-7) is used.
  • -Functional group- Polyurethane preferably has a functional group for enhancing the wettability or adsorptivity of solid particles such as an inorganic solid electrolyte to the surface.
  • a functional group include a group that exhibits a physical interaction such as a hydrogen bond on the surface of a solid particle and a group that can form a chemical bond with a group existing on the surface of the solid particle. It is more preferable to have at least one group selected from the following functional group group (I).
  • Carboxy group, a sulfonic acid group (-SO 3 H), phosphoric acid group (-PO 4 H 2), hydroxy group and an alkoxysilyl group has a high adsorptivity of the inorganic solid electrolyte or the cathode active material, 3 or more rings condensed
  • a group having a ring structure has high adsorptivity with a negative electrode active material or the like.
  • the amino group (-NH 2 ), sulfanil group and isocyanato group have high adsorptivity with the inorganic solid electrolyte.
  • Polyurethane may have a functional group selected from the functional group group (I) in any of the constituent components forming the polymer, and may have a functional group in either the main chain or the side chain of the polymer. Good.
  • the constituent component having the functional group include the constituent component represented by the formula (I-3A).
  • the content of the functional group selected from the functional group group (I) in the polyurethane is not particularly limited, but for example, the polyurethane is composed of the constituent components having the functional group selected from the functional group group (I).
  • the ratio in the total components is preferably 0.01 to 50 mol%, preferably 0.02 to 49 mol%, more preferably 0.1 to 40 mol%, further preferably 1 to 30 mol%, and 3 to 3 to 30 mol%. 25 mol% is particularly preferred.
  • Polyurethane (each constituent and raw material compound) may have a substituent.
  • the substituent is not particularly limited, but preferably, a group selected from the following substituent Z can be mentioned.
  • Polyurethane can be synthesized by selecting a raw material compound by a known method according to the type of bond possessed by the main chain and subjecting the raw material compound to polyaddition or polycondensation.
  • a synthesis method for example, International Publication No. 2018/151118 can be referred to.
  • each polyurethane described in International Publication No. 2018/020827, International Publication No. 2015/046313, and JP-A-2015-08480 has two types of polyether structures as main chains. Examples include those incorporated.
  • the water concentration of the polymer binder is preferably 100 ppm (mass basis) or less.
  • the fluorine-based copolymer may be crystallized and dried, or the polymer binder dispersion may be used as it is.
  • the fluorine-based copolymer is preferably amorphous.
  • the term "amorphous" as a polymer typically means that no endothermic peak due to crystal melting is observed when measured at the glass transition temperature.
  • the shape of the polymer binder is not particularly limited, but may be in the form of particles.
  • the particle shape at this time may be flat, amorphous, or the like, but is preferably spherical or granular.
  • the particle size of the particulate polymer binder is not particularly limited, but is preferably 0.1 nm or more, more preferably 1 nm or more, further preferably 5 nm or more, and particularly preferably 10 nm or more. It is preferably 50 nm or more, and most preferably 50 nm or more.
  • the upper limit value is preferably 1.0 ⁇ m or less, more preferably 700 nm or less, and particularly preferably 500 nm or less.
  • the average particle size of the composite polymer particles can be measured in the same manner as the average particle size of the inorganic solid electrolyte.
  • the average particle size of the polymer binder in the constituent layers of the all-solid-state secondary battery is measured in advance by, for example, disassembling the battery and peeling off the constituent layer containing the polymer binder, and then measuring the constituent layers. It can be measured by excluding the measured value of the particle size of the particles other than the polymer binder.
  • the mass average molecular weight of the polymer is not particularly limited, but for example, 5,000 or more is preferable, 10,000 or more is more preferable, 20,000 or more is further preferable, and 50,000 or more is particularly preferable.
  • the upper limit is substantially 5,000,000 or less, preferably 3,000,000 or less, more preferably 1,000,000 or less, and particularly preferably 500,000 or less.
  • the molecular weights of the polymer and the polymerized chain refer to the mass average molecular weight or the number average molecular weight in terms of standard polystyrene by gel permeation chromatography (GPC) unless otherwise specified.
  • GPC gel permeation chromatography
  • the measuring method basically, the value measured by the method of the following condition 1 or condition 2 (priority) is used. However, depending on the type of polymer, an appropriate eluent may be appropriately selected and used.
  • Condition 1 Column: Connect two TOSOH TSKgel Super AWM-H (trade name, manufactured by Tosoh Corporation) Carrier: 10 mM LiBr / N-methylpyrrolidone Measurement temperature: 40 ° C.
  • Carrier flow rate 1.0 ml / min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector (condition 2) Column: A column connected with TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 (all trade names, manufactured by Tosoh Corporation) is used.
  • Carrier tetrahydrofuran Measurement temperature: 40 ° C
  • Carrier flow rate 1.0 ml / min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector
  • the polymer forming the polymer binder may be a non-crosslinked polymer or a crosslinked polymer. Further, when the cross-linking of the polymer proceeds by heating or application of a voltage, the molecular weight may be larger than the above molecular weight. Preferably, the polymer has a mass average molecular weight in the above range at the start of use of the all-solid-state secondary battery.
  • the mass ratio of the total mass (total mass) of the inorganic solid electrolyte and the active material to the mass of the binder [(mass of the inorganic solid electrolyte + mass of the active material) / (total mass of the binder)] is 1,000.
  • the range of ⁇ 1 is preferable. This ratio is more preferably 500 to 2, and even more preferably 100 to 10.
  • the composition containing an inorganic solid electrolyte of the present invention may be a solid mixture without containing a dispersion medium for dispersing each of the above components, but it is preferable to contain a dispersion medium, and solid particles such as an inorganic solid electrolyte are used as a dispersion medium. It is preferably a slurry dispersed therein.
  • the dispersion medium may be an organic compound that is liquid in the environment of use, and examples thereof include various organic solvents. Specifically, an alcohol compound, an ether compound, an amide compound, an amine compound, a ketone compound, and an aromatic compound. , An aliphatic compound, a nitrile compound, an ester compound and the like.
  • the dispersion medium may be a non-polar dispersion medium (hydrophobic dispersion medium) or a polar dispersion medium (hydrophilic dispersion medium), but a non-polar dispersion medium is preferable because it can exhibit excellent dispersibility.
  • the non-polar dispersion medium generally refers to a property having a low affinity for water, and in the present invention, for example, an ester compound, a ketone compound, an ether compound, a perfume compound, an aliphatic compound and the like can be mentioned.
  • alcohol compounds include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, and 2 -Methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol can be mentioned.
  • ether compound examples include alkylene glycol (diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.), alkylene glycol monoalkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc.).
  • alkylene glycol diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.
  • alkylene glycol monoalkyl ether ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc.
  • amide compound examples include N, N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, ⁇ -caprolactam, formamide, N-methylformamide and acetamide. , N-Methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.
  • Examples of the amine compound include triethylamine, diisopropylethylamine, tributylamine and the like.
  • Examples of the ketone compound include acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, cycloheptanone, dipropyl ketone, dibutyl ketone, diisopropyl ketone, diisobutyl ketone (DIBK), isobutyl propyl ketone, sec-. Examples thereof include butyl propyl ketone, pentyl propyl ketone and butyl propyl ketone.
  • Examples of the aromatic compound include benzene, toluene, xylene and the like.
  • Examples of the aliphatic compound include hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, paraffin, gasoline, naphtha, kerosene, and light oil.
  • Examples of the nitrile compound include acetonitrile, propionitrile, isobutyronitrile and the like.
  • ester compound examples include ethyl acetate, butyl acetate, propyl acetate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, butyl pentanate, ethyl isobutyrate, propyl isobutyrate, isopropyl isobutyrate, isobutyl isobutyrate, and pivalic acid.
  • Examples thereof include propyl, isopropyl pivalate, butyl pivalate, and isobutyl pivalate.
  • ether compounds, ketone compounds, aromatic compounds, aliphatic compounds and ester compounds are preferable, and ketone compounds, aliphatic compounds or ester compounds are more preferable.
  • the number of carbon atoms of the compound constituting the dispersion medium is not particularly limited, and is preferably 2 to 30, more preferably 4 to 20, further preferably 6 to 15, and particularly preferably 7 to 12.
  • the dispersion medium preferably has a boiling point of 50 ° C. or higher at normal pressure (1 atm), and more preferably 70 ° C. or higher.
  • the upper limit is preferably 250 ° C. or lower, and more preferably 220 ° C. or lower.
  • the dispersion medium may be at least one type and may be two or more types. Further, the content of the dispersion medium is not particularly limited and can be appropriately set. For example, in the composition containing an inorganic solid electrolyte, 20 to 80% by mass is preferable, 30 to 70% by mass is more preferable, and 40 to 60% by mass is particularly preferable.
  • the inorganic solid electrolyte-containing composition of the present invention may also contain an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table.
  • the active material include a positive electrode active material and a negative electrode active material, which will be described below.
  • an inorganic solid electrolyte-containing composition containing an active material positive electrode active material or negative electrode active material
  • an electrode composition positive electrode composition or negative electrode composition
  • the positive electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table, and is preferably one capable of reversibly inserting and releasing lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, and may be a transition metal oxide, an organic substance, an element that can be composited with Li such as sulfur, or the like by decomposing the battery.
  • a transition metal oxide having preferably used a transition metal oxide, a transition metal element M a (Co, Ni, Fe , Mn, 1 or more elements selected from Cu and V) the Things are more preferred.
  • this transition metal oxide contains element Mb (elements of Group 1 (Ia), Group 2 (IIa), Al, Ga, In, Ge, Sn, Pb, etc. of the periodic table of metals other than lithium. Elements such as Sb, Bi, Si, P and B) may be mixed.
  • the mixing amount is preferably 0 to 30 mol% relative to the amount of the transition metal element M a (100 mol%). That the molar ratio of li / M a was synthesized were mixed so that 0.3 to 2.2, more preferably.
  • transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt type structure, (MB) a transition metal oxide having a spinel type structure, (MC) a lithium-containing transition metal phosphoric acid compound, and (MD). ) Lithium-containing transition metal halide phosphoric acid compound, (ME) lithium-containing transition metal silicic acid compound, and the like.
  • transition metal oxide having a layered rock salt structure examples include LiCoO 2 (lithium cobalt oxide [LCO]), LiNi 2 O 2 (lithium nickel oxide), LiNi 0.85 Co 0.10 Al 0. 05 O 2 (Lithium Nickel Cobalt Oxide [NCA]), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (Lithium Nickel Manganese Cobalt Oxide [NMC]) and LiNi 0.5 Mn 0.5 O 2 ( Lithium manganese nickel oxide).
  • LiCoO 2 lithium cobalt oxide [LCO]
  • LiNi 2 O 2 lithium nickel oxide
  • LiNi 0.85 Co 0.10 Al 0. 05 O 2 Lithium Nickel Cobalt Oxide [NCA]
  • LiNi 1/3 Co 1/3 Mn 1/3 O 2 Lithium Nickel Manganese Cobalt Oxide [NMC]
  • LiNi 0.5 Mn 0.5 O 2 Lithium manganese nickel oxide
  • (MB) Specific examples of the transition metal oxide having a spinel structure, LiMn 2 O 4 (LMO) , LiCoMnO 4, Li 2 FeMn 3 O 8, Li 2 CuMn 3 O 8, Li 2 CrMn 3 O 8 and Li 2 Nimn 3 O 8 can be mentioned.
  • Examples of the (MC) lithium-containing transition metal phosphate compound include olivine-type iron phosphate salts such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , and LiCoPO 4.
  • Examples thereof include cobalt phosphates of the above, and monoclinic panocycon-type vanadium phosphate salts such as Li 3 V 2 (PO 4 ) 3 (lithium vanadium phosphate).
  • (MD) as the lithium-containing transition metal halogenated phosphate compound for example, Li 2 FePO 4 F such fluorinated phosphorus iron salt, Li 2 MnPO 4 hexafluorophosphate manganese salts such as F and Li 2 CoPO 4 F Fluorophosphate cobalts such as.
  • Examples of the (ME) lithium-containing transition metal silicic acid compound include Li 2 FeSiO 4 , Li 2 MnSiO 4 , and Li 2 CoSiO 4 .
  • a transition metal oxide having a (MA) layered rock salt type structure is preferable, and LCO or NMC is more preferable.
  • the shape of the positive electrode active material is not particularly limited, but is preferably in the form of particles.
  • the particle size (volume average particle size) of the positive electrode active material is not particularly limited. For example, it can be 0.1 to 50 ⁇ m.
  • the particle size of the positive electrode active material particles can be measured in the same manner as the particle size of the above-mentioned inorganic solid electrolyte.
  • a normal crusher or classifier is used to adjust the positive electrode active material to a predetermined particle size. For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling airflow type jet mill, a sieve, or the like is preferably used.
  • wet pulverization in which a dispersion medium such as water or methanol coexists can also be performed. It is preferable to perform classification in order to obtain a desired particle size.
  • the classification is not particularly limited and can be performed using a sieve, a wind power classifier, or the like. Both dry and wet classifications can be used.
  • the positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
  • the content of the positive electrode active material in the composition containing an inorganic solid electrolyte is not particularly limited, and is preferably 10 to 97% by mass, more preferably 30 to 95% by mass, and 40 to 93% by mass in terms of solid content of 100% by mass. More preferably, 50 to 90% by mass is particularly preferable.
  • the negative electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table, and is preferably one capable of reversibly inserting and releasing lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, and is a negative electrode activity capable of forming an alloy with a carbonaceous material, a metal oxide, a metal composite oxide, a single lithium substance, a lithium alloy, or lithium. Examples include substances. Of these, carbonaceous materials, metal composite oxides, or elemental lithium are preferably used from the viewpoint of reliability.
  • An active material that can be alloyed with lithium is preferable in that the capacity of the all-solid-state secondary battery can be increased.
  • a negative electrode active material capable of forming an alloy with lithium can be used as the negative electrode active material. This makes it possible to increase the capacity of the all-solid-state secondary battery and extend the life of the battery.
  • the carbonaceous material used as the negative electrode active material is a material substantially composed of carbon.
  • carbon black such as acetylene black (AB), graphite (artificial graphite such as natural graphite and vapor-grown graphite), and PAN (polyacrylonitrile) -based resin or furfuryl alcohol resin.
  • a carbonaceous material obtained by firing a resin can be mentioned.
  • various carbon fibers such as PAN-based carbon fibers, cellulose-based carbon fibers, pitch-based carbon fibers, vapor-grown carbon fibers, dehydrated PVA (polypoly alcohol) -based carbon fibers, lignin carbon fibers, graphitic carbon fibers, and activated carbon fibers.
  • carbonaceous materials can also be divided into non-graphitizable carbonaceous materials (also referred to as hard carbon) and graphite-based carbonaceous materials depending on the degree of graphitization. Further, the carbonaceous material preferably has the plane spacing or density and the size of crystallites described in JP-A No. 62-22066, JP-A No. 2-6856, and JP-A-3-45473.
  • the carbonaceous material does not have to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, and the like should be used. You can also.
  • As the carbonaceous material hard carbon or graphite is preferably used, and graphite is more preferably used.
  • the metal or semi-metal element oxide applied as the negative electrode active material is not particularly limited as long as it is an oxide capable of storing and releasing lithium, and is a composite of a metal element oxide (metal oxide) and a metal element.
  • metal oxide metal oxide
  • examples thereof include oxides or composite oxides of metal elements and semi-metal elements (collectively referred to as metal composite oxides) and oxides of semi-metal elements (semi-metal oxides).
  • metal composite oxides oxides or composite oxides of metal elements and semi-metal elements
  • oxides of semi-metal elements semi-metal elements
  • amorphous oxides are preferable, and chalcogenides, which are reaction products of metal elements and elements of Group 16 of the Periodic Table, are also preferable.
  • the metalloid element means an element exhibiting properties intermediate between a metalloid element and a non-metalloid element, and usually contains six elements of boron, silicon, germanium, arsenic, antimony and tellurium, and further selenium. , Polonium and Astatine.
  • amorphous means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering band having an apex in a region of 20 ° to 40 ° in 2 ⁇ value, and a crystalline diffraction line is used. You may have.
  • the inorganic solid electrolyte-containing composition of the present invention may not contain a dispersant other than this polymer binder, but may contain a dispersant.
  • the dispersant those usually used for all-solid-state secondary batteries can be appropriately selected and used. Generally, compounds intended for particle adsorption, steric repulsion and / or electrostatic repulsion are preferably used.
  • the composition containing an inorganic solid electrolyte of the present invention contains, as other components other than the above components, an ionic liquid, a thickener, and a cross-linking agent (such as those that undergo a cross-linking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization).
  • a cross-linking agent such as those that undergo a cross-linking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization.
  • Polymerization initiators such as those that generate acids or radicals by heat or light
  • defoaming agents leveling agents, dehydrating agents, antioxidants and the like
  • the ionic liquid is contained in order to further improve the ionic conductivity, and known ones can be used without particular limitation.
  • a polymer other than the polymer contained in the above-mentioned binder, a commonly used binder and the like may be contained.
  • the composition containing an inorganic solid electrolyte of the present invention comprises an inorganic solid electrolyte and the above-mentioned compound (LB), preferably a polymer binder, a dispersion medium, an active material depending on the application, a conductive auxiliary agent, and optionally a lithium salt.
  • LB a compound that is a polymer binder
  • Any other component can be prepared, for example, as a mixture, preferably as a slurry, by mixing with various commonly used mixers.
  • the mixing method is not particularly limited, and the mixture may be mixed all at once or sequentially.
  • the mixing environment is not particularly limited, and examples thereof include under dry air and under an inert gas.
  • the sheet for an all-solid-state secondary battery of the present invention is a sheet-like molded body capable of forming a constituent layer of an all-solid-state secondary battery, and includes various aspects depending on its use.
  • a sheet preferably used for a solid electrolyte layer also referred to as a solid electrolyte sheet for an all-solid secondary battery
  • an electrode or a sheet preferably used for a laminate of an electrode and a solid electrolyte layer (an electrode for an all-solid secondary battery).
  • Sheet and the like.
  • these various sheets are collectively referred to as an all-solid-state secondary battery sheet.
  • the solid electrolyte sheet for an all-solid secondary battery of the present invention may be a sheet having a solid electrolyte layer, and even a sheet in which the solid electrolyte layer is formed on a base material does not have a base material and is a solid electrolyte layer. It may be a sheet formed of.
  • the solid electrolyte sheet for an all-solid secondary battery may have another layer in addition to the solid electrolyte layer. Examples of other layers include a protective layer (release sheet), a current collector, a coat layer, and the like.
  • the solid electrolyte sheet for an all-solid secondary battery of the present invention for example, a sheet having a layer composed of the inorganic solid electrolyte-containing composition of the present invention, a normal solid electrolyte layer, and a protective layer on a substrate in this order.
  • the solid electrolyte layer contained in the solid electrolyte sheet for an all-solid secondary battery is preferably formed of the inorganic solid electrolyte-containing composition of the present invention.
  • the content of each component in the solid electrolyte layer is not particularly limited, but is preferably synonymous with the content of each component in the solid content of the inorganic solid electrolyte-containing composition of the present invention.
  • the layer thickness of each layer constituting the solid electrolyte sheet for an all-solid-state secondary battery is the same as the layer thickness of each layer described in the all-solid-state secondary battery described later.
  • the base material is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include a material described in the current collector described later, a sheet body (plate-like body) of an organic material, an inorganic material, and the like.
  • the organic material include various polymers, and specific examples thereof include polyethylene terephthalate, polypropylene, polyethylene, and cellulose.
  • the inorganic material include glass, ceramic and the like.
  • the electrode sheet for an all-solid-state secondary battery of the present invention may be an electrode sheet having an active material layer, and the active material layer is formed on a base material (current collector).
  • the sheet may be a sheet that does not have a base material and is formed from an active material layer.
  • This electrode sheet is usually a sheet having a current collector and an active material layer, but has an embodiment having a current collector, an active material layer and a solid electrolyte layer in this order, and a current collector, an active material layer and a solid electrolyte. An embodiment having a layer and an active material layer in this order is also included.
  • the solid electrolyte layer and the active material layer of the electrode sheet are preferably formed of the inorganic solid electrolyte-containing composition of the present invention.
  • the content of each component in the solid electrolyte layer or the active material layer is not particularly limited, but preferably, the content of each component in the solid content of the inorganic solid electrolyte-containing composition (electrode composition) of the present invention. Is synonymous with.
  • the layer thickness of each layer constituting the electrode sheet of the present invention is the same as the layer thickness of each layer described in the all-solid-state secondary battery described later.
  • the electrode sheet of the present invention may have the other layers described above.
  • the all-solid-state secondary battery sheet of the present invention at least one of the solid electrolyte layer and the active material layer is formed of the inorganic solid electrolyte-containing composition of the present invention, and the active material layer preferably contains the inorganic solid electrolyte of the present invention. Formed from the composition. Therefore, the constituent layers formed of the inorganic solid electrolyte-containing composition of the present invention have solid particles firmly bound to each other, and high layer strength can be realized as shown in Examples described later.
  • the sheet for the all-solid-state secondary battery of the present invention as a constituent layer of the all-solid-state secondary battery, excellent cycle characteristics and low resistance of the all-solid-state secondary battery can be realized.
  • the negative electrode sheet for an all-solid secondary battery and the all-solid secondary battery in which the negative electrode active material is formed of the inorganic solid electrolyte-containing composition of the present invention may use a negative electrode active material capable of forming an alloy with lithium as the negative electrode active material. , Low resistance and high cycle characteristics can be achieved while showing high active material capacity.
  • the method for producing the sheet for an all-solid secondary battery of the present invention is not particularly limited, and the sheet can be produced by forming each of the above layers using the inorganic solid electrolyte-containing composition of the present invention.
  • the inorganic solid electrolyte-containing composition of the present invention is a solid mixture, a method of forming it by pressure molding on a base material or a current collector can be mentioned.
  • the inorganic solid electrolyte-containing composition of the present invention contains a dispersion medium, it is preferably formed (coated and dried) on a base material or a current collector (may be via another layer).
  • Examples thereof include a method of forming a layer (coating dry layer) composed of an inorganic solid electrolyte-containing composition.
  • a layer coating dry layer
  • the coating dry layer is a layer formed by applying the inorganic solid electrolyte-containing composition of the present invention and drying the dispersion medium (that is, the inorganic solid electrolyte-containing composition of the present invention is used.
  • the all-solid secondary battery of the present invention comprises a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer arranged between the positive electrode active material layer and the negative electrode active material layer.
  • the positive electrode active material layer is preferably formed on the positive electrode current collector and constitutes the positive electrode.
  • the negative electrode active material layer is preferably formed on the negative electrode current collector to form the negative electrode.
  • At least one layer of the negative electrode active material layer, the positive electrode active material layer and the solid electrolyte layer is formed by the inorganic solid electrolyte-containing composition of the present invention, and the negative electrode active material layer is formed by the inorganic solid electrolyte-containing composition of the present invention.
  • the electrode is used. It is also one of the preferred embodiments that all layers are formed of the inorganic solid electrolyte-containing composition of the present invention.
  • the active material layer or solid electrolyte layer formed of the inorganic solid electrolyte-containing composition of the present invention preferably contains the component species and their content ratios in the solid content of the inorganic solid electrolyte-containing composition of the present invention. Is the same as.
  • a known material can be used.
  • the thicknesses of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer are not particularly limited.
  • each layer is preferably 10 to 1,000 ⁇ m, more preferably 20 ⁇ m or more and less than 500 ⁇ m, respectively, in consideration of the dimensions of a general all-solid-state secondary battery.
  • the thickness of at least one of the positive electrode active material layer and the negative electrode active material layer is more preferably 50 ⁇ m or more and less than 500 ⁇ m.
  • the positive electrode active material layer and the negative electrode active material layer may each have a current collector on the opposite side of the solid electrolyte layer.
  • FIG. 1 is a sectional view schematically showing an all-solid-state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention.
  • the all-solid-state secondary battery 10 of the present embodiment has a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 in this order when viewed from the negative electrode side. ..
  • Each layer is in contact with each other and has an adjacent structure.
  • the lithium ions (Li + ) accumulated in the negative electrode are returned to the positive electrode side, and electrons are supplied to the operating portion 6.
  • a light bulb is used as a model for the operating portion 6, and the light bulb is turned on by electric discharge.
  • the all-solid-state secondary battery having the layer structure shown in FIG. 1 When the all-solid-state secondary battery having the layer structure shown in FIG. 1 is placed in a 2032-inch coin case, the all-solid-state secondary battery is referred to as an all-solid-state secondary battery laminate, and the all-solid-state secondary battery laminate is referred to as an all-solid-state secondary battery laminate. Batteries manufactured in a 2032 type coin case are sometimes referred to as all-solid-state secondary batteries.
  • the all-solid-state secondary battery 10 In the all-solid-state secondary battery 10, all of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer are formed of the inorganic solid electrolyte-containing composition of the present invention.
  • the all-solid-state secondary battery 10 exhibits excellent battery performance.
  • the inorganic solid electrolyte, the compound (LB), and the polymer binder contained in the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 may be of the same type or different from each other.
  • either or both of the positive electrode active material layer and the negative electrode active material layer may be simply referred to as an active material layer or an electrode active material layer.
  • either or both of the positive electrode active material and the negative electrode active material may be collectively referred to as an active material or an electrode active material.
  • an all-solid-state secondary battery having excellent cycle characteristics and an all-solid-state secondary battery having low resistance can be realized.
  • the negative electrode active material layer can be a lithium metal layer.
  • the lithium metal layer include a layer formed by depositing or molding a lithium metal powder, a lithium foil, a lithium vapor deposition film, and the like.
  • the thickness of the lithium metal layer can be, for example, 1 to 500 ⁇ m regardless of the thickness of the negative electrode active material layer.
  • the positive electrode current collector 5 and the negative electrode current collector 1 are preferably electron conductors.
  • either or both of the positive electrode current collector and the negative electrode current collector may be collectively referred to as a current collector.
  • a current collector As a material for forming the positive electrode current collector, in addition to aluminum, aluminum alloy, stainless steel, nickel and titanium, the surface of aluminum or stainless steel is treated with carbon, nickel, titanium or silver (a thin film is formed). Of these, aluminum and aluminum alloys are more preferable.
  • As a material for forming the negative electrode current collector in addition to aluminum, copper, copper alloy, stainless steel, nickel and titanium, carbon, nickel, titanium or silver is treated on the surface of aluminum, copper, copper alloy or stainless steel. Aluminum, copper, copper alloy and stainless steel are more preferable.
  • the shape of the current collector is usually a film sheet, but a net, a punched body, a lath body, a porous body, a foam body, a molded body of a fiber group, or the like can also be used.
  • the thickness of the current collector is not particularly limited, but is preferably 1 to 500 ⁇ m. Further, it is also preferable that the surface of the current collector is made uneven by surface treatment.
  • a layer formed of a known constituent layer-forming material can be applied to the positive electrode active material layer.
  • a functional layer, a member, or the like is appropriately interposed or arranged between or outside each of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector. You may. Further, each layer may be composed of a single layer or a plurality of layers.
  • the all-solid-state secondary battery can be manufactured by a conventional method. Specifically, the all-solid-state secondary battery can be manufactured by forming each of the above layers using the inorganic solid electrolyte-containing composition or the like of the present invention. The details will be described below.
  • the inorganic solid electrolyte-containing composition of the present invention is appropriately applied onto a base material (for example, a metal foil serving as a current collector) to form a coating film (film formation).
  • a method including (via) a step a method for producing a sheet for an all-solid-state secondary battery of the present invention
  • an inorganic solid electrolyte-containing composition containing a positive electrode active material is applied as a positive electrode material (positive electrode composition) on a metal foil which is a positive electrode current collector to form a positive electrode active material layer, and the entire solid is formed.
  • a positive electrode sheet for a secondary battery is produced.
  • an inorganic solid electrolyte-containing composition for forming the solid electrolyte layer is applied onto the positive electrode active material layer to form the solid electrolyte layer.
  • an inorganic solid electrolyte-containing composition containing a negative electrode active material is applied as a negative electrode material (negative electrode composition) on the solid electrolyte layer to form a negative electrode active material layer.
  • a negative electrode current collector metal foil
  • an all-solid secondary battery having a structure in which a solid electrolyte layer is sandwiched between the positive electrode active material layer and the negative electrode active material layer can be obtained. Can be done. This can be enclosed in a housing to obtain a desired all-solid-state secondary battery.
  • a negative electrode active material layer, a solid electrolyte layer and a positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collectors are superposed to manufacture an all-solid secondary battery. You can also do it.
  • a positive electrode sheet for an all-solid-state secondary battery is produced. Further, an inorganic solid electrolyte-containing composition containing a negative electrode active material is applied as a negative electrode material (negative electrode composition) on a metal foil which is a negative electrode current collector to form a negative electrode active material layer, and the entire solid is formed. A negative electrode sheet for a secondary battery is manufactured. Next, a solid electrolyte layer is formed on the active material layer of any one of these sheets as described above.
  • the other of the positive electrode sheet for the all-solid secondary battery and the negative electrode sheet for the all-solid secondary battery is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other.
  • an all-solid-state secondary battery can be manufactured.
  • the following method can be mentioned. That is, as described above, a positive electrode sheet for an all-solid-state secondary battery and a negative electrode sheet for an all-solid-state secondary battery are produced. Separately from this, an inorganic solid electrolyte-containing composition is applied onto a base material to prepare a solid electrolyte sheet for an all-solid secondary battery composed of a solid electrolyte layer.
  • the positive electrode sheet for the all-solid-state secondary battery and the negative electrode sheet for the all-solid-state secondary battery are laminated so as to sandwich the solid electrolyte layer peeled from the base material. In this way, an all-solid-state secondary battery can be manufactured. Further, as described above, a positive electrode sheet for an all-solid-state secondary battery or a negative electrode sheet for an all-solid-state secondary battery, and a solid electrolyte sheet for an all-solid-state secondary battery are produced. Next, the positive electrode sheet for the all-solid secondary battery or the negative electrode sheet for the all-solid secondary battery and the solid electrolyte sheet for the all-solid secondary battery were brought into contact with the positive electrode active material layer or the negative electrode active material layer and the solid electrolyte layer.
  • the solid electrolyte layer is transferred to the positive electrode sheet for the all-solid-state secondary battery or the negative electrode sheet for the all-solid-state secondary battery.
  • the pressurizing method and pressurizing conditions in this method are not particularly limited, and the methods and pressurizing conditions described later in the pressurization of the applied composition can be applied.
  • the solid electrolyte layer or the like can be formed by, for example, press-molding an inorganic solid electrolyte-containing composition or the like on a substrate or an active material layer under the pressure conditions described later, or sheet molding of the solid electrolyte or the active material. You can also use the body.
  • the inorganic solid electrolyte-containing composition of the present invention may be used as any one of the positive electrode composition, the inorganic solid electrolyte-containing composition and the negative electrode composition, and the present invention may be used as the negative electrode composition. It is preferable to use the inorganic solid electrolyte-containing composition of the above, and the inorganic solid electrolyte-containing composition of the present invention can be used for any of the compositions.
  • the solid electrolyte layer or the active material layer is formed by a composition other than the solid electrolyte composition of the present invention
  • examples of the material include commonly used compositions and the like. Further, it belongs to the first group or the second group of the periodic table, which is accumulated in the negative electrode current collector by the initialization or charging during use, which will be described later, without forming the negative electrode active material layer at the time of manufacturing the all-solid secondary battery.
  • a negative electrode active material layer can also be formed by combining metal ions with electrons and precipitating them as a metal on a negative electrode current collector or the like.
  • the dispersion medium can be removed and a solid state (coating dry layer) can be obtained. Further, it is preferable because the temperature is not raised too high and each member of the all-solid-state secondary battery is not damaged. As a result, in an all-solid-state secondary battery, it is possible to obtain excellent overall performance, good binding properties, and good ionic conductivity even without pressurization.
  • the all-solid-state secondary battery manufactured as described above is preferably initialized after manufacturing or before use.
  • the initialization is not particularly limited, and can be performed, for example, by performing initial charging / discharging with the press pressure increased, and then releasing the pressure until the pressure reaches the general working pressure of the all-solid-state secondary battery.
  • negative electrode compositions S-32 to S-50 and cS-1 to cS-3 were prepared as non-aqueous compositions, respectively.
  • the following solution of compound (LB) The above compounds (LB) A-11, 13, 17-22 and C-01 were each dissolved in butyl butyrate to prepare a solution having a concentration of 3% by mass.
  • Table 3 shows the content ratios: [LB] / [SE] and [BR] / [LB] in each of the negative electrode compositions thus obtained.
  • composition S-51 for negative electrode ⁇ Preparation of composition S-51 for negative electrode>
  • the binder PVDF-HFP was changed to the polyurethane binder B-1 synthesized in Synthesis Example 1 below, and the mixture amount of the binder and butyl butyrate were mixed so that the solid content was the same.
  • the negative electrode composition S-51 was prepared as a non-aqueous composition in the same manner as in the preparation of the negative electrode composition S-35 except that the amount was adjusted.
  • binder dispersion B-1 15.00 g of the polymer solution obtained above was diluted with 15.00 g of THF, and 90.00 g of butyl butyrate was added dropwise over 1 hour with stirring to obtain an emulsion of polymer B-1. This emulsion is concentrated to about 70 g, and butyl butyrate is added to bring the total amount to 100.00 g to obtain a 3% by mass butyl butyrate dispersion (binder dispersion B-1) of a binder composed of polymer B-1. It was.
  • the content is the content in 100% by mass of the solid content of the composition for the negative electrode, and the unit is mass%.
  • Si The silicon conductive aid is acetylene black.
  • the binder is a polymer binder made of PVDF-HFP or a polyurethane binder B-1.
  • composition containing inorganic solid electrolyte 180 zirconia beads having a diameter of 5 mm were put into a zirconia 45 mL container (manufactured by Fritsch), 4.85 g of LPS synthesized in Synthesis Example A, 0.15 g (solid content mass) of the following polymer binder solution, and 16.0 g of butyl butyrate was added. Then, this container was set in a planetary ball mill P-7 manufactured by Fritsch, and mixed at a temperature of 25 ° C. and a rotation speed of 150 rpm for 10 minutes to prepare an inorganic solid electrolyte-containing composition.
  • Binder solution A polymer binder solution having a solid content concentration of 3% by mass, prepared by dissolving PVDF-HFP (KYNER FLEX 2500-20 manufactured by Arkema) in butyl butyrate.
  • the inorganic solid electrolyte-containing composition obtained above is applied onto an aluminum foil having a thickness of 20 ⁇ m using an applicator (trade name: SA-201) and heated at 80 ° C. for 2 hours to prepare the inorganic solid electrolyte-containing composition.
  • the inorganic solid electrolyte-containing composition dried at a temperature of 120 ° C. and a pressing force of 600 MPa for 10 seconds was heated and pressurized to prepare a solid electrolyte sheet for an all-solid secondary battery.
  • the layer thickness of the solid electrolyte layer was 50 ⁇ m.
  • a disk-shaped positive electrode sheet is laminated on the solid electrolyte layer of the disk-shaped sheet so that the solid electrolyte layer and the positive electrode active material layer are in contact with each other, and the laminate 12 for an all-solid secondary battery (aluminum foil-positive electrode active material layer- A laminated body composed of a solid electrolyte layer-negative electrode active material layer-stainless steel foil) was formed. After that, by crimping the 2032 type coin case 11, the all-solid-state secondary battery No. 2 shown in FIG. 1 to 20 and C1 to C3 were produced, respectively.
  • the all-solid-state secondary battery manufactured in this manner has the layer structure shown in FIG.
  • Table 3 shows the results of evaluating the following characteristics for 1 to 20 and C1 to C3 and the like.
  • Table 3 shows the ratio of the content [SE] of the inorganic solid electrolyte to the content [LB] of the compound (LB) in 100% by mass of the solid content (negative negative active material layer) of the composition containing the inorganic solid electrolyte: [ LB] / [SE] and the ratio of the content [BR] of the polymer binder to the content [LB] of the compound (LB): [BR] / [LB] are calculated and shown, respectively.
  • the compound described in the "Compound (LB)" column in Table 3 indicates the compound (LB) contained in the negative electrode active material layer.
  • the inorganic solid electrolyte-containing composition of the present invention in which the compound (LB) specified in the present invention is used in combination with the inorganic solid electrolyte has high layer strength and can firmly bind the inorganic solid electrolytes to each other.
  • the all-solid-state secondary battery of the present invention having a constituent layer formed of these inorganic solid electrolyte-containing compositions can achieve both low resistance and excellent cycle characteristics.
  • Si which has a large expansion and contraction due to charge and discharge, is used as the negative electrode active material, it is possible to achieve both low resistance and excellent cycle characteristics while exhibiting a high active material capacity.
  • an inorganic solid electrolyte-containing composition containing or not containing an ordinary active material can also form a constituent layer exhibiting high layer strength, and can provide an all-solid-state secondary battery with low resistance and excellent cycle characteristics. It turns out that it can be granted.

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CN117716524A (zh) * 2021-09-29 2024-03-15 富士胶片株式会社 电极用片材及全固态二次电池、以及电极用片材、电极片及全固态二次电池的制造方法

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