WO2015147281A1 - 全固体二次電池、これに用いる固体電解質組成物および電池用電極シート、ならびに電池用電極シートおよび全固体二次電池の製造方法 - Google Patents

全固体二次電池、これに用いる固体電解質組成物および電池用電極シート、ならびに電池用電極シートおよび全固体二次電池の製造方法 Download PDF

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WO2015147281A1
WO2015147281A1 PCT/JP2015/059679 JP2015059679W WO2015147281A1 WO 2015147281 A1 WO2015147281 A1 WO 2015147281A1 JP 2015059679 W JP2015059679 W JP 2015059679W WO 2015147281 A1 WO2015147281 A1 WO 2015147281A1
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group
chain
formula
solid electrolyte
solid
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French (fr)
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雅臣 牧野
宏顕 望月
目黒　克彦
智則 三村
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Fujifilm Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • 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
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to an all-solid secondary battery, a solid electrolyte composition used therefor, and an electrode sheet for a battery, and an electrode sheet for a battery and a method for producing an all-solid secondary battery.
  • the inorganic solid electrolyte exhibits higher ionic conductivity than the polymer electrolyte.
  • a further advantage of the all-solid-state secondary battery is that it is suitable for increasing the energy density by stacking electrodes. Specifically, a battery having a structure in which an electrode and an electrolyte are directly arranged in series can be obtained. At this time, since the metal package for sealing the battery cell, the copper wire and the bus bar for connecting the battery cell can be omitted, the energy density of the battery is greatly increased. In addition, good compatibility with the positive electrode material capable of increasing the potential is also mentioned as an advantage.
  • Non-patent Document 1 Developed as a next-generation lithium ion secondary battery due to the above-described advantages, it has been vigorously developed (Non-patent Document 1).
  • an inorganic all-solid secondary battery has a disadvantage because the electrolyte is a hard solid. For example, the interface resistance between solid particles is increased.
  • Patent Document 1 uses a surfactant having a polyoxyethylene chain.
  • Patent Document 2 discloses the use of a hydrogenated butadiene copolymer.
  • Patent Document 3 exemplifies application of polyalkyleneimine-fatty acid amide compounds to electrode materials, although it is not clear how to use them in all solid state secondary batteries.
  • the increase in interface resistance and heat resistance in all solid state secondary batteries may be improved accordingly.
  • the binder made of the polymer compound disclosed in the above document cannot satisfy the recent high demand level, and further improvement is desired. Therefore, the present invention achieves high ionic conductivity without relying on the pressurization of the active material layer and the inorganic solid electrolyte layer in the all solid state secondary battery. It is an object of the present invention to provide an all-solid secondary battery that achieves stability over time, a solid electrolyte composition and an electrode sheet for the battery, and a method for producing the battery electrode sheet and the all-solid secondary battery.
  • An all-solid secondary battery having a positive electrode active material layer, a negative electrode active material layer, and an inorganic solid electrolyte layer, and at least one of a positive electrode active material layer, a negative electrode active material layer, and an inorganic solid electrolyte layer
  • the conductivity of the nitrogen-containing polymer having a repeating unit having at least one of the following substituent X, substituent Y and substituent Z and ions of metals belonging to group 1 or group 2 of the periodic table
  • An all-solid secondary battery comprising an inorganic solid electrolyte.
  • X represents a group containing a functional group having a pKa of 14 or less.
  • Y represents a group having a polymer chain containing a hetero atom. Y may be linked to other nitrogen-containing polymer molecules to form a linking chain.
  • Z represents a hydrogen atom which is bonded to a nitrogen atom to form —NH—, a group having an alkyl group having 1 to 30 carbon atoms, a group having a halogenated alkyl group having 1 to 30 carbon atoms, or a silicone chain having 1 to 100 silicon atoms.
  • the nitrogen-containing polymer has a repeating unit represented by any of the following formulas (1-1) to (1-3) and (2-1) to (2-3) All-solid secondary battery.
  • R 3 represents a hydrogen atom, a halogen atom, or an alkyl group.
  • R 5 represents a hydrogen atom or an alkyl group.
  • L 2 represents a single bond, an alkylene group, CO, O, or a combination thereof.
  • X, Y, and Z are as defined above. * Represents a connecting part between repeating units. [3] above Z is, # - L R - (L 1) all-solid secondary battery according to have the structure represented by p -Z 1 (1) or (2). # Represents the site
  • L R represents an alkylene group having 1 to 12 carbon atoms.
  • L 1 represents CO, NR N , O, or a combination thereof.
  • p represents 0 or 1;
  • RN represents a hydrogen atom or a substituent.
  • Z 1 represents an alkyl group having 1 to 30 carbon atoms, a halogenated alkyl group having 1 to 30 carbon atoms, or a silicone chain having 1 to 100 silicon atoms.
  • the substituent X is a group having a functional group selected from a carboxyl group, a sulfonic acid group, a phosphoric acid group, and —COCH 2 CO—.
  • Y 1 represents a group having a monovalent polyester chain, polyamide chain, polyimide chain, polyacryl chain, polyether chain, or polycarbonate chain having a number average molecular weight of 500 to 1,000,000.
  • Y 2 represents a group having a divalent polyester chain, polyamide chain, polyimide chain, polyacryl chain, polyether chain, or polycarbonate chain having a number average molecular weight of 500 to 1,000,000.
  • Y 1 represents a group having a monovalent polyester chain, polyamide chain, polyimide chain, polyacryl chain, polyether chain, or polycarbonate chain having a number average molecular weight of 500 to 1,000,000.
  • Y 2 represents a group having a divalent polyester chain, polyamide chain, polyimide chain, polyacryl chain, polyether chain, or polycarbonate chain having a number average molecular weight of 500 to 1,000,000.
  • Y 11 represents any one of a monovalent polyether chain, a polyester chain, a polycarbonate chain, and a polyacryl chain.
  • R 6 represents a hydrogen atom or a methyl group.
  • Y 21 represents a divalent polyether chain, a polyester chain, a polycarbonate chain, or a polyacryl chain.
  • R 6 represents a hydrogen atom or a methyl group.
  • X represents a group containing a functional group having a pKa of 14 or less.
  • Y represents a group having a polymer chain containing a hetero atom. Y may be linked to other nitrogen-containing polymer molecules to form a linking chain.
  • Z represents a hydrogen atom which is bonded to a nitrogen atom to form —NH—, a group having an alkyl group having 1 to 30 carbon atoms, a group having a halogenated alkyl group having 1 to 30 carbon atoms, or a silicone chain having 1 to 100 silicon atoms.
  • a method for producing an all-solid secondary battery comprising producing an all-solid secondary battery via the production method according to [17].
  • each substitution may be the same as or different from each other. Further, when a plurality of substituents and the like are close to each other, they may be bonded to each other or condensed to form a ring.
  • the all-solid-state secondary battery of the present invention realizes high ionic conductivity without depending on the pressure of the active material layer and the inorganic solid electrolyte layer, and further has excellent material binding, and if necessary, stable over time during production. Realize sex.
  • the above-described battery electrode sheet and all-solid secondary battery can be suitably produced. .
  • FIG. 1 is a cross-sectional view schematically showing an all solid lithium ion secondary battery according to a preferred embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing a test apparatus used in the examples.
  • the all-solid-state secondary battery of the present invention comprises a positive electrode active material layer, a negative electrode active material layer, and an inorganic solid electrolyte layer, and any of these layers has an ion conductive inorganic solid electrolyte and a specific nitrogen-containing polymer. Containing.
  • the “solid electrolyte composition” means a composition containing an inorganic solid electrolyte.
  • FIG. 1 is a cross-sectional view schematically showing an all solid state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention.
  • the all-solid-state secondary battery 10 of the present embodiment includes a negative electrode current collector 1, a negative electrode active material layer 2, an inorganic solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 in that order as viewed from the negative electrode side. Have in.
  • Each layer is in contact with each other and has a laminated structure.
  • the solid electrolyte composition of the present invention is preferably used as a constituent material of the negative electrode active material layer, the positive electrode active material layer or the inorganic solid electrolyte layer, and among them, the inorganic solid electrolyte layer, the positive electrode active material layer, and the negative electrode active material layer. It is preferable to use as all constituent materials.
  • the positive electrode active material layer and the negative electrode active material layer may be collectively referred to as an “active material layer”.
  • the inorganic solid electrolyte layer may be referred to as “solid electrolyte layer” or “electrolyte layer”.
  • the thicknesses of the positive electrode active material layer 4 and the negative electrode active material layer 2 can be determined according to the target battery capacity. In consideration of general element dimensions, it is preferably 1 ⁇ m or more, and more preferably 3 ⁇ m. As an upper limit, it is preferable that it is 1000 micrometers or less, and it is more preferable that it is 400 micrometers or less.
  • the inorganic solid electrolyte layer 3 is desirably as thin as possible while preventing a short circuit between the positive and negative electrodes. Furthermore, it is preferable that the effect of the present invention is remarkably exhibited. Specifically, it is preferably 1 ⁇ m or more, and more preferably 3 ⁇ m.
  • a laminate including a current collector, an active material layer, and a solid electrolyte layer is referred to as an “all-solid secondary battery”.
  • the secondary battery electrode sheet may be housed in a casing (case) to be an all-solid secondary battery (for example, a coin battery, a laminate battery, or the like).
  • An inorganic solid electrolyte is an inorganic solid electrolyte.
  • the term “solid electrolyte” means a solid electrolyte capable of moving ions therein. From this viewpoint, the inorganic solid electrolyte may be referred to as an ion conductive inorganic solid electrolyte in consideration of the distinction from the electrolyte salt (supporting electrolyte) described later.
  • the ionic conductivity of the inorganic solid electrolyte is not particularly limited, but is preferably 1 ⁇ 10 ⁇ 6 S / cm or more, more preferably 1 ⁇ 10 ⁇ 5 S / cm or more in lithium ions.
  • the ion conductivity measurement method is based on the non-pressurized conditions measured in Examples described later.
  • inorganic solid electrolytes do not contain organic substances such as polymer compounds and complex salts, they are clearly distinguished from organic solid electrolytes (polymer electrolytes typified by PEO and the like, organic electrolyte salts typified by LiTFSI and the like). .
  • organic solid electrolytes polymer electrolytes typified by PEO and the like, organic electrolyte salts typified by LiTFSI and the like.
  • the inorganic solid electrolyte is a non-dissociable solid in a steady state, it does not dissociate or release into cations and anions even in the liquid.
  • inorganic electrolyte salts LiPF 6 , LiBF 4 , LiFSI, LiCl, etc.
  • the inorganic solid electrolyte has conductivity of metal ions (preferably lithium ions) belonging to Group 1 or Group 2 of the periodic table, but does not have electronic conductivity.
  • the electrolyte layer or the active material layer contains a metal ion (preferably lithium ion) conductive inorganic solid electrolyte belonging to Group 1 or Group 2 of the Periodic Table.
  • a metal ion preferably lithium ion
  • the inorganic solid electrolyte a solid electrolyte material applied to this type of product can be appropriately selected and used.
  • Typical examples of the inorganic solid electrolyte include (i) sulfide-based inorganic solid electrolyte (sometimes referred to as sulfide solid electrolyte) and (ii) oxide-based inorganic solid electrolyte (sometimes referred to as oxide solid electrolyte). As mentioned.
  • the sulfide solid electrolyte contains sulfur (S), has ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and has electronic insulation. Those having properties are preferred.
  • a lithium ion conductive inorganic solid electrolyte that satisfies the composition represented by the following formula (1) can be given.
  • L a1 M b1 P c1 S d1 A e1 (1) (In the formula, L represents an element selected from Li, Na, and K, and Li is preferable.
  • M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge.
  • E1 represents the composition ratio of each element, and a1: b1: c1: d1: e1 satisfies 1 to 12: 0 to 1: 1: 2 to 12: 0 to 5. a1 is more preferably 1 to 9 1.5 to 4 is more preferable, b1 is preferably 0 to 0.5, d1 is further preferably 3 to 7, more preferably 3.25 to 4.5, and e1 is further preferably 0 to 3. 0 to 1 are more preferable.)
  • the composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based solid electrolyte as described below.
  • the sulfide-based solid electrolyte may be amorphous (glass) or crystallized (glass ceramics), or only part of it may be crystallized.
  • the ratio of Li 2 S to P 2 S 5 in the Li—PS system glass and the Li—PS system glass ceramic is a molar ratio of Li 2 S: P 2 S 5 , preferably 65:35 to 85:15, more preferably 68:32 to 75:25.
  • the lithium ion conductivity can be increased.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 ⁇ 4 S / cm or more, more preferably 1 ⁇ 10 ⁇ 3 S / cm or more. Although there is no particular upper limit, it is practical that it is 1 ⁇ 10-1 or less.
  • the compound include those using a raw material composition containing, for example, Li 2 S and a sulfide of an element belonging to Group 13 to Group 15.
  • Li 2 S—P 2 S 5 Li 2 S—LiI—P 2 S 5 , Li 2 S—LiI—Li 2 O—P 2 S 5 , Li 2 S—LiBr—P 2 S 5 Li 2 S—Li 2 O—P 2 S 5 , Li 2 S—Li 3 PO 4 —P 2 S 5 , Li 2 S—P 2 S 5 —P 2 O 5 , Li 2 SP—P 2 S 5 —SiS 2 , Li 2 S—P 2 S 5 —SnS, Li 2 S—P 2 S 5 —Al 2 S 3 , Li 2 S—GeS 2 , Li 2 S—GeS 2 —ZnS, Li 2 S—Ga 2 S 3 , Li 2 S—GeS 2 —Ga 2 S 3 , Li 2 S—GeS 2 —GeS 2
  • a crystalline and / or amorphous raw material composition comprising Li 2 S—GeS 2 —P 2 S 5 or Li 10 GeP 2 S 12 is preferred because it has high lithium ion conductivity.
  • Examples of a method for synthesizing a sulfide solid electrolyte material using such a raw material composition include an amorphization method.
  • Examples of the amorphization method include a mechanical milling method and a melt quenching method, and among them, the mechanical milling method is preferable. This is because processing at room temperature is possible, and the manufacturing process can be simplified.
  • the sulfide solid electrolyte is more preferably represented by the following formula (2).
  • Li l P m Sn formula (2) In the formula, l to n represent the composition ratio of each element, and l: m: n satisfies 2 to 4: 1: 3 to 10.
  • Oxide-based inorganic solid electrolyte contains oxygen (O), has an ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is an electron What has insulation is preferable.
  • Li xc B yc M cc zc Onc (M cc is C, S, Al, Si, Ga, Ge, In, Sn are at least one element, xc satisfies 0 ⁇ xc ⁇ 5, yc satisfies 0 ⁇ yc ⁇ 1, and zc satisfies 0 ⁇ zc ⁇ met 1, nc satisfies 0 ⁇ nc ⁇ 6.), Li xd ( l, Ga) yd (Ti, Ge) zd Si ad P md O nd ( provided that, 1 ⁇ xd ⁇ 3,0 ⁇ yd ⁇ 1,0 ⁇ zd ⁇ 2,0 ⁇ ad ⁇ 1,1 ⁇ md
  • D ee represents a halogen atom or Represents a combination of two or more halogen atoms.
  • Li 3 BO 3 —Li 2 SO 4 Li 2 O—B 2 O 3 —P 2 O 5 , Li 2 O—SiO 2 , Li 6 BaLa 2 ta 2 O 12, Li 3 PO (4-3 / 2w) N w (w is w ⁇ 1), LI ICON (Lithium super ionic conductor) type Li 3.5 Zn 0.25 GeO 4 having a crystal structure, La 0.55 Li 0.35 TiO 3 having a perovskite crystal structure, NASICON (Natrium super ionic conductor) type crystal structure
  • Li, P and O Phosphorus compounds containing Li, P and O are also desirable.
  • lithium phosphate Li 3 PO 4
  • LiPON obtained by replacing a part of oxygen of lithium phosphate with nitrogen
  • LiPOD 1 LiPOD 1
  • LiA 1 ON A 1 is at least one selected from Si, B, Ge, Al, C, Ga, etc.
  • the ionic conductivity of the lithium ion conductive oxide-based inorganic solid electrolyte is preferably 1 ⁇ 10 ⁇ 6 S / cm or more, more preferably 1 ⁇ 10 ⁇ 5 S / cm or more.
  • X 10 ⁇ 5 S / cm or more is particularly preferable.
  • an oxide-based inorganic solid electrolyte Since the oxide-based inorganic solid electrolyte generally has a higher hardness, the interface resistance is likely to increase in the all-solid secondary battery. By applying the present invention, the effect becomes more prominent.
  • an oxide-based inorganic solid electrolyte and the following nitrogen-containing polymer act to form a more suitable adsorption state.
  • an oxide-based inorganic solid electrolyte may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the 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. As an upper limit, it is preferable that it is 100 micrometers or less, and it is more preferable that it is 50 micrometers or less.
  • the concentration of the inorganic solid electrolyte in the solid electrolyte composition is preferably 50% by mass or more and 100% by mass in 100% by mass of the solid component when considering both the battery performance and the reduction / maintenance effect of the interface resistance. % Or more is more preferable, and 90% by mass or more is particularly preferable. As an upper limit, it is preferable that it is 99.9 mass% or less from the same viewpoint, It is more preferable that it is 99.5 mass% or less, It is especially preferable that it is 99 mass% or less. However, when used together with a positive electrode active material or a negative electrode active material to be described later, the sum is preferably in the above concentration range.
  • a nitrogen-containing polymer having a repeating unit having at least one of the following substituent X, substituent Y, and substituent Z is used.
  • X represents a group containing a functional group having a pKa of 14 or less.
  • Y represents a group having a polymer chain containing a hetero atom. Y may be linked to other nitrogen-containing polymer molecules to form a linking chain.
  • Z represents a hydrogen atom which is bonded to a nitrogen atom to form —NH—, a group having an alkyl group having 1 to 30 carbon atoms, a group having a halogenated alkyl group having 1 to 30 carbon atoms, or a silicone chain having 1 to 100 silicon atoms. Represents a group having
  • the substituent X is typically a group having an acid group, and is understood to be responsible for adsorption with a solid electrolyte or an active material and to improve adhesion.
  • the substituent Y include a long graft chain, and the polymer chain is expected to exhibit ionic conductivity.
  • the substituent Z is typically a hydrophobic group, and is understood to protect the solid electrolyte and the active material from moisture in the atmosphere and impart storage stability. The functions related to these substituents can be used properly or combined to exhibit the desired effect of the present invention.
  • the substituents Y and Z include a chain structure having a large molecular weight, but may be referred to as a substituent.
  • groups having substituents X, Y, and Z may be referred to as side chains X, Y, and Z, respectively, depending on the molecular weight.
  • Z is referred to as a substituent including a hydrogen atom.
  • the main chain of the nitrogen-containing polymer may be a polymer structure containing a nitrogen atom.
  • a polymer structure having an amino structure (—N ⁇ ) in the main chain or a polymer structure having an amino structure (—N ⁇ ) in the side chain near the main chain is preferable.
  • the nitrogen atom contained in the main chain or the nitrogen atom in the side chain closest to the main chain may be referred to as a nitrogen atom contained in the base of the nitrogen-containing polymer.
  • a polymer that is a raw material constituting the main chain of the nitrogen-containing polymer is sometimes referred to as a prepolymer or main chain prepolymer.
  • the prepolymer is preferably polyethyleneimine or polyallylamine. Specific examples include polymers having a structure represented by the following formula (1) or (2). In the formula, R 3 , R 5 , and L 2 have the same meanings as in formula (2-1) described later.
  • the number average molecular weight of the main chain (prepolymer) of the nitrogen-containing polymer is preferably 500 or more, more preferably 700 or more, and particularly preferably 1,000 or more.
  • the upper limit is preferably 1,000,000 or less, more preferably 100,000 or less, and particularly preferably 10,000 or less. By setting the molecular weight within this range, it is preferable because both the solubility of the polymer and the binding property to the active material and the inorganic solid electrolyte can be achieved.
  • the substituent X represents a group containing a functional group (functional group x) having a pKa of 14 or less, preferably pKa of 10 or less, more preferably 8 or less, and particularly preferably 6 or less.
  • the lower limit is preferably pKa-10 or more, more preferably -5 or more, and particularly preferably 0 or more.
  • pKa has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
  • the measurement temperature is a water temperature of 25 ° C.
  • the functional group having a pKa of 14 or less is not particularly limited as long as its physical properties satisfy this condition. Specifically, for example, a carboxyl group (about pKa 3 to 5), a sulfonic acid group (about pKa -3 to -2), a phosphoric acid group (about pKa 2), -COCH 2 CO- (about pKa 8 to 10).
  • the substituent X is preferably bonded to the nitrogen atom of the polymer base.
  • the molecular weight of the substituent X incorporated in the nitrogen-containing polymer is preferably 50 to 1000 even if the nitrogen atom and X are linked not only by a covalent bond but also in a form that forms a salt by ionic bond. 50 to 500 is most preferable. By being in this range, the adhesion becomes good.
  • substituent X those having a structure represented by the formula (V-1), the formula (V-2) or the formula (V-3) are particularly preferable.
  • U represents a single bond or a divalent linking group.
  • the divalent linking group represented by U include an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), and an alkylene group intervening with oxygen atoms (described later).
  • Formula OA1 a cycloalkylene group (preferably having 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms, particularly preferably 3 to 6 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms, more preferably 6 to 14 carbon atoms).
  • alkyleneoxy groups for example, ethyleneoxy, propyleneoxy, phenyleneoxy, etc.
  • -(L R -O-) n -L R- OA1 LR is an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 2 carbon atoms).
  • n is preferably 1 to 200, more preferably 1 to 100, and particularly preferably 1 to 50.
  • d and e each independently represents 0 or 1; From the viewpoint of productivity, d is preferably 1, and e is preferably 0. V-1 and V-2 are particularly preferably those in which d or e is 1 and U is an ethylene group.
  • W represents an acyl group or an alkoxycarbonyl group.
  • the acyl group for W is preferably an acyl group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 2 to 3 carbon atoms.
  • formyl, acetyl, n-propanoyl and benzoyl are preferable, and acetyl is particularly preferable.
  • the alkoxycarbonyl group in W is preferably an alkoxycarbonyl group having 2 to 30 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 3 carbon atoms.
  • W is particularly preferably an acyl group, and an acetyl group is preferable from the viewpoint of ease of production and availability of raw materials.
  • the substituent X is preferably bonded to the nitrogen atom of the polymer base.
  • adsorptivity improves.
  • the nitrogen atom in the base usually exists in the structure of an amino group, an ammonium group or an amide group, and these are considered to adsorb by interacting with the acidic part on the surface of the inorganic solid electrolyte, such as hydrogen bond / ion bond.
  • the substituent X can function as an acid group, it can interact with a basic part (such as a nitrogen atom) or a metal atom of the active material. In other words, this resin can adsorb both the basic part and the acidic part of the inorganic solid electrolyte and the active material with the nitrogen atom and the substituent X (side chain X). Is thought to have improved dramatically.
  • the content of the substituent X is not particularly limited, but is preferably 0.01 to 5 mmol, most preferably 0.05 to 1 mmol with respect to 1 g of the nitrogen-containing polymer. From the viewpoint of the acid value, it is preferable that the acid value is contained in an amount of about 5 to 50 mgKOH / g from the viewpoint of adhesion when used in an all-solid secondary battery.
  • the acid value titration can be performed by a known method. For example, an indicator method (a method for determining a neutralization point with an indicator), a potentiometric method, or the like can be used. A commercially available aqueous solution of sodium hydroxide can be used as the titrant used in the acid value titration. If the acid value is difficult to measure, a non-aqueous titrant such as a sodium methoxide-dioxane solution is prepared. It is possible to measure.
  • Substituent Y is a polymer chain containing a hetero atom (any one of an oxygen atom, a sulfur atom and a nitrogen atom is preferred), a polyester chain, a polyamide chain, a polyimide chain, and a polyacryl (poly (meth) acrylate) chain.
  • a polyether chain and a polycarbonate chain are preferred.
  • the substituent Y may be bonded to another nitrogen-containing polymer molecule at the other end opposite to the one end.
  • the substituent Y may be bonded to the nitrogen atom of the polymer base. At this time, some of them may be ionic bonds instead of covalent bonds.
  • the substituent Y preferably has an amide bond with a nitrogen atom, and a part of the substituent Y may have an ionic bond as a carboxylate.
  • the number average molecular weight of the substituent Y can be measured by the polystyrene conversion value by GPC method.
  • the number average molecular weight of Y is preferably 500 or more, more preferably 700 or more, and particularly preferably 1,000 or more.
  • the upper limit is preferably 1,000,000 or less, more preferably 100,000 or less, and particularly preferably 10,000 or less. A molecular weight within this range is preferable from the viewpoints of ionic conductivity, adhesion, and stability over time.
  • Two or more substituents Y (side chains Y) are preferably linked to the main chain in one molecule of the resin, and most preferably 5 or more.
  • the method for introducing the substituent Y includes, for example, a polymer comprising a polyester chain having a carboxylic acid at the end, a polyamide chain, a polyimide chain, a polyacryl (poly (meth) acrylate ester) chain, a polyether chain, or a polycarbonate chain. It can be obtained by condensation with a prepolymer which forms the main chain of the polymer.
  • the polyether chain preferably has a structure having a repeating unit of the following formula PE1. -(L S -O-) ns -... PE1 L S is an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1-6, 2 is particularly preferred), an alkenylene group (preferably having 1 to 12 carbon atoms, more preferably 1-6, 2 is particularly preferred) It is.
  • the ns is preferably 2 to 200, more preferably 5 to 100, and particularly preferably 10 to 50.
  • the polyester chain preferably has a structure having a repeating unit of the following formula PE2. - (CO-L S -O-) ns - ⁇ PE2 L S and ns are as defined above.
  • the polyamide chain preferably has a structure having a repeating unit of the following formula PE3. -(CO-L S -NR N- ) ns -... PE3 L S and ns are as defined above.
  • the polyimide chain preferably has a structure having a repeating unit of the following formula PE4. - (NR N CO-L S -CO-) ns - ⁇ PE4 L S and ns are as defined above.
  • the polycarbonate chain preferably has a structure having a repeating unit of the following formula PE5. - (O-CO-L S -O-) ns - ⁇ PE5 L S and ns are as defined above.
  • the polyacryl chain preferably has a structure having a repeating unit of the following formula PE6. -(L S -C (Ac)) ns -... PE6 L S and ns are as defined above.
  • Ac is an acyl group or an alkoxycarbonyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms).
  • JP, 2009-203462, A can be referred to for the kind of polymer which makes the above-mentioned side chain Y, and the method of introducing this into the prepolymer used as the principal chain, for example.
  • (Substituent Z [side chain Z]) Z represents a hydrogen atom which forms —NH— by bonding to a nitrogen atom, a group having an alkyl group having 1 to 30 carbon atoms (preferably having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms), or having 1 to 30 carbon atoms.
  • a group having a halogenated alkyl group (preferably having a carbon number of 1 to 24, more preferably 1 to 18) and a silicon chain having a silicon number of 1 to 100 (preferably having a silicon number of 1 to 80, more preferably 1 to 60) Represents a group.
  • the number average molecular weight of the substituent Z (side chain Z) is preferably 500 or more, more preferably 700 or more, and particularly preferably 1,000 or more.
  • the upper limit is preferably 1,000,000 or less, more preferably 100,000 or less, and particularly preferably 10,000 or less. By setting the molecular weight within this range, it is preferable because both the solubility of the polymer and the storage stability can be achieved.
  • Z described above preferably has a structure represented by # —L R — (L 1 ) p —Z 1 .
  • # represents the site
  • LR represents an alkylene group having 1 to 12 carbon atoms (preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms).
  • L 1 represents CO, NR N , O, or a combination thereof. Of these, CO and COO are preferable.
  • p represents 0 or 1; RN represents a hydrogen atom or a substituent.
  • substituents examples include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), and an alkenyl group (preferably having 2 to 24 carbon atoms and 2 carbon atoms).
  • To 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is particularly preferable, and an alkynyl group (2 to 24 carbon atoms is preferable, 2 to 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is Particularly preferred), an aralkyl group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, 6 to 14 carbon atoms). 10 is particularly preferred).
  • Z 1 represents a group having an alkyl group having 1 to 30 carbon atoms (preferably 1 to 24 carbon atoms, more preferably 1 to 18), or a group having a halogenated alkyl group having 1 to 30 carbon atoms (preferably a carbon number). 1 to 24, more preferably 1 to 18), and a group having a silicone chain having 1 to 100 silicon (preferably 1 to 80 silicon, more preferably 1 to 60).
  • the halogen substitution degree of the halogenated alkyl group (a value obtained by dividing the number of halogens by the number of substitutions) is preferably 0.6 or more, more preferably 0.8 or more, and further preferably 0.9 or more. Particularly preferred is 1. Of the halogen atoms, a fluorine atom is preferred. Of these, a perfluoroalkyl group is preferred.
  • the silicone chain preferably has a structure represented by the following formula S1. -(Si (R S1 ) 2 -O) m -R S2 ... S1
  • R S1 represents a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, 6 to 14 carbon atoms). More preferably, 6 to 10 is particularly preferable), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 15 and particularly preferably 7 to 11), or a hydroxyl group.
  • R S2 represents a hydrogen atom, a silyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms). 1 to 3 are particularly preferred), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 10 carbon atoms), and an aralkyl group (preferably having 7 to 23 carbon atoms, preferably 7 to 15 carbon atoms). Is more preferable, and 7 to 11 are particularly preferable.
  • m is a natural number, preferably 1 to 100, and more preferably 3 to 20.
  • the nitrogen-containing polymer preferably has a repeating unit represented by any of the following formulas (1-1) to (1-3) and (2-1) to (2-3).
  • R 3 represents a hydrogen atom, a halogen atom, or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, more preferably 1 to 3, and particularly preferably a methyl group).
  • R 5 represents a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms).
  • L 2 represents a single bond, an alkylene group (preferably a methylene group, an ethylene group or a propylene group), CO, O, or a combination thereof.
  • L 3 is a methylene group, an ethylene group, or a propylene group.
  • X, Y, and Z are as defined above. * Represents a connecting part between repeating units.
  • the repeating unit represented by the above formula (1-2) is preferably represented by the following formula (1-2I) or formula (1-2II).
  • * represents the connection part between repeating units.
  • Y 1 represents a monovalent polyester chain, polyamide chain, polyimide chain, polyacryl chain, polyether chain or polycarbonate chain having a number average molecular weight of 500 to 1,000,000. Its preferred molecular weight is the same as Y described above.
  • Y 2 represents a divalent polyester chain, polyamide chain, polyimide chain, polyacryl chain, polyether chain or polycarbonate chain having a number average molecular weight of 500 to 1,000,000. Its preferred molecular weight is the same as Y described above.
  • the repeating unit represented by the above formula (2-2) is preferably represented by the following formula (2-2I) or formula (2-2II).
  • R 3 , R 5 and L 2 represent the same groups as described above.
  • Y 1 represents a monovalent polyester chain, polyamide chain, polyimide chain, polyacryl chain, polyether chain or polycarbonate chain having a number average molecular weight of 500 to 1,000,000. Its preferred molecular weight is the same as Y described above.
  • Y 2 represents a divalent polyester chain, polyamide chain, polyimide chain, polyacryl chain, polyether chain or polycarbonate chain having a number average molecular weight of 500 to 1,000,000. Its preferred molecular weight is the same as Y described above.
  • Y 1 is preferably L 4 COY 11 or L 4 COOY 11 and more preferably represented by the following formula.
  • L 4 is a single bond or an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms).
  • Y 11 represents any one of a monovalent polyether chain, a polyester chain, a polycarbonate chain, and a polyacryl chain.
  • R 6 represents a hydrogen atom or a methyl group.
  • a preferred range of Y 11 is synonymous with Y.
  • Y 2 is preferably L 4 COY 11 COL 4 or L 4 COOY 11 OCOL 4 , and more preferably represented by the following formula.
  • Y 21 represents a divalent polyether chain, a polyester chain, a polycarbonate chain, or a polyacryl chain.
  • R 6 represents a hydrogen atom or a methyl group. A preferred range of Y 21 is the same as Y.
  • the nitrogen-containing polymer is preferably a copolymer, and preferably includes a repeating unit in any of the following combinations.
  • -Repeating unit of formula (1-1) and repeating unit of formula (1-2) -Repeating unit of formula (1-1) and repeating unit of formula (1-3)-Repeating unit of formula (1-2)
  • the preferable range of the copolymerization ratio is as follows.
  • the Z part, the X part, the Y1 part, and the Y2 part satisfy 100 in total.
  • nitrogen-containing polymer examples include polyethyleneimine, polyallylamine, and aminoethylated acrylic polymer (aziridine ring-opening polymer).
  • Polyethyleneimine is commercially available as SP-003 (polyethyleneimine (made by Nippon Shokubai) number average molecular weight 300), SP-006 (polyethyleneimine (made by Nippon Shokubai) number average molecular weight 600), SP-012 (polyethyleneimine (made by Nippon Shokubai) ) Number average molecular weight 1,200), SP-018 (polyethyleneimine (made by Nippon Shokubai) number average molecular weight 1,800), SP-020 (polyethyleneimine (made by Nippon Shokubai) number average molecular weight 10,000) and the like.
  • Polyallylamine is a commercially available product such as PAA-01 (polyallylamine (manufactured by Nittobo), weight average molecular weight 1,000), PAA-03 (polyallylamine (manufactured by Nittobo), weight average molecular weight 3,000), PAA-05 (polyallylamine). (Nittobo) weight average molecular weight 5,000), PAA-08 (polyallylamine (Nittobo) weight average molecular weight 8,000), PAA-15 (polyallylamine (Nittobo) weight average molecular weight 15,000) Is mentioned.
  • aminoethylated acrylic polymers examples include polyment NK-100PM (aminoethylated acrylic polymer (made by Nippon Shokubai)), polyment NK-200PM (aminoethylated acrylic polymer (made by Nippon Shokubai)), and polyment NK-350 (aminoethylated).
  • Acrylic polymer manufactured by Nippon Shokubai
  • polyment NK-380 aminoethylated acrylic polymer (manufactured by Nippon Shokubai)).
  • p and q represent the number of linked polyester chains, and each independently represents 5 to 100,000.
  • s represents a repeating unit and represents 1 to 100.
  • R ' represents a hydrogen atom or an alkoxycarbonyl group.
  • the linking group R of A-77 is a propylene group.
  • the substituent R is a propyl group.
  • A-80 will be described in detail in Examples below.
  • the number average molecular weight of the nitrogen-containing polymer is preferably 1,000 or more, more preferably 5,000 or more, and particularly preferably 10,000 or more.
  • the upper limit is preferably 500,000 or less, more preferably 100,000 or less, and particularly preferably 50,000 or less.
  • the compounding amount of the nitrogen-containing polymer is preferably 0.1 parts by mass or more, and 0.3 parts by mass or more with respect to 100 parts by mass of the inorganic solid electrolyte (including this when an active material is used). It is more preferable that the amount is 1 part by mass or more. As an upper limit, it is preferable that it is 20 mass parts or less, and it is more preferable that it is 10 mass parts or less.
  • the nitrogen-containing polymer in the solid content is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and 1% by mass or more. Is particularly preferred. As an upper limit, it is preferable that it is 20 mass% or less, and it is more preferable that it is 10 mass% or less.
  • the acid value of the nitrogen-containing polymer is preferably 0.05 mmol / g or more, more preferably 0.1 mmol / g or more, and particularly preferably 0.3 mmol / g or more.
  • the upper limit is preferably 10 mmol / g or less, more preferably 5 mmol / g or less, and particularly preferably 2 mmol / g or less.
  • the amine value of the nitrogen-containing polymer is preferably 0.1 mmol / g or more, more preferably 0.5 mmol / g or more, and particularly preferably 0.8 mmol / g or more.
  • the upper limit is preferably 20 mmol / g or less, more preferably 10 mmol / g or less, and particularly preferably 5 mmol / g or less.
  • the nitrogen-containing polymer may be used alone or in combination of a plurality of types. Further, it may be used in combination with other particles.
  • the nitrogen-containing polymer may have a particle shape.
  • the average particle size of the particles is preferably 1,000 nm or less, more preferably 750 nm or less, further preferably 500 nm or less, further preferably 300 nm or less, and particularly preferably 200 nm or less.
  • the lower limit is preferably 10 nm or more, more preferably 20 nm or more, further preferably 30 nm or more, and particularly preferably 50 nm or more.
  • the nitrogen-containing polymer preferably has a smaller particle size than the average particle size of the inorganic solid electrolyte.
  • the measurement from the created all-solid-state secondary battery is, for example, after disassembling the battery and peeling off the electrode, then measuring the electrode material according to the method of particle size measurement of the binder described later, and measuring in advance. This can be done by eliminating the measured value of the particle size of the particles other than the binder.
  • alkyl group preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • alkenyl A group preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl and the like
  • an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl and the like
  • a cycloalkyl group preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.
  • each of the groups listed as the substituent T may be further substituted with the substituent T described above.
  • a compound or a substituent / linking group includes an alkyl group / alkylene group, an alkenyl group / alkenylene group, an alkynyl group / alkynylene group, etc., these may be cyclic or linear, and may be linear or branched These may be substituted as described above or may be unsubstituted.
  • an alkyl group, an alkylene group, an alkenyl group, an alkenylene group, an alkynyl group, an alkynylene group is a group containing a hetero atom (e.g., O, S, CO, NR N and the like) with or intervening, this ring structure May be formed.
  • a hetero atom e.g., O, S, CO, NR N and the like
  • an aryl group, a heterocyclic group, etc. may be monocyclic or condensed and may be similarly substituted or unsubstituted.
  • the solid electrolyte composition of the present invention may contain an electrolyte salt (supporting electrolyte).
  • the electrolyte salt is preferably a lithium salt.
  • a lithium salt usually used in this type of product is preferable, and there is no particular limitation, but for example, the following are preferable.
  • Inorganic lithium salts inorganic fluoride salts such as LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 ; perhalogenates such as LiClO 4 , LiBrO 4 , LiIO 4 ; inorganic chloride salts such as LiAlCl 4 etc.
  • (L-3) Oxalatoborate salt lithium bis (oxalato) borate, lithium difluorooxalatoborate and the like.
  • Rf 1 and Rf 2 each represent a perfluoroalkyl group.
  • the content of the lithium salt is preferably 0.1 parts by mass or more and more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the inorganic solid electrolyte.
  • As an upper limit it is preferable that it is 10 mass parts or less, and it is more preferable that it is 5 mass parts or less.
  • the electrolyte used for electrolyte solution may be used individually by 1 type, or may combine 2 or more types arbitrarily.
  • a dispersion medium in which the above components are dispersed may be used.
  • a dispersion medium When producing an all-solid secondary battery, it is preferable to add a dispersion medium to the solid electrolyte composition to make a paste from the viewpoint of uniformly coating the solid electrolyte composition to form a film.
  • the dispersion medium When forming the solid electrolyte layer of the all-solid secondary battery, the dispersion medium is removed by drying.
  • the dispersion medium include water-soluble or water-insoluble organic solvents. Specific examples include the following.
  • Alcohol compound solvent Methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl- 2,4-pentanediol, 1,3-butanediol, 1,4-butanediol, etc.
  • Ether compound solvents (including hydroxyl group-containing ether compounds) Dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, cyclohexyl methyl ether, anisole, tetrahydrofuran, alkylene glycol alkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether , Diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.) Amide compound solvents N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolid
  • the dispersion medium preferably has a boiling point of 50 ° C. or higher, more preferably 80 ° C. or higher at normal pressure (1 atm).
  • the upper limit is preferably 220 ° C. or lower, and more preferably 180 ° C. or lower.
  • the said dispersion medium may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the quantity of the dispersion medium in a solid electrolyte composition can be made into arbitrary quantity with the balance of the viscosity of a solid electrolyte composition, and a dry load. Generally, it is preferably 20 to 99% by weight in the solid electrolyte composition.
  • the solid electrolyte composition may contain a positive electrode active material to form a positive electrode active material layer. Thereby, it can be set as the composition for positive electrode materials. It is preferable to use a transition metal oxide for the positive electrode active material, and it is preferable to have a transition element M a (one or more elements selected from Co, Ni, Fe, Mn, Cu, and V). Further, mixed element M b (elements of the first (Ia) group of the metal periodic table other than lithium, elements of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si , P, B, etc.) may be mixed.
  • a transition element M a one or more elements selected from Co, Ni, Fe, Mn, Cu, and V.
  • mixed element M b (elements of the first (Ia) group of the metal periodic table other than lithium, elements of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si
  • transition metal oxide examples include specific transition metal oxides including those represented by any of the following formulas (MA) to (MC), or other transition metal oxides such as V 2 O 5 and MnO 2. Is mentioned.
  • the positive electrode active material a particulate positive electrode active material may be used. Specifically, a transition metal oxide capable of reversibly inserting and releasing lithium ions can be used, but the specific transition metal oxide is preferably used.
  • the transition metal oxides, oxides containing the above transition element M a is preferably exemplified.
  • a mixed element M b (preferably Al) or the like may be mixed.
  • the mixing amount is preferably 0 to 30 mol% with respect to the amount of the transition metal. That the molar ratio of li / M a was synthesized were mixed so that 0.3 to 2.2, more preferably.
  • M 1 is as defined above Ma.
  • a represents 0 to 1.2 (preferably 0.2 to 1.2), and preferably 0.6 to 1.1.
  • b represents 1 to 3 and is preferably 2.
  • a part of M 1 may be substituted with the mixed element M b .
  • the transition metal oxide represented by the above formula (MA) typically has a layered rock salt structure.
  • the transition metal oxide is more preferably one represented by the following formulas.
  • g has the same meaning as a.
  • j represents 0.1 to 0.9.
  • i represents 0 to 1; However, 1-ji is 0 or more.
  • k has the same meaning as b above.
  • Specific examples of the transition metal compound include LiCoO 2 (lithium cobaltate [LCO]), LiNi 2 O 2 (lithium nickelate) LiNi 0.85 Co 0.01 Al 0.05 O 2 (nickel cobalt aluminum acid Lithium [NCA]), LiNi 0.33 Co 0.33 Mn 0.33 O 2 (lithium nickel manganese cobaltate [NMC]), LiNi 0.5 Mn 0.5 O 2 (lithium manganese nickelate).
  • the transition metal oxide represented by the formula (MA) partially overlaps, but when represented by changing the notation, those represented by the following are also preferable examples.
  • (I) Li g Ni x Mn y Co z O 2 (x> 0.2, y> 0.2, z ⁇ 0, x + y + z 1) Representative: Li g Ni 1/3 Mn 1/3 Co 1/3 O 2 Li g Ni 1/2 Mn 1/2 O 2
  • (Ii) Li g Ni x Co y Al z O 2 (x> 0.7, y>0.1,0.1> z ⁇ 0.05, x + y + z 1) Representative: Li g Ni 0.8 Co 0.15 Al 0.05 O 2
  • M 2 is as defined above Ma.
  • c represents 0 to 2 (preferably 0.2 to 2), and preferably 0.6 to 1.5.
  • d represents 3 to 5 and is preferably 4.
  • the transition metal oxide represented by the formula (MB) is more preferably one represented by the following formulas.
  • (MB-1) Li m Mn 2 O n
  • (MB-2) Li m Mn p Al 2-p O n
  • (MB-3) Li m Mn p Ni 2-p O n
  • m is synonymous with c.
  • n is synonymous with d.
  • p represents 0-2.
  • Specific examples of the transition metal compound are LiMn 2 O 4 and LiMn 1.5 Ni 0.5 O 4 .
  • Preferred examples of the transition metal oxide represented by the formula (MB) include those represented by the following.
  • an electrode containing Ni is more preferable from the viewpoint of high capacity and high output.
  • Transition metal oxide represented by formula (MC) As the lithium-containing transition metal oxide, it is also preferable to use a lithium-containing transition metal phosphor oxide, and among them, one represented by the following formula (MC) is also preferable. Li e M 3 (PO 4 ) f ... (MC)
  • e represents 0 to 2 (preferably 0.2 to 2), and is preferably 0.5 to 1.5.
  • f represents 1 to 5, and preferably 0.5 to 2.
  • the M 3 represents one or more elements selected from V, Ti, Cr, Mn, Fe, Co, Ni, and Cu.
  • the M 3 are, in addition to the mixing element M b above, Ti, Cr, Zn, Zr, may be substituted by other metals such as Nb.
  • Specific examples include, for example, olivine-type iron phosphates such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , cobalt phosphates such as LiCoPO 4 , and Li 3.
  • Monoclinic Nasicon type vanadium phosphate salts such as V 2 (PO 4 ) 3 (lithium vanadium phosphate) can be mentioned.
  • the a, c, g, m, and e values representing the composition of Li are values that change due to charge and discharge, and are typically evaluated as values in a stable state when Li is contained.
  • the composition of Li is shown as a specific value, but this also varies depending on the operation of the battery.
  • the average particle size of the positive electrode active material is not particularly limited, but is preferably 0.1 ⁇ m to 50 ⁇ m.
  • an ordinary pulverizer or classifier may be used.
  • the positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
  • the concentration of the positive electrode active material is not particularly limited, but is preferably 20 to 90% by mass, and more preferably 40 to 80% by mass in 100% by mass of the solid component in the solid electrolyte composition.
  • the positive electrode active materials may be used alone or in combination of two or more.
  • the material is not particularly limited, and is a carbonaceous material, a metal oxide such as tin oxide or silicon oxide, a metal composite oxide, a lithium alloy such as lithium alone or a lithium aluminum alloy, and an alloy with lithium such as Sn or Si. Examples thereof include metals that can be formed. Of these, carbonaceous materials or lithium composite oxides are preferably used from the viewpoint of reliability. In addition, the metal composite oxide is preferably capable of inserting and extracting lithium.
  • the material is not particularly limited, but preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
  • the carbonaceous material used as the negative electrode active material is a material substantially made of carbon.
  • Examples thereof include carbonaceous materials obtained by baking various synthetic resins such as artificial pitches such as petroleum pitch, natural graphite, and vapor-grown graphite, and PAN-based resins and furfuryl alcohol resins.
  • various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA-based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber, mesophase micro
  • Examples thereof include spheres, graphite whiskers, and flat graphite.
  • carbonaceous materials can be divided into non-graphitizable carbon materials and graphite-based carbon materials depending on the degree of graphitization.
  • the carbonaceous material preferably has a face spacing, density, and crystallite size described in JP-A-62-222066, JP-A-2-6856, and 3-45473.
  • the carbonaceous material does not have to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, or the like is used. You can also.
  • an amorphous oxide is particularly preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used. It is done.
  • amorphous as used herein means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering band having a peak in the region of 20 ° to 40 ° in terms of 2 ⁇ , and is a crystalline diffraction line. You may have.
  • the strongest intensity of crystalline diffraction lines seen from 2 ° to 40 ° to 70 ° is 100 times the diffraction line intensity at the peak of the broad scattering band seen from 2 ° to 20 °. It is preferable that it is 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.
  • amorphous metal oxides and chalcogenides are more preferable, and elements in groups 13 (IIIB) to 15 (VB) of the periodic table are preferable.
  • oxides and chalcogenides composed of one kind of Al, Ga, Si, Sn, Ge, Pb, Sb, Bi or a combination of two or more kinds thereof.
  • preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , SiO, GeO, SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , Bi 2 O 3 , Bi 2 O 4 , SnSiO 3 , GeS, SnS, SnS 2 , PbS, PbS 2 , Sb 2 S 3 , Sb 2 S 5 , such as SnSiS 3 may preferably be mentioned. Moreover, these may be a complex oxide with lithium oxide, for example, Li 2 SnO 2 .
  • the average particle size of the negative electrode active material is preferably 0.1 ⁇ m to 60 ⁇ m.
  • a well-known pulverizer or classifier is used.
  • a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill or a sieve is preferably used.
  • wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary.
  • classification is preferably performed.
  • the classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be used both dry and wet.
  • the chemical formula of the compound obtained by the above firing method can be calculated from an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method, and from a mass difference between powders before and after firing as a simple method.
  • ICP inductively coupled plasma
  • Examples of the negative electrode active material that can be used in combination with the amorphous oxide negative electrode active material centering on Sn, Si, and Ge include carbon materials that can occlude and release lithium ions or lithium metal, lithium, lithium alloys, lithium A metal that can be alloyed with is preferable.
  • the negative electrode active material preferably contains a titanium atom. More specifically, since Li 4 Ti 5 O 12 has a small volume fluctuation at the time of occlusion and release of lithium ions, it has excellent rapid charge / discharge characteristics, suppresses electrode deterioration, and improves the life of lithium ion secondary batteries. This is preferable. By combining a specific negative electrode and a specific electrolyte, the stability of the secondary battery is improved even under various usage conditions.
  • the concentration of the negative electrode active material is not particularly limited, but is preferably 10 to 80% by mass, more preferably 20 to 70% by mass in 100% by mass of the solid component in the solid electrolyte composition.
  • said embodiment considered and demonstrated the example which makes a solid electrolyte composition contain a positive electrode active material or a negative electrode active material
  • this invention is not limitedly interpreted by this.
  • An inorganic solid electrolyte layer may be formed using the solid electrolyte composition according to a preferred embodiment of the present invention in combination with such a commonly used positive electrode material or negative electrode material.
  • carbon fibers such as graphite, carbon black, acetylene black, ketjen black, carbon nanotubes, metal powders, metal fibers, polyphenylene derivatives, and the like can be included.
  • the said negative electrode active material may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the positive / negative current collector an electron conductor that does not cause a chemical change is preferably used.
  • the current collector of the positive electrode in addition to aluminum, stainless steel, nickel, titanium, etc., the surface of aluminum or stainless steel is preferably treated with carbon, nickel, titanium, or silver. Among them, aluminum and aluminum alloys are preferable. More preferred.
  • the negative electrode current collector aluminum, copper, stainless steel, nickel, and titanium are preferable, and aluminum, copper, and a copper alloy are more preferable.
  • a film sheet is usually used, but a net, a punched one, a lath body, a porous body, a foamed body, a molded body of a fiber group, and the like can also be used.
  • the thickness of the current collector is not particularly limited, but is preferably 1 ⁇ m to 500 ⁇ m.
  • the current collector surface is roughened by surface treatment.
  • the all-solid-state secondary battery may be manufactured by a conventional method. Specifically, a method of forming an electrode sheet for a battery in which the solid electrolyte composition is applied onto a metal foil serving as a current collector to form a film is exemplified. For example, a composition to be a positive electrode material is applied on a metal foil to form a film. Next, an inorganic solid electrolyte composition is applied to the upper surface of the positive electrode active material layer of the battery electrode sheet to form a film. Further, a desired all-solid secondary battery structure can be obtained by similarly forming a negative electrode active material film and applying a negative electrode current collector (metal foil).
  • coating method of said each composition should just follow a conventional method. At this time, it is preferable to heat-treat after each application
  • heating temperature is not specifically limited, 30 degreeC or more is preferable and 60 degreeC or more is more preferable.
  • the upper limit is preferably 300 ° C. or lower, and more preferably 250 ° C. or lower. By heating in such a temperature range, the nitrogen-containing polymer can be suitably softened. Thereby, in an all-solid secondary battery, good binding properties and non-pressurized ion conductivity can be obtained.
  • the all solid state secondary battery according to the present invention can be applied to various uses.
  • the application mode is not particularly limited, for example, when installed in an electronic device, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a cellular phone, a cordless phone, a pager, a handy terminal, a portable fax machine, a portable copy.
  • Examples include portable printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, minidiscs, electric shavers, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, and memory cards.
  • Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military use and space use. Moreover, it can also combine with a solar cell.
  • a solid electrolyte composition (positive electrode or negative electrode composition) containing an active material capable of inserting and releasing metal ions belonging to Group 1 or Group 2 of the Periodic Table.
  • the battery electrode sheet which formed the said solid electrolyte composition on metal foil.
  • An all-solid secondary battery comprising a positive electrode active material layer, a negative electrode active material layer, and an inorganic solid electrolyte layer, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the inorganic solid electrolyte layer is All-solid-state secondary battery made into the layer comprised with the solid electrolyte composition.
  • the manufacturing method of the electrode sheet for batteries which arrange
  • the manufacturing method of the all-solid-state secondary battery which manufactures an all-solid-state secondary battery via the manufacturing method of the said battery electrode sheet.
  • An all-solid secondary battery refers to a secondary battery in which the positive electrode, the negative electrode, and the electrolyte are all solid. In other words, it is distinguished from an electrolyte type secondary battery using a carbonate-based solvent as an electrolyte.
  • this invention presupposes an inorganic all-solid-state secondary battery.
  • the all-solid-state secondary battery is classified into an organic (polymer) all-solid-state secondary battery that uses a polymer compound such as polyethylene oxide as an electrolyte, and an inorganic all-solid-state secondary battery that uses the above LLT, LLZ, or the like. .
  • the application of the polymer compound to the inorganic all-solid secondary battery is not hindered, and the polymer compound can be applied as a binder for the positive electrode active material, the negative electrode active material, and the inorganic solid electrolyte particles.
  • the inorganic solid electrolyte is distinguished from an electrolyte (polymer electrolyte) using the above-described polymer compound as an ion conductive medium, and the inorganic compound serves as an ion conductive medium. Specific examples include the above LLT and LLZ.
  • the inorganic solid electrolyte itself does not release cations (Li ions) but exhibits an ion transport function.
  • a material that is added to the electrolytic solution or the solid electrolyte layer and serves as a source of ions that release cations is sometimes called an electrolyte, but it is distinguished from the electrolyte as the ion transport material.
  • electrolyte salt or “supporting electrolyte”.
  • the electrolyte salt include LiTFSI (lithium bistrifluoromethanesulfonimide).
  • the term “composition” means a mixture in which two or more components are uniformly mixed. However, as long as the uniformity is substantially maintained, aggregation or uneven distribution may partially occur within a range in which a desired effect is achieved.
  • the solid electrolyte composition basically refers to a composition (typically a paste) that is a material for forming the electrolyte layer, and the electrolyte layer formed by curing the composition includes It shall not be included.
  • the amine titer was 0.52 mmol / g and the acid titer was 0.52 mmol / g, and the composition ratio was 36 mol% / 33 mol% / 31 from 1HNMR. Mol%.
  • the number average molecular weight by GPC method was 18,000.
  • acid value titration was performed, it was confirmed that the acid value was 0.27 mol / g, and the composition ratio was 23 mol% / 35 mol% / 42 mol% from 1HNMR.
  • the number average molecular weight by GPC method was 21,000.
  • acid value titration was performed, it was confirmed that the acid value was 0.13 mol / g, and the composition ratio was 5 mol% / 78 mol% / 17 mol% from 1HNMR.
  • the number average molecular weight by GPC method was 13,000.
  • polyester (i-1) 6.4 g of n-octanoic acid, 200 g of ⁇ -caprolactone and 5 g of titanium (IV) tetrabutoxide were mixed, heated at 160 ° C. for 8 hours, then cooled to room temperature, and polyester (i- 1) was obtained.
  • the scheme is shown below.
  • the resin (A-80) has a side chain derived from polyester (i-1) and a group having a functional group (carboxyl group) having a pKa derived from succinic anhydride of 14 or less.
  • a synthesis scheme is shown below.
  • the acid value of the intermediate (A′-80) was titrated, it was confirmed that the acid value was 0.11 mmol / g. Further, when amine titration and acid titration of the resin (A-80) were performed, the acid value was 0.31 mmol / g and the amine value was 0.83 mmol / g. That is, based on the difference between the acid value of the resin (A-80) and the acid value of the intermediate (A′-80), the mol% of the repeating unit corresponding to the formula (A-80) is the resin (A-80).
  • (A-80) x and y are both 40.
  • Polyester (i-3) was synthesized in the same manner as in Synthesis Example 9 using 2-hydroxyethyl acrylate instead of octanoic acid.
  • the length of the polyester can be appropriately synthesized by adjusting the charging ratio of ⁇ -caprolactone and alcohol.
  • Resin (A-57) has a side chain derived from polyesters (i-2) and (i-3) and a group having a functional group (carboxyl group) having a pKa derived from succinic anhydride of 14 or less It is.
  • the polymer obtained had an acid value of 0.22 mmol / g and an amine value of 0.43 mmol / g.
  • composition for positive electrode of secondary battery In a planetary mixer (TK Hibismix, manufactured by PRIMIX), 100 parts of a positive electrode active material described in Table 3 below, 5 parts of acetylene black, solid electrolyte composition S- obtained above 1 75 parts and 270 parts of N-methylpyrrolidone were added and stirred at 40 rpm for 1 hour.
  • TK Hibismix manufactured by PRIMIX
  • the secondary battery positive electrode composition obtained above was applied onto an aluminum foil having a thickness of 20 ⁇ m with an applicator having an arbitrary clearance, and heated at 80 ° C. for 1 hour and further at 110 ° C. for 1 hour. The coating solvent was dried. Then, it heated and pressurized so that it might become arbitrary density using the heat press machine, and the positive electrode for secondary batteries was obtained.
  • the solid electrolyte composition obtained above was applied with an applicator having an arbitrary clearance, and 80 ° C. for 1 hour and further 110 ° C. Heated for 1 hour and dried. Then, the composition for secondary battery negative electrodes obtained above was further applied, heated at 80 ° C. for 1 hour and further at 110 ° C. for 1 hour, and dried. A copper foil having a thickness of 20 ⁇ m was combined on the negative electrode layer, and heated and pressurized to a desired density using a heat press machine. An electrode sheet for secondary battery 102 was obtained.
  • the binding property was evaluated using the electrode sheet in a state before applying the negative electrode composition (a state where the solid electrolyte composition was dried).
  • An adhesive tape (cellophane tape (“CT24”, manufactured by Nichiban Co., Ltd.)) was applied to the cured solid electrolyte composition surface, and when peeled at a constant speed, the peeled area was visually confirmed.
  • the area ratio of the part that was not peeled was evaluated as follows. A: 100% B: 95% or more and less than 100% C: 80% or more and less than 95% D: 50% or more and less than 80% E: Less than 50%
  • the electrode sheet obtained above was cut into a disk shape having a diameter of 14.5 mm and placed in a stainless steel 2032 type coin case incorporating a spacer and a washer to produce a coin battery. From the outside of the coin battery, it was sandwiched between jigs capable of applying pressure between the electrodes, and used for various electrochemical measurements. The pressure between the electrodes was 500 kgf / cm 2 . It calculated
  • 11 is an upper support plate
  • 12 is a lower support plate
  • 13 is a coin battery
  • S is a screw.
  • Table 3 shows the measurement results of the electrode binding properties of the solid electrolyte sheet, and the ionic conductivity in the pressurized and non-pressurized states.
  • the measurement in the pressurized state is a case where measurement is performed with the coin battery sandwiched between the jigs, and the measurement in the non-pressurized state indicates that the coin battery is measured as it is.
  • the molecular weight of the polymer is measured by gel permeation chromatography (GPC) in terms of standard polystyrene. The weight average or number average is refused each time.
  • GPC gel permeation chromatography
  • a value measured by the method of Condition 1 or Condition 2 (priority) below is basically used. However, an appropriate eluent may be selected and used depending on the polymer type.
  • the use of the nitrogen-containing polymer according to the present invention exhibits excellent performance in all of binding properties, stability, and ionic conductivity.
  • the binding properties are improved by the presence of a carbonyl group, a carbonyloxy group, or an acid group (carboxyl group) in the side chain.
  • a hydrophobic group sicone, fluorine
  • the side chain suppresses deterioration of the inorganic solid electrolyte, thereby improving the temporal stability.

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WO2020110993A1 (ja) * 2018-11-26 2020-06-04 株式会社大阪ソーダ 無機固体電解質二次電池用電極、および無機固体電解質二次電池
CN114074934A (zh) * 2020-08-14 2022-02-22 中国科学院上海硅酸盐研究所 一种非晶无机固态电解质及其制备方法

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