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WO2016017759A1 - Batterie secondaire tout électronique, composition électrolytique solide, feuille d'électrode pour batterie l'utilisant, procédé de production de feuille d'électrode pour batterie, et procédé de production de batterie secondaire tout électronique - Google Patents

Batterie secondaire tout électronique, composition électrolytique solide, feuille d'électrode pour batterie l'utilisant, procédé de production de feuille d'électrode pour batterie, et procédé de production de batterie secondaire tout électronique Download PDF

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WO2016017759A1
WO2016017759A1 PCT/JP2015/071642 JP2015071642W WO2016017759A1 WO 2016017759 A1 WO2016017759 A1 WO 2016017759A1 JP 2015071642 W JP2015071642 W JP 2015071642W WO 2016017759 A1 WO2016017759 A1 WO 2016017759A1
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group
solid electrolyte
active material
electrode active
secondary battery
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Japanese (ja)
Inventor
智則 三村
宏顕 望月
雅臣 牧野
目黒　克彦
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Fujifilm Corp
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Fujifilm Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an all-solid secondary battery, a solid electrolyte composition, a battery electrode sheet using the same, a method for producing a battery electrode sheet, and a method for producing an all-solid secondary battery.
  • 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 next-generation lithium ion secondary batteries
  • the electrolyte is a hard solid
  • the liquid electrolyte does not have.
  • the interface resistance between solid particles is increased.
  • a specific polymer compound is used as a binder.
  • those using butadiene rubber or polyethylene glycol-based resin disclosed in Patent Documents 1 and 2 are representative examples.
  • the increase in the interface resistance in the all-solid secondary battery may be improved accordingly by the resins disclosed in the above patent documents.
  • the binders made of the polymer compounds disclosed in the above documents cannot satisfy the recent high demand level, and further improvements are desired. Therefore, the present invention provides an all-solid secondary material in which an increase in interfacial resistance in an inorganic solid electrolyte is suppressed without applying pressure, and good ionic conductivity and binding properties, as well as storage stability at high temperatures are realized. It is an object of the present invention to provide a battery, a solid electrolyte composition used therefor, a battery electrode sheet using the same, a method for producing a battery electrode sheet, and a method for producing an all-solid secondary battery.
  • An all-solid secondary battery comprising a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer Includes an inorganic solid electrolyte having conductivity of ions of metal elements belonging to Group 1 or Group 2 of the periodic table, and a binder composed of a polymer compound satisfying the following conditions (i) and (ii): All-solid secondary battery. (I) having a repeating unit represented by the following formula (1-1) (ii) having at least one of the following functional group (a)
  • Z 11 to Z 14 are each independently a hydrogen atom, a chlorine atom, an alkyl group, or a specific fluorine-containing substituent.
  • the specific fluorine-containing substituent is a fluorine atom, a fluoroalkyl group, or a fluoroalkyloxy group. At least one of Z 11 to Z 14 is a specific fluorine-containing substituent.
  • the specific fluorine-containing substituent is a fluorine atom, —CF 3 , —CH 2 CF 3 , —CF 2 CF 3 , —CF 2 CF 2 CF 3 , —OCF 3, —OCF 2 CF 3 or —OCF all-solid secondary battery according to a 2 CF 2 CF 3 (1) or (2).
  • the group selected from the functional group (a) is selected from a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a hydroxy group, a dicarboxylic anhydride group, and a silyl group. 4].
  • [6] The all-solid-state secondary battery according to any one of [1] to [5], wherein the inorganic solid electrolyte is an oxide-based inorganic solid electrolyte.
  • M bb represents at least one element selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, and Sn.
  • M cc represents C, S, Al, Si, Ga, Ge, In, at least one element of Sn.
  • a 1 represents at least one element selected from Si, B, Ge, Al, C, and Ga.
  • Z 11 to Z 14 are each independently a hydrogen atom, a chlorine atom, an alkyl group, or a specific fluorine-containing substituent.
  • the specific fluorine-containing substituent is a fluorine atom, a fluoroalkyl group, or a fluoroalkyloxy group. At least one of Z 11 to Z 14 is a specific fluorine-containing substituent.
  • a battery electrode sheet comprising a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer
  • a battery comprising an inorganic solid electrolyte having conductivity of ions of metal elements belonging to Group 1 or Group 2 of the periodic table, and a binder composed of a polymer compound satisfying the following conditions (i) and (ii) Electrode sheet. (I) having a repeating unit represented by the following formula (1-1) (ii) having at least one of the following functional group (a)
  • Z 11 to Z 14 are each independently a hydrogen atom, a chlorine atom, an alkyl group, or a specific fluorine-containing substituent.
  • the specific fluorine-containing substituent is a fluorine atom, a fluoroalkyl group, or a fluoroalkyloxy group. At least one of Z 11 to Z 14 is a specific fluorine-containing substituent.
  • each substitution The groups and the like 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. At this time, a linking group L described later may be incorporated in the ring.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the all-solid-state secondary battery of the present invention does not depend on pressurization (the effect of pressurization is small), and suppresses an increase in interfacial resistance in an inorganic solid electrolyte. Exhibits excellent performance with storage stability at.
  • the solid electrolyte composition of the present invention the battery electrode sheet using the same, the method for manufacturing the battery electrode sheet, and the method for manufacturing the all-solid secondary battery, the all-solid-state battery that exhibits the above-described excellent performance can be obtained.
  • a secondary battery can be suitably manufactured.
  • FIG. 1 is a longitudinal 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 this 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 as viewed from the negative electrode side to the positive electrode side. , In that order.
  • Each layer is in contact with each other and has a laminated structure. By adopting such a structure, at the time of charging, electrons (e ⁇ ) are supplied to the negative electrode side, and lithium ions (Li + ) are accumulated therein.
  • lithium ions (Li + ) accumulated in the negative electrode are returned to the positive electrode side, and electrons are supplied to the working part 6.
  • a light bulb is adopted as the operation part 6 and is turned on by discharge.
  • an inorganic solid electrolyte described later and a specific binder described later are used as constituent materials for the negative electrode active material layer, the positive electrode active material layer, and the inorganic solid electrolyte layer.
  • the thicknesses of the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 are not particularly limited. In consideration of general battery dimensions, the thickness is preferably 10 to 1,000 ⁇ m, more preferably 20 ⁇ m or more and less than 500 ⁇ m. In the all solid state secondary battery of the present invention, it is more preferable that the thickness of at least one of the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 is 50 ⁇ m or more and less than 500 ⁇ m. In this specification, the positive electrode active material layer and the negative electrode active material layer may be collectively referred to as an electrode layer. In addition, the electrode active material used in the present invention includes a positive electrode active material contained in the positive electrode active material layer and a negative electrode active material contained in the negative electrode active material layer. Sometimes referred to as an active material or an electrode active material.
  • the solid electrolyte composition of the present invention contains an inorganic solid electrolyte and a specific binder described later.
  • the inorganic solid electrolyte is an inorganic solid electrolyte, and the solid electrolyte is a solid electrolyte capable of moving ions inside. From this point of view, it may be referred to as an ion conductive inorganic solid electrolyte in consideration of distinction from an electrolyte salt (supporting electrolyte) described later. Since the inorganic solid electrolyte used in the present invention does not contain organic substances (carbon atoms), organic solid electrolytes (polymer electrolytes typified by polyethylene oxide (PEO), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), etc.
  • organic solid electrolytes polymer electrolytes typified by polyethylene oxide (PEO), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), etc.
  • organic electrolyte salts represented by Further, since the inorganic solid electrolyte is solid in a steady state, it is not dissociated or released into cations and anions. In this respect, it is also clearly distinguished from inorganic electrolyte salts (LiPF 6 , LiBF 4 , lithium bis (fluorosulfonyl) imide (LiFSI), LiCl, etc.) in which cations and anions are dissociated or liberated in the electrolyte and polymer. .
  • the inorganic solid electrolyte is not particularly limited as long as it has conductivity of ions of metal elements belonging to Group 1 or Group 2 of the periodic table, and generally does not have electron conductivity.
  • the inorganic solid electrolyte has ion conductivity of a metal element belonging to Group 1 or Group 2 of the periodic table.
  • a solid electrolyte material applied to this type of product can be appropriately selected and used.
  • Representative examples of the inorganic solid electrolyte include (i) a sulfide-based inorganic solid electrolyte and (ii) an oxide-based inorganic solid electrolyte.
  • the sulfide-based inorganic solid electrolyte contains elemental sulfur (S) and has ionic conductivity of a metal element belonging to Group 1 or Group 2 of the periodic table. And what has electronic insulation is preferable.
  • the sulfide-based inorganic solid electrolyte preferably contains at least Li, S and P as elements and has lithium ion conductivity. However, depending on the purpose or the case, other than Li, S and P may be used. An element may be included.
  • a lithium ion conductive inorganic solid electrolyte that satisfies the composition represented by the following general formula (SE) is preferable.
  • L aa represents an element selected from Li, Na, and K, and Li is preferable.
  • M aa represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge. Among these, B, Sn, Si, Al, or Ge is preferable, and Sn, Al, or Ge is more preferable.
  • a aa represents I, Br, Cl or F, preferably I or Br, and particularly preferably I.
  • a1 to e1 indicate the composition ratio of each element, and a1: b1: c1: d1: e1 satisfies 1 to 12: 0 to 1: 1: 2 to 12: 0 to 5.
  • a1 is further preferably 1 to 9, and more preferably 1.5 to 4.
  • b1 is preferably 0 to 0.5.
  • d1 is preferably 3 to 7, and more preferably 3.25 to 4.5.
  • e1 is preferably 0 to 3, more preferably 0 to 1.
  • the composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based inorganic solid electrolyte.
  • the sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass ceramic), or only a part may be crystallized.
  • glass glass
  • glass ceramic glass ceramic
  • Li—PS system glass containing Li, P and S, or Li—PS system glass ceramics containing Li, P and S can be used.
  • the sulfide-based inorganic solid electrolyte includes [1] lithium sulfide (Li 2 S) and phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), [2] at least one of lithium sulfide, simple phosphorus and simple sulfur, Or [3] It can be produced by a reaction of lithium sulfide, phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )) and at least one of simple phosphorus and simple sulfur.
  • 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 77:23.
  • the lithium ion conductivity can be increased.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 ⁇ 4 S / cm or more, more preferably 1 ⁇ 10 ⁇ 3 S / cm or more. Although there is no particular upper limit, it is practical that it is 1 ⁇ 10 ⁇ 1 S / cm or less.
  • the compound include those using a raw material composition containing Li 2 S and a sulfide of an element belonging to Group 13 to Group 15. Specifically, Li 2 S—P 2 S 5 , Li 2 S—LiI—P 2 S 5 , Li 2 S—LiI—Li 2 O—P 2 S 5 , Li 2 S—LiBr—P 2 S 5 Li 2 S—Li 2 O—P 2 S 5 , Li 2 S—Li 3 PO 4 —P 2 S 5 , Li 2 S—P 2 S 5 —P 2 O 5 , Li 2 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 —P 2 S 2 S
  • Examples of a method for synthesizing a sulfide-based inorganic solid electrolyte material using such a raw material composition include an amorphization method.
  • Examples of the amorphization method include a mechanical milling method and a melt quenching method, and among them, the mechanical milling method is preferable. This is because processing at room temperature is possible, and the manufacturing process can be simplified.
  • Oxide-based inorganic solid electrolyte contains an oxygen element (O) and has ion conductivity of a metal element belonging to Group 1 or Group 2 of the periodic table, and Those having electronic insulating properties are preferred.
  • Li xa La ya TiO 3 [xa satisfies 0.3 ⁇ xa ⁇ 0.7, and ya satisfies 0.3 ⁇ ya ⁇ 0.7. ]
  • Li xb La yb Zr zb M bb mb Onb (M bb is at least one element of Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, Sn)
  • Xb satisfies 5 ⁇ xb ⁇ 10
  • yb satisfies 1 ⁇ yb ⁇ 4
  • zb satisfies 1 ⁇ zb ⁇ 4
  • mb satisfies 0 ⁇ mb ⁇ 2
  • nb satisfies 5 ⁇ nb ⁇ 20 .
  • Li xc B yc M cc zc O nc (M cc is C, S, Al, Si, Ga, Ge
  • Li, P and O Phosphorus compounds containing Li, P and O are also desirable.
  • lithium phosphate Li 3 PO 4
  • LiPON obtained by substituting a part of oxygen atoms of lithium phosphate with nitrogen atoms
  • LiPOD 1 LiPOD 1
  • LiA 1 ON LiA 1 represents at least one element selected from Si, B, Ge, Al, C, Ga and the like
  • Si, B, Ge, Al, C, Ga and the like can be preferably used.
  • Li xa La ya TiO 3 and Li xb La yb Zr zb M bb mb Onb are preferable because they have high lithium ion conductivity and are chemically stable and easy to handle. These may be used alone or in combination of two or more. Further, next to the above, a lithium ion conductive inorganic solid electrolyte satisfying the composition represented by the general formula (SE) is preferable.
  • an oxide-based inorganic solid electrolyte it is particularly preferable to use 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-state secondary battery. By applying the present invention, the effect becomes more prominent. At this time, since the oxide-based inorganic solid electrolyte has an oxygen atom in its structure, it is preferable to use a binder having high binding properties. From this point of view, a group selected from the functional group group (a) (specific functional group (a)) is introduced in the polymer compound forming the binder described later.
  • the binder is more firmly fixed to the inorganic solid electrolyte particles, and better performance can be obtained in terms of reduction in interface resistance.
  • a group selected from the functional group group (a) (specific functional group (a)) is introduced in the polymer compound forming the binder described later.
  • the binder is more firmly fixed to the inorganic solid electrolyte particles, and better performance can be obtained in terms of reduction in interface resistance.
  • the said inorganic solid electrolyte may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the volume average particle diameter 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 measurement of the volume average particle diameter of an inorganic solid electrolyte is performed in the following procedures.
  • An inorganic solid electrolyte is prepared by diluting a 1% by weight dispersion in a 20 ml sample bottle using water (heptane in the case of water labile substances). The diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes and used immediately after that.
  • 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, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. 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 solid component means the component which does not volatilize or evaporate, when a drying process is performed at 160 degreeC for 6 hours. Typically, it refers to components other than the dispersion medium described below.
  • binder The binder applied to the present invention is preferably composed of a polymer compound that satisfies the following conditions (i) and (ii).
  • each of Z 11 to Z 14 independently represents a hydrogen atom, a chlorine atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), or a specific fluorine-containing substituent. It is.
  • the specific fluorine-containing substituent is a fluorine atom, a fluoroalkyl group, or a fluoroalkyloxy group. At least one, preferably 2 to 4 of Z 11 to Z 14 is a specific fluorine-containing substituent.
  • the fluoroalkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • the fluoroalkyloxy group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • the specific fluorine-containing substituent is a fluorine atom, —CF 3 , —CH 2 CF 3 , —CF 2 CF 3 , —CF 2 CF 2 CF 3 , —OCF 3, —OCF 2 CF 3, or —OCF 2 CF 2.
  • CF 3 is preferred.
  • at least one of Z 11 to Z 14 is preferably a fluoroalkyl group or a fluoroalkyloxy group, and particularly preferably a fluoroalkyloxy group.
  • Z 11 to Z 14 are groups that may have a substituent, they may have a substituent T described later or may have a linking group L interposed as long as the effects of the present invention are achieved.
  • the substituent that Z 11 to Z 14 may have is preferably a group other than the group included in the functional group group (a) described later.
  • repeating unit represented by the formula (1-1) Specific examples of the repeating unit represented by the formula (1-1) are exemplified below, but the present invention is not construed as being limited thereto.
  • the group included in the functional group (a) includes a carboxyl group (—COOH), a sulfonic acid group (—SO 3 H) (including ester), and a phosphoric acid group (—OP (O) (OH) 2 ) (ester ), Phosphonic acid groups (—P (O) (OH) 2 ) (including esters), hydroxy groups, thiol groups (sulfanyl groups), isocyanate groups, oxetane groups, epoxy groups, dicarboxylic anhydride groups and A silyl group (preferably having 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms).
  • silyl group examples include an alkylsilyl group, an alkoxysilyl group, an arylsilyl group, and an aryloxysilyl group, and among them, an alkoxysilyl group is preferable.
  • the specific functional group (a) selected from the functional group group (a) may be one type selected from the above group or two or more types.
  • the group constituting the ester is 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).
  • An alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, 6 to 14 are more preferable, and 6 to 10 are particularly preferable.)
  • an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 15 carbon atoms, and particularly preferably 7 to 11 carbon atoms). More preferably.
  • the carboxy group, phosphoric acid group, phosphonic acid group, and sulfonic acid group may form a salt with any counter ion.
  • the functional group (a) is more preferably selected from a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a hydroxy group, a dicarboxylic anhydride group, and a silyl group. Particularly preferred are phosphonic acid groups and silyl groups.
  • the binder only needs to have the functional group (a), and preferably has a repeating unit having the functional group (a).
  • the repeating unit having the functional group (a) is preferably represented by the following formula (2).
  • Z 21 and Z 22 are each independently a hydrogen atom, a halogen atom, a cyano group, a methyl group, or an ethyl group.
  • Z 23 is a group represented by Z 21 or a group represented by L 1 -Z 24 .
  • Z 24 is the functional group (a) described above.
  • L 1 is a single bond or a linking group L described later, and a preferred range is also synonymous. Note that the linking group L 1 may be appropriately selected in relation to the effects of the present invention in view of the convenience of synthesis.
  • L 1 is, among others, a single bond, a hydrocarbon linking group (preferably an alkylene group), a hetero linking group (preferably O, NR N , or CO), or a linking group having 1 to 10 linking atoms in combination thereof. Is preferred.
  • a linked structure in which an (oligo) alkyleneoxy group (-(Lr-O-) x-: x is preferably an integer of 1 or more and 10,000 or less) is further present is preferable.
  • Z 21 and Z 22 , Z 23 and Z 24 may be bonded to each other or condensed to form a ring.
  • Z 21 to Z 24 may further have an arbitrary substituent T within the range where the effects of the present invention are exhibited.
  • the dicarboxylic anhydride group is preferably a group having a structure of the following formulas (2a) and (2b). * Is a bonding position.
  • the CC bond indicated by # corresponds to the CC bond incorporated in the main chain of the formula (2). That is, in the formula (2b), the main chain is included, and the dicarboxylic anhydride group is a —CO—O—CO— moiety.
  • N in the formula is a natural number, preferably 1 to 10,000, more preferably 1 to 8,000, and particularly preferably 1 to 5,000.
  • the functional group (a) for example, when polymerizing a polymer having a repeating structure represented by the above formula (1-1), a monomer that forms the repeating structure represented by the above formula (1-1); The method of copolymerizing the monomer containing the functional group (a) which forms the repeating unit represented by the above formula (2) is mentioned.
  • the functional group (a) may be introduced into the polymer terminal by polymerizing the monomer that forms the repeating structure represented by the above formula (1-1) with a functional group-containing initiator or chain transfer agent.
  • the functional group (a) may be introduced into the side chain or terminal of the polymer having a repeating structure represented by the above formula (1-1) by a polymer reaction (for example, anhydrous maleic acid is added to the polymer having the repeating unit structure).
  • a polymer reaction for example, anhydrous maleic acid is added to the polymer having the repeating unit structure.
  • a maleic anhydride group as a dicarboxylic anhydride group can be introduced into this polymer, or a different functional group can be formed by reacting with the functional group of the side chain of the polymer having the above repeating unit structure.
  • Commercially available functional group-introduced fluororesins may also be used (for example, KYNAR ADX series manufactured by Arkema Co., Ltd.).
  • the polymer compound constituting the specific binder substantially consists of only the repeating unit represented by the above formula (1-1) and the repeating unit represented by the above formula (2).
  • the polymer compound constituting the specific binder substantially consists of only the repeating unit represented by the above formula (1-1) and the repeating unit represented by the above formula (2).
  • a cyano group is introduced into the functional group portion, a rigid structure is obtained, so that flexibility is lowered, and since it is not an interacting functional group, low binding properties are expected.
  • “substantially” means that other repeating units may be incorporated within the scope of the effects of the present invention.
  • the polymer compound constituting the specific binder preferably has a weight average molecular weight of 15,000 or more.
  • the molecular weight is further preferably 20,000 or more, and more preferably 30,000 or more.
  • the upper limit of the molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less, and further preferably 200,000 or less.
  • the molecular weight of the polymer compound means a weight average molecular weight unless otherwise specified, and adopts a value measured by gel permeation chromatography (GPC) in terms of the standard sample below.
  • the measuring device and measurement conditions are basically based on the following condition 1 and are allowed to be set to condition 2 depending on the solubility of the sample.
  • an appropriate carrier (eluent) and a column suitable for it may be selected and used.
  • Measuring instrument EcoSEC HLC-8320 (trade name, manufactured by Tosoh Corporation) Column: Two TOSOH TSKgel Super AWM-Hs are connected 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 Standard sample: Polystyrene (Condition 2) Measuring instrument: Same as above Column: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, TOSOH TSKgel Super HZ2000 Carrier: tetrahydrofuran Measurement temperature: 40 ° C Carrier flow rate: 1.0 ml / min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector Standard sample: Polystyrene
  • the polymer compound forming the binder preferably contains 80% by mass or more of the repeating unit (non-functional group repeating unit) represented by the formula (1-1) in the molecule.
  • the copolymerization ratio of the non-functional group repeating unit is further preferably 85% by mass or more, and more preferably 90% by mass or more. Although there is no upper limit in particular, it is practical that it is 99.9 mass% or less.
  • the copolymerization ratio of the non-functional group repeating unit can be specified by the amount of the monomer blended at the time of synthesizing the polymer compound.
  • the 13 C-NMR quantitative spectrum (inverse gate decoupling method) of the polymer compound is measured, and the copolymerization ratio is calculated by calculating from the integral ratio. Can be calculated.
  • the copolymerization ratio of the repeating unit having the functional group (a) (functional group repeating unit) is preferably 0.1% by mass or more, and 0.3% by mass or more. It is more preferable that it is 0.5 mass% or more. As an upper limit, it is preferable that it is 30 mass parts or less, It is more preferable that it is 20 mass% or less, It is further more preferable that it is 15 mass% or less, It is especially preferable that it is 10 mass% or less.
  • the copolymerization ratio of a functional group repeating unit can be specified by the amount of the monomer compounded at the time of synthesizing the polymer compound.
  • the 13 C-NMR quantitative spectrum (inverse gate decoupling method) of the polymer compound is measured, and the copolymerization ratio is calculated by calculating from the integral ratio. Can be calculated.
  • the compounding quantity of the binder in a solid electrolyte composition is 0.1 mass part or more with respect to 100 mass parts of said inorganic solid electrolyte (this is included when using an active material), 0.3 mass More preferably, it is more than 0.5 part by weight.
  • the upper limit is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 15 parts by mass or less, and particularly preferably 5 parts by mass or less.
  • the binder in the solid content, is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and 0.5% by mass or more. Is particularly preferred.
  • the binder in the above range, it is possible to more effectively achieve both the adhesion of the inorganic solid electrolyte and the suppression of the interface resistance.
  • the binder applied to the present invention may be used in combination with other binders and various additives in addition to the above-mentioned specific polymer compound.
  • the above blending amount is defined as the total amount of the binder, but it is more preferable to look at the amount of the specific polymer compound.
  • the electrolyte is solid, the interfacial resistance between solid particles increases. It is understood that by using a polymer compound having a specific functional group introduced as a binder, not only the binding properties of the solid electrolytes but also the active material and the solid electrolyte can be connected. As a result, not only the adhesion to the current collector is improved, but also the contact between the solid electrolytes or between the active material and the solid electrolyte can be secured and the resistance can be reduced. On the other hand, it is understood that the main chain of the polymer compound has a repeating unit containing a specific fluorine-containing substituent and contributes particularly to the improvement of stability.
  • substituent T examples include the following.
  • An 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, etc.
  • an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms, such as ethynyl, 1,3-butadiynyl, phenyl Ethynyl, etc.
  • a cycloalkyl group preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl
  • Alkylthio groups such as methylthio, ethylthio Isopropylthio, benzylthio, etc.), arylthio groups (preferably arylthio groups having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), alkylsulfonyl groups (preferably An alkylsulfonyl group having 1 to 20 carbon atoms such as methylsulfonyl and ethylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 22 carbon atoms such as benzenesulfonyl), an alkylsilyl group (preferably Is an alkylsilyl group having 1 to 20 carbon atoms, such as monomethylsilyl, dimethylsilyl, trimethylsilyl, trieth
  • 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.
  • Each substituent defined in the present specification may be substituted via the following linking group L within a range that exhibits the effects of the present invention.
  • the alkyl group / alkylene group, alkenyl group / alkenylene group and the like may further have the following hetero-linking group interposed in the structure.
  • the linking group L includes a hydrocarbon linking group [an alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), an alkenylene group having 2 to 10 carbon atoms (more preferably carbon atoms).
  • the said hydrocarbon coupling group may form the double bond and the triple bond suitably, and may connect.
  • the ring to be formed is preferably a 5-membered ring or a 6-membered ring.
  • a nitrogen-containing five-membered ring is preferable, and examples of the compound forming the ring include pyrrole, imidazole, pyrazole, indazole, indole, benzimidazole, pyrrolidine, imidazolidine, pyrazolidine, indoline, carbazole, or these And derivatives thereof.
  • 6-membered ring examples include piperidine, morpholine, piperazine, and derivatives thereof. Moreover, when an aryl group, a heterocyclic group, etc. are included, they may be monocyclic or condensed and may be similarly substituted or unsubstituted.
  • RN is a hydrogen atom or a substituent. Examples of the substituent 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).
  • RP is a hydrogen atom, a hydroxyl group, 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).
  • an alkoxy group preferably having 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 1 to 6 and particularly preferably 1 to 3
  • an alkenyloxy group having carbon number
  • More preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 to 3, and an alkynyloxy group preferably having 2 to 24 carbon atoms, more preferably 2 to 12 and more preferably 2 to 6.
  • More preferably, 2 to 3 are particularly preferred
  • an aralkyloxy group preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms
  • an aryloxy group preferably 6 to 22 carbon atoms, 6 to 14 are more preferable, and 6 to 10 are particularly preferable.
  • the number of atoms constituting the linking group is preferably from 1 to 36, more preferably from 1 to 24, still more preferably from 1 to 12, and from 1 to 6 Is particularly preferred.
  • the number of linking atoms in the linking group is preferably 10 or less, and more preferably 8 or less.
  • the lower limit is 1 or more.
  • the number of connected atoms refers to the minimum number of atoms that are located in a path connecting predetermined structural portions and are involved in the connection. For example, in the case of —CH 2 —C ( ⁇ O) —O—, the number of atoms constituting the linking group is 6, but the number of linking atoms is 3.
  • Specific examples of the combination of linking groups include the following.
  • x is an integer of 1 or more, preferably 1 to 500, and more preferably 1 to 100.
  • Lr is preferably an alkylene group, an alkenylene group or an alkynylene group.
  • the carbon number of Lr is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3.
  • a plurality of Lr, R N , R P , x, etc. need not be the same.
  • the direction of the linking group is not limited by the above description, and may be understood as appropriate according to a predetermined chemical formula.
  • a dispersion medium in which the above components are dispersed may be used.
  • the dispersion medium include a water-soluble organic solvent. Specific examples include the following, which are preferable.
  • 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, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, alkylene glycol alkyl ether (ethylene glycol mono (di) methyl) Ether, ethylene glycol mono (di) butyl ether, propylene glycol mono (di) methyl ether, diethylene glycol mono (di) methyl ether, propylene glycol mono (di) methyl ether, dipropylene glycol mono (di) methyl ether, tripropylene glycol mono (Di) methyl ether, diethylene glycol mono (di) butyl ether Amide compounds solvents N, N-dimethylformamide, 1-methyl-2-pyrrol
  • Ketone compound solvents Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
  • Aromatic compound solvents Benzene, toluene, etc.
  • Fat Group compound solvent Hexane, heptane, cyclohexane, methylcyclohexane, octane, pentane, cyclopentane, decane, etc.
  • 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 positive electrode active material is preferably one that can reversibly insert and release lithium ions.
  • the material is not particularly limited, and may be a transition metal oxide or an element that can be combined with Li such as sulfur. Among these, it is preferable to use a transition metal oxide, and it is more preferable to have one or more elements selected from Co, Ni, Fe, Mn, Cu, and V as a transition metal element.
  • transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt structure, (MB) a transition metal oxide having a spinel structure, (MC) a lithium-containing transition metal phosphate compound, (MD And lithium-containing transition metal halide phosphate compounds, (ME) lithium-containing transition metal silicate compounds, and the like.
  • transition metal oxide having a layered rock salt structure LiCoO 2 (lithium cobaltate [LCO]), LiNi 2 O 2 (lithium nickelate) LiNi 0.85 Co 0.10 Al 0.05 O 2 (nickel cobalt lithium aluminum oxide [NCA]), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (nickel manganese lithium cobalt oxide [NMC]), LiNi 0.5 Mn 0.5 O 2 (manganese) Lithium nickelate).
  • LCO lithium cobaltate
  • NCA nickelate
  • NMC nickel manganese lithium cobalt oxide
  • NMC nickel manganese lithium cobalt oxide
  • (MB) As specific examples of the transition metal oxide having a spinel structure, LiMn 2 O 4 (lithium manganate [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 are mentioned.
  • Examples of (MC) lithium-containing transition metal phosphate compounds include olivine-type iron phosphate salts such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , LiCoPO 4 and the like. And monoclinic Nasicon type vanadium phosphate salts such as Li 3 V 2 (PO 4 ) 3 (vanadium lithium phosphate).
  • the (MD) lithium-containing transition metal halogenated phosphate compound for example, Li 2 FePO 4 F such fluorinated phosphorus iron salt, Li 2 MnPO 4 hexafluorophosphate manganese salts such as F, Li 2 CoPO 4 F Cobalt fluorophosphates such as
  • Examples of the (ME) lithium-containing transition metal silicate compound include Li 2 FeSiO 4 , Li 2 MnSiO 4 , Li 2 CoSiO 4, and the like.
  • the volume average particle diameter (sphere conversion average particle diameter) of the positive electrode active material that can be used in the solid electrolyte composition of the present invention is not particularly limited. For example, 0.1 ⁇ m to 50 ⁇ m is preferable. In order to make the positive electrode active material have a predetermined particle size, 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 volume average particle diameter of the positive electrode active material can be measured using a laser diffraction / scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA).
  • the concentration of the positive electrode active material is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 80% by mass in 100% by mass of the solid component in the positive electrode composition.
  • the positive electrode active materials may be used alone or in combination of two or more. Moreover, you may make the composition for positive electrodes (positive electrode active material layer) contain a conductive support agent suitably as needed. As the conductive assistant, those described below can be used.
  • the negative electrode active material used for the solid electrolyte composition (hereinafter also referred to as the negative electrode composition) for forming the negative electrode active material layer of the all-solid-state secondary battery of the present invention will be described.
  • the negative electrode active material those capable of reversibly inserting and releasing lithium ions are preferable.
  • 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 a lithium such as Sn, Si, or In. And metals capable of forming an alloy.
  • carbonaceous materials or metal composite oxides are preferably used from the viewpoint of reliability.
  • the metal composite oxide is preferably capable of inserting and extracting lithium.
  • the material is not particularly limited, but preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
  • the carbonaceous material used as the negative electrode active material is a material substantially made of carbon.
  • Examples thereof include carbonaceous materials obtained by firing various synthetic resins such as artificial pitches such as petroleum pitch, natural graphite, and vapor-grown graphite, and polyacrylonitrile (PAN) 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 polyvinyl alcohol (PVA) -based carbon fiber, lignin carbon fiber, glassy carbon fiber, and activated carbon fiber. And mesophase microspheres, graphite whiskers, flat graphite and the like.
  • carbonaceous materials can be divided into non-graphitizable carbonaceous materials and graphite-based carbonaceous materials according to 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 a group 16 element 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.
  • an amorphous oxide of a metalloid element and a chalcogenide are more preferable, and elements of Groups 13 (IIIB) to 15 (VB) of the periodic table, Al , Ga, Si, Sn, Ge, Pb, Sb, Bi, one kind of oxide, or a combination of two or more kinds thereof, and chalcogenide are particularly preferable.
  • preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , SiO, GeO, SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 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 average particle diameter of the negative electrode active material particles can be measured by the same method as the method for measuring the volume average particle diameter of the positive electrode active material.
  • the chemical formula of the compound obtained by the above firing method can be calculated from an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method, and from a mass difference between powders before and after firing as a simple method.
  • ICP inductively coupled plasma
  • Examples of the negative electrode active material that can be used in combination with the amorphous oxides centered on Sn, Si, and Ge include carbonaceous materials that can occlude and release lithium ions or lithium metal, lithium, lithium alloys, lithium, and the like. A metal capable of forming an alloy is preferred.
  • At least one active material represented by the following formula (A) is included.
  • xx represents a number of 0.01 or more and less than 1, and means a mole fraction.
  • M represents a chalcogen element, a metalloid element, an alkali metal element, an alkaline earth metal element, a transition metal element, or a combination thereof.
  • M is preferably a chalcogen element such as O, S or Se, a metalloid element such as B or Ge, an alkali metal element such as Li or Na, an alkaline earth metal element such as Mg or Ca, Ti, V, It can be selected from transition metal elements such as Mn, Fe, Co, Ni, and Cu. Further, a combination of two or more of these elements may be used. Among these, chalcogen elements and transition metal elements are preferable, and transition metal elements are more preferable. Among the transition metal elements, the first transition metal element is preferable, Ti, V, Mn, Fe, Co, Ni, and Cu are more preferable, and Ti, Mn, Fe, Co, and Ni are particularly preferable.
  • Xx is preferably 0.1 or more and less than 1, more preferably 0.1 or more and 0.99 or less, further preferably 0.2 or more and 0.98 or less, and particularly preferably 0.3 or more and 0.95 or less.
  • the negative electrode active material contains a titanium atom. More specifically, Li 4 Ti 5 O 12 (lithium titanate [LTO]) is excellent in rapid charge / discharge characteristics due to small volume fluctuations during the insertion and release of lithium ions, and the deterioration of the electrodes is suppressed, and the lithium ion secondary This is preferable in that the battery life can be improved.
  • Li 4 Ti 5 O 12 lithium titanate [LTO]
  • 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.
  • the negative electrode active materials may be used alone or in combination of two or more.
  • the negative electrode composition (negative electrode active material layer) may appropriately contain a conductive additive as necessary.
  • a conductive assistant those described below can be used.
  • a general conductive support agent can be used.
  • graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black and furnace black, amorphous carbon such as needle coke, vapor-grown carbon fiber and carbon nanotubes, which are electron conductive materials
  • Carbon fibers such as graphene, carbonaceous materials such as graphene and fullerene, metal powders such as copper and nickel, and metal fibers may be used, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives May be used.
  • 1 type may be used among these and 2 or more types may be used.
  • the present invention is not construed as being limited thereto.
  • the solid electrolyte composition according to the preferred embodiment of the present invention is used to form an inorganic solid electrolyte layer. Good.
  • the positive / negative current collector an electron conductor that does not cause a chemical change is preferably used.
  • the current collector for the positive electrode in addition to aluminum, aluminum alloy, stainless steel, nickel, titanium, etc., the surface of aluminum, aluminum alloy or stainless steel treated with carbon, nickel, titanium or silver is preferable. More preferably, aluminum, aluminum alloy, or stainless steel is used.
  • the negative electrode current collector is a surface of aluminum, stainless steel, copper or copper alloy treated with carbon, nickel, titanium or silver.
  • aluminum, copper, copper alloy, or stainless steel is used.
  • 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.
  • An electrode sheet having the basic structure of an all-solid-state secondary battery can be produced by arranging the above members. Depending on the application, it may be used as an all-solid secondary battery as it is, but in order to form a dry battery, it is further enclosed in a suitable housing.
  • the housing may be metallic or made of resin (plastic). In the case of using a metallic material, for example, an aluminum alloy or a stainless steel material can be used.
  • the metallic casing is divided into a positive casing and a negative casing, and is electrically connected to the positive collector and the negative collector, respectively.
  • the casing on the positive electrode side and the casing on the negative electrode side are joined and integrated via a gasket for preventing a short circuit.
  • the all-solid-state secondary battery may be manufactured by a conventional method. Specifically, a method for producing an all-solid-state secondary battery using a battery electrode sheet in which a film is formed by applying the solid electrolyte composition on a metal foil serving as a current collector is mentioned. . For example, a composition (positive electrode composition) serving as a positive electrode material is applied onto a metal foil to form a film. Next, an inorganic solid electrolyte composition (solid electrolyte composition) is applied to the upper surface of the obtained positive electrode active material layer to form a film (solid electrolyte layer).
  • a composition as a negative electrode material (negative electrode composition) is applied to the upper surface of the solid electrolyte to form a negative electrode active material film (negative electrode active material layer), and the upper surface of this negative electrode active material layer
  • a battery electrode sheet having the same layer structure as that of the desired all-solid-state secondary battery can be obtained by applying a current collector (metal foil) on the negative electrode side. If necessary, this can be enclosed in a housing to obtain a desired all-solid secondary battery.
  • coating method of said each composition should just follow a conventional method.
  • 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.
  • the solid electrolyte composition of the present invention may be mechanically dispersed or pulverized.
  • Examples of the method for pulverizing the inorganic solid electrolyte in the solid electrolyte composition include a mechanical dispersion method.
  • a ball mill, a bead mill, a planetary mixer, a blade mixer, a roll mill, a kneader, a disk mill, or the like is used as the mechanical dispersion method.
  • the material of the ball mill ball includes meno, sintered alumina, tungsten carbide, chrome steel, stainless steel, zirconia, plastic polyamide, nylon, silicon nitride, Teflon (registered trademark), and the like.
  • the same balls may be used, or two or more different balls may be used.
  • a ball may be added or changed to a ball having a different shape, size, and material.
  • the preferred amount of balls for the container is not particularly specified and may be fully filled.
  • the amount of ball or device-derived contamination generated by impact due to mechanical dispersion is not particularly specified. The amount of contamination can also be suppressed to 10 ppm (mass basis) or less.
  • the inorganic solid electrolyte may be dispersed singly or in combination of two or more.
  • the dispersion may be one stage or two or more stages.
  • a positive electrode or negative electrode active material, an inorganic solid electrolyte, a binder, a dispersant, a dispersion medium, a conductive additive, a lithium salt, or the like can be added between the steps.
  • the parameters (dispersion time, dispersion speed, dispersion substrate, etc.) of the apparatus relating to dispersion in each stage can be changed.
  • the dispersion method may be a wet dispersion containing a dispersion medium or a dry dispersion without a dispersion medium, but in the present invention, a wet dispersion is preferred.
  • the dispersion medium may dissolve a part of the inorganic solid electrolyte during dispersion.
  • the dissolution part can be regenerated to the original inorganic solid electrolyte by heating at the time of drying.
  • the dispersion medium is a water-containing solvent (water content of 100 ppm or more (mass basis)
  • the inorganic solid electrolyte can be regenerated by heat drying or vacuum heat drying after dispersion.
  • the dispersion time is not particularly specified, but is generally 10 seconds to 10 days.
  • the dispersion temperature is not particularly specified, but is generally in the range of ⁇ 50 ° C. to 100 ° C.
  • the volume average particle diameter of the inorganic solid electrolyte dispersed as described above is not particularly limited, but is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, and further preferably 0.1 ⁇ m or more. As an upper limit, 500 micrometers or less are preferable, 100 micrometers or less are more preferable, 50 micrometers is further more preferable, 10 micrometers or less are especially preferable, and 5 micrometers or less are the most preferable.
  • the volume average particle diameter can be measured using a laser diffraction / scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA).
  • the inorganic solid electrolyte may maintain the original shape before and after the dispersion step, or the shape may be changed.
  • a battery sheet such as a battery electrode sheet, a solid electrolyte sheet (a sheet including a solid electrolyte layer, preferably including a metal foil as a current collector), and
  • a drying in the above-described method for producing a solid electrolyte composition of the present invention is not immediately dried, but is dried after forming a coating film after coating. Any drying method such as blow drying, heat drying, or vacuum drying can be used.
  • the dispersion of the solid electrolyte composition prepared above may be used as it is, but the dispersion medium used in the above dispersion operation or a solvent different from this is added, or once dried. Then, it may be redispersed with a dispersion medium different from the dispersion medium used in the dispersion operation.
  • the solid electrolyte composition used for coating may be prepared by mixing two or more types of slurries having different particle dispersity and volume average particle diameter depending on the dispersion process.
  • the positive electrode or the negative electrode active material may be added later, or the positive electrode or the negative electrode active material, the inorganic solid electrolyte, and the dispersion medium may be added. You may distribute in a lump.
  • the binder or various additives may be added before or after the dispersion of the inorganic solid electrolyte.
  • Application may be either wet application or dry application.
  • Rod bar coating bar coating method
  • reverse roll coating direct roll coating
  • blade coating knife coating
  • extrusion coating curtain coating
  • gravure coating dip coating
  • squeeze coating and the like
  • the speed of application can be changed depending on the viscosity of the solid electrolyte composition. It is desirable that the coating film has a uniform film thickness from the beginning to the end of coating.
  • the first part of the application is thicker and it is thinner as it is finished.
  • the clearance between the bar coat and the coating table is larger at the end of coating than at the beginning of coating.
  • a slit is carved on the coating table, and the slit groove can be designed to be deeper in the later stage than in the initial stage of application.
  • a support to be coated is placed on the slit.
  • the application bar remains level with respect to the application table. By doing so, the clearance can be gradually widened.
  • the positive electrode active material layer, the inorganic solid electrolytic layer, and the negative electrode active material layer can be applied stepwise while being dried, or a plurality of different layers can be applied while being wet.
  • each composition which forms a different layer it can also apply
  • the inorganic solid electrolyte used in the inorganic solid electrolyte layer may be one kind or two or more kinds in the above-mentioned sulfide-based inorganic solid electrolyte and oxide-based inorganic solid electrolyte, elemental composition and crystal structure. Moreover, you may use the inorganic solid electrolyte which differs in the part which touches an electrode layer (a positive electrode or a negative electrode active material layer), and the inside of an inorganic solid electrolyte layer.
  • the battery electrode sheet, the solid electrolyte sheet prepared by coating, the two or more layers of a combination thereof, and the battery sheet are dried from the coating solvent or the dispersion medium. Any drying method such as blow drying, heat drying, or vacuum drying can be used.
  • the pressurizing method is a hydraulic cylinder press.
  • the pressure for pressurization is generally in the range of 40 to 1500 MPa, and may be 50 to 1500 MPa. You may heat simultaneously with pressurization.
  • the heating temperature is generally in the range of 30 ° C to 300 ° C. It can also be pressed at a temperature higher than the glass transition temperature of the inorganic solid electrolyte.
  • pressing can be performed at a temperature higher than the glass transition temperature of the binder. However, in general, the temperature does not exceed the melting point of the binder.
  • the pressurization may be performed in a state where the coating solvent or the dispersion medium is previously dried, or may be performed in a state where the solvent or the dispersion medium remains.
  • the atmosphere during pressurization may be any of air, dry air (dew point ⁇ 20 ° C. or lower), inert gas (for example, argon gas, helium gas, nitrogen gas).
  • the pressing time may be a high pressure in a short time (for example, within several hours), or a medium pressure may be applied for a long time (1 day or more).
  • a restraint (screw tightening pressure or the like) of the all-solid-state secondary battery can be used in order to keep applying moderate pressure.
  • the pressing pressure may be uniform or different with respect to the pressed part such as the sheet surface.
  • the pressing pressure can be changed according to the area and film thickness of the pressed part. Also, the same part can be changed stepwise with different pressures.
  • the press surface may be smooth or roughened.
  • the surfaces that are in contact with each other are wet with an organic solvent, an organic substance, or the like.
  • the solid electrolyte composition forming the solid electrolyte layer may be applied to both layers or one of the layers and bonded before they are dried.
  • the temperature at the time of bonding may be close to the glass transition temperature of the inorganic solid electrolyte as a temperature higher than that at room temperature.
  • 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 purposes and space. Moreover, it can also combine with a solar cell.
  • a solid electrolyte composition (positive electrode composition or negative electrode composition) containing an active material capable of inserting and releasing ions of metal elements 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.
  • the solid electrolyte composition is formed on a positive electrode active layer or a negative electrode active layer formed on a metal foil, and the negative electrode active layer or the negative electrode active layer is formed on the obtained solid electrolyte layer.
  • a battery electrode sheet formed by forming a positive electrode active material layer.
  • a battery electrode sheet comprising a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and an inorganic solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer, the positive electrode
  • An electrode sheet for a battery wherein at least one of an active material layer, a negative electrode active material layer, and an inorganic solid electrolyte layer includes the inorganic solid electrolyte of the present invention and the specific binder described above.
  • An all-solid-state secondary battery comprising a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and an inorganic solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer,
  • An all-solid secondary battery wherein at least one of a positive electrode active material layer, a negative electrode active material layer, and an inorganic solid electrolyte layer is a layer formed of the solid electrolyte composition.
  • the solid electrolyte composition was disposed on a positive electrode active layer or a negative electrode active layer formed on a metal foil, formed into a film, and further obtained.
  • the manufacturing method of the electrode sheet for batteries which forms a negative electrode active material layer or a positive electrode active material layer on a solid electrolyte layer. -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 a polymer all-solid-state secondary battery using a polymer compound such as polyethylene oxide as an electrolyte and an inorganic all-solid-state secondary battery using the above LLT, LLZ, or the like.
  • the inorganic solid electrolyte is distinguished from the above-described electrolyte (polymer electrolyte) using a polymer compound such as polyethylene oxide as an ion conductive medium, and the inorganic compound serves as an ion conductive medium. Specific examples include the above 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).
  • composition means a mixture in which two or more components are uniformly mixed. However, as long as the uniformity is substantially maintained, aggregation or uneven distribution may partially occur within a range in which a desired effect is achieved.
  • a solid electrolyte composition when referring to a solid electrolyte composition, it basically refers to a composition (typically a paste) that is a material for forming an electrolyte layer or the like, and an electrolyte layer or the like formed by curing the composition is This shall not be included.
  • binder synthesis > 200 parts of ion exchange water, 190 parts of vinylidene fluoride and 10 parts of acrylic acid were added to the autoclave, 2 parts of diisopropyl peroxydicarbonate was added, and the mixture was stirred at 30 ° C. for 24 hours. After completion of the polymerization, the precipitate was filtered and dried at 100 ° C. for 10 hours to obtain a polymer compound (binder) B-1.
  • the obtained binder had a weight average molecular weight of 50,000.
  • Table 1 summarizes the composition and weight average molecular weight of each binder synthesized in the same manner as Binder B-1. In this example, the molecular weight is rounded off to the nearest 100.
  • Table 2 summarizes the composition of each solid electrolyte composition obtained in the same manner as the solid electrolyte composition S-1.
  • Li-PS glass ⁇ Synthesis of sulfide inorganic solid electrolyte (Li-PS glass)>
  • Li 2 S lithium sulfide
  • P 2 S 5 diphosphorus pentasulfide
  • Purity> 99% 3.90 g was weighed, put into an agate mortar, and mixed for 5 minutes using an agate pestle.
  • 66 zirconia beads having a diameter of 5 mm were introduced into a 45 mL zirconia container (manufactured by Fritsch), and the whole amount of the mixture obtained above was introduced, and the container was completely sealed under an argon atmosphere.
  • a container is set on a planetary ball mill P-7 (trade name) manufactured by Frichtu, and mechanical milling is performed at 25 ° C. and a rotation speed of 510 rpm for 20 hours, whereby a yellow powder sulfide-based inorganic solid electrolyte (Li-PS) System glass) 6.20 g was obtained.
  • the solid electrolyte composition obtained above is applied onto an aluminum foil having a thickness of 20 ⁇ m with an applicator having an arbitrary clearance, heated at 80 ° C. for 1 hour, and further at 110 ° C. for 1 hour to dry the coating solvent (dispersion medium). It was. Then, it heated and pressurized so that it might become arbitrary density using a heat press machine, and obtained each solid electrolyte sheet of Table 3.
  • the film thickness of the solid electrolyte layer was 30 ⁇ m.
  • composition for positive electrode In a planetary mixer (TK Hibismix, manufactured by PRIMIX), 100 parts of the positive electrode active material shown in Table 4, 5 parts of acetylene black, 75 parts of each solid electrolyte composition obtained above, N -270 parts of methylpyrrolidone was added and stirred at 40 rpm for 1 hour to prepare a positive electrode composition used for each positive electrode active layer (also referred to simply as positive electrode layer) shown in Table 4.
  • TK Hibismix manufactured by PRIMIX
  • positive electrode sheet for secondary battery- The positive electrode composition obtained above is applied onto an aluminum foil having a thickness of 20 ⁇ m with an applicator having an arbitrary clearance, heated at 80 ° C. for 1 hour, and further at 110 ° C. for 1 hour to dry the coating solvent (dispersion medium). It was. Then, it heated and pressurized so that it might become arbitrary density using the heat press machine, and the positive electrode sheet for secondary batteries which has a positive electrode active material layer on aluminum foil was obtained.
  • the solid electrolyte composition obtained above is applied with an applicator having an arbitrary clearance, 80 ° C. for 1 hour, and further 110 ° C. for 1 hour.
  • the solid electrolyte layer was formed by heating.
  • the negative electrode composition obtained above was further applied onto the solid electrolyte layer and heated at 80 ° C. for 1 hour and further at 110 ° C. for 1 hour to form a negative electrode layer.
  • a copper foil having a thickness of 20 ⁇ m was combined on the negative electrode layer, and this was heated and pressurized to a desired density using a heat press machine to obtain each battery electrode sheet described in Table 4.
  • the battery electrode sheet has the structure of FIG.
  • both the positive electrode layer and the negative electrode layer had a thickness of 80 ⁇ m, and the inorganic solid electrolyte layer had a thickness of 30 ⁇ m.
  • Cellotape (registered trademark) having a width of 12 mm and a length of 60 mm on the entire surface of the inorganic solid electrolyte layer of the solid electrolyte sheet obtained above or the positive electrode active material layer (length: 50 mm, width: 12 mm) of the positive electrode sheet for a secondary battery (trade name) , Manufactured by Nichiban Co., Ltd.) and 50 mm was peeled off at a speed of 10 mm / min. In that case, it evaluated by the area ratio of the sheet
  • the solid electrolyte sheet (Table 3) or battery electrode sheet (Table 4) obtained above is 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 ( When a solid electrolyte sheet is used, an aluminum foil cut into a disk shape having a diameter of 14.5 mm is placed in a coin case so as to be in contact with the solid electrolyte layer), a coin battery (cell for measuring ion conductivity by non-pressurization) ) was produced. Further, as shown in FIG.
  • the coin battery is sandwiched between jigs that can apply pressure between the electrodes from the outside of the coin battery, and restraint pressure is applied so that the pressure between the electrodes becomes 500 kgf / cm 2 (49 MPa).
  • a cell for measuring ion conductivity by pressure was prepared.
  • the coin battery 13 is manufactured, but this is replaced with the ion conductivity measuring cell 13.
  • 11 is an upper support plate
  • 12 is a lower support plate
  • 14 is a coin case
  • 15 is an electrode sheet (solid electrolyte sheet or battery electrode sheet)
  • S is a screw.
  • Ionic conductivity 1000 ⁇ sample film thickness (cm) / (resistance ( ⁇ ) ⁇ sample area (cm 2 )) (1)
  • LMO LiMn 2 O 4 lithium manganate
  • LTO Li 4 Ti 5 O 12 lithium titanate
  • LCO LiCoO 2 lithium cobaltate
  • NMC Li (Ni 1/3 Mn 1/3 Co 1/3 ) O 2 nickel, manganese, Lithium cobalt oxide

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Abstract

L'invention concerne : une batterie secondaire tout électronique, comprenant une couche de matériau actif d'électrode positive, une couche de matériau actif d'électrode négative, et une couche d'électrolyte solide, la couche de matériau actif d'électrode positive et/ou la couche de matériau actif d'électrode négative et/ou la couche d'électrolyte solide comprenant un électrolyte solide inorganique ayant la conductivité ionique d'un élément métallique appartenant au groupe 1 ou au groupe 2 de la table périodique, et un liant formé à partir d'un composé polymère spécifique ; une composition électrolytique solide ; une feuille d'électrode pour batterie, ladite feuille d'électrode utilisant ladite composition électrolytique solide ; un procédé de production de ladite feuille d'électrode pour batterie ; et un procédé de production d'une batterie secondaire tout électronique.
PCT/JP2015/071642 2014-07-31 2015-07-30 Batterie secondaire tout électronique, composition électrolytique solide, feuille d'électrode pour batterie l'utilisant, procédé de production de feuille d'électrode pour batterie, et procédé de production de batterie secondaire tout électronique Ceased WO2016017759A1 (fr)

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