WO2019208347A1 - Feuille comprenant un électrolyte solide, feuille d'électrode pour batterie secondaire entièrement solide, batterie secondaire entièrement solide, dispositif électronique, véhicule électrique, et procédés de fabrication de ceux-ci - Google Patents

Feuille comprenant un électrolyte solide, feuille d'électrode pour batterie secondaire entièrement solide, batterie secondaire entièrement solide, dispositif électronique, véhicule électrique, et procédés de fabrication de ceux-ci Download PDF

Info

Publication number
WO2019208347A1
WO2019208347A1 PCT/JP2019/016403 JP2019016403W WO2019208347A1 WO 2019208347 A1 WO2019208347 A1 WO 2019208347A1 JP 2019016403 W JP2019016403 W JP 2019016403W WO 2019208347 A1 WO2019208347 A1 WO 2019208347A1
Authority
WO
WIPO (PCT)
Prior art keywords
solid electrolyte
solid
secondary battery
state secondary
sheet
Prior art date
Application number
PCT/JP2019/016403
Other languages
English (en)
Japanese (ja)
Inventor
昭人 福永
信 小澤
山本　健一
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2020516262A priority Critical patent/JP7014900B2/ja
Publication of WO2019208347A1 publication Critical patent/WO2019208347A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solid electrolyte-containing sheet, an electrode sheet for an all-solid-state secondary battery, an all-solid-state secondary battery, an electronic device and an electric vehicle, and methods for producing these.
  • a lithium ion secondary battery is a storage battery that includes a negative electrode, a positive electrode, and an electrolyte sandwiched between the negative electrode and the positive electrode, and enables charging and discharging by reciprocating lithium ions between the two electrodes.
  • an organic electrolytic solution has been used as an electrolyte in a lithium ion secondary battery.
  • the organic electrolyte is liable to leak, and there is a possibility that a short circuit may occur inside the battery due to overcharge or overdischarge, resulting in ignition, and further improvements in safety and reliability are required. Under such circumstances, an all-solid secondary battery using an inorganic solid electrolyte instead of an organic electrolyte has been attracting attention.
  • the all-solid-state secondary battery is composed of a solid anode, electrolyte, and cathode, which can greatly improve safety and reliability, which is a problem for batteries using organic electrolytes, and can also extend the service life. It will be. Furthermore, the all-solid-state secondary battery can have a laminated structure in which electrodes and an electrolyte are directly arranged in series. Therefore, the energy density can be increased as compared with the secondary battery using the organic electrolyte, and application to various electronic devices, electric vehicles, large-sized storage batteries, and the like is expected.
  • Patent Document 1 discloses that at least one of a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer has a specific inorganic solid electrolyte, an average diameter of 0.001 to 1 ⁇ m, and an average length. All solid state secondary batteries containing fibers with an average length of 0.1 to 150 ⁇ m, an average length to average diameter of 10 to 100,000, and an electrical conductivity of 1 ⁇ 10 ⁇ 6 S / m or less are described. Has been.
  • This all-solid-state secondary battery has low resistance and excellent cycle characteristics.
  • Patent Document 2 in an all-solid-state secondary battery having a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer, spherical carbon and fibrous materials are added to the positive electrode active material layer as a conductive additive for the positive electrode active material.
  • An all solid state secondary battery containing carbon in combination is described. This all-solid-state secondary battery can reduce the resistance of the positive electrode active material layer even if fibrous carbon is used as a conductive additive.
  • the solid electrolyte layer and the electrode active material layer constituting the all solid state secondary battery include It is desirable to be able to handle without using a support. Furthermore, from the viewpoint of suitability for production, these solid electrolyte layer and electrode active material layer need to withstand winding of a large curvature when wound into a roll. Therefore, improvement in flexibility is also desired.
  • the present invention is a solid electrolyte-containing sheet that is excellent in flexibility and can be used as a self-supporting film, and can be used as a constituent member to realize an all-solid-state secondary battery having an excellent battery voltage. It is an object to provide an electrolyte-containing sheet.
  • the present invention also provides an electrode sheet for an all-solid-state secondary battery having the above-described solid electrolyte-containing sheet, an all-solid-state secondary battery having the electrode sheet for an all-solid-state secondary battery, and the all-solid-state secondary battery. It is an object to provide an electronic device and an electric vehicle that are provided.
  • this invention makes it a subject to provide the manufacturing method of each of the said solid electrolyte containing sheet
  • the present inventors made extensive studies in view of the above problems. As a result, it has a solid electrolyte-containing layer containing a fiber having a specific average diameter and a specific average length, and an inorganic solid electrolyte. Further, the thickness of the average length and the solid electrolyte-containing layer is specified. The present inventors have found that the above problems can be solved by satisfying the relationship. The present invention has been further studied based on these findings and has been completed.
  • ⁇ 3> The solid electrolyte-containing sheet according to ⁇ 1> or ⁇ 2>, wherein the fiber is an electrospun fiber.
  • ⁇ 4> The solid electrolyte-containing sheet according to any one of ⁇ 1> to ⁇ 3>, which contains a binder.
  • ⁇ 5> The solid electrolyte-containing sheet according to any one of ⁇ 1> to ⁇ 4>, which is a self-supporting film.
  • An electrode sheet for an all-solid-state secondary battery comprising the solid electrolyte-containing sheet according to any one of ⁇ 1> to ⁇ 5> and an electrode active material layer.
  • the all-solid-state secondary battery which has an electrode sheet for all-solid-state secondary batteries as described in ⁇ 6>.
  • ⁇ 8> ⁇ 7>
  • Electronic equipment having the all-solid-state secondary battery described in ⁇ 7>.
  • ⁇ 9> An electric vehicle having the all solid state secondary battery according to ⁇ 7>.
  • ⁇ 10> ⁇ 1> including a step of casting a solid electrolyte composition including a fiber having an average diameter d of 0.1 to 2 ⁇ m and an average length L of 0.2 to 50 mm, an inorganic solid electrolyte, and a dispersion medium.
  • ⁇ 11> A step of applying a dry powder of an inorganic solid electrolyte to a non-woven fabric of fibers having an average diameter d of 0.1 to 2 ⁇ m and an average length L of 0.2 to 50 mm; and the inorganic solid electrolyte and a dispersion medium on the non-woven fabric Any one of ⁇ 1> to ⁇ 5>, including a step of applying a solid electrolyte composition containing a solid electrolyte composition, or a step of impregnating the nonwoven fabric with a solid electrolyte composition containing an inorganic solid electrolyte and a dispersion medium The manufacturing method of the solid electrolyte containing sheet of description.
  • a fiber nonwoven fabric having an average diameter d of 0.1 to 2 ⁇ m and an average length L of 0.2 to 50 mm is present in the same system (in the liquid phase) when the inorganic solid electrolyte is liquid-phase synthesized.
  • a solid electrolyte-containing sheet is obtained by the method for producing a solid electrolyte-containing sheet according to any one of ⁇ 10> to ⁇ 13>, and an electrode sheet for an all-solid-state secondary battery is produced using the solid electrolyte-containing sheet.
  • the manufacturing method of the electrode sheet for all-solid-state secondary batteries including this.
  • An electrode sheet for an all-solid-state secondary battery is obtained by the method for producing an electrode sheet for an all-solid-state secondary battery described in ⁇ 14>, and an all-solid-state secondary battery is manufactured using this electrode sheet for an all-solid-state secondary battery.
  • the manufacturing method of the all-solid-state secondary battery including this.
  • the manufacturing method of an electronic device including obtaining an all-solid-state secondary battery by the manufacturing method of the all-solid-state secondary battery as described in ⁇ 15>, and incorporating this all-solid-state secondary battery in an electronic device.
  • a method for producing an electric vehicle comprising: obtaining an all solid state secondary battery by the method for producing an all solid state secondary battery according to ⁇ 15>; and incorporating the all solid state secondary battery into an electric vehicle.
  • the solid electrolyte-containing sheet of the present invention is excellent in flexibility and can be a self-supporting film. By using this solid electrolyte-containing sheet as a constituent member, an all-solid secondary battery having an excellent battery voltage is realized. be able to. According to the present invention, an electrode sheet for an all-solid-state secondary battery having the above-described solid electrolyte-containing sheet, an all-solid-state secondary battery having the electrode sheet for an all-solid-state secondary battery, and the all-solid-state secondary battery are provided. An electronic device and an electric vehicle can be provided.
  • the above-described solid electrolyte-containing sheet, all-solid secondary A battery electrode sheet, an all-solid secondary battery, an electronic device, and an electric vehicle can be obtained.
  • FIG. 1 is a longitudinal sectional view schematically showing a transfer sheet having a solid electrolyte-containing sheet of the present invention. It is a longitudinal cross-sectional view which shows typically the all-solid-state secondary battery which concerns on preferable embodiment of this invention.
  • the solid electrolyte-containing sheet can be ⁇ self-supporting membrane '' means that the solid electrolyte-containing sheet passes the self-supporting membrane property test described in Examples below without using a support. means.
  • the solid electrolyte layer usually does not contain an active material, but may contain an active material as long as it does not impair the effects of the present invention and does not function as an active material layer.
  • “transfer” means that the solid electrolyte-containing sheet and the electrode active material layer are brought into contact with the solid electrolyte layer formed on the release film (support) and the electrode active material layer. This means that the solid electrolyte layer is transferred on the electrode active material layer.
  • the solid electrolyte-containing sheet of the present invention can also be a sheet for transferring a solid electrolyte layer (solid electrolyte layer transfer sheet).
  • 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 solid electrolyte-containing sheet of the present invention includes a fiber having an average diameter d of 0.1 to 2 ⁇ m and an average length L of 0.2 to 50 mm, and an inorganic solid electrolyte, and has a thickness t (unit: ⁇ m), and the above L and t satisfy the relationship represented by the following formula.
  • the solid electrolyte-containing sheet of the present invention has the above-described configuration, thereby achieving the effects described above.
  • the reason is not yet clear, but is estimated as follows.
  • the fiber used in the present invention maintains a high dispersibility of the inorganic solid electrolyte and forms a three-dimensional network structure using the fiber as a matrix. Conceivable.
  • a fiber having an average diameter d and an average length L within the above-described ranges, that is, a fiber having a specific aspect ratio, is used as a matrix, so that the interval between the inorganic solid electrolytes taken into the three-dimensional network structure is in a preferable range.
  • the solid electrolyte-containing sheet of the present invention can improve battery performance with a desired physical property using a small amount of binder or without using a binder. Presumed.
  • the fiber has a network structure in both plane and three dimensions, and solid particles such as an inorganic solid electrolyte are dispersed in the network.
  • the fiber exists as a fiber.
  • the solid electrolyte-containing layer of the solid electrolyte-containing sheet of the present invention may contain a dispersion medium described later.
  • the content of the dispersion medium is, for example, 1000 ppm or less on a mass basis.
  • t can be appropriately set according to the size of the all-solid-state secondary battery, and is, for example, 5 to 250 ⁇ m, preferably 10 to 100 ⁇ m, and more preferably 15 to 40 ⁇ m.
  • the solid electrolyte-containing sheet of the present invention is a sheet (self-supporting film) composed of the solid electrolyte-containing layer. However, it can also be used as a transfer sheet having a release film (support).
  • the transfer sheet having the solid electrolyte-containing sheet of the present invention which is a transfer sheet, may be referred to as “the transfer sheet of the present invention”.
  • the transfer sheet of the present invention is suitable for transferring the solid electrolyte-containing layer onto the electrode active material layer.
  • a preferred form of the transfer sheet of the present invention is the transfer sheet shown in FIG.
  • a transfer sheet 10 of the present invention shown in FIG. 1 has a release film 2 and a solid electrolyte layer 1 in this order.
  • the release film used for the transfer sheet of the present invention is not particularly limited.
  • metal films such as aluminum film, stainless steel (SUS) film, copper film, polyethylene terephthalate film, polyethylene naphthalate film, polyimide film, polytetra
  • resin film such as a fluoroethylene (PTFE) film.
  • a releasability adjusting layer such as a silicone resin layer, a fluororesin layer, or an olefin resin layer is provided between the solid electrolyte layer and the release film. May be.
  • Specific examples of the release film having a release property adjusting layer include Toray Film Processing Co., Ltd., Peelac Panapeel, Unitika Co., Ltd. Unipeel.
  • the solid electrolyte-containing sheet of the present invention may have a protective film.
  • the protective film the film mentioned in the above release film can be used.
  • the film that needs to be peeled off before transfer is the protective film, and the film that peels off after the solid electrolyte layer is laminated on the electrode active material layer is the release film.
  • the solid electrolyte-containing sheet of the present invention is a film that protects the end face of a solid electrolyte-containing layer in order to prevent short circuit due to contact of the positive electrode and the negative electrode caused by moisture, foreign matter intrusion prevention, misalignment during lamination after transfer, etc. You may have.
  • the electrode sheet for an all-solid-state secondary battery of the present invention has the solid electrolyte-containing sheet (solid electrolyte layer) of the present invention and an electrode active material layer.
  • an electrode sheet for an all-solid-state secondary battery of the present invention for example, a sheet having an electrode active material layer on a current collector, a solid electrolyte layer on the electrode active material layer, and a conductive material on the current collector Examples thereof include a sheet having a body layer, an electrode active material layer on the conductor layer, and a solid electrolyte layer on the electrode active material layer.
  • the solid electrolyte layer may contain a dispersion medium described later.
  • the content of the dispersion medium is, for example, 1000 ppm or less on a mass basis.
  • Examples of the conductor layer include conductor layers (carbon coated foils) described in JP2013-23654A and JP2013-229187A.
  • the electrode active material layer and the current collector may be the electrode active material layer and the current collector used in a normal all-solid secondary battery.
  • an electrode active material layer and a current collector described in JP-A-2015-088486 can be used.
  • an electrode active material layer (a positive electrode active material layer (hereinafter also referred to as a positive electrode layer) and a negative electrode active material layer (hereinafter also referred to as a negative electrode layer)) may be referred to as an active material layer. .
  • An all solid state secondary battery of the present invention comprises a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer disposed between the positive electrode active material layer and the negative electrode active material layer.
  • the positive electrode active material layer is formed on the positive electrode current collector as necessary to constitute a positive electrode.
  • the negative electrode active material layer is formed on the negative electrode current collector as necessary, and constitutes the negative electrode.
  • the all-solid-state secondary battery of the present invention has the above-described electrode sheet for an all-solid-state secondary battery of the present invention.
  • the thicknesses of the negative electrode active material layer and the positive electrode active material layer are not particularly limited.
  • each layer is preferably 10 to 1,000 ⁇ m, more preferably 20 ⁇ m or more and less than 500 ⁇ m, considering the dimensions of a general all solid state secondary battery.
  • the thickness of at least one of the positive electrode active material layer and the negative electrode active material layer is 50 ⁇ m or more and less than 500 ⁇ m.
  • the thickness of the solid electrolyte layer is synonymous with the above “t ( ⁇ m)”, and the preferred range is also the same.
  • a lithium metal layer lithium metal layer may be used as the negative electrode.
  • a layer formed by depositing or molding lithium powder, a lithium foil, a lithium vapor deposition film, and the like Is included.
  • the thickness of the lithium metal layer is not particularly limited, and may be, for example, 0.01 to 100 ⁇ m or 0.1 to 100 ⁇ m.
  • Each of the positive electrode active material layer and the negative electrode active material layer may include a current collector on the side opposite to the solid electrolyte layer.
  • the all-solid-state secondary battery of the present invention may be used as an all-solid-state secondary battery with the above-mentioned structure depending on the application. Is preferred.
  • the housing may be metallic or made of resin (plastic). In the case of using a metallic material, for example, an aluminum alloy or a stainless steel material can be used.
  • the metallic housing is preferably divided into a positive-side housing and a negative-side housing, and electrically connected to the positive current collector and the negative current collector, respectively.
  • the casing on the positive electrode side and the casing on the negative electrode side are preferably joined and integrated through a gasket for preventing a short circuit.
  • FIG. 2 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 100 of this embodiment has a negative electrode current collector 3, a negative electrode active material layer 4, a solid electrolyte layer 5, a positive electrode active material layer 6, and a positive electrode current collector 7 in this order as viewed from the negative electrode side. .
  • Each layer is in contact with each other and has an adjacent structure.
  • lithium ions (Li + ) accumulated in the negative electrode are returned to the positive electrode side, and electrons are supplied to the working part 8.
  • a light bulb is used as a model for the operating part 8 and is lit by discharge.
  • this all-solid-state secondary battery When the all-solid-state secondary battery having the layer configuration shown in FIG. 2 is put in a 2032 type coin case, this all-solid-state secondary battery is referred to as an all-solid-state secondary battery laminate.
  • a battery produced by placing it in a 2032 type coin case may be referred to as an all-solid secondary battery.
  • the all-solid secondary battery 100 has a small electric resistance and exhibits excellent battery performance.
  • the inorganic solid electrolytes contained in the positive electrode active material layer 6, the solid electrolyte layer 5 and the negative electrode active material layer 4 may be the same or different from each other. In the present invention, either or both of the positive electrode active material and the negative electrode active material may be simply referred to as an active material or an electrode active material.
  • the binder when used in combination with solid particles such as an inorganic solid electrolyte, contact failure between the solid particles and peeling of the solid particles from the current collector can be suppressed. Therefore, excellent battery characteristics can be maintained even when bending stress acts on the solid electrolyte-containing sheet or the all-solid secondary battery of the present invention in the manufacturing process, for example.
  • the positive electrode current collector 5 and the negative electrode current collector 1 are preferably electronic conductors. In the present invention, either or both of the positive electrode current collector and the negative electrode current collector may be simply referred to as a current collector.
  • Materials for forming the positive electrode current collector include aluminum, aluminum alloy, stainless steel, nickel, and titanium, as well as aluminum or stainless steel surface treated with carbon, nickel, titanium, or silver (forming a thin film) Among them, aluminum and aluminum alloys are more preferable.
  • the material for forming the negative electrode current collector is treated with carbon, nickel, titanium, or silver on the surface of aluminum, copper, copper alloy, or stainless steel. What was made to do is preferable, and aluminum, copper, a copper alloy, and stainless steel are more preferable.
  • the current collector is usually in the form of a film sheet, but a net, a punched one, a lath, a porous body, a foam, a fiber group molded body, or the like can also be used.
  • the thickness of the current collector is not particularly limited, but is preferably 1 to 500 ⁇ m.
  • the current collector surface is roughened by surface treatment.
  • a functional layer, a member, or the like is appropriately interposed or disposed between or outside each of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector. May be.
  • Each layer may be composed of a single layer or a plurality of layers.
  • the inorganic solid electrolyte is an inorganic solid electrolyte
  • the solid electrolyte is a solid electrolyte capable of moving ions inside. Since it does not contain organic substances as the main ion conductive material, organic solid electrolytes (polymer electrolytes typified by polyethylene oxide (PEO), etc., organics typified by lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), etc. It is clearly distinguished from the electrolyte salt).
  • PEO polyethylene oxide
  • LiTFSI lithium bis (trifluoromethanesulfonyl) imide
  • the inorganic solid electrolyte is solid in a steady state, it is not usually dissociated or released into cations and anions. In this respect, it is also clearly distinguished from an electrolyte or an inorganic electrolyte salt in which cations and anions are dissociated or liberated in the polymer (LiPF 6 , LiBF 4 , lithium bis (fluorosulfonyl) imide (LiFSI), LiCl, etc.). Is done.
  • the inorganic solid electrolyte is not particularly limited as long as it has conductivity of ions of metals belonging to Group 1 or Group 2 of the periodic table, and generally does not have electron conductivity.
  • the inorganic solid electrolyte preferably has lithium ion ionic conductivity.
  • a solid electrolyte material usually used for an all-solid secondary battery can be appropriately selected and used.
  • Typical examples of inorganic solid electrolytes include (i) sulfide-based inorganic solid electrolytes and (ii) oxide-based inorganic solid electrolytes.
  • a sulfide-based inorganic solid electrolyte is preferably used in order to further improve ionic conductivity.
  • the sulfide-based inorganic solid electrolyte contains a sulfur atom (S) and has ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and Those having electronic insulating properties are preferred.
  • 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.
  • Examples of the sulfide-based inorganic solid electrolyte include a lithium ion conductive inorganic solid electrolyte that satisfies the composition represented by the following formula (1).
  • L represents an element selected from Li, Na and K, and Li is preferred.
  • M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge.
  • A represents an element selected from I, Br, Cl and F.
  • a1 to e1 indicate the composition ratio of each element, and a1: b1: c1: d1: e1 satisfies 1 to 12: 0 to 5: 1: 2 to 12: 0 to 10.
  • a1 is preferably 1 to 9, and more preferably 1.5 to 7.5.
  • b1 is preferably 0 to 3, and more preferably 0 to 1.
  • d1 is preferably 2.5 to 10, and more preferably 3.0 to 8.5.
  • e1 is preferably from 0 to 5, and more preferably from 0 to 3.
  • composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based inorganic solid electrolyte as described below.
  • the sulfide-based inorganic solid electrolyte may be 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, for example, lithium sulfide (Li 2 S), phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), simple phosphorus, simple sulfur, sodium sulfide, hydrogen sulfide, lithium halide (for example, LiI, LiBr, LiCl) and a sulfide of the element represented by M (for example, SiS 2 , SnS, GeS 2 ) can be produced by reaction of at least two raw materials.
  • Li 2 S lithium sulfide
  • P 2 S 5 diphosphorus pentasulfide
  • simple phosphorus simple sulfur
  • sodium sulfide sodium sulfide
  • hydrogen sulfide lithium halide
  • a sulfide of the element represented by M for example, SiS 2 , SnS, GeS 2
  • the ratio of Li 2 S to P 2 S 5 in the Li—PS system glass and Li—PS system glass ceramics is a molar ratio of Li 2 S: P 2 S 5 , preferably 60:40 to 90:10, more preferably 68:32 to 78:22.
  • the lithium ion conductivity can be increased.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 ⁇ 4 S / cm or more, more preferably 1 ⁇ 10 ⁇ 3 S / cm or more. Although there is no particular upper limit, it is practical that it is 1 ⁇ 10 ⁇ 1 S / cm or less.
  • Li 2 S—P 2 S 5 Li 2 S—P 2 S 5 —LiCl, Li 2 S—P 2 S 5 —H 2 S, Li 2 S—P 2 S 5 —H 2 S—LiCl, Li 2 S—LiI—P 2 S 5 , Li 2 S—LiI—Li 2 O—P 2 S 5 , Li 2 S—LiBr—P 2 S 5 , Li 2 S—Li 2 O—P 2 S 5 , Li 2 S—Li 3 PO 4 —P 2 S 5 , Li 2 S—P 2 S 5 —P 2 O 5 , Li 2 S—P 2 S 5 —SiS 2 , Li 2 S—P 2 S 5 —SiS 2- LiCl, Li 2 S—P 2 S 5 —SnS, Li 2 S—P 2 S 5 —Al 2 S 3 , Li 2 S—G
  • Examples of a method for synthesizing a sulfide-based inorganic solid electrolyte material using such a raw material composition include an amorphization method.
  • Examples of the amorphization method include a mechanical milling method, a solution method, and a melt quench method. This is because processing at room temperature is possible, and the manufacturing process can be simplified.
  • the oxide-based inorganic solid electrolyte contains an oxygen atom (O) and has ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and Those having electronic insulating properties are preferred.
  • the oxide-based inorganic solid electrolyte preferably has an ionic conductivity of 1 ⁇ 10 ⁇ 6 S / cm or more, more preferably 5 ⁇ 10 ⁇ 6 S / cm or more, and 1 ⁇ 10 ⁇ 5 S. / Cm or more is particularly preferable.
  • the upper limit is not particularly limited, but is practically 1 ⁇ 10 ⁇ 1 S / cm or less.
  • Li xa La ya TiO 3 [xa satisfies 0.3 ⁇ xa ⁇ 0.7, and ya satisfies 0.3 ⁇ ya ⁇ 0.7.
  • LLT Li xb La yb Zr zb M bb mb Onb
  • M bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In and Sn
  • Xb satisfies 5 ⁇ xb ⁇ 10
  • yb satisfies 1 ⁇ yb ⁇ 4
  • zb satisfies 1 ⁇ zb ⁇ 4
  • mb satisfies 0 ⁇ mb ⁇ 2
  • nb satisfies 5 ⁇ nb ⁇ 20.
  • Li xc B yc M cc zc Onc (M cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In and Sn.
  • Xc is 0 ⁇ xc ⁇ 5
  • Yc satisfies 0 ⁇ yc ⁇ 1,
  • zc satisfies 0 ⁇ zc ⁇ 1,
  • nc satisfies 0 ⁇ nc ⁇ 6
  • Li xd (Al, Ga) yd (Ti, Ge) zd Si ad P md Ond (xd satisfies 1 ⁇ xd ⁇ 3, yd Satisfies 0 ⁇ yd ⁇ 1, zd satisfies 0 ⁇ zd ⁇ 2, ad satisfies 0 ⁇ ad ⁇ 1, md satisfies 1 ⁇ md ⁇ 7, and nd satisfies 3 ⁇ nd ⁇
  • Li, P and O Phosphorus compounds containing Li, P and O are also desirable.
  • lithium phosphate Li 3 PO 4
  • LiPON obtained by substituting a part of oxygen of lithium phosphate with nitrogen
  • LiPOD 1 (D 1 is preferably Ti, V, Cr, Mn, Fe, Co, Ni, And at least one element selected from Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt, and Au.
  • LiA 1 ON (A 1 is one or more elements selected from Si, B, Ge, Al, C, and Ga) can be preferably used.
  • the inorganic solid electrolyte is preferably a particle.
  • 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 volume average particle size of the inorganic solid electrolyte is measured by the following procedure.
  • the inorganic solid electrolyte particles are prepared by diluting a 1 mass% dispersion in a 20 mL sample bottle using water (heptane in the case of a substance unstable to water).
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes and used immediately after that.
  • a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA)
  • data was acquired 50 times using a quartz cell for measurement at a temperature of 25 ° C., Obtain the volume average particle size.
  • JIS Z 8828 2013 “Particle Size Analysis—Dynamic Light Scattering Method” as necessary. Five samples are prepared for each level, and the average value is adopted.
  • An inorganic solid electrolyte may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the mass (mg) (weight per unit area) of the inorganic solid electrolyte per unit area (cm 2 ) of the solid electrolyte-containing layer is not particularly limited. It can be determined as appropriate according to the designed battery capacity, for example, 1 to 100 mg / cm 2 .
  • the content of the inorganic solid electrolyte in the solid electrolyte-containing layer is preferably 48% by mass or more and 61% by mass or more at a solid content of 100% by mass in terms of reduction in interface resistance and binding properties. It is more preferable that the content is 74% 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 97 mass% or less, It is especially preferable that it is 95 mass% or less.
  • the solid content (solid component) is a component that does not disappear by evaporation or evaporation when the solid electrolyte composition described below is dried at 170 ° C. in a nitrogen atmosphere at a pressure of 1 mmHg for 6 hours. Say. Typically, it refers to components other than the dispersion medium described below.
  • the fiber used in the present invention has an average diameter d of 0.1 to 2 ⁇ m and an average length L of 0.2 to 50 mm.
  • the thickness of the L and the solid electrolyte-containing layer containing the fiber t (unit: ⁇ m) satisfies the relationship represented by the following formula.
  • the average diameter d is preferably 0.3 to 2 ⁇ m, more preferably 0.4 to 1 ⁇ m.
  • the average length L is preferably 0.3 to 45 mm, and more preferably 0.4 to 35 mm.
  • the aspect ratio L / d is preferably 150 to 150,000, and more preferably 400 to 87,500. This is because both d and L are in the above range, so that flexibility and battery performance can be achieved at a higher level.
  • L and t preferably satisfy the relationship represented by 200 ⁇ t ⁇ L ⁇ 2000 ⁇ t, more preferably satisfy the relationship represented by 500 ⁇ t ⁇ L ⁇ 1500 ⁇ t, and 550 ⁇ t ⁇ It is more preferable to satisfy the relationship represented by L ⁇ 1500 ⁇ t. By being in the above range, flexibility and battery performance can be achieved at a higher level.
  • the average diameter d, the average length L, and the aspect ratio of the fiber can be calculated by SEM (Scanning Electron Microscope), TEM (Transmission Electron Microscope), or the like. For specific measurement conditions and the like, the SEM analysis described in the Examples section can be referred to.
  • the average diameter means the number average diameter
  • the average length means the number average length
  • the aspect ratio means the aspect ratio of the number average length to the number average diameter.
  • the fiber used in the present invention may be organic or inorganic, and is preferably organic.
  • the fiber exhibits insulating properties, and for example, the volume resistivity is preferably 1 ⁇ 10 12 ( ⁇ ⁇ cm) or more, and more preferably 1 ⁇ 10 14 ( ⁇ ⁇ cm) or more. It is practical that the upper limit is 1 ⁇ 10 19 ( ⁇ ⁇ cm) or less. For this reason, it is different from the carbon nanofiber used as a conductive additive.
  • the volume resistivity of a fiber can be measured by the method as described in the term of an Example.
  • the fiber used for this invention may be formed from one type of material, and may be formed from two or more types of materials.
  • the center part of the fiber is a part that can itself become a fiber.
  • the surface of the fiber means a surface portion outside the center. Therefore, when formed from one kind of material, the surface is not covered, and a fiber consisting only of the central portion is formed.
  • the fiber whose surface is coated with resin will be described as an example.
  • the center portion of the fiber is a fiber before being coated with resin, and the surface of the center portion is covered with resin.
  • the surface When the central part is made of an organic substance, the surface may or may not be covered with another organic substance, and the central part is made of an inorganic substance having an electric conductivity of 1 ⁇ 10 ⁇ 6 S / m or less.
  • the surface may or may not be coated with an organic substance.
  • the central part is made of a semiconductor or conductor having an electric conductivity exceeding 1 ⁇ 10 ⁇ 6 S / m, the surface is covered with a material having an electric conductivity of 1 ⁇ 10 ⁇ 6 S / m or less. Is preferred.
  • the electrical conductivity of the fiber may be 1 ⁇ 10 ⁇ 6 S / m or less.
  • the material having an electric conductivity of 1 ⁇ 10 ⁇ 6 S / m or less is preferably an organic material, and may be any of a low molecular compound and a polymer (oligomer or polymer) as long as it is an organic material, but is preferably a polymer. .
  • the polymer examples include polyimide, cellulose acetate, acrylic polymer, methyl methacrylate-acrylic acid copolymer, urethane resin, and polyacrylamine. These can be polymerized by conventional methods. Moreover, you may use a commercial item. Since the polymer has a hydroxy group, a carboxy group, an ester group, etc., the binding property between the polymer and the inorganic solid electrolyte can be further improved, so that the flexibility and battery voltage are further improved. Can do.
  • the content of a functional group such as a hydroxy group, a carboxy group or an ester group is preferably 0.001 to 50% by mass, more preferably 0.01 to 5% by mass, per polymer repeating unit.
  • the catalog value of the vendor can be adopted as the content of the carboxy group in the polymer.
  • the method for preparing the polymer fiber is not particularly limited, and examples thereof include an electrospinning method, a dry spinning method, and a wet spinning method.
  • a fiber (electrospun fiber) prepared by an electrospinning method in that d and L can be set in a predetermined range to further improve flexibility and battery voltage. .
  • a polymer solution is obtained by dissolving the polymer in an organic solvent.
  • the organic solvent include methylene chloride, n-methyl-2-pyrrolidone, formic acid, and formalin.
  • examples of the apparatus used for preparing the fiber by the electrospinning method include NANON-3 (trade name, manufactured by MEC) and NEU (trade name, manufactured by Kato Tech).
  • NANON-3 trade name, manufactured by MEC
  • NEU trade name, manufactured by Kato Tech
  • a positive voltage is applied to the nozzle tip
  • the collector is negatively charged
  • the polymer solution is discharged from the nozzle tip at a constant temperature (for example, 5 to 40 ° C.)
  • fibers are accumulated on the collector.
  • a gas at a constant temperature for example, 5 to 15 ° C.
  • the electrospinning method can be performed with reference to, for example, Japanese Patent Application Laid-Open Nos. 2008-013873 and 2009-270210.
  • the dry spinning method can be performed with reference to, for example, Japanese Patent Application Laid-Open Nos. 2008-069291 and 2013-130404.
  • the wet spinning method can be performed with reference to, for example, JP-A-2006-248272 and JP-A-2016-53241.
  • fibers made of inorganic materials include fibers made of metals (silver nanowires, copper nanowires, nickel nanowires, cobalt nanowires, gold nanowires, etc.), and fibers made of ceramics (alumina oxide wires, copper hydroxide nanos). Wire, hydroxyapatite nanowire, iron oxide hydrate nanowire, iron oxide nanowire, nickel hydroxide nanowire, magnesium oxide nanowire, molybdenum oxide nanowire, silicon carbide nanowire, titanium oxide nanowire, manganese oxide nanowire, Nickel oxide nanowires, tungsten oxide nanowires, vanadium oxide nanowires, zinc oxide nanowires, etc.), fibers made of glass (silica glass nanofibers, etc.) .
  • the fiber content in the solid electrolyte-containing layer of the solid electrolyte-containing sheet of the present invention is preferably 0.1 to 40% by volume, more preferably 1 to 30% by volume, and still more preferably 5 to 20% by volume.
  • the volume of the solid electrolyte-containing layer is an apparent volume including voids and is calculated from the height and width.
  • the content can be calculated as follows. [ ⁇ Mass of fiber in sheet (g) ⁇ specific gravity of fiber raw material (g / cm 3 ) ⁇ ⁇ total volume of sheet (cm 3 )] ⁇ 100 (%). By being in the preferred range, both flexibility and battery voltage can be enhanced.
  • the above fibers may be used alone or in combination of two or more, and are preferably used alone.
  • the solid electrolyte-containing layer of the solid electrolyte-containing sheet of the present invention preferably contains a binder.
  • the polymer constituting the binder may be in any form, and for example, in the solid electrolyte-containing sheet or the all-solid secondary battery, it may be in the form of particles or indefinite shape.
  • the polymer constituting the binder is preferably particulate.
  • the polymer which comprises the binder used by this invention is a resin particle, if resin which forms this resin particle is an organic resin, it will not specifically limit.
  • the polymer constituting the binder is not particularly limited, and for example, the form of particles made of the following resin is preferable.
  • fluorine-containing resin examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and a copolymer of polyvinylidene fluoride and hexafluoropropylene (PVdF-HFP).
  • hydrocarbon-based thermoplastic resin examples include polyethylene, polypropylene, styrene butadiene rubber (SBR), hydrogenated styrene butadiene rubber (HSBR), butylene rubber, acrylonitrile butadiene rubber, polybutadiene, and polyisoprene.
  • acrylic resin examples include various (meth) acrylic monomers, (meth) acrylamide monomers, and copolymers of these monomers (preferably a copolymer of acrylic acid and methyl acrylate). It is done. Further, a copolymer (copolymer) with other vinyl monomers is also preferably used. Examples thereof include a copolymer of methyl (meth) acrylate and styrene, a copolymer of methyl (meth) acrylate and acrylonitrile, and a copolymer of butyl (meth) acrylate, acrylonitrile, and styrene.
  • the copolymer may be either a statistical copolymer or a periodic copolymer, and a block copolymer is preferred.
  • other resins include polyurethane resin, polyurea resin, polyamide resin, polyimide resin, polyester resin, polyether resin, polycarbonate resin, and cellulose derivative resin.
  • binder one synthesized or prepared by a conventional method may be used, or a commercially available product may be used.
  • a binder may be used individually by 1 type, or may use 2 or more types.
  • the content of the binder in the solid electrolyte-containing layer is determined by considering the reduction of the interface resistance when used in an all-solid secondary battery and the maintenance of the reduced interface resistance.
  • 100% by mass of the component 0.01% by mass or more is preferable, 0.1% by mass or more is more preferable, and 1% by mass or more is further preferable.
  • 20 mass% or less is preferable, 10 mass% or less is more preferable, and 5 mass% or less is still more preferable.
  • the solid electrolyte-containing layer of the solid electrolyte-containing sheet of the present invention can be an electrode active material layer containing an active material.
  • This active material is a material capable of inserting and releasing ions of metal elements belonging to Group 1 or Group 2 of the Periodic Table. Examples of such an active material include a positive electrode active material and a negative electrode active material.
  • a metal oxide preferably a transition metal oxide
  • the negative electrode active material a carbonaceous material, a metal oxide, or a metal capable of forming an alloy with lithium such as Sn, Si, Al, and In Is preferred.
  • the positive electrode active material is preferably one that can reversibly insert and release lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, and may be a transition metal oxide, an organic substance, an element that can be complexed with Li such as sulfur, or a complex of sulfur and metal.
  • the positive electrode active material it is preferable to use a transition metal oxide, and a transition metal oxide having a transition metal element M a (one or more elements selected from Co, Ni, Fe, Mn, Cu, and V). More preferred.
  • this transition metal oxide includes an element M b (an element of the first (Ia) group of the metal periodic table other than lithium, an element of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Elements such as Sb, Bi, Si, P, or B) may be mixed.
  • the mixing amount is preferably 0 ⁇ 30 mol% relative to the amount of the transition metal element M a (100mol%). Those synthesized by mixing so that the molar ratio of Li / Ma is 0.3 to 2.2 are more preferable.
  • transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt structure, (MB) a transition metal oxide having a spinel structure, (MC) a lithium-containing transition metal phosphate compound, (MD And lithium-containing transition metal halogenated phosphate compounds and (ME) lithium-containing transition metal silicate compounds.
  • 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]) and LiNi 0.5 Mn 0.5 O 2 ( Lithium manganese nickelate).
  • transition metal oxides having (MB) spinel structure include LiMn 2 O 4 (LMO), LiCoMnO 4 , Li 2 FeMn 3 O 8 , Li 2 CuMn 3 O 8 , Li 2 CrMn 3 O 8 and Li 2 NiMn 3 O 8 is mentioned.
  • (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).
  • (MD) as the lithium-containing transition metal halogenated phosphate compound for example, Li 2 FePO 4 F such fluorinated phosphorus iron salt, Li 2 MnPO 4 hexafluorophosphate manganese salts such as F and Li 2 CoPO 4 F Cobalt fluorophosphates such as
  • Examples of the (ME) lithium-containing transition metal silicate compound include Li 2 FeSiO 4 , Li 2 MnSiO 4, and Li 2 CoSiO 4 .
  • a transition metal oxide having a (MA) layered rock salt structure is preferable, and LCO or NMC is more preferable.
  • the shape of the positive electrode active material is not particularly limited, but is preferably particulate.
  • the median diameter D50 of the positive electrode active material is not particularly limited, but is preferably larger than the median diameter of the inorganic solid electrolyte in terms of electric capacity of the all-solid secondary battery.
  • the median diameter of the positive electrode active material can be 0.1 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 median diameter of the positive electrode active material can be measured in the same manner as the median diameter of the inorganic solid electrolyte.
  • the positive electrode active materials may be used alone or in combination of two or more.
  • the mass (mg) (weight per unit area) of the positive electrode active material per unit area (cm 2 ) of the positive electrode active material layer is not particularly limited. This can be determined as appropriate according to the designed battery capacity.
  • the content of the positive electrode active material in the solid electrolyte-containing layer of the solid electrolyte-containing sheet is not particularly limited, preferably 10 to 95% by mass, more preferably 30 to 90% by mass, and still more preferably 50 to 85% by mass. 55 to 80% by mass is particularly preferable.
  • the negative electrode active material is preferably one that can reversibly insert and release lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, and is a carbonaceous material, metal oxide such as tin oxide, silicon oxide, metal composite oxide, lithium alloy such as lithium simple substance and lithium aluminum alloy, and , Metals such as Sn, Si, Al, and In that can form an alloy with lithium.
  • a carbonaceous material or a lithium composite oxide is preferably used from the viewpoint of reliability.
  • the metal composite oxide is preferably capable of inserting and extracting lithium.
  • the material is not particularly limited, but preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
  • the carbonaceous material used as the negative electrode active material is a material substantially made of carbon.
  • Examples thereof include carbonaceous materials obtained by firing various synthetic resins such as graphite (natural graphite, artificial graphite such as vapor-grown graphite), and PAN (polyacrylonitrile) -based resin or furfuryl alcohol resin.
  • various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA (polyvinyl alcohol) -based carbon fiber, lignin carbon fiber, glassy carbon fiber, and activated carbon fiber.
  • Other examples include mesophase microspheres, graphite whiskers, and flat graphite.
  • an amorphous oxide is particularly preferable, and chalcogenite which is a reaction product of a metal element and 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 amorphous oxide of the metalloid element and the chalcogenide are more preferable, and elements of Groups 13 (IIIB) to 15 (VB) of the periodic table, Al , Ga, Si, Sn, Ge, Pb, Sb and Bi are used alone or in combination of two or more thereof, and chalcogenides are particularly preferable.
  • preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , SiO, GeO, SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 8 Bi 2 O 3 , Sb 2 O 8 Si 2 O 3 , Bi 2 O 4 , SnSiO 3 , GeS, SnS, SnS 2 , PbS, PbS 2 , Sb 2 S 3 , Sb 2 S 5 and SnSiS 3 are preferred. Moreover, these may be a complex oxide with lithium oxide, for example, Li 2 SnO 2 .
  • the negative electrode active material contains a titanium atom. More specifically, Li 4 Ti 5 O 12 (lithium titanate [LTO]) is excellent in rapid charge / discharge characteristics due to small volume fluctuations during 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]
  • a Si-based negative electrode it is also preferable to apply a Si-based negative electrode.
  • a Si negative electrode can occlude more Li ions than a carbon negative electrode (such as graphite and acetylene black). That is, the amount of occlusion of Li ions per unit mass increases. Therefore, the battery capacity can be increased. As a result, there is an advantage that the battery driving time can be extended.
  • the shape of the negative electrode active material is not particularly limited, but is preferably particulate.
  • the median diameter D50 of the negative electrode active material is not particularly limited, but is preferably larger than the median diameter of the inorganic solid electrolyte.
  • the median diameter of the negative electrode active material is preferably 0.1 to 60 ⁇ m.
  • a normal 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.
  • 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 median diameter of the negative electrode active material can be measured in the same manner as the median diameter of the inorganic solid electrolyte.
  • 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
  • the said negative electrode active material may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the mass (mg) (weight per unit area) of the negative electrode active material per unit area (cm 2 ) of the negative electrode active material layer is not particularly limited. This can be determined as appropriate according to the designed battery capacity.
  • the content of the negative electrode active material in the solid electrolyte-containing layer of the solid electrolyte-containing sheet is not particularly limited, and is preferably 10 to 80% by mass, more preferably 20 to 80% by mass.
  • the surfaces of the positive electrode active material and the negative electrode active material may be coated with another metal oxide.
  • the surface coating agent include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si, or Li. Specific examples include spinel titanate, tantalum oxide, niobium oxide, and lithium niobate compound. Specifically, Li 4 Ti 5 O 12 , Li 2 Ti 2 O 5 , and LiTaO 3.
  • the electrode surface containing a positive electrode active material or a negative electrode active material may be surface-treated with sulfur or phosphorus.
  • the particle surface of the positive electrode active material or the negative electrode active material may be subjected to surface treatment with actinic rays or an active gas (plasma or the like) before and after the surface coating.
  • the solid electrolyte-containing layer of the solid electrolyte-containing sheet of the present invention may contain a lithium salt (supporting electrolyte).
  • the lithium salt is preferably a lithium salt usually used in this type of product, and is not particularly limited.
  • the lithium salts described in paragraphs 0082 to 0085 of JP-A-2015-088486 are preferable.
  • a solid electrolyte content layer contains lithium salt, 0.1 mass part or more is preferable with respect to 100 mass parts of inorganic solid electrolyte, and 5 mass parts or more is more preferable. As an upper limit, 50 mass parts or less are preferable, and 20 mass parts or less are more preferable.
  • the solid electrolyte-containing layer of the solid electrolyte-containing sheet of the present invention may contain an ionic liquid in order to further improve the ionic conductivity.
  • an ionic liquid it does not specifically limit as an ionic liquid, From the viewpoint of improving an ionic conductivity effectively, what melt
  • the compound which consists of a combination of the following cation and an anion is mentioned.
  • (I) Cation Examples of the cation include an imidazolium cation, a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a morpholinium cation, a phosphonium cation, and a quaternary ammonium cation.
  • these cations have the following substituents.
  • one kind of these cations may be used alone, or two or more kinds may be used in combination.
  • it is a quaternary ammonium cation, a piperidinium cation or a pyrrolidinium cation.
  • Examples of the substituent that the cation has include an alkyl group (an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms), a hydroxyalkyl group (a hydroxyalkyl group having 1 to 3 carbon atoms).
  • alkyloxyalkyl group (preferably an alkyloxyalkyl group having 2 to 8 carbon atoms, more preferably an alkyloxyalkyl group having 2 to 4 carbon atoms), an ether group, an allyl group, an aminoalkyl group (carbon An aminoalkyl group having 1 to 8 carbon atoms is preferred, an aminoalkyl group having 1 to 4 carbon atoms is preferred, and an aryl group (an aryl group having 6 to 12 carbon atoms is preferred, and an aryl group having 6 to 8 carbon atoms is more preferred). .).
  • the substituent may form a cyclic structure containing a cation moiety.
  • the ether group is used in combination with other substituents. Examples of such a substituent include an alkyloxy group and an aryloxy group.
  • Anions As anions, chloride ions, bromide ions, iodide ions, boron tetrafluoride ions, nitrate ions, dicyanamide ions, acetate ions, iron tetrachloride ions, bis (trifluoromethanesulfonyl) imide ions, bis ( Fluorosulfonyl) imide ion, bis (perfluorobutylmethanesulfonyl) imide ion, allyl sulfonate ion, hexafluorophosphate ion, trifluoromethane sulfonate ion and the like.
  • these anions may be used alone or in combination of two or more.
  • Preferred are boron tetrafluoride ion, bis (trifluoromethanesulfonyl) imide ion, bis (fluorosulfonyl) imide ion or hexafluorophosphate ion, dicyanamide ion and allyl sulfonate ion, more preferably bis (trifluoromethanesulfonyl) imide ion.
  • a bis (fluorosulfonyl) imide ion and an allyl sulfonate ion are examples of the anion.
  • the ionic liquid examples include 1-allyl-3-ethylimidazolium bromide, 1-ethyl-3-methylimidazolium bromide, 1- (2-hydroxyethyl) -3-methylimidazolium bromide, 1- ( 2-methoxyethyl) -3-methylimidazolium bromide, 1-octyl-3-methylimidazolium chloride, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate, 1- Ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazolium dicyanamide, 1-butyl-1-methyl Pyrrolidinium bis (trifluoromethanesulfonyl) Trimethylbutylammonium bis
  • the content of the ionic liquid in the solid electrolyte-containing layer is preferably 0 part by mass or more, more preferably 1 part by mass or more, and most preferably 2 parts by mass or more with respect to 100 parts by mass of the inorganic solid electrolyte.
  • 50 mass parts or less are preferable, 20 mass parts or less are more preferable, and 10 mass parts or less are especially preferable.
  • the casting method is a solid electrolyte composition (slurry) containing an inorganic solid electrolyte and a dispersion medium, having an average diameter d of 0.1 to 1 ⁇ m and an average length L of 0.2 to 50 mm.
  • a step of dipping the fiber For example, the fiber obtained by the electrospinning method can be directly added to the solid electrolyte composition and immersed in the slurry.
  • the time for immersing the fiber in the slurry is preferably 5 to 60 minutes, for example.
  • the dispersion medium may be evaporated or volatilized from the fiber.
  • the dispersion medium can be evaporated or volatilized by heating at 50 to 200 ° C. for 1 to 60 minutes, for example.
  • the dispersion medium may be pressed after evaporation or volatilization.
  • the pressing pressure is, for example, 5 to 50 MPa, and may be heated (for example, 50 to 200 ° C.) when pressing.
  • the pressing time is, for example, 1 to 30 minutes. In the casting method, a desired sheet can be obtained without previously forming the fiber into a nonwoven fabric.
  • the slurry application or impregnation method is A fiber nonwoven fabric having an average diameter d of 0.1 to 1 ⁇ m and an average length L of 0.2 to 50 mm is present in the same system (in the liquid phase) when the inorganic solid electrolyte is liquid-phase synthesized.
  • the step of causing the nonwoven fabric to be present in the same system when the inorganic solid electrolyte is subjected to liquid phase synthesis specifically includes, for example, applying a slurry containing an inorganic solid electrolyte precursor to the nonwoven fabric or the inorganic solid electrolyte. This can be done by immersing the nonwoven fabric in the slurry containing the precursor.
  • a fiber nonwoven fabric having an average diameter d of 0.1 to 1 ⁇ m and an average length L of 0.2 to 50 mm has an average diameter d of 0.1 to 2 ⁇ m and an average length L of 0 by an ordinary method.
  • the fiber having a thickness of 2 to 50 mm can be obtained by making it into a nonwoven fabric form.
  • the coating method known means such as doctor blade, bar coater, applicator coating, spray coating, electrostatic coating, brush coating, electrostatic printing method, electrostatic spray deposition method, aerosol deposition method, etc. Can be adopted.
  • the dispersion medium may be evaporated or volatilized from the fiber.
  • the dispersion medium can be evaporated or volatilized by heating at 50 to 200 ° C. for 1 to 60 minutes, for example.
  • the dispersion medium may be pressed after evaporation or volatilization.
  • the pressing pressure is, for example, 5 to 50 MPa, and may be heated (for example, 50 to 200 ° C.) when pressing.
  • the pressing time is, for example, 1 to 30 minutes.
  • the “inorganic solid electrolyte precursor” means a raw material for the above-mentioned inorganic solid electrolyte that can be obtained by heating to obtain an inorganic solid electrolyte.
  • the step of evaporating or volatilizing the dispersion medium from the step of filling the inorganic solid electrolyte such as the step of immersing the fiber Or the process to a press process can also be performed repeatedly.
  • the number of repetitions is preferably 2 to 4 times, more preferably 2 to 3 times, and even more preferably 2 times.
  • the volume average particle diameter of the inorganic solid electrolyte can be reduced to further increase the filling rate of the inorganic solid electrolyte.
  • the volume average particle diameter of the inorganic solid electrolyte filled in the second time can be made about 3/4 of the volume average particle diameter of the inorganic solid electrolyte filled in the first time.
  • the solid electrolyte composition used in the method for producing a solid electrolyte-containing sheet of the present invention can be prepared by a conventional method. Specifically, it can be prepared by mixing or adding an inorganic solid electrolyte, a fiber and a dispersion medium and, if necessary, other components such as a binder. Moreover, it can prepare by mixing or adding an inorganic solid electrolyte and a dispersion medium, and other components, such as a binder as needed. For example, it can prepare by mixing the said component using various mixers.
  • the mixing conditions are not particularly limited, and examples thereof include a ball mill, a bead mill, a planetary mixer, a blade mixer, a roll mill, a kneader, and a disk mill.
  • Dispersion medium examples include the following.
  • the alcohol compound solvent include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, 1,3-butanediol, and 1,4-butane. Diols are mentioned.
  • ether compound solvents examples include alkylene glycol alkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol dimethyl ether, dipropylene glycol.
  • alkylene glycol alkyl ethers ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol dimethyl ether, dipropylene glycol.
  • amide compound solvent examples include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ⁇ -caprolactam, formamide, N -Methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide and hexamethylphosphoric triamide.
  • amino compound solvents examples include triethylamine and tributylamine.
  • ketone compound solvent examples include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dibutyl ketone, and diisobutyl ketone.
  • Ester compound solvents include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyric acid
  • Examples include butyl, isobutyl isobutyrate, pentyl butyrate, methyl valerate, ethyl valerate, propyl valerate, butyl valerate, methyl caproate, ethyl caproate, propyl caproate, and butyl caproate.
  • aromatic compound solvent examples include benzene, toluene, xylene, and mesitylene.
  • aliphatic compound solvent examples include hexane, heptane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin, octane, pentane, cyclopentane and cyclooctane.
  • nitrile compound solvent examples include acetonitrile, propyronitrile, and butyronitrile.
  • the method for producing an electrode sheet for an all-solid-state secondary battery of the present invention comprises a solid electrolyte-containing layer (solid electrolyte layer) possessed by a solid electrolyte-containing sheet obtained by the method for producing a solid electrolyte-containing sheet of the present invention. Laminating on the layer.
  • the manufacturing method of the electrode sheet for all-solid-state secondary batteries of this invention can be performed by a conventional method except including the manufacturing method of the said solid electrolyte containing sheet.
  • It can be manufactured by a method including (intervening) a step of applying a composition for an electrode on a metal foil to be a current collector and forming (forming) a coating film.
  • a conductive layer forming composition may be applied onto a metal foil to form a conductive layer, and the electrode composition may be applied onto the conductive layer.
  • a negative electrode composition containing a negative electrode active material is applied as a negative electrode composition on a metal foil that is a negative electrode current collector to form a negative electrode active material layer, and a negative electrode sheet for an all solid secondary battery is formed. Make it.
  • the solid electrolyte layer of the solid electrolyte-containing sheet obtained by the method for producing a solid electrolyte-containing sheet of the present invention is laminated on the negative electrode active material layer. Taking the transfer sheet shown in FIG. 1 as an example, the transfer sheet is overlaid on the all-solid-state secondary battery negative electrode sheet so that the solid electrolyte layer 1 is in contact with the negative electrode active material layer.
  • the negative electrode sheet for all-solid-state secondary batteries of this invention can be obtained.
  • the release film 2 can be peeled from the transfer sheet shown in FIG. 1, and the solid electrolyte layer 1 can be laminated on the negative electrode active material layer to obtain a negative electrode sheet for an all solid secondary battery.
  • the electrode active material layer which comprises a normal all-solid-state secondary battery can be used for the electrode active material layer of the electrode sheet for all-solid-state secondary batteries of this invention.
  • an electrode composition for forming such an electrode active material layer for example, an electrode composition described in JP-A-2015-088486 can be used.
  • the manufacturing method of the all-solid-state secondary battery of this invention includes the manufacturing method of the electrode sheet for all-solid-state secondary batteries of this invention.
  • the manufacturing method of the all-solid-state secondary battery of this invention can be performed by a conventional method except including the manufacturing method of the said electrode sheet for all-solid-state secondary batteries.
  • the positive electrode composition is applied on the solid electrolyte layer of the prepared negative electrode sheet for an all-solid-state secondary battery to form a positive electrode active material layer.
  • the all-solid-state secondary battery 100 having the layer configuration shown in FIG. 2 can be obtained. If necessary, this can be enclosed in a housing to obtain a desired all-solid secondary battery.
  • a negative electrode sheet for an all-solid secondary battery is produced as described above.
  • a positive electrode composition containing a positive electrode active material is applied as a positive electrode composition on a metal foil that is a positive electrode current collector to form a positive electrode active material layer, and a positive electrode sheet for an all-solid-state secondary battery is formed.
  • a positive electrode sheet for an all-solid secondary battery is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other. You may pressurize under a heating condition as needed. In this way, an all-solid secondary battery can be manufactured.
  • the method for applying the electrode composition is not particularly limited, and can be appropriately selected. Examples thereof include coating (preferably wet coating), spray coating, spin coating coating, dip coating, slit coating, stripe coating, and bar coating coating.
  • the electrode composition may be dried after being applied.
  • the drying temperature is not particularly limited.
  • the lower limit is preferably 30 ° C or higher, more preferably 60 ° C or higher, and still more preferably 80 ° C or higher.
  • the upper limit is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 200 ° C. or lower.
  • a dispersion medium can be removed and it can be set as a solid state.
  • it is preferable because the temperature is not excessively raised and each member of the all-solid-state secondary battery is not damaged. Thereby, in the all-solid-state secondary battery, excellent overall performance can be exhibited and good binding properties can be obtained.
  • the pressurizing method is a hydraulic cylinder press.
  • the applied pressure is not particularly limited and is generally preferably in the range of 50 to 1500 MPa.
  • the heating temperature is not particularly limited, and is generally in the range of 30 to 300 ° C. It is also possible to press at a temperature higher than the glass transition temperature of the inorganic solid electrolyte.
  • the pressurization may be performed in a state where the coating solvent or the dispersion medium is previously dried, or may be performed in a state where the solvent or the dispersion medium remains.
  • the atmosphere during pressurization is not particularly limited and may be any of the following: air, dry air (dew point -20 ° C. or less), and 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.
  • the pressing pressure may be uniform or different with respect to the pressed part such as the sheet surface.
  • the pressing pressure can be changed according to the area and film thickness of the pressed part. Also, the same part can be changed stepwise with different pressures.
  • the press surface may be smooth or roughened.
  • the all solid state secondary battery manufactured as described above is preferably initialized after manufacture or before use.
  • the initialization is not particularly limited, and can be performed, for example, by performing initial charging / discharging in a state where the press pressure is increased, and then releasing the pressure until the general use pressure of the all-solid secondary battery is reached.
  • the all solid state secondary battery of the present invention can be applied to various uses.
  • the application mode for example, when installed in an electronic device, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a mobile phone, a cordless phone, a pager, a handy terminal, a mobile fax machine, a mobile phone Copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, minidisc, electric shaver, transceiver, electronic notebook, calculator, portable tape recorder, radio, backup power supply, memory card, etc.
  • Others for consumer use include automobiles (electric cars, etc.), electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (pacemakers, hearing aids, shoulder massagers, etc.) . Furthermore, it can be used for various military use and space use. Moreover, it can also combine with a solar cell.
  • NMP N-methyl-2-pyrrolidone
  • MENO Corporation's NANON-3 trade name
  • the average diameter d and the average length L were adjusted while confirming with an SEM image according to the solid content concentration of the solution, the applied voltage, and the solution flux.
  • cellulose triacetate cycloolefin polymer (Arton (registered trademark), manufactured by JSR Corporation), modified polyphenylene ether (Zylon (registered trademark) manufactured by Asahi Kasei Co., Ltd.), or polyacrylonitrile (Stylac (registered trademark) manufactured by Asahi Kasei Corporation)
  • a cycloolefin polymer electrospun fiber, a modified polyphenylene ether electrospun fiber, and a polyacrylonitrile electrospun fiber were prepared in the same manner as described above except that was used.
  • a fiber was prepared by the microfluidic dicer method as follows. 50 g of cedar-derived wood flour (30 mesh (500 ⁇ m) to 60 mesh (250 ⁇ m), particle size with an aspect ratio of 1 to 100 in a JIS Z8801-1 (2006) standard sieve) 50 g, distilled water 1500 ml, sodium chlorite 15 g, acetic acid It was placed in 3 ml of the solution and heated in an 80-90 ° C. water bath with occasional stirring for 1 hour. After 1 hour, 15 g of sodium chlorite and 3 ml of acetic acid were added without cooling and the mixture was further heated for 1 hour.
  • a fiber was prepared by a wet spinning method as follows.
  • Cellulose diacetate (Daisail Chemical Industries, Ltd., trade name: MBH, acetylation degree: about 55% powder) 338 g, N-methylmorpholine N-oxide (2000 g) containing about 41% by mass of water and propyl gallate (Wako Pure Chemical Industries, Ltd.) 15 g) was put into a mixer (ACM-5 type) with a vacuum deaerator manufactured by Kodaira Seisakusho, and 648 g of water was dehydrated while mixing for about 2 hours under reduced pressure heating to prepare a uniform solution of cellulose acetate.
  • ACM-5 type a vacuum deaerator manufactured by Kodaira Seisakusho
  • the kettle temperature was kept at 100 ° C.
  • the obtained cellulose acetate solution was a viscous liquid with a brown color.
  • a homogeneous solution containing 20% by mass was prepared, and then the obtained solution was extruded under nitrogen pressure of 1.5 kg / cm 2 while being kept at 100 ° C., and quantitatively supplied to the nozzle portion using a gear pump.
  • the discharge amount of the cellulose acetate solution was defined by the rotation speed of the gear pump.
  • the following examination was performed with the nozzle portion kept at 90 ° C. Using a nozzle composed of 36 capillaries having a diameter of 0.2 mm, a length of 3 mm, and a circular cross-sectional shape, spinning was examined using the apparatus shown in FIG.
  • the number average diameter and number average length of the fiber were determined by SEM analysis. Specifically, the fibers in the solid electrolyte-containing layer were observed with an SEM, and the fiber diameter and length values were read for 10 fibers.
  • the “fiber diameter” means the maximum diameter among the diameters in the cross section of the fiber (a cross section perpendicular to the length direction of the straight fiber). In other words, the diameter of the cross section may differ depending on the position of the cross section. In this case, the diameter of the cross section that gives the maximum diameter is defined as the “fiber diameter”.
  • volume resistivity of fiber The fiber before making into the nonwoven fabric prepared above was dispersed in water and cast on a polyphenylenesulfone sheet film. Drying and coating were repeated 5 times and peeled from the polyphenylene sulfone sheet to obtain a film composed of a linear structure. About this film
  • the hydroxyl group content of cellulose acetate was the manufacturer's catalog value (acetylation degree 2.9, hydroxyl group content 0.025% by mass).
  • Li 2 S and P 2 S 5 at a molar ratio of Li 2 S: P 2 S 5 75: was 25.
  • 66 zirconia beads having a diameter of 5 mm were introduced into a 45 mL container (manufactured by Fritsch) made of zirconia, the whole mixture of lithium sulfide and phosphorous pentasulfide was introduced, and the container was 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 a temperature of 25 ° C. and a rotation speed of 510 rpm for 20 hours to obtain a yellow powder sulfide-based inorganic solid electrolyte (Li-PS system). Glass, also referred to as “LPS”.) 6.20 g was obtained.
  • Liquid prepared in a separate container (93.1 g of 40% by weight heptane solution of macromonomer M-1, 222.8 g of methyl acrylate, 120.0 g of acrylic acid, 300.0 g of heptane, azoisobutyronitrile 2 .1 g) was added dropwise over 4 hours. After completion of the dropwise addition, 0.5 g of azoisobutyronitrile was added. Thereafter, the mixture was stirred at 100 ° C. for 2 hours, cooled to room temperature, and filtered to obtain a dispersion of binder A. The solid component concentration was 39.2%.
  • Macromonomer obtained by reacting acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) with a polymer polymerized at a ratio of 1: 0.99: 0.01 (molar ratio) with methyl acrylate and glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) M-1 was obtained.
  • the macromonomer M-1 had an SP value of 9.3 and a number average molecular weight of 11,000.
  • the estimated structural formulas of the polymer and macromonomer M-1 constituting the binder A are shown below.
  • a liquid prepared in a separate container (90 parts by mass of butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 20 parts by mass of methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), acrylic acid (Japanese (Manufactured by Kojun Pharmaceutical Co., Ltd.) 10 parts by mass, 20 parts by mass of B-27 (composed product), 60 parts by mass of macromonomer MM-1 (solid content), polymerization initiator V-601 (trade name, Wako Pure Chemicals) A liquid obtained by mixing 2.0 parts by mass of Kogyo Co., Ltd.) was added dropwise over 2 hours, followed by stirring at 80 ° C.
  • Example 1 The prepared solid electrolyte composition was put into a petri dish, and the nonwoven fabric was immersed for 30 minutes. The nonwoven fabric was taken out and drained for 30 seconds, and then dried on a 150 ° C. hot plate for 30 minutes to evaporate the solvent. The dried nonwoven fabric was sandwiched between aluminum foils and pressed at 20 MPa at 150 ° C. for 5 minutes to produce a solid electrolyte-containing sheet of Example 1 having a thickness of 20 ⁇ m.
  • Example 2 to 22 In the production of the solid electrolyte-containing sheet of Example 1, the solid electrolyte-containing sheets of Examples 2 to 22 were produced in the same manner as in Example 1 except that the description in Table 1 was followed. In Examples 21 and 22, 2.94 g of LPS and 0.06 g of binder were used instead of 3.0 g of LPS.
  • Example 23 A solid electrolyte-containing sheet of Example 23 was produced in the same manner as in Example 2 except that the electrospun fiber was directly added to the above-described solid electrolyte composition from the NANON-3 discharge port.
  • Example 24 The solid electrolyte composition described above was applied to one side of the nonwoven fabric with an applicator (trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.) so that the thickness of the solid electrolyte layer alone was 10 ⁇ m, and at 80 ° C. After heating for 1 hour, it was further dried at 110 ° C. for 1 hour. Then, it pressurized (20 Mpa, 1 minute), heating (120 degreeC) using the heat press machine. Thereafter, the same operation was performed on the other surface of the nonwoven fabric to obtain a solid electrolyte-containing sheet.
  • an applicator trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.
  • the slurry was added and vibrated in a dry Ar atmosphere for 24 hours at 1500 rpm with an amplitude of 1 cm to obtain a slurry containing a precursor of a sulfide-based inorganic solid electrolyte.
  • the slurry was impregnated into a nonwoven fabric and dried under reduced pressure at room temperature to prepare a sheet containing a sulfide-based inorganic solid electrolyte precursor.
  • the sheet was heat-treated at 170 ° C. overnight (7 hours) under reduced pressure ( ⁇ 100 kPa) to cause the precursor to react to obtain a solid electrolyte-containing sheet.
  • the obtained solid electrolyte-containing sheet had an ionic conductivity of 1 ⁇ 10 ⁇ 4 Scm ⁇ 1 .
  • Example 26 The sulfide-based inorganic solid electrolyte powder obtained in “Synthesis of sulfide-based inorganic solid electrolyte (Li—PS—based glass)” was electrostatically printed on both surfaces of the nonwoven fabric of Example 2, and a heated roll press ( Using Takumi Giken SA-602-S (trade name)), heating and pressing were performed under the conditions of 100 ° C., 20 kN, and a roll rotation speed of 0.4 m / min to obtain a solid electrolyte-containing sheet having a thickness of 20 ⁇ m. .
  • Example 27 to 30 In the production of the solid electrolyte-containing sheet of Example 1, the solid electrolyte-containing sheets of Examples 27 to 30 were produced in the same manner as in Example 1 except that the description in Table 1 was followed.
  • Example 31 In the production of the solid electrolyte-containing sheet of Example 2, the sheet after pressing at 20 MPa at 150 ° C. for 5 minutes was again subjected to the process from immersion to pressurization to produce the solid electrolyte-containing sheet of Example 31. .
  • Example 32 and 33 and Comparative Examples 1 to 12 In the production of the solid electrolyte-containing sheet of Example 1, the solid electrolyte-containing sheets of Examples 32 and 33 and Comparative Examples 1 to 12 were the same as Example 1 except that the description in Tables 1 to 3 below was followed. Was made.
  • Example 32 a 60 ⁇ m-thick urethane non-woven fabric (“Pandex T8175N”, manufactured by DIC Covestro Polymer Co., Ltd.) was used.
  • the produced solid electrolyte-containing sheet is a sheet having a length of 50 mm and a width of 50 mm.
  • composition for positive electrode prepared above is applied on an aluminum foil (positive electrode current collector) with an applicator (trade name: SA-201 Baker-type applicator, manufactured by Tester Sangyo Co., Ltd.) to give a basis weight of 30 mg / cm 2. After heating at 80 ° C. for 1 hour, it was further dried at 110 ° C. for 1 hour. Then, using a heat press machine, it pressurized (20 Mpa, 1 minute), heating (120 degreeC), and produced the positive electrode sheet which has a positive electrode active material layer on a positive electrode electrical power collector.
  • an applicator trade name: SA-201 Baker-type applicator, manufactured by Tester Sangyo Co., Ltd.
  • the positive electrode sheet used in Examples 28 and 30 was produced as follows. A cellulose acetate nonwoven fabric having a thickness of 80 ⁇ m was immersed in the positive electrode composition prepared above for 30 minutes. The nonwoven fabric was taken out and drained for 30 seconds, and then dried on a 110 ° C. hot plate for 1 hour to volatilize the solvent. The upper and lower sides of the dried nonwoven fabric were sandwiched between aluminum foils, pressed at 120 ° C. for 1 minute at 20 MPa, peeled off one aluminum foil, and a positive electrode sheet having a positive electrode active material layer on the positive electrode current collector was produced.
  • composition for negative electrode prepared above is applied to a basis weight of 15 mg / cm 2 on an SUS foil (negative electrode current collector) by an applicator (trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.). After heating at 80 ° C. for 1 hour, it was further dried at 110 ° C. for 1 hour. Then, using a heat press machine, it pressurized (20 Mpa, 1 minute), heating (120 degreeC), and produced the negative electrode sheet which has a negative electrode active material layer on a negative electrode collector.
  • the negative electrode sheet used in Examples 29 and 30 was produced as follows. A cellulose acetate nonwoven fabric having a thickness of 60 ⁇ m was immersed in the negative electrode composition prepared above for 30 minutes. The nonwoven fabric was taken out and drained for 30 seconds, and then dried on a 110 ° C. hot plate for 1 hour to volatilize the solvent. The top and bottom of the dried negative electrode sheet were sandwiched between SUS foils, pressed at 120 ° C. for 1 minute at 20 MPa, and one of the SUS foils was peeled off to produce a negative electrode sheet having a negative electrode active material layer on the negative electrode current collector.
  • the negative electrode sheet used in Example 32 and Comparative Example 11 was produced as follows. 180 pieces of zirconia beads having a diameter of 5 mm are put into a 45 mL container (manufactured by Fritsch) made of zirconia, and 4.7 g of the Li—PS system glass synthesized above and 0.1 g of the dispersion of binder B are converted into solid content. Then, 12.3 g of heptane was added as a dispersion medium. The container was set on a planetary ball mill P-7 manufactured by Fricht and mixed for 2 hours at a temperature of 25 ° C. and a rotation speed of 300 rpm.
  • An all-solid secondary battery having the layer configuration shown in FIG. 2 was formed.
  • the solid electrolyte-containing sheet (solid electrolyte layer) obtained above was overlaid so that the negative electrode active material layer of the negative electrode sheet was in contact, and pressurized at 50 MPa for 10 seconds.
  • a member composed of the negative electrode current collector 3 / the negative electrode active material layer 4 / the solid electrolyte layer 5 was produced and cut into a diameter of 15 mm ⁇ .
  • the positive electrode active material layer 6 of the positive electrode sheet cut into a diameter of 14 mm ⁇ in a 2032 type coin case is stacked so that the solid electrolyte layer 5 is in contact with each other to form a laminate for an all-solid-state secondary battery.
  • the all-solid-state secondary battery was produced.
  • the all-solid-state secondary battery was measured by a charge / discharge evaluation apparatus “TOSCAT-3000” (trade name) manufactured by Toyo System.
  • the all solid state secondary battery was charged at a current value of 0.2 mA until the battery voltage reached 4.2 V, and then discharged at a current value of 2.0 mA until the battery voltage reached 3.0 V.
  • the battery voltage 10 seconds after the start of discharge was read according to the following criteria to evaluate the resistance.
  • Evaluation standard 1 is a standard for evaluation in Tables 1 and 2
  • evaluation standard 2 is a standard for evaluation in Table 3.
  • “ ⁇ ” in the battery performance evaluation means that the battery performance evaluation could not be performed because the strength was weak and the battery could not be formed.
  • Example 33 c12 Comparative Example 12 LLZ: Li 7 La 3 Zr 2 O 12 (Lithium lanthanum zirconate average particle size 5.0 ⁇ m Toshima Seisakusho)
  • the solid electrolyte-containing sheet of the present invention satisfying all of the relationship represented by the numerical range of d, the numerical range of L, and 100 ⁇ t ⁇ L ⁇ 2500 ⁇ t is a self-supporting film, It turns out that it is excellent in both flexibility and battery performance.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Conductive Materials (AREA)

Abstract

L'invention concerne une feuille comprenant un électrolyte solide, une feuille d'électrode pour une batterie secondaire entièrement solide, ladite feuille d'électrode ayant ladite feuille comprenant un électrolyte solide, une batterie secondaire entièrement solide qui a ladite feuille d'électrode pour une batterie secondaire entièrement solide, un dispositif électronique et un véhicule électrique qui sont dotés de ladite batterie secondaire entièrement solide, et des procédés de fabrication de ceux-ci, ladite feuille comprenant un électrolyte solide ayant une couche comprenant un électrolyte solide d'épaisseur t μm qui comprend un électrolyte solide inorganique et des fibres ayant un diamètre moyen d de 0,1 à 2 µm et une longueur moyenne L de 0,2 à 50 mm, L et t satisfaisant la relation 100 × t ≤ L ≤ 2500 × t.
PCT/JP2019/016403 2018-04-27 2019-04-17 Feuille comprenant un électrolyte solide, feuille d'électrode pour batterie secondaire entièrement solide, batterie secondaire entièrement solide, dispositif électronique, véhicule électrique, et procédés de fabrication de ceux-ci WO2019208347A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020516262A JP7014900B2 (ja) 2018-04-27 2019-04-17 固体電解質含有シート、全固体二次電池用電極シート、全固体二次電池、電子機器及び電気自動車、並びに、これらの製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2018-087792 2018-04-27
JP2018087792 2018-04-27
JP2018-164231 2018-09-03
JP2018164231 2018-09-03

Publications (1)

Publication Number Publication Date
WO2019208347A1 true WO2019208347A1 (fr) 2019-10-31

Family

ID=68294024

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/016403 WO2019208347A1 (fr) 2018-04-27 2019-04-17 Feuille comprenant un électrolyte solide, feuille d'électrode pour batterie secondaire entièrement solide, batterie secondaire entièrement solide, dispositif électronique, véhicule électrique, et procédés de fabrication de ceux-ci

Country Status (2)

Country Link
JP (1) JP7014900B2 (fr)
WO (1) WO2019208347A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020218422A1 (fr) * 2019-04-26 2020-10-29 株式会社日本製鋼所 Procédé de production de membrane électrolytique solide, procédé de production de batterie entièrement solide, appareil de production de membrane électrolytique solide et appareil de production de batterie entièrement solide
WO2021089066A1 (fr) * 2019-11-05 2021-05-14 ŠKODA AUTO a.s. Cellule de batterie secondaire pour éléments électromobiles, contenant des matériaux en verre amorphe et des micromatériaux et des nanomatériaux, et son procédé de production
CN114400368A (zh) * 2022-01-14 2022-04-26 厦门海辰新能源科技有限公司 硫化物固态电解质层及其制备方法和锂离子电池
WO2023054333A1 (fr) 2021-09-30 2023-04-06 マクセル株式会社 Batterie tout solide
WO2023054293A1 (fr) 2021-09-30 2023-04-06 マクセル株式会社 Batterie entièrement à électrolyte solide
CN116072960A (zh) * 2023-03-24 2023-05-05 江苏时代新能源科技有限公司 固态电解质膜及其制备方法、全固态电池和用电装置
CZ309795B6 (cs) * 2020-11-04 2023-10-18 ŠKODA AUTO a.s Sekundární bateriový článek pro elektromobily, obsahující amorfní skelné materiály a mikro a nano materiály a způsob jeho výroby

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008103258A (ja) * 2006-10-20 2008-05-01 Idemitsu Kosan Co Ltd 固体電解質シート、電極シート及びそれを用いた全固体二次電池
WO2011070893A1 (fr) * 2009-12-09 2011-06-16 日清紡ホールディングス株式会社 Tissu non tisse de fibre de carbone souple
JP2012102422A (ja) * 2010-11-09 2012-05-31 Toray Ind Inc 繊維、不織布および炭化不織布、ならびにそれらの製造方法。
JP2014096311A (ja) * 2012-11-12 2014-05-22 National Institute Of Advanced Industrial & Technology 固体電解質シート、電極シート、及び全固体二次電池
JP2016031789A (ja) * 2014-07-25 2016-03-07 ニッポン高度紙工業株式会社 固体電解質シート、及び、全固体二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008103258A (ja) * 2006-10-20 2008-05-01 Idemitsu Kosan Co Ltd 固体電解質シート、電極シート及びそれを用いた全固体二次電池
WO2011070893A1 (fr) * 2009-12-09 2011-06-16 日清紡ホールディングス株式会社 Tissu non tisse de fibre de carbone souple
JP2012102422A (ja) * 2010-11-09 2012-05-31 Toray Ind Inc 繊維、不織布および炭化不織布、ならびにそれらの製造方法。
JP2014096311A (ja) * 2012-11-12 2014-05-22 National Institute Of Advanced Industrial & Technology 固体電解質シート、電極シート、及び全固体二次電池
JP2016031789A (ja) * 2014-07-25 2016-03-07 ニッポン高度紙工業株式会社 固体電解質シート、及び、全固体二次電池

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020218422A1 (fr) * 2019-04-26 2020-10-29 株式会社日本製鋼所 Procédé de production de membrane électrolytique solide, procédé de production de batterie entièrement solide, appareil de production de membrane électrolytique solide et appareil de production de batterie entièrement solide
WO2021089066A1 (fr) * 2019-11-05 2021-05-14 ŠKODA AUTO a.s. Cellule de batterie secondaire pour éléments électromobiles, contenant des matériaux en verre amorphe et des micromatériaux et des nanomatériaux, et son procédé de production
CZ309795B6 (cs) * 2020-11-04 2023-10-18 ŠKODA AUTO a.s Sekundární bateriový článek pro elektromobily, obsahující amorfní skelné materiály a mikro a nano materiály a způsob jeho výroby
WO2023054333A1 (fr) 2021-09-30 2023-04-06 マクセル株式会社 Batterie tout solide
WO2023054293A1 (fr) 2021-09-30 2023-04-06 マクセル株式会社 Batterie entièrement à électrolyte solide
KR20240064633A (ko) 2021-09-30 2024-05-13 맥셀 주식회사 전고체전지
KR20240064619A (ko) 2021-09-30 2024-05-13 맥셀 주식회사 전고체전지
CN114400368A (zh) * 2022-01-14 2022-04-26 厦门海辰新能源科技有限公司 硫化物固态电解质层及其制备方法和锂离子电池
CN116072960A (zh) * 2023-03-24 2023-05-05 江苏时代新能源科技有限公司 固态电解质膜及其制备方法、全固态电池和用电装置
CN116072960B (zh) * 2023-03-24 2023-09-05 江苏时代新能源科技有限公司 固态电解质膜及其制备方法、全固态电池和用电装置

Also Published As

Publication number Publication date
JP7014900B2 (ja) 2022-02-01
JPWO2019208347A1 (ja) 2021-05-13

Similar Documents

Publication Publication Date Title
JP6607937B2 (ja) 固体電解質組成物、全固体二次電池用電極シートおよび全固体二次電池ならびに全固体二次電池用電極シートおよび全固体二次電池の製造方法
JP7014900B2 (ja) 固体電解質含有シート、全固体二次電池用電極シート、全固体二次電池、電子機器及び電気自動車、並びに、これらの製造方法
JPWO2017141735A1 (ja) 固体電解質組成物、全固体二次電池用電極シートおよび全固体二次電池、並びに、全固体二次電池用電極シートおよび全固体二次電池の製造方法
WO2018047946A1 (fr) Matériau de couche d'électrode, feuille destinée à une électrode de batterie rechargeable entièrement solide, batterie rechargeable entièrement solide, feuille d'électrode destinée à une batterie rechargeable entièrement solide, et procédé de production d'une batterie rechargeable entièrement solide
WO2019188487A1 (fr) Batterie secondaire à électrolyte entièrement solide et son procédé de fabrication
CN111201660B (zh) 固体电解质组合物、全固态二次电池及其制造方法
JP7064613B2 (ja) 全固体二次電池用積層部材の製造方法及び全固体二次電池の製造方法
JP6572063B2 (ja) 全固体二次電池、全固体二次電池用電極シート及びこれらの製造方法
JP7059302B2 (ja) 固体電解質組成物、固体電解質含有シート及び全固体二次電池、並びに、固体電解質含有シート及び全固体二次電池の製造方法
CN111194492A (zh) 固体电解质组合物、含固体电解质的片材及全固态二次电池、以及含固体电解质的片材及全固态二次电池的制造方法
WO2020059549A1 (fr) Batterie secondaire entierement solide et feuille d'électrode négative de batterie secondaire entierement solide
JPWO2018163976A1 (ja) 固体電解質含有シート、固体電解質組成物および全固体二次電池、ならびに、固体電解質含有シートおよび全固体二次電池の製造方法
JP7100196B2 (ja) 全固体リチウムイオン二次電池とその製造方法、及び負極用積層シート
JP7014899B2 (ja) 固体電解質含有シート、全固体二次電池用電極シート、全固体二次電池、電子機器及び電気自動車、並びに、これらの製造方法
JP4751502B2 (ja) ポリマー電池
JP6665343B2 (ja) 無機固体電解質材料、並びに、これを用いたスラリー、全固体二次電池用固体電解質膜、全固体二次電池用固体電解質シート、全固体二次電池用正極活物質膜、全固体二次電池用負極活物質膜、全固体二次電池用電極シート、全固体二次電池及び全固体二次電池の製造方法
JP6948382B2 (ja) 全固体二次電池及びその製造方法、並びに全固体二次電池用固体電解質シート及び全固体二次電池用正極活物質シート
JP7061728B2 (ja) 複合電極活物質、電極用組成物、全固体二次電池用電極シート及び全固体二次電池、並びに、複合電極活物質、全固体二次電池用電極シート及び全固体二次電池の製造方法
JP7119214B2 (ja) 全固体二次電池及びその製造方法
JP6670641B2 (ja) 電極用材料、これを用いた全固体二次電池用電極シートおよび全固体二次電池ならびに全固体二次電池用電極シートおよび全固体二次電池の製造方法
WO2018164051A1 (fr) Batterie secondaire entièrement solide, son procédé de production, film d'électrolyte solide pour batterie à électrolyte solide entièrement solide, et son procédé de production
WO2022202901A1 (fr) Feuille stratifiée d'électrolyte solide, batterie secondaire tout solide, et procédé de production de batterie secondaire tout solide
JP7245847B2 (ja) 電極用組成物、全固体二次電池用電極シート及び全固体二次電池、並びに、電極用組成物、全固体二次電池用電極シート及び全固体二次電池の各製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19791654

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
ENP Entry into the national phase

Ref document number: 2020516262

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19791654

Country of ref document: EP

Kind code of ref document: A1