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WO2017111131A1 - Accumulateur tout solide, particules destinées à des accumulateurs tout solide, composition d'électrolyte solide destinée à des accumulateurs tout solide, feuille d'électrode destinée à des accumulateurs tout solide, et leurs procédés de fabrication - Google Patents

Accumulateur tout solide, particules destinées à des accumulateurs tout solide, composition d'électrolyte solide destinée à des accumulateurs tout solide, feuille d'électrode destinée à des accumulateurs tout solide, et leurs procédés de fabrication Download PDF

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Publication number
WO2017111131A1
WO2017111131A1 PCT/JP2016/088572 JP2016088572W WO2017111131A1 WO 2017111131 A1 WO2017111131 A1 WO 2017111131A1 JP 2016088572 W JP2016088572 W JP 2016088572W WO 2017111131 A1 WO2017111131 A1 WO 2017111131A1
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Prior art keywords
solid
group
secondary battery
solid electrolyte
organic compound
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English (en)
Japanese (ja)
Inventor
雅臣 牧野
智則 三村
宏顕 望月
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2017558311A priority Critical patent/JP6762319B2/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an all-solid secondary battery, all-solid-state secondary battery particles, all-solid-state secondary battery solid electrolyte composition, all-solid-state secondary battery electrode sheet, and methods for producing these.
  • Electrolytic solutions have been used for lithium ion batteries. Attempts have been made to replace the electrolytic solution with a solid electrolyte to obtain an all-solid-state secondary battery in which all constituent materials are solid.
  • An advantage of a technology that uses an inorganic solid electrolyte is the reliability of the battery that combines the overall performance of the battery. For example, a flammable material such as a carbonate-based solvent is applied as a medium to an electrolytic solution used in a lithium ion secondary battery.
  • Various safety measures have been taken for lithium ion secondary batteries. However, there is a risk of inconvenience during overcharging, and further measures are desired.
  • An all-solid-state secondary battery that employs a solid electrolyte is positioned as a fundamental solution.
  • a further advantage of the all-solid-state secondary battery is that it is suitable for increasing the energy density by stacking electrodes. Specifically, a battery having a structure in which an electrode and an electrolyte are directly arranged in series can be obtained. At this time, since the metal package for sealing the battery cell, the copper wire and the bus bar for connecting the battery cell can be omitted, the energy density of the battery is greatly increased. In addition, good compatibility with the positive electrode material capable of increasing the potential is also mentioned as an advantage.
  • Patent Document 1 describes a solid battery containing a hydrocarbon polymer having a crosslinked structure in any one of a positive electrode, a negative electrode, and an electrolyte layer containing a sulfide solid electrolyte.
  • Patent Document 2 discloses an all-solid secondary battery having a positive electrode, a solid electrolyte layer, and a negative electrode, wherein the all-solid secondary battery contains a graft polymer in at least one of the positive electrode, the solid electrolyte layer, and the negative electrode.
  • Patent Document 1 uses a hydrocarbon polymer having a crosslinked structure so as not to cause a decrease in adhesion between the electrode layer and the solid electrolyte layer. It aims to prevent generation and improve cycle characteristics.
  • the solid battery described in the document has a low binding property between solid particles such as a solid electrolyte, and this low binding property causes a low handling property when the solid battery is manufactured.
  • a graft polymer is used as a binder, but further improvement in binding property between solid particles is desired.
  • an object of the present invention is to provide an all-solid-state secondary battery having excellent binding properties between solid particles in each layer, between each layer and between the layer and the current collector. Moreover, this invention makes it a subject to provide the particle
  • the present inventors have found that the surface of the solid particles is based on an organic compound by exposing at least one solid particle contained in an all-solid-state secondary battery such as an electrode active material or an inorganic solid electrolyte to an actinic ray. Introducing the organic compound group improves the affinity between the solid particles, and improves the binding between the solid particles in each layer of the all-solid-state secondary battery, between each layer and between the layer and the current collector. I found it to improve. The present invention has been made based on this finding.
  • ⁇ 4> The all-solid-state secondary battery according to any one of ⁇ 1> to ⁇ 3>, wherein the inorganic solid electrolyte particles are oxide-based or sulfide-based inorganic solid electrolyte particles.
  • ⁇ 5> The organic compound group according to any one of ⁇ 1> to ⁇ 4>, wherein the organic compound group is supported on the particle surface via a linking group containing at least one of an O atom, an N atom, and an S atom. All-solid secondary battery.
  • ⁇ 6> The all-solid-state secondary battery according to any one of ⁇ 1> to ⁇ 5>, wherein the film thickness of the organic compound group supported via a covalent bond is 20 nm or less.
  • ⁇ 7> The all-solid-state secondary battery according to any one of ⁇ 1> to ⁇ 6>, wherein the organic compound group is a group of an organic compound having a mass average molecular weight of 3000 or more.
  • the organic compound group is an alkyl group having 8 or more carbon atoms, a halogenated alkyl group having 8 or more carbon atoms, an aryl group having 8 or more carbon atoms, a halogenated aryl group having 8 or more carbon atoms, the following formula (1) or
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group.
  • ⁇ 9> The all-solid-state secondary battery according to any one of ⁇ 1> to ⁇ 8>, wherein the organic compound group forms a crosslinking group at the molecular end.
  • ⁇ 11> The all-solid-state secondary battery according to any one of ⁇ 1> to ⁇ 10>, wherein the organic compound group is a group of a surface-initiated graft polymerization conjugate.
  • ⁇ 12> The particle surface is exposed to actinic rays, the exposed particles are mixed with an organic compound, and an organic compound group is supported on the particle surface via a covalent bond, so that the amount of covalent bond on the particle surface is 1 ⁇ 10 ⁇ 10
  • ⁇ 13> The all-solid secondary according to ⁇ 12>, wherein the actinic ray is a plasma generated from any gas of nitrogen, oxygen, hydrogen, carbon dioxide, ammonia, helium and argon, or a mixed gas of two or more thereof. Battery manufacturing method.
  • ⁇ 14> The method for producing an all solid state secondary battery according to ⁇ 13>, wherein the plasma is low-temperature atmospheric pressure plasma.
  • a solid electrolyte composition for an all-solid secondary battery which is used for an all-solid secondary battery according to any one of ⁇ 1> to ⁇ 11>.
  • Solid electrolyte composition for all-solid-state secondary battery that is / cm 2 or more.
  • the particle surface is exposed to actinic rays, reacted with an organic compound, and an organic compound group is supported on the particle surface via a covalent bond, and the amount of covalent bond on the particle surface is 1 ⁇ 10 ⁇ 10 mol / cm 2 or more
  • An electrode sheet for an all-solid-state secondary battery is 1 ⁇ 10 ⁇ 10 mol / cm 2 or more.
  • Solid electrolyte composition After irradiating the material with actinic rays, the organic compound group is supported on the particle surface via a covalent bond by mixing with an organic compound, and the amount of the covalent bond on the particle surface is 1 ⁇ 10 ⁇ 10 mol / cm 2 or more.
  • a step of applying a solid electrolyte composition containing inorganic solid electrolyte particles having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table, electrode active material particles, and conductive auxiliary particles [ 2] After irradiating the solid electrolyte composition with actinic rays and then mixing with an organic compound, the organic compound group is supported on the particle surface via a covalent bond, and the amount of the covalent bond on the particle surface is 1 ⁇ 10 ⁇ 10 mol / The process of making it cm 2 or more
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • acryl or “(meth) acryl” is described, it is used in the meaning including both methacryl and acryl.
  • the all solid state secondary battery of the present invention is excellent in the binding property between solid particles in each layer, between each layer and between the layer and the current collector.
  • the particles for an all-solid-state secondary battery of the present invention are excellent in binding properties.
  • the solid electrolyte composition for an all-solid secondary battery of the present invention is used for the production of an all-solid secondary battery, so that the solid particles in each layer of the all-solid secondary battery, the respective layers, the layers and the current collector The binding property can be improved.
  • the electrode sheet for an all-solid secondary battery of the present invention is used for an all-solid-state secondary battery, thereby binding between solid particles in each layer of the all-solid-state secondary battery, between each layer and between the layer and the current collector. Can increase the sex.
  • the production method of the present invention makes it possible to produce the all-solid secondary battery, the all-solid-state secondary battery particles, the all-solid-state secondary battery solid electrolyte composition, and the all-solid-state secondary battery electrode sheet.
  • FIG. 1 is a cross-sectional view schematically showing an all solid state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention.
  • the all-solid-state secondary battery 10 of this embodiment has a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 in this order as viewed from the negative electrode side. .
  • Each layer is in contact with each other and has a laminated structure.
  • the solid electrolyte composition for an all-solid-state secondary battery of the present invention can be preferably used as a molding material for the negative electrode active material layer, the positive electrode active material layer, and the solid electrolyte layer.
  • the thicknesses of the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 are not particularly limited. In consideration of general battery dimensions, the thickness is preferably 10 to 1,000 ⁇ m, more preferably 20 ⁇ m or more and less than 500 ⁇ m. In the all solid state secondary battery of the present invention, it is more preferable that the thickness of at least one of the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 is 50 ⁇ m or more and less than 500 ⁇ m. In this specification, the positive electrode active material layer and the negative electrode active material layer may be collectively referred to as an electrode layer.
  • the electrode active material that can be used in the present invention includes a positive electrode active material contained in the positive electrode active material layer and a negative electrode active material contained in the negative electrode active material layer. May be simply referred to as an active material or an electrode active material.
  • solid electrolyte composition for an all-solid secondary battery of the present invention that can be suitably used for the production of the all-solid secondary battery of the present invention will be described.
  • the solid electrolyte composition for an all-solid-state secondary battery of the present invention includes inorganic solid electrolyte particles and electrode active material particles having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table. Moreover, it is preferable that the solid electrolyte composition for all-solid-state secondary batteries of this invention contains a conductive support agent particle.
  • an organic compound group is supported on a surface of at least one of the inorganic solid electrolyte particles and the electrode active material particles via a covalent bond.
  • the amount of covalent bonds on the particle surface is 1 ⁇ 10 ⁇ 10 mol / cm 2 or more.
  • the solid electrolyte composition for an all-solid-state secondary battery of the present invention contains conductive aid particles, an organic substance is formed on at least one surface of the inorganic solid electrolyte particles, the electrode active material particles, and the conductive aid particles.
  • the compound group is supported via a covalent bond, and the amount of the covalent bond on the particle surface is 1 ⁇ 10 ⁇ 10 mol / cm 2 or more.
  • inorganic solid electrolyte particles carrying an organic compound group with the above-mentioned covalent bond amount electrode active material particles carrying an organic compound group with the above-mentioned covalent bond amount
  • conductive assistant particles carrying an organic compound group with the above-mentioned covalent bond amount The particles for the all-solid-state secondary battery of the present invention may be referred to simply as particles.
  • the inorganic solid electrolyte particles may be referred to as inorganic solid electrolytes
  • the electrode active material particles may be referred to as electrode active materials
  • the conductive aid particles may be referred to as conductive aids.
  • inorganic solid electrolyte particles, electrode active material particles, and conductive additive particles that do not carry an organic compound group may be referred to as solid particles.
  • the inorganic solid electrolyte is an inorganic solid electrolyte, and the solid electrolyte is a solid capable of moving ions inside thereof.
  • Organic solid electrolytes polymer electrolytes typified by polyethylene oxide (PEO) and the like, organic electrolyte salts typified by lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) and the like) because they do not contain organic substances, that is, carbon atoms Clearly distinguished.
  • the inorganic solid electrolyte is solid in a steady state, the cation and the anion are not dissociated or released, and the cation and the anion are dissociated or released in the electrolyte or polymer (LiPF 6 , LiBF 4 And lithium bis (fluorosulfonyl) imide (LiFSI), LiCl, etc.).
  • the inorganic solid electrolyte is not particularly limited as long as it has conductivity of ions of metal elements belonging to Group 1 or Group 2 of the periodic table, and generally does not have electron conductivity.
  • the solid electrolyte composition for an all-solid-state secondary battery includes an inorganic solid electrolyte. Especially, it is preferable to contain the inorganic solid electrolyte which has the conductivity of the ion of the metal element which belongs to periodic table group 1 or 2 group.
  • the inorganic solid electrolyte a solid electrolyte material commonly used for this type of product 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.
  • the sulfide inorganic solid electrolyte contains a sulfur atom (S) and has ionic conductivity of a metal element belonging to Group 1 or Group 2 of the periodic table, and There is no particular limitation as long as it has electronic insulation.
  • S sulfur atom
  • A lithium ion conductive inorganic solid electrolyte that satisfies the composition represented by the following formula (A).
  • M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge. Of these, B, Sn, Si, Al, and Ge are preferable, and Sn, Al, and Ge are more preferable.
  • A represents I, Br, Cl or F, preferably I or Br, and particularly preferably I.
  • a to e represent the composition ratio of each element, and a: b: c: d: e preferably satisfies 1 to 12: 0 to 1: 1: 2 to 12: 0 to 5.
  • a is further preferably 1 to 9, and more preferably 1.5 to 4.
  • b is preferably 0 to 0.5.
  • d is further preferably 3 to 7, and more preferably 3.25 to 4.5.
  • e is preferably from 0 to 3, more preferably from 0 to 2.
  • the composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based inorganic solid electrolyte.
  • the sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass ceramic), or only part of it may be crystallized.
  • the ratio of Li 2 S to P 2 S 5 in the Li—PS system glass and the Li—PS system glass ceramic is a molar ratio of Li 2 S: P 2 S 5 , preferably 65:35 to 85:15, more preferably 68:32 to 75:25.
  • the lithium ion conductivity can be increased.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 ⁇ 4 S / cm or more, more preferably 1 ⁇ 10 ⁇ 3 S / cm or more. Although there is no particular upper limit, it is practical that it is 1 ⁇ 10 ⁇ 1 S / cm or less.
  • Li—PS glass is preferably used.
  • the compound of the sulfide-based inorganic solid electrolyte include those formed using a raw material composition containing, for example, Li 2 S and a sulfide of an element belonging to Group 13 to Group 15. . More specifically, Li 2 S—P 2 S 5 , Li 2 S—LiI—P 2 S 5 , Li 2 S—LiI—Li 2 O—P 2 S 5 , Li 2 S—LiBr—P 2 S 5 , Li 2 S—Li 2 O—P 2 S 5 , Li 2 S—Li 3 PO 4 —P 2 S 5 , Li 2 S—P 2 S 5 —P 2 O 5 , Li 2 S—P 2 S 5- SiS 2 , Li 2 S—P 2 S 5 —SnS, Li 2 S—P 2 S 5 —Al 2 S 3 , Li 2 S—GeS 2 , Li 2 S—GeS 2 —ZnS, Li 2 S— Ga 2 S 3 , Li 2 S—GeS 2
  • Examples of a method for synthesizing a sulfide-based inorganic solid electrolyte material using such a raw material composition include an amorphization method.
  • Examples of the amorphization method include a mechanical milling method and a melt quenching method, and among them, the mechanical milling method is preferable. This is because processing at room temperature is possible, and the manufacturing process can be simplified.
  • 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 There is no particular limitation as long as it has electronic insulation.
  • the ionic conductivity of the lithium ion conductive oxide-based inorganic solid electrolyte is preferably 1 ⁇ 10 ⁇ 6 S / cm or more, more preferably 5 ⁇ 10 ⁇ 6 S / cm or more.
  • X 10 ⁇ 5 S / cm or more is particularly preferable. Is no particular upper limit, but it is practical is 1 ⁇ 10 -2 S / cm or less.
  • Xb satisfies 5 ⁇ xb ⁇ 10
  • yb satisfies 1 ⁇ yb ⁇ 4
  • zb satisfies 1 ⁇ zb ⁇ 4
  • mb satisfies 0 ⁇ mb ⁇ 2
  • nb satisfies 5 ⁇ nb.
  • Li xc B yc M cc zc Onc (wherein M cc is one or more elements selected from the group consisting of C, S, Al, Si, Ga, Ge, In, and Sn).
  • M cc is one or more elements selected from the group consisting of C, S, Al, Si, Ga, Ge, In, and Sn).
  • Xc satisfies 0 ⁇ xc ⁇ 5, yc satisfies 0 ⁇ yc ⁇ 1, zc satisfies 0 ⁇ zc ⁇ 1, and nc satisfies 0 ⁇ nc ⁇ 6);
  • Li xd (Al, Ga) yd (Ti, Ge) zd Si ad P md O nd ( only Xd satisfies 1 ⁇ xd ⁇ 3, yd satisfies 0 ⁇ yd ⁇ 1, zd satisfies 0 ⁇ zd
  • Li 7 La 3 Zr 2 O 12 having a garnet-type crystal structure.
  • Phosphorus compounds containing Li, P and O are also desirable.
  • lithium phosphate Li 3 PO 4
  • LiPON LiPOD
  • LiPOD LiPOD
  • LiPOD LiPOD
  • LiPOD LiPOD
  • LiPOD LiPOD
  • LiPOD LiPOD
  • LiPOD LiPOD
  • LiPOD LiPOD
  • LiPOD is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb
  • LiAON is at least one selected from Si, B, Ge, Al, C and Ga
  • LiAON A is at least one selected from Si, B, Ge, Al, C and Ga
  • LLT Li xb La yb Zr zb M bb mb Onb
  • M bb is one or more selected from the group consisting of 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.
  • LLZ Li 3 BO 3, Li 3 BO 3 -Li 2 SO 4, Li xd (Al, Ga) yd (Ti, Ge) zd Si ad P md O nd (although, xd 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 is 3 ⁇ nd ⁇ 13) is preferable, and LLZ More preferable. These may be used alone or in combination of two or more.
  • the inorganic solid electrolyte may be used singly or in combination of two or more.
  • the average particle size of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more. As an upper limit, it is preferable that it is 100 micrometers or less, and it is more preferable that it is 50 micrometers or less.
  • the content of the inorganic solid electrolyte in the solid electrolyte composition for an all-solid-state secondary battery is 5% by mass or more in 100% by mass of the solid component when considering both battery performance, reduction in interface resistance and maintenance effect. It is preferable that it is 10 mass% or more, and it is especially preferable that it is 20 mass% or more. As an upper limit, it is preferable that it is 99.9 mass% or less from the same viewpoint, It is more preferable that it is 99.5 mass% or less, It is especially preferable that it is 99.0 mass% or less. However, when used together with a positive electrode active material or a negative electrode active material described later, the total content is preferably within the above range.
  • the solid component refers to a component that does not disappear by volatilization or evaporation when dried at 170 ° C. for 6 hours. Typically, it refers to components other than the dispersion medium described below. Moreover, it is preferable that content of the solid component in the all-solid-state secondary battery and the electrode sheet for all-solid-state secondary batteries is the same as content of the solid component in the solid electrolyte composition for all-solid-state secondary batteries.
  • the electrode active material used in the solid electrolyte composition for an all-solid secondary battery of the present invention will be described.
  • the solid electrolyte composition for an all-solid-state secondary battery for forming the positive electrode active material layer may be referred to as a positive electrode composition.
  • the solid electrolyte composition for an all-solid-state secondary battery for forming the negative electrode active material layer may be referred to as a negative electrode composition.
  • the positive electrode active material used for the composition for positive electrodes for forming the positive electrode active material layer of the all-solid-state secondary battery of this invention is demonstrated.
  • the positive electrode active material is preferably one that can reversibly insert and release lithium ions.
  • the material is not particularly limited, and may be a transition metal oxide or an element that can be combined with Li such as sulfur. Among these, it is preferable to use a transition metal oxide, and it is more preferable to have a transition metal element M a (one or more elements selected from Co, Ni, Fe, Mn, Cu, and V).
  • mixed element M b (elements of the first (Ia) group of the metal periodic table other than lithium, elements of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si , P, B, etc.) may be mixed.
  • the mixing amount is preferably 0 to 30 mol% with respect to the amount of the transition metal element. That the molar ratio of li / M a was synthesized were mixed so that 0.3 to 2.2, more preferably.
  • transition metal oxides include (MA) transition metal compounds having a layered rock salt structure, (MB) transition metal oxides having a spinel structure, (MC) lithium-containing transition metal phosphate compounds, (MD) Examples include lithium-containing transition metal halide phosphate compounds, (ME) lithium-containing transition metal silicates, and the like.
  • transition metal compound having a layered rock salt structure is preferably a transition metal compound (electrode active material particles) having a layered rock salt structure represented by the following formula (B1).
  • M 1 represents Co, Ni, Fe, Mn, a metal containing at least one selected from the group consisting of Cu and V, a1 represents 0 ⁇ 1.2, b1 is 1 ⁇ 3 is represented.
  • M 1 may contain the mixed element M b .
  • M 1 may be a metal mixed so that the total molar ratio of each element of the plurality of metal elements is 1, such as LiNi 0.85 Co 0.1 Al 0.05 O 2 below. Good (including metals mixed so that the total molar ratio of each element is 0.99 or more).
  • transition metal compound having a layered rock salt structure represented by the above formula (B1) include LiCoO 2 (lithium cobaltate [LCO]), LiNiO 2 (lithium nickelate), LiNi 0.85 Co 0.1.
  • Al 0.05 O 2 nickel cobalt lithium aluminum oxide [NCA]
  • LiNi 0.33 Co 0.33 Mn 0.33 O 2 nickel manganese lithium lithium lithium [NMC]
  • LiNi 0.5 Mn 0.5 O 2 lithium manganese nickelate
  • Transition metal oxide having a spinel structure is preferably a transition metal oxide (electrode active material particles) having a spinel structure represented by the following formula (B2).
  • m1 represents an integer of 2 to 8
  • the plurality of M 2 each independently include at least one selected from the group consisting of Co, Ni, Fe, Mn, Cu, Cr and V Represents a metal
  • c1 represents 0 to 2
  • d1 represents 3 to 8.
  • M 2 may comprise the mixing element M b.
  • transition metal oxide having the spinel structure represented by the above formula (B2) LiCoMnO 4, Li 2 FeMn 3 O 8 , Li 2 CuMn 3 O 8 , Li 2 CrMn 3 O 8, Li 2 NiMn 3 O 8 is mentioned.
  • the lithium-containing transition metal phosphoric acid oxide is preferably a lithium-containing transition metal phosphoric acid oxide (electrode active material particle) represented by the following formula (B3).
  • M 3 represents a metal containing at least one selected from the group consisting of V, Ti, Cr, Mn, Fe, Co, Ni and Cu, m2 represents an integer of 1 to 8, e1 represents 0.1 to 3, and f1 represents 1 to 5.
  • M 3 may include the mixed element M b , and M 3 may be substituted with other metals such as Ti, Cr, Zn, Zr, and Nb. If M 3 there is a plurality, a plurality of M 3 may be the same or different.
  • lithium-containing transition metal phosphate represented by the above formula (B3) examples include olivine-type phosphate iron salts such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , and cobalt phosphates such as LiCoPO 4. And monoclinic nasicon type vanadium phosphate salts such as Li 3 V 2 (PO 4 ) 3 (lithium vanadium phosphate).
  • iron pyrophosphates such as LiFeP 2 O 7 can also be used as the lithium-containing transition metal phosphate.
  • the lithium-containing transition metal halogenated phosphoric acid oxide is preferably a lithium-containing transition metal halogenated phosphoric acid oxide (electrode active material particle) represented by the following formula (B4).
  • M 4 represents a metal including at least one selected from the group consisting of V, Ti, Cr, Mn, Fe, Co, Ni, and Cu
  • X represents a halogen element
  • g1 represents 0 1 to 3
  • h1 represents 1 to 5
  • i1 represents 0.1 to 5.
  • M 4 may comprise the mixing element M b, further M 4 is Ti, Cr, Zn, Zr, may be substituted by other metals such as Nb.
  • lithium-containing transition metal halide phosphorus oxide represented by the formula (B4) for example, Li 2 FePO 4 F such fluorinated phosphorus iron salt, Li 2 MnPO 4 hexafluorophosphate manganese salts such as F And cobalt fluorophosphates such as Li 2 CoPO 4 F.
  • Li 2 FePO 4 F such fluorinated phosphorus iron salt
  • Li 2 MnPO 4 hexafluorophosphate manganese salts such as F
  • cobalt fluorophosphates such as Li 2 CoPO 4 F.
  • the lithium-containing transition metal silicate is preferably a lithium-containing transition metal silicate (electrode active material particles) represented by the following formula (B5).
  • M 5 represents a metal containing at least one selected from the group consisting of Co, Fe, Mn, Ni, Cu and V, j1 represents 0 to 3, k1 represents 1 to 5 To express.
  • M 5 may contain the mixed element M b , and M 5 may be substituted with another metal such as Ti, Cr, Zn, Zr, or Nb.
  • lithium-containing transition metal silicate represented by the above formula (B5) examples include Li 2 FeSiO 4 , Li 2 MnSiO 4 , Li 2 CoSiO 4, and the like.
  • electrode active material particles represented by any of the above formulas (B1) to (B5) are preferably used, electrode active material particles represented by the above formula (B1) are preferred, and LCO and NCA are More preferred is LCO, and particularly preferred.
  • the volume average particle diameter (sphere conversion average particle diameter) of the positive electrode active material used in the all solid state secondary battery of the present invention is not particularly limited. For example, 0.1 ⁇ m to 50 ⁇ m is preferable. In order to make the positive electrode active substance have a predetermined particle size, a normal 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 average particle diameter of the positive electrode active material particles is determined by measuring the volume average particle diameter (sphere-converted average particle diameter) using a laser diffraction / scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA).
  • the chemical formula of the positive electrode active material obtained by the above firing method can be calculated from an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method and a mass difference between powders before and after firing as a simple method.
  • the content of the positive electrode active material is not particularly limited, but is preferably 10 to 90% by mass, preferably 20 to 90% by mass in 100% by mass of the solid component in the solid electrolyte composition for an all-solid secondary battery for forming the positive electrode active material layer. 80 mass% is more preferable.
  • the positive electrode active materials may be used singly or in combination of two or more.
  • the positive electrode active material layer may contain a conductive additive as necessary.
  • a conductive additive those described below can be used.
  • the negative electrode active material used in the solid electrolyte composition for an all solid secondary battery for forming the negative electrode active material layer of the all solid secondary battery of the present invention will be described.
  • the negative electrode active material those capable of reversibly inserting and releasing lithium ions are preferable.
  • the material is not particularly limited, and is a carbonaceous material, a metal oxide such as tin oxide or silicon oxide, a metal composite oxide, a lithium alloy such as lithium alone or a lithium aluminum alloy, and a lithium such as Sn, Si, or In. And metals capable of forming an alloy. Of these, carbonaceous materials or lithium composite oxides are preferably used from the viewpoint of reliability.
  • the metal composite oxide is preferably capable of inserting and extracting lithium.
  • the material is not particularly limited, but preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
  • the carbonaceous material used as the negative electrode active material is a material substantially made of carbon.
  • Examples thereof include carbonaceous materials obtained by firing various synthetic resins such as artificial pitches such as petroleum pitch, natural graphite, and vapor-grown graphite, and PAN (polyacrylonitrile) -based resins and furfuryl alcohol resins.
  • various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA (polyvinyl alcohol) -based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber, etc. And mesophase microspheres, graphite whiskers, flat graphite and the like.
  • an amorphous oxide is particularly preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used. It is done.
  • amorphous as used herein means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering band having a peak in the region of 20 ° to 40 ° in terms of 2 ⁇ , and is a crystalline diffraction line. You may have.
  • the strongest intensity of crystalline diffraction lines seen from 2 ° to 40 ° to 70 ° is 100 times the diffraction line intensity at the peak of the broad scattering band seen from 2 ° to 20 °. It is preferable that it is 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.
  • amorphous metal oxides and chalcogenides are more preferable, and elements in groups 13 (IIIB) to 15 (VB) of the periodic table are preferable.
  • oxides and chalcogenides composed of one kind of Al, Ga, Si, Sn, Ge, Pb, Sb, Bi or a combination of two or more kinds thereof.
  • preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , SiO, GeO, SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , Bi 2 O 3 , Bi 2 O 4 , SnSiO 3 , GeS, SnS, SnS 2 , PbS, PbS 2 , Sb 2 S 3 , Sb 2 S 5 , such as SnSiS 3 may preferably be mentioned. Moreover, these may be a complex oxide with lithium oxide, for example, Li 2 SnO 2 .
  • the negative electrode active material contains a titanium atom. More specifically, Li 4 Ti 5 O 12 (lithium titanate [LTO]) is excellent in rapid charge / discharge characteristics due to small volume fluctuations during the insertion and release of lithium ions, and the deterioration of the electrodes is suppressed, and the lithium ion secondary This is preferable in that the battery life can be improved.
  • Li 4 Ti 5 O 12 lithium titanate [LTO]
  • the average particle size of the negative electrode active material is preferably 0.1 ⁇ m 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.
  • wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary.
  • classification is preferably performed.
  • the classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be used both dry and wet.
  • the chemical formula of the carbonaceous material obtained by firing the above various synthetic resins can be calculated from the mass difference between the powders before and after firing as an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method.
  • ICP inductively coupled plasma
  • Examples of the negative electrode active material that can be used in combination with the amorphous oxide negative electrode active material centering on Sn, Si, and Ge include carbonaceous materials that can occlude and release lithium ions or lithium metal, lithium, lithium alloys, A metal that can be alloyed with lithium is preferable.
  • At least one negative electrode active material represented by the following formula (B) is included.
  • x represents a number of 0.01 or more and less than 1, and means a mole fraction.
  • M represents a chalcogen element, a metalloid element, an alkali metal element, an alkaline earth metal element, a transition metal element, or a combination thereof.
  • M is preferably a chalcogen element such as O, S or Se, a metalloid element such as B or Ge, an alkali metal element such as Li or Na, an alkaline earth metal element such as Mg or Ca, Ti, V, It can be selected from transition metal elements such as Mn, Fe, Co, Ni and Cu. Further, a combination of two or more of these elements may be used. Of these, chalcogen elements and transition metal elements are preferable, and transition metal elements are more preferable. Among the transition metal elements, the first transition metal element is preferable, Ti, V, Mn, Fe, Co, Ni, and Cu are more preferable, and Ti, Mn, Fe, Co, and Ni are particularly preferable.
  • X is preferably from 0.1 to less than 1, more preferably from 0.1 to 0.99, further preferably from 0.2 to 0.98, particularly preferably from 0.3 to 0.95.
  • the negative electrode active material contains a titanium atom. More specifically, since Li 4 Ti 5 O 12 has a small volume fluctuation at the time of occlusion and release of lithium ions, it has excellent rapid charge / discharge characteristics, suppresses electrode deterioration, and improves the life of an all-solid-state secondary battery. This is preferable.
  • the content of the negative electrode active material is not particularly limited, but is preferably 10 to 80% by mass, and preferably 20 to 70% by mass in 100% by mass of the solid component in the solid electrolyte composition for an all-solid secondary battery. Is more preferable.
  • the negative electrode active materials may be used alone or in combination of two or more.
  • the negative electrode active material layer may contain a conductive additive as necessary.
  • a conductive additive those described below can be used.
  • 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 a metal oxide that contains Ti, Nb, Ta, W, Zr, Si, or the like and may further contain Li.
  • the surface coating method include the following, which can be appropriately used in the present invention.
  • a positive electrode active material having a coating portion made of a lithium niobate compound formed on the surface of an oxide positive electrode active material is disclosed in JP 2010-225309 A and Non-Patent Document Narumi Ohta et al. , “LiNbO 3 -coated LiCoO 2 as cathode material for all solid-state lithium secondary batteries”, Electrochemistry Communications 9 (2007) 1486-1490.
  • lithium metal acid Li Y X 1 O Z (wherein X 1 is Co, Mn or Ni, and Y and Z are each an integer of 1 to 10).
  • a coating material on the active material surface examples include titanic acid spinel, tantalum-based oxide, niobium-based oxide, and the like.
  • Li 4 Ti 5 O 12 , LiTaO 3 , LiNbO 3 , LiAlO 2 , Li 2 ZrO 3 , Li 2 WO 4 , Li JP-A-2008-103280 describes that 2 TiO 3 , Li 2 B 4 O 7 , Li 3 PO 4 , Li 2 MoO 4 , LiBO 2 and the like can be mentioned.
  • An electrode material for an all solid state secondary battery surface-treated with sulfur and / or phosphorus is described in JP-A-2008-027581. Further, lithium chloride may be supported on the surface of the oxide positive electrode active material, as described in JP-A-2001-052733.
  • negative electrode active materials carbonaceous materials, tin, silicon, indium, oxides and sulfides thereof are preferable, and negative electrode active materials containing carbonaceous materials or titanium atoms are more preferable.
  • natural graphite is particularly preferable.
  • a general conductive support agent can be used.
  • graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black and furnace black, amorphous carbon such as needle coke, vapor-grown carbon fiber and carbon nanotubes, which are electron conductive materials
  • Carbon fibers such as graphene, carbonaceous materials such as graphene and fullerene, metal powders such as copper and nickel, and metal fibers may be used, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives may be used. It may be used.
  • 1 type may be used among these and 2 or more types may be used.
  • acetylene black is preferably used.
  • the particles for the all-solid-state secondary battery of the present invention are modified on the surface of the inorganic solid electrolyte particles, the electrode active material particles or the conductive auxiliary particles, and the organic compound groups are supported on the particle surfaces via covalent bonds.
  • the amount of covalent bonds on the particle surface is 1 ⁇ 10 ⁇ 10 mol / cm 2 or more.
  • the amount of covalent bonds is preferably 5 ⁇ 10 ⁇ 9 mol / cm 2 or more, and more preferably 1 ⁇ 10 ⁇ 8 mol / cm 2 or more.
  • the upper limit is not particularly limited but is preferably 1 ⁇ 10 -1 mol / cm 2 or less, more preferably 1 ⁇ 10 -2 mol / cm 2 or less, particularly preferably 1 ⁇ 10 -3 mol / cm 2 or less.
  • the surface covalent bond amount (mol / cm 2 ) means the mass a (g) of an organic compound that is an organic compound group carried on the particle surface per 1 g of the particle, and the mass average molecular weight of the organic compound.
  • Mw mass average molecular weight of the organic compound.
  • S specific surface area S (cm 2 / g) of the solid particle surface are calculated and mean values calculated from the following formula.
  • the organic compound group is bonded to the particle surface activated with actinic rays through a covalent bond.
  • the organic compound group means a group in which an organic compound reacts with the solid particle surface through a covalent bond, and includes a group in which a polymer of the organic compound is bonded as a group.
  • it is an organic compound group in which a functional group on the organic compound and a functional group on the surface of the solid particle form a crosslink reaction to form a covalent bond.
  • the organic compound group By mixing the solid particles after the actinic ray treatment and an organic compound capable of reacting with the solid particles, the organic compound group is supported on the solid particles through a covalent bond.
  • the “mixing” will be described later. Since the organic compound group is supported on the particle through a covalent bond, the organic compound group can be prevented from being separated from the particle by being washed with an organic solvent or the like. The organic compound group does not need to be uniformly supported on the particle surface, and there may be an uncoated portion.
  • the film thickness of the organic compound group supported via the covalent bond is preferably 20 nm or less in order to bond the particles forming the all-solid-state secondary battery with sufficient mechanical strength. More preferably, it is more preferably 5 nm or less.
  • the lower limit is not particularly limited, but is practically 0.1 nm or more.
  • the organic compound used in the present invention is not particularly limited, but the mass average molecular weight is preferably 3,000 or more, more preferably 5,000 or more, and particularly preferably 7,000 or more.
  • the upper limit is preferably 100,000 or less, more preferably 50,000 or less, and particularly preferably 30,000 or less.
  • the organic compound used for this invention is an oligomer or a polymer.
  • the mass average molecular weight is within the above range, adverse effects on battery performance such as ion conductivity and electron conductivity can be minimized while exhibiting high binding properties.
  • the mass mean molecular weight of the said organic compound can be measured as a molecular weight of polystyrene conversion by gel permeation chromatography (GPC). The measuring method is based on the measuring method in the examples described later.
  • the organic compound group is an alkyl group having 8 or more carbon atoms, a halogenated alkyl group having 8 or more carbon atoms, an aryl group having 8 or more carbon atoms, a halogenated aryl group having 8 or more carbon atoms, or the following formula (1) or (2) Containing at least one kind, preferably at least two of the silica-containing substituents represented by the formula, improves the binding property by entanglement of organic compound groups while suppressing aggregation between particles by steric repulsion Is also preferable.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group.
  • the alkyl group having 8 or more carbon atoms may be linear, branched or cyclic.
  • the upper limit of the carbon number is not particularly limited, but is preferably 100 or less, more preferably 50 or less, and particularly preferably 30 or less. Specific examples include octyl, dodecyl, heptadecyl, nonadecyl, triacontyl, and stearyl.
  • the alkyl group of the halogenated alkyl group having 8 or more carbon atoms has the same definition as the alkyl group having 8 or more carbon atoms, and the preferred range is also the same.
  • Examples of the halogen atom of the halogenated alkyl group having 8 or more carbon atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
  • the aryl group having 8 or more carbon atoms may be an aryl group having 8 or more carbon atoms, and is not limited to being a hydrocarbon, and may contain a hetero atom between carbon-carbon bonds.
  • the aryl group having 8 or more carbon atoms is preferably an aryl group having 8 to 50 carbon atoms, more preferably an aryl group having 8 to 30 carbon atoms, still more preferably an aryl group having 8 to 20 carbon atoms, An aryl group having 8 or more and 18 or less is particularly preferable.
  • the aryl group of the halogenated aryl group having 8 or more carbon atoms has the same meaning as the aryl group having 8 or more carbon atoms, and the preferred range is also the same.
  • Examples of the halogen atom of the halogenated alkyl group having 8 or more carbon atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
  • the alkyl group in R 1 , R 2 and R 3 may be any of chain, branched or cyclic, and the carbon number is preferably 1 to 30, more preferably 1 to 25, still more preferably 1 to 18, Is particularly preferred. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, octyl, dodecyl, and stearyl.
  • the alkenyl group in R 1 , R 2 and R 3 may be any of chain, branched or cyclic, and the carbon number is preferably 2 to 20, more preferably 2 to 10, and particularly preferably 2 to 8. Examples include vinyl, propenyl, butenyl, and phenylethenyl.
  • the alkynyl group in R 1 , R 2 and R 3 may be any of chain, branched or cyclic, and the carbon number is preferably 2 to 20, more preferably 2 to 10, and particularly preferably 2 to 8. Examples include ethynyl, propynyl, butynyl, phenylethynyl.
  • R 1 , R 2 and R 3 are preferably all alkyl groups having 1 to 8 carbon atoms, and are preferably methyl groups.
  • the organic compound group used in the present invention preferably forms a crosslinking group at the molecular end.
  • a cross-linking group is formed at the molecular end means that a bond is formed by a cross-linkable group at the end of the longest chain (main chain) of the organic compound and a functional group on the surface of the solid particle. To do.
  • the carbon number of the longest chain is preferably 2 to 100, more preferably 2 to 50, and particularly preferably 2 to 20.
  • the organic compound group used in the present invention for forming a crosslinking group may have a functional group different from the functional group necessary for forming a bond with the functional group on the surface of the solid particle.
  • a group at the molecular end (preferably main chain end) of an organic compound group different from the crosslinking group includes methacryl, acrylic, epoxy, oxetanyl, ethynyl, vinyl group, hydroxy Groups and carboxy groups. Since such a crosslinkable functional group is crosslinked by an external stimulus such as heat or actinic light to form a crosslinkable group, the particles can be bonded to each other, thereby having a three-dimensional crosslinked structure. It is preferable because it exhibits a stronger binding property.
  • the organic compound group used in the present invention is any group of acrylic resin, epoxy resin, amide resin, urethane resin, urea resin, imide resin, or silicone resin. Therefore, it is preferable.
  • the organic compound group is preferably formed by surface graft polymerization in order to reliably form a bond on the particle surface and control the wettability of the surface.
  • the surface graft polymerization in the present invention is a polymerization method based on the surface graft method.
  • active species such as radicals and reactive functional groups are generated on the surface of solid particles by actinic ray treatment, and the polymer is polymerized from the solid particle surface based on the active species, and the polymer is directly bonded to the particle surface.
  • This is a surface modification method to be formed.
  • the monomer a monomer that is usually used for radical polymerization or polycondensation can be used without any particular limitation.
  • radical polymerization monomers include acrylic monomers.
  • the polycondensation monomer include monomers of carboxylic acid dichloride, diisocyanate, carboxylic dianhydride, alkoxysilane, and halogenated silane.
  • the organic compound used in the present invention may be used singly or in combination of two or more. Moreover, the organic compound used in the present invention may have a substituent. Examples of the substituent include the substituents described in paragraphs 0019 to 0092 of JP2010-254971A.
  • the solid particle surface can be hydrophilized by exposing the surface of the solid particle to actinic rays and mixing it with the organic compound.
  • mixing with an organic compound does not mean simply mixing solid particles and an organic compound. It means that a reaction is caused on the particle surface to bond the organic compound to the surface of the solid particle through a covalent bond as an organic compound group (copolymerization by formation of a covalent bond and further a chained covalent bond).
  • solid particles exposed to actinic rays are reacted with an acid chloride compound, and the acid chloride compound group is supported on the solid particle surface via an ester bond.
  • the solid particles exposed to actinic rays are reacted with the isocyanate compound to carry the isocyanate compound group on the surface of the solid particles via a urethane bond.
  • Examples include reacting solid particles exposed to actinic rays with an alkoxysilane compound and supporting them on the surface of the solid particles through a siloxane bond.
  • a polymer incorporating an inorganic surface can be obtained by bifunctionalizing the reactive group (functional group).
  • the said surface graft polymerization is mentioned as a method of extending superposition
  • the surface of the inorganic solid electrolyte, the electrode active material, and the conductive auxiliary agent is usually oxidized or contaminated with attached oils and fats, so there are few reaction active surfaces.
  • highly active reactive species such as oxygen radicals, nitrogen radicals, and sulfur radicals can be generated on the surface.
  • oxygen radicals By exposing each radical to moisture in the air, the oxygen radical can be changed to a hydroxy group, a carboxy group, an epoxy group, the nitrogen radical can be changed to an amino group, and the sulfur radical can be changed to a mercapto group.
  • Oxygen radical density can be increased by exposing particles to actinic rays in an oxygen atmosphere.
  • the nitrogen radical density can be increased by exposure to actinic rays in a nitrogen atmosphere.
  • exposure to a sulfide-based inorganic solid electrolyte with actinic rays in an argon atmosphere tends to cause the cleavage of the SS bond and the generation of sulfur radicals associated therewith.
  • Highly active reactive species can form covalent bonds with organic compounds added later. Since the covalent bond is a strong bond unlike physical adsorption, peeling from the particles can be suppressed, which contributes not only to improving the binding property but also to extending the life of the all-solid-state secondary battery.
  • the organic compound group is supported on the surface of the solid particle through a covalent bond.
  • An example of a covalent bond is shown below. The mixing may be performed in the presence of a reaction accelerator.
  • reaction accelerators include radical polymerization initiators (azo-based initiators, peroxides, etc.), cationic polymerization initiators (sulfonium salts, iodonium salts, etc.), dehydration condensing agents (carbodiimide, diphenyl phosphate azide, BOP).
  • radical polymerization initiators azo-based initiators, peroxides, etc.
  • cationic polymerization initiators sulfonium salts, iodonium salts, etc.
  • dehydration condensing agents carbbodiimide, diphenyl phosphate azide, BOP.
  • Reagents 2-chloro-4,6, -dimethoxytriazine, 2,4,6-trichlorobenzoyl chloride, ketene imine, etc.
  • halogenating agents trichloroacetyl chloride, thionyl chloride, phosphoryl chloride, phosgene, etc.
  • Lewis acid catalyst Alkyl ammonium halide, BBr 3 , tin oxide, bismuth catalyst, etc.
  • acid carbboxylic acid, sulfonic acid, phosphoric acid, HPF 6 , HBF 4 etc.
  • base tributylamine, 4-dimethylaminopyridine, imidazole, diazabicyclo
  • the organic compound group used in the present invention is bonded through a linking group containing at least one of an O atom, an N atom, and an S atom from the viewpoint of high affinity with an element present on the particle surface. It is preferably supported on the particle surface.
  • the surface of the solid particles can be implanted (embedded with functional groups) by exposing the solid particles to actinic rays.
  • Preferred examples of the actinic rays in the present invention include infrared rays, microwaves, ultraviolet rays, excimer laser light, electron beams (EB), X-rays, high-energy rays having a wavelength of 50 nm or less (such as EUV), and plasma.
  • the actinic ray is more preferably plasma, and particularly preferably low-temperature atmospheric pressure plasma.
  • Plasma is preferably used in that the effect of improving the property is exhibited.
  • the atmosphere for exposing the solid particles to actinic rays is not particularly limited, and may be a vacuum, air, or other gas atmosphere. Nitrogen is preferably present for nitriding the surface.
  • the exposure time is not particularly limited, but is preferably 1 second to 24 hours, more preferably 5 seconds to 1 hour, and particularly preferably 10 seconds to 10 minutes.
  • the actinic ray treatment can be performed even when the solid particles are in a powder state or dispersed in a liquid such as a slurry. Furthermore, even if it is the state contained in the apply
  • the plasma used in the present invention may be either vacuum plasma or atmospheric pressure plasma.
  • non-equilibrium plasma jet, low-temperature plasma by AC pulse discharge, powder plasma, in-liquid plasma, torch type plasma, tube plasma, etc. can be used, all using plasma generated under conditions near atmospheric pressure. Is preferred.
  • Various atmospheric pressure plasma devices can be used for plasma irradiation.
  • a device that can generate low-temperature atmospheric pressure plasma by performing intermittent discharge while passing an inert gas having a pressure near atmospheric pressure between electrodes covered with a dielectric is preferable.
  • Various modified examples of the plasma apparatus can be selected according to the purpose of use. More specifically, in Japanese Patent Application Laid-Open No. 2008-60115, an apparatus used for substrate plasma processing, an atmospheric pressure plasma apparatus described in Japanese Patent Application Laid-Open No. 2004-228136, Japanese Patent Application Laid-Open No. 2006-21972, and Japanese Patent Application Laid-Open No. 2007-2007. Examples thereof include plasma apparatuses described in specifications such as 188690 and International Publication No. 2005/062338, International Publication No. 2007/024134, and International Publication No. 2007/145513.
  • atmospheric pressure plasma devices such as ATMP-1000 from Arios Co., Ltd., atmospheric pressure plasma device from HEIDEN LABORATORIES, INC., S5000 type atmospheric pressure low-temperature plasma jet device from SAMURAI Semiconductor Co., Ltd., ASS. -Atmospheric plasma currently on the market, such as powder plasma equipment shown by -400, PPU-800, and SKIp-ZKB, MyPL100 and ILP-1500 from Well Co., Ltd., and RD550 from Sekisui Chemical Co., Ltd.
  • An apparatus can also be used suitably (all are brand names).
  • the “pressure near atmospheric pressure” in the “low temperature atmospheric plasma” refers to a range of 70 kPa to 130 kPa, preferably 90 kPa to 110 kPa.
  • a rare gas such as He and Ar, which is an inert gas, or nitrogen gas (N 2 )
  • a rare gas such as Ar or He is particularly preferable.
  • plasma treatment may be performed in a batch system or an inline system connected to other processes.
  • the plasma action site is separated from the discharge site, or the local concentration of the plasma (streamer) is suppressed by devising the discharge circuit. It is effective to generate a uniform plasma.
  • the latter is particularly preferable in that a uniform plasma treatment over a large area can be performed.
  • a method in which the plasma generated by the discharge is brought into contact with the surface of the solid electrolyte layer or the electrode active material layer by an inert gas stream is preferable, and a so-called plasma jet method is particularly preferable.
  • the path (conducting tube) for transporting the inert gas containing plasma is preferably a dielectric such as glass, porcelain, or organic polymer.
  • the latter includes a uniform glow in which streamers are suppressed by applying current to an electrode covered with a dielectric via a pulse control element, as described in WO 2005/062338 and WO 2007/024134. A method of generating plasma is preferable.
  • the distance from the supply nozzle of the inert gas containing plasma to the surface of the solid electrolyte layer or the electrode active material layer is preferably 0.01 mm to 100 mm, and more preferably 1 mm to 20 mm.
  • An inert gas may be sufficiently supplied to a region where plasma treatment is performed, or the region may be filled with an inert gas.
  • an inert gas is allowed to flow through the plasma generation site before the plasma is turned on, and the inert gas is allowed to continue even after the plasma is extinguished.
  • the inert gas after the plasma treatment may be exhausted without performing any special treatment because the plasma has a short life, but the inert gas that has been treated by providing an inlet in the vicinity of the treatment region. May be recovered.
  • the temperature at the time of plasma irradiation can be selected arbitrarily depending on the characteristics of the material in the solid electrolyte layer or electrode active material layer irradiated with plasma, but the temperature rise caused by irradiation with low-temperature atmospheric pressure plasma is small Is preferable because damage can be reduced. The effect is further improved by separating the plasma application region from the plasma generator.
  • the supply of thermal energy from the plasma can be reduced, and the temperature rise of the solid electrolyte layer or the electrode active material layer can be suppressed.
  • the temperature rise of the solid electrolyte layer or the electrode active material layer due to the plasma irradiation is preferably 50 ° C. or less, more preferably 40 ° C. or less, and particularly preferably 20 ° C. or less.
  • the temperature at the time of plasma irradiation is preferably equal to or lower than the temperature that can be withstood by the material in the solid electrolyte layer or electrode active material layer irradiated with plasma, and is generally ⁇ 196 ° C.
  • the temperature is from 100 ° C to 100 ° C. Furthermore, it is preferably ⁇ 10 ° C. or more and 80 ° C. or less, and more preferably near room temperature (25 ° C.) in an ambient temperature atmosphere.
  • the low temperature atmospheric pressure plasma in this invention means the plasma irradiated at the said 0 degreeC or more and 50 degrees C or less.
  • the solid electrolyte composition for an all-solid secondary battery of the present invention preferably contains a binder.
  • the binder used in the present invention is not particularly limited as long as it is an organic polymer.
  • the binder that can be used in the present invention is preferably a binder that is usually used as a binder for a positive electrode or a negative electrode of a battery material, and is not particularly limited.
  • a binder made of a resin described below is preferable.
  • fluorine-containing resin examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), a copolymer of polyvinylidene fluoride and hexafluoropropylene (PVdF-HFP), and the like.
  • hydrocarbon-based thermoplastic resin examples include polyethylene, polypropylene, styrene butadiene rubber (SBR), hydrogenated styrene butadiene rubber (HSBR), butylene rubber, acrylonitrile butadiene rubber, polybutadiene, and polyisoprene.
  • acrylic resin examples include poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate isopropyl, poly (meth) acrylate isobutyl, poly (meth) butyl acrylate, poly (meth) ) Hexyl acrylate, poly (meth) acrylate octyl, poly (meth) acrylate dodecyl, poly (meth) acrylate stearyl, poly (meth) acrylate 2-hydroxyethyl, poly (meth) acrylic acid, poly (meth) ) Benzyl acrylate, poly (meth) acrylate glycidyl, poly (meth) acrylate dimethylaminopropyl, and copolymers of monomers constituting these resins.
  • copolymers with other vinyl monomers are also preferably used.
  • examples thereof include poly (meth) acrylate methyl-polystyrene copolymer, poly (meth) acrylate methyl-acrylonitrile copolymer, poly (meth) acrylate butyl-acrylonitrile-styrene copolymer, and the like.
  • a polycondensation polymer can also be used.
  • the polycondensation polymer for example, urethane resin, urea resin, amide resin, imide resin, polyester resin, and the like can be suitably used.
  • the polycondensation polymer preferably has a hard segment part and a soft segment part.
  • the hard segment site indicates a site capable of forming an intermolecular hydrogen bond
  • the soft segment site generally indicates a flexible site having a glass transition temperature (Tg) of room temperature (25 ⁇ 5 ° C.) or lower and a molecular weight of 400 or higher. These may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the upper limit of the glass transition temperature of the binder is preferably 50 ° C. or lower, more preferably 0 ° C. or lower, and most preferably ⁇ 20 ° C. or lower.
  • the lower limit is preferably ⁇ 100 ° C. or higher, more preferably ⁇ 70 ° C. or higher, and particularly preferably ⁇ 50 ° C. or higher.
  • the glass transition temperature (Tg) is measured under the following conditions using a dry sample and a differential scanning calorimeter “X-DSC7000” (trade name, manufactured by SII Nanotechnology Co., Ltd.). The measurement is performed twice on the same sample, and the second measurement result is adopted.
  • Measurement chamber atmosphere Nitrogen (50 mL / min) Temperature increase rate: 5 ° C / min Measurement start temperature: -100 ° C Measurement end temperature: 200 ° C
  • Sample pan Aluminum pan Mass of measurement sample: 5 mg Calculation of Tg: Tg is calculated by rounding off the decimal point of the intermediate temperature between the lowering start point and the lowering end point of the DSC chart.
  • the water concentration of the polymer constituting the binder used in the present invention is preferably 100 ppm (mass basis) or less, and Tg is preferably 100 ° C. or less.
  • the solvent used for the polymerization reaction of the polymer is not particularly limited. It is desirable to use a solvent that does not react with the inorganic solid electrolyte or the active material and that does not decompose them.
  • hydrocarbon solvents toluene, heptane, xylene
  • ester solvents ethyl acetate, propylene glycol monomethyl ether acetate
  • ether solvents tetrahydrofuran, dioxane, 1,2-diethoxyethane
  • ketone solvents acetone
  • Methyl ethyl ketone Methyl ethyl ketone, cyclohexanone
  • nitrile solvents acetonitrile, propionitrile, butyronitrile, isobutyronitrile
  • halogen solvents dichloromethane, chloroform
  • the polymer constituting the binder used in the present invention preferably has a mass average molecular weight of 10,000 or more, more preferably 20,000 or more, and even more preferably 50,000 or more. As an upper limit, 1,000,000 or less is preferable, 200,000 or less is more preferable, and 100,000 or less is more preferable.
  • the molecular weight of the polymer means a mass average molecular weight unless otherwise specified. The mass average molecular weight can be measured as a molecular weight in terms of polystyrene by GPC.
  • GPC device HLC-8220 manufactured by Tosoh Corporation
  • G3000HXL + G2000HXL is used as the column
  • the flow rate is 1 mL / min at 23 ° C.
  • detection is performed by RI.
  • the eluent can be selected from THF (tetrahydrofuran), chloroform, NMP (N-methyl-2-pyrrolidone), m-cresol / chloroform (manufactured by Shonan Wako Pure Chemical Industries, Ltd.) and dissolves. If present, use THF.
  • the content of the binder in the solid electrolyte composition for an all-solid-state secondary battery is 100% by mass of the solid component in consideration of a good interfacial resistance reduction property and its maintainability when used in an all-solid-state secondary battery. 0.01% by mass or more is preferable, 0.1% by mass or more is more preferable, and 1% by mass or more is more preferable. As an upper limit, from a viewpoint of a battery characteristic, 20 mass% or less is preferable, 10 mass% or less is more preferable, and 10 mass% or less is further more preferable.
  • the mass ratio [(mass of inorganic solid electrolyte + mass of electrode active material) / mass of binder] of the total mass (total amount) of the inorganic solid electrolyte and the electrode active material to be included if necessary with respect to the mass of the binder is: A range of 1,000 to 1 is preferred. This ratio is more preferably 500 to 2, and further preferably 100 to 10.
  • the binder used in the present invention is a polymer particle that retains the particle shape.
  • PMMA poly (meth) methyl acrylate
  • PMMA-PMA poly (methyl methacrylate-methacrylic acid) copolymer
  • PMMA-PHM poly (methyl methacrylate-ethyl methacrylate phosphate) copolymer
  • -PHM poly (meth) methyl acrylate
  • the “polymer particles” refer to particles that do not completely dissolve even when added to the dispersion medium described later, and are dispersed in the dispersion medium in the form of particles and exhibit an average particle diameter of more than 0.01 ⁇ m.
  • the shape of the polymer particles is not limited as long as they are solid.
  • the polymer particles may be monodispersed or polydispersed.
  • the polymer particles may be spherical or flat and may be amorphous.
  • the surface of the polymer particles may be smooth or may have an uneven shape.
  • the polymer particles may have a core-shell structure, and the core (inner core) and the shell (outer shell) may be made of the same material or different materials. Moreover, it may be hollow and the hollow ratio is not limited.
  • the polymer particles can be synthesized by a method of polymerizing in the presence of a surfactant, an emulsifier or a dispersant, or a method of depositing in a crystalline form as the molecular weight increases. Moreover, you may use the method of crushing the existing polymer mechanically, and the method of making a polymer liquid fine particle by reprecipitation.
  • the average particle diameter of the polymer particles is preferably 0.01 ⁇ m to 100 ⁇ m, more preferably 0.05 ⁇ m to 50 ⁇ m, further preferably 0.1 ⁇ m to 20 ⁇ m, and particularly preferably 0.2 ⁇ m to 10 ⁇ m.
  • the average particle size of the polymer particles used in the present invention shall be based on the measurement conditions and definitions described below.
  • the polymer particles are diluted and prepared in a 20 ml sample bottle using an arbitrary solvent (dispersion medium used for preparation of the solid electrolyte composition for an all-solid-state secondary battery, for example, heptane).
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes and used immediately after that.
  • the measurement from the produced all-solid-state secondary battery is performed, for example, after disassembling the battery and peeling off the electrode, then measuring the electrode material according to the method for measuring the average particle diameter of the polymer particles, This can be done by eliminating the measured value of the average particle diameter of the particles other than the polymer particles that have been measured.
  • a commercial item can be used for the binder used for this invention. Moreover, it can also prepare by a conventional method.
  • the solid electrolyte composition for an all-solid secondary battery of the present invention preferably contains a lithium salt.
  • a lithium salt the lithium salt normally used for this kind of product is preferable and there is no restriction
  • the content of the lithium salt is preferably 0 parts by mass or more, more preferably 5 parts by mass or more with respect to 100 parts by mass of the solid electrolyte.
  • As an upper limit 50 mass parts or less are preferable, and 20 mass parts or less are more preferable.
  • the composition for all-solid-state secondary batteries of this invention contains a dispersing agent. Since the organic compound group is supported on the particle surface, the wettability with the dispersant is improved, which is preferable from the viewpoint of improving the binding property.
  • the dispersant is preferably composed of a low molecular weight or oligomer having a molecular weight of 200 or more and less than 3000, and at least one selected from the following functional group group (I) and an alkyl group having 8 or more carbon atoms or 10 or more carbon atoms. It is preferable to contain an aryl group in the same molecule.
  • Functional group (I) acidic group, group having basic nitrogen atom, (meth) acryl group, (meth) acrylamide group, alkoxysilyl group, epoxy group, oxetanyl group, isocyanate group, cyano group, mercapto group and hydroxy Base
  • the molecular weight of the dispersant is more preferably 300 or more and less than 2000, and particularly preferably 500 or more and less than 1000.
  • the molecular weight of the dispersant is more preferably 300 or more and less than 2000, and particularly preferably 500 or more and less than 1000.
  • an acidic group for example, carboxy group, sulfonic acid group, phosphoric acid group
  • a group having a basic nitrogen atom (for example, amino group) or a cyano group is preferable, and an acidic group is more preferable.
  • the acidic groups a carboxy group is particularly preferable.
  • the dispersant has an alkyl group having 8 or more carbon atoms or an aryl group having 10 or more carbon atoms.
  • the alkyl group having 8 or more carbon atoms may be an alkyl group having 8 or more carbon atoms in total, and may be linear, branched, cyclic, or hydrocarbon, and is not limited to a carbon-carbon bond. A hetero atom may be contained in between.
  • the alkyl group having 8 or more carbon atoms may be unsubstituted, may further have a substituent, and when it has a substituent, the substituent is preferably a halogen atom.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
  • the alkyl group having 8 or more carbon atoms is preferably an alkyl group having 8 to 50 carbon atoms, more preferably an alkyl group having 8 to 30 carbon atoms, still more preferably an alkyl group having 8 to 20 carbon atoms, 8 to 18 alkyl groups are particularly preferred.
  • normal octyl group normal decyl group, normal dodecyl group, normal tetradecyl group, normal hexadecyl group, stearyl group, lauryl group, linol group, linolene group, 2-ethylhexyl group, 2-ethyloctyl group, Examples thereof include 2-ethyldodecyl group, polyethylene glycol monomethyl group, perfluorooctyl group, and perfluorododecyl group.
  • normal octyl group 2-ethylhexyl group, normal nonyl group, normal decyl group, normal undecyl group, normal dodecyl group, normal tetradecyl group or normal octadecyl group (stearyl group) are preferable.
  • alkyl group having 8 or more carbon atoms has a substituent
  • substituents include an aryl group having 6 or more carbon atoms such as a phenyl group or a naphthyl group, or a halogen atom.
  • an alkyl group substituted with an aryl group or a halogenated alkyl group substituted with a halogen may be used.
  • the aryl group having 10 or more carbon atoms may be an aryl group having a total carbon number of 10 or more, and is not limited to being a hydrocarbon, and may contain a hetero atom between carbon-carbon bonds.
  • the aryl group having 10 or more carbon atoms may be unsubstituted or may further have a substituent.
  • the substituent is preferably a halogen atom.
  • the aryl group having 10 or more carbon atoms is preferably an aryl group having 10 to 50 carbon atoms, more preferably an aryl group having 10 to 30 carbon atoms, still more preferably an aryl group having 10 to 20 carbon atoms,
  • An aryl group of 10 to 18 is particularly preferred.
  • Specific examples include a naphthyl group, anthracenyl group, pyrenyl group, terphenyl group, naphthacenyl group, pentacenyl group, benzopyrenyl group, chrysenyl group, triphenylenyl group, corannulenyl group, coronenyl group, and obalenyl group.
  • a condensed aromatic hydrocarbon group is preferable.
  • the substituent include an alkyl group having 8 or more carbon atoms such as a normal octyl group or a halogen atom.
  • an aryl group substituted with an alkyl group may be used.
  • a particularly preferred combination is a combination having a carboxy group and an alkyl group having 8 or more carbon atoms in the same molecule.
  • a long-chain saturated fatty acid or a long-chain unsaturated fatty acid can be used more suitably.
  • it has two or more groups represented by the functional group (I) in the same molecule, and two or more alkyl groups having 8 or more carbon atoms or two or more aryl groups having 10 or more carbon atoms.
  • the solid electrolyte composition for an all-solid secondary battery of the present invention may contain a dispersion medium. Any dispersion medium may be used as long as it can disperse the above-described components. Specific examples thereof include the following.
  • alcohol compound solvents examples include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, t-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, and sorbitol.
  • ether compound solvent examples include alkylene glycol alkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether (diglyme), triethylene glycol.
  • alkylene glycol alkyl ether ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether (diglyme), triethylene glycol.
  • amide compound solvent examples include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ⁇ -caprolactam, formamide, N-methylformamide, and acetamide. , N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide.
  • amino compound solvent examples include triethylamine, diisopropylethylamine, and tributylamine.
  • ketone compound solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diisobutyl ketone.
  • aromatic compound solvent examples include benzene, toluene, and xylene.
  • the ester compound solvent is, for example, ethyl acetate, propyl acetate, butyl acetate, ethyl formate, propyl formate, butyl formate, ethyl lactate, propylene glycol monomethyl ether acetate, methyl isobutyrate, isopropyl isobutyrate, methyl pivalate, isopropyl cyclohexanecarboxylate Is mentioned.
  • Examples of the aliphatic compound solvent include pentane, hexane, heptane, octane, decane, and cyclohexane.
  • nitrile compound solvent examples include acetonitrile, propyronitrile, and butyronitrile.
  • the said dispersion medium may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the dispersion medium preferably has a boiling point of 50 ° C. or higher, more preferably 70 ° C. or higher at normal pressure (1 atm).
  • the upper limit is preferably 250 ° C. or lower, and more preferably 220 ° C. or lower.
  • an alcohol compound solvent preferably t-butanol
  • an ether compound solvent preferably dibutyl ether, propylene glycol dimethyl ether, diglyme
  • an amide compound solvent preferably N, N-dimethylformamide
  • an aromatic compound solvent preferably toluene
  • an ester compound solvent preferably propylene glycol monomethyl ether acetate
  • an aliphatic compound solvent preferably heptane
  • the dispersion medium comprising an ester compound solvent and a hydrocarbon solvent
  • a hydrocarbon solvent is particularly preferable.
  • the hydrocarbon solvent include the aromatic compound solvent and the aliphatic compound solvent.
  • the water content of the solid electrolyte composition for an all solid secondary battery of the present invention is preferably 50 ppm or less, more preferably 40 ppm or less. 30 ppm or less is more preferable.
  • the lower limit of the moisture content is not particularly limited, but 0.001 ppm or more is practical.
  • the moisture content of the solid electrolyte composition for all-solid-state secondary batteries can be measured by the Karl Fischer method.
  • a trace moisture measuring device CA-200 (trade name, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) may be used as the measuring device, and Aquamicron AX (trade name, manufactured by Mitsubishi Chemical Corporation) may be used as the Karl Fischer liquid. it can.
  • Aquamicron AX (trade name, manufactured by Mitsubishi Chemical Corporation) may be used as the Karl Fischer liquid.
  • the content of the dispersion medium is preferably 10 to 300 parts by mass, more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the total solid content of the solid electrolyte composition for an all-solid secondary battery.
  • the positive electrode current collector and the negative electrode current collector are preferably electron conductors.
  • the positive electrode current collector is preferably made by treating the surface of aluminum or stainless steel with carbon, nickel, titanium or silver in addition to aluminum, stainless steel, nickel, titanium, etc. Among them, aluminum and aluminum alloys are more preferable. preferable.
  • the current collector of the negative electrode is preferably aluminum, copper, stainless steel, nickel, or titanium, and more preferably aluminum, copper, or a copper alloy.
  • 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 ⁇ m to 500 ⁇ m.
  • the current collector surface is roughened by surface treatment.
  • the all-solid-state secondary battery may be manufactured by a conventional method. Specifically, the solid electrolyte composition for an all-solid-state secondary battery of the present invention is applied on a metal foil as a current collector to form an electrode sheet for an all-solid-state secondary battery in which a coating film is formed. .
  • the electrode layer contains an active material. From the viewpoint of improving ion conductivity, the electrode layer preferably contains the inorganic solid electrolyte.
  • the electrode layer preferably contains a binder from the viewpoint of improving the binding between the solid particles, between each layer, and between the electrode active material layer and the current collector.
  • the solid electrolyte layer contains an inorganic solid electrolyte. From the viewpoint of improving the binding between the solid particles and between the layers, the solid electrolyte layer preferably also contains a binder.
  • a solid electrolyte composition for an all-solid secondary battery of the present invention as a positive electrode material is applied onto a metal foil that is a positive electrode current collector, a positive electrode active material layer is formed, and a positive electrode sheet for an all-solid secondary battery is formed. Make it.
  • a composition for forming a solid electrolyte layer is applied on the positive electrode active material layer to form a solid electrolyte layer.
  • the solid electrolyte composition for an all-solid-state secondary battery of the present invention which is a negative electrode material, is applied to form a negative electrode active material layer.
  • coating method of said each composition should just follow a conventional method.
  • the solid electrolyte composition for an all-solid-state secondary battery of the present invention for forming the positive electrode active material layer, the composition for forming the inorganic solid electrolyte layer, and the book for forming the negative electrode active material layer The solid electrolyte composition for an all-solid-state secondary battery of the invention may be subjected to a drying treatment after being applied, or may be subjected to a drying treatment after being applied in multiple layers.
  • the drying temperature is not particularly limited.
  • the lower limit is preferably 30 ° C or higher, more preferably 60 ° C or higher, and the upper limit is preferably 300 ° C or lower, more preferably 250 ° C or lower. By heating in such a temperature range, a dispersion medium can be removed and it can be set as a solid state.
  • the all solid state secondary battery of the present invention can be applied to various uses. Although there is no particular limitation on the application mode, for example, when installed in an electronic device, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a mobile phone, a cordless phone, a pager, a handy terminal, a mobile fax machine, a mobile phone Copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, mini-disc, electric shaver, transceiver, electronic notebook, calculator, memory card, portable tape recorder, radio, backup power supply, etc.
  • Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military use and space use. Moreover, it can also combine with a solar cell.
  • a solid electrolyte composition for a secondary battery positive electrode or negative electrode composition).
  • Secondary battery electrode sheet [3] An all-solid secondary battery configured using the electrode sheet for an all-solid secondary battery.
  • a method for producing an electrode sheet for an all-solid-state secondary battery wherein the solid electrolyte composition for an all-solid-state secondary battery is applied onto a metal foil to form a film.
  • a method for producing an electrode sheet for an all-solid-state secondary battery wherein the solid electrolyte composition for an all-solid-state secondary battery is coated with a wet slurry.
  • a method for producing an all-solid-state secondary battery wherein an all-solid-state secondary battery is produced via the above-described method for producing an electrode sheet for an all-solid-state secondary battery.
  • the solid electrolyte composition for an all-solid-state secondary battery of the present invention for example, coating (wet coating, spray coating, spin coating coating, slit coating, stripe coating, bar coating coating) Dip coating), and wet coating (coating) is preferred.
  • An all-solid secondary battery refers to a secondary battery in which the positive electrode, the negative electrode, and the electrolyte are all solid. In other words, it is distinguished from an electrolyte type secondary battery using a carbonate-based solvent as an electrolyte.
  • this invention presupposes an inorganic all-solid-state secondary battery.
  • the all-solid-state secondary battery includes an organic (polymer) all-solid-state secondary battery that uses a polymer compound such as polyethylene oxide as an electrolyte, and an inorganic all-solid-state that uses the above-described Li—PS glass, LLT, LLZ, or the like. It is divided into secondary batteries.
  • the application of the polymer compound to the inorganic all-solid secondary battery is not hindered, and the polymer compound can be applied as a binder for the positive electrode active material, the negative electrode active material, and the inorganic solid electrolyte.
  • the inorganic solid electrolyte is distinguished from an electrolyte (polymer electrolyte) using the above-described polymer compound as an ion conductive medium, and the inorganic compound serves as an ion conductive medium. Specific examples include the above-described Li—PS glass, LLT, and LLZ.
  • the inorganic solid electrolyte itself does not release cations (Li ions) but exhibits an ion transport function.
  • electrolyte a material that is added to the electrolytic solution or the solid electrolyte layer and serves as a source of ions that release cations (Li ions) is sometimes called an electrolyte.
  • electrolyte salt When distinguishing from the electrolyte as the above ion transport material, this is called “electrolyte salt” or “supporting electrolyte”.
  • electrolyte salt An example of the electrolyte salt is LiTFSI.
  • composition means a mixture in which two or more components are uniformly mixed. However, as long as the uniformity is substantially maintained, aggregation or uneven distribution may partially occur within a range in which a desired effect is achieved.
  • Li 2 S lithium sulfide
  • P 2 S 5 diphosphorus pentasulfide
  • 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.
  • This container is set in 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 solid electrolyte (Li-PS system). 6.20 g of glass) was obtained.
  • Teflon (registered trademark, EI DuPont de Nemours & Co.) vat is conditioned with LCO (LiCoO 2 , lithium cobaltate) 20 g in a uniform manner and put into a UV processing apparatus OPL1102 (trade name, manufactured by Mario Network) At room temperature, nitrogen gas was blown into the apparatus for 10 minutes to form a nitrogen atmosphere. This was irradiated with UV for 60 minutes to obtain a surface-treated LCO powder. Further, the surface-treated LCO powder was exposed to moisture in air (room temperature, humidity 50%) for about 3 minutes.
  • LCO LiCoO 2 , lithium cobaltate
  • the surface-treated LCO powder was added to a 100 mL sample bottle, a diluted solution of 50 g of toluene in 1 g of tricosafluorododecanoic acid chloride was added, and the mixture was rotated and stirred at room temperature for 24 hours by a rotor. After stirring, the solution was filtered, and the filtrate was washed with toluene and dried at 100 ° C. for 6 hours to obtain particles YR-11. Note that organic substances that were not covalently bonded to the particles were washed by washing with toluene. Similarly, particles YR-21 and YR-31 shown in Table 1 described later were obtained.
  • the powder of the particle YR-11 was observed with a transmission electron microscope (TEM) (trade name: JEM-3200FS (manufactured by JEOL)), and the thickness of the surface-modified portion was measured. It was 6 nm.
  • TEM transmission electron microscope
  • the specific surface area was measured by the BET method as follows. A BET specific surface area was measured by a one-point method using liquid nitrogen using a fully automatic specific surface area measuring device manufactured by Mountec Co., Ltd., trade name “Macsorb HM model-1208”. The specific surface area of LCO was 2.2 ⁇ 10 4 cm 2 / g.
  • the mass of the organic compound that became the organic compound group that modifies the surface of the particle YR-11 was determined by the volatile content in TG / DTA (thermal analyzer DTG-60H, trade name, manufactured by Shimadzu Corporation). .
  • the mass of the organic compound was 0.003 g per 1 g of particles.
  • EB treatment- [Preparation of Particle YR-12] Acquire 20g of LCO powder in a Teflon bat so that it is uniform, and place it in an EB processing device EC250 / 15 / 180L (trade name, manufactured by I. Electron Beam Co., Ltd.). And surface-treated LCO powder was obtained. Further, the surface-treated LCO powder was exposed to moisture in air (room temperature, humidity 50%) for about 3 minutes.
  • the surface-treated LCO powder was added to a 100 mL sample bottle, and a 50 g diluted solution of 1 g of dodecyl methacrylate in toluene was added thereto, and the mixture was rotated and stirred at room temperature for 24 hours by a rotor. After stirring, the solution was filtered, and the filtrate was washed with toluene and dried at 100 ° C. for 6 hours to obtain particles YR-12. Note that organic substances that were not covalently bonded to the particles were washed by washing with toluene.
  • Irradiation temperature Room temperature (25 ° C)
  • Distance between LCO powder and atmospheric pressure powder plasma device nozzle 100 mm
  • Output 250W
  • the LCO powder after the low-temperature plasma treatment is exposed to moisture in air (room temperature, humidity 50%) for about 3 minutes, it is added to a 100 mL sample bottle, a diluted solution of 50 g of toluene of 1 g of undecene acrylate is added to the rotor, The mixture was stirred at room temperature for 24 hours. This was filtered, washed with toluene, and dried at 100 ° C. for 6 hours to obtain particles YR-13. Similarly, particles YR-14, particles YR-22 to 24, particles YR-32 to 36, particles YR-41, particles YR-42 and particles YR-51 to 53 shown in Table 1 described later were obtained.
  • LCO LiCoO 2 (lithium cobaltate)
  • LLZ Li 7 La 3 Zr 2 O 12 (Lithium lanthanum zirconate, average particle size 5.06 ⁇ m, manufactured by Toshima Seisakusho)
  • Li-PS Li-PS system glass AB synthesized above: Acetylene black
  • D-1 Surface-supported tricosafluorododecanoic acid ester group (organic compound: tricosafluorododecanoic acid chloride) (Mw 614)
  • D-2 Surface-supported polydodecyl methacrylate group (organic compound: dodecyl methacrylate) (Mw8900)
  • D-3 Surface-supported polyacrylic acid undecene group (organic compound: acrylic acid undecene) (Mw7500)
  • D-4 Surface-supported poly (methacrylic acid silicone) group (organic compound: silicone methacrylate (Shin-Etsu Silicone x-22-174
  • a solid electrolyte composition slurry for an all-solid-state secondary battery After applying the solid electrolyte composition slurry for an all-solid-state secondary battery to an aluminum foil having a thickness of 20 ⁇ m with an applicator (trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.) and heating at 80 ° C. for 1 hour. Further, the dispersion medium was dried by heating at 120 ° C. for 1 hour.
  • an applicator trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.
  • the electrode active material layer was pressurized while being heated (150 ° C.) using a heat press machine (600 MPa, 10 seconds), and the electrode sheet S-1 for an all-solid-state secondary battery having an electrode active material layer thickness of 150 ⁇ m. Got.
  • electrode sheets S-2 to S-10 and HS-1 to HS-4 for all solid state secondary batteries were obtained.
  • the usage-amount of a negative electrode active material is 8.0g
  • the usage-amount of a conductive support agent is 0.5g.
  • composition slurry for forming solid electrolyte layer [Preparation of composition slurry for forming solid electrolyte layer]
  • a 45 mL zirconia container manufactured by Fritsch
  • 180 zirconia beads having a diameter of 5 mm were charged, 5 g of a surface-modified inorganic solid electrolyte (particle YR-35), and 10 g of propylene glycol monomethyl ether acetate as a dispersion medium.
  • this container was set in a planetary ball mill P-7 (manufactured by Fritsch), and stirring was continued for 2 hours at a temperature of 25 ° C. and a rotation speed of 300 rpm to prepare a composition slurry for forming a solid electrolyte layer.
  • the positive electrode active material layer forming composition slurry was applied onto an aluminum foil having a thickness of 20 ⁇ m by an applicator (trade name SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.), heated at 80 ° C. for 1 hour, The dispersion medium was dried by heating at 120 ° C. for 1 hour. Thereafter, using a heat press, the electrode active material layer was pressurized while being heated (150 ° C.) (600 MPa, 10 seconds) to obtain a positive electrode sheet for an all-solid-state secondary battery having a positive electrode active material layer thickness of 150 ⁇ m. .
  • the solid electrolyte layer forming composition slurry is applied onto the positive electrode sheet for an all-solid-state secondary battery prepared above by an applicator (trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.), and 80 ° C. And then heated at 110 ° C. for 1 hour to form a solid electrolyte layer having a thickness of 50 ⁇ m. Thereafter, the negative electrode active material layer-forming composition slurry prepared above was further applied, heated at 80 ° C. for 1 hour, and further heated at 110 ° C. for 1 hour to form a negative electrode active material layer having a thickness of 100 ⁇ m.
  • an applicator trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.
  • An all-solid-state secondary battery electrode sheet HS-5 was obtained in the same manner as the all-solid-state secondary battery electrode sheet S-11 except that the components listed in Table 2 below were used.
  • the amount of the conductive aid used for each slurry is 0.5 g.
  • S-1 to S-11 are all-solid-state secondary battery electrode sheets that satisfy the provisions of the present invention, and HS-1 to HS-5 are all-solid-state secondary battery electrode sheets for comparison.
  • Table 2 the electrode sheet for an all-solid-state secondary battery is described as “sheet”.
  • the obtained electrode sheet for an all-solid-state secondary battery was subjected to a 180 ° peel strength test (JIS Z0237-2009).
  • An adhesive tape (width 24 mm, length 300 mm) (trade name: Cellotape CT-24, manufactured by Nichiban Co., Ltd.) was attached to the electrode active material layer of the electrode sheet for an all-solid-state secondary battery.
  • One end of the electrode sheet was fixed, and an adhesive tape was fixed to the upper jig.
  • the test was carried out at a load speed of 300 mm / min. After the measurement was started, the 25 mm adhesive tape was peeled off, and then the measured adhesive strength value for each 0.05 mm of the 50 mm length peeled from the electrode active material layer was averaged, and the peel adhesive value (average peel strength) (N)). The higher the average peel strength, the higher the binding force.
  • the peel strength was measured by combining a standard type digital force gauge ZTS-5N and a vertical electric measurement stand MX2 series (both trade names, manufactured by Imada Co., Ltd.). For the all-solid-state secondary battery electrode sheets S-11 and HS-5, the above test was performed on the negative electrode active material layer.
  • the electrode sheet for an all-solid secondary battery containing the particles for an all-solid secondary battery of the present invention in which the particle surface is modified with an organic compound group, has high peel strength and binding properties. It is understood that it is excellent. From Table 2 above, it is clear that the all-solid-state secondary battery of the present invention has high peel strength and excellent binding properties.

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Abstract

L'invention concerne un accumulateur tout solide qui comprend des particules d'électrolyte solide inorganiques possédant de la conductivité d'ions d'un métal appartenant au groupe 1 ou au groupe 2 du tableau périodique, et des particules de matériau actif d'électrode. Des groupes de composés organiques sont tenus sur les surfaces des particules d'électrolyte solide inorganiques et/ou les particules de matériau actif d'électrode par des liaisons covalentes, et la quantité de liaisons covalentes sur les surfaces des particules est supérieure ou égale à 1 × 10-10 mol/cm2. L'invention concerne également : des particules destinées à des accumulateurs tout solide; une composition d'électrolyte solide destinée à des accumulateurs tout solide, une feuille d'électrode destinée à des accumulateurs tout solide et l'accumulateur tout solide qui utilisent les particules destinées à des accumulateurs tout solide; et leurs procédés de fabrication.
PCT/JP2016/088572 2015-12-25 2016-12-22 Accumulateur tout solide, particules destinées à des accumulateurs tout solide, composition d'électrolyte solide destinée à des accumulateurs tout solide, feuille d'électrode destinée à des accumulateurs tout solide, et leurs procédés de fabrication Ceased WO2017111131A1 (fr)

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JP2020126777A (ja) * 2019-02-05 2020-08-20 トヨタ自動車株式会社 全固体電池の製造方法
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JP2022141348A (ja) * 2021-03-15 2022-09-29 本田技研工業株式会社 固体電池用電極及びこれを備える固体電池

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JP2019503565A (ja) * 2016-01-25 2019-02-07 ハイドロ−ケベック コア−シェル電極材料粒子および電気化学セルにおけるこれらの使用
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JP2020126777A (ja) * 2019-02-05 2020-08-20 トヨタ自動車株式会社 全固体電池の製造方法
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WO2021166975A1 (fr) 2020-02-20 2021-08-26 国立大学法人静岡大学 Électrolyte solide, batterie secondaire et condensateur
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JP2022141348A (ja) * 2021-03-15 2022-09-29 本田技研工業株式会社 固体電池用電極及びこれを備える固体電池

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