WO2017104583A1 - Pile rechargeable tout solide, feuille d'électrode pour pile rechargeable tout solide, et procédé de fabrication desdites pile et feuille - Google Patents

Pile rechargeable tout solide, feuille d'électrode pour pile rechargeable tout solide, et procédé de fabrication desdites pile et feuille Download PDF

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WO2017104583A1
WO2017104583A1 PCT/JP2016/086820 JP2016086820W WO2017104583A1 WO 2017104583 A1 WO2017104583 A1 WO 2017104583A1 JP 2016086820 W JP2016086820 W JP 2016086820W WO 2017104583 A1 WO2017104583 A1 WO 2017104583A1
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secondary battery
solid
active material
positive electrode
negative electrode
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PCT/JP2016/086820
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English (en)
Japanese (ja)
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目黒　克彦
宏顕 望月
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富士フイルム株式会社
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Priority to JP2017556032A priority Critical patent/JP6640874B2/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or 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
    • H01M4/13—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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • 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-state secondary battery, an electrode sheet for an all-solid-state secondary battery, and methods for producing them.
  • a lithium ion secondary battery is a storage battery that has a negative electrode, a positive electrode, and an electrolyte sandwiched between the negative electrode and the positive electrode, and can be charged and discharged by reciprocating lithium ions between the two electrodes.
  • an organic electrolytic solution has been used as an electrolyte in a lithium ion secondary battery.
  • the organic electrolyte is liable to leak, and there is a possibility that a short circuit occurs inside the battery due to overcharge and overdischarge, resulting in ignition, and further improvements in reliability and safety are required. Under such circumstances, an all-solid secondary battery using an inorganic solid electrolyte instead of an organic electrolyte has been attracting attention.
  • the all-solid-state secondary battery consists of a solid negative electrode, electrolyte, and positive electrode, which can greatly improve safety and reliability, which is a problem of batteries using organic electrolytes, and can extend the service life. It will be. Furthermore, the all-solid-state secondary battery can have a structure in which electrodes and an electrolyte are directly arranged in series. Therefore, it is possible to increase the energy density compared to a secondary battery using an organic electrolyte, and application to an electric vehicle or a large storage battery is expected.
  • the electrode of the all-solid-state secondary battery has a current collector and an active material layer formed on the current collector.
  • a conductive film may be provided between the current collector and the active material layer for the purpose of improving the adhesion between the active material layer and the current collector or good ionic conductivity of the electrode (for example, Patent Document 1).
  • the inorganic solid electrolyte is usually fine particles, a certain amount of fine voids (also simply referred to as voids) are generated between the electrolyte particles forming the solid electrolyte layer. It is considered that reducing the voids between the particles greatly contributes to improvement of battery characteristics such as ion conductivity. This applies to the case where the electrode is formed using a particulate electrode active material, preferably a particulate inorganic solid electrolyte.
  • an all-solid-state secondary battery using solid particles such as an electrode active material or an inorganic solid electrolyte
  • a pressure load is applied to the solid particles of the inorganic solid electrolyte layer or the active material layer in order to exert a desired ionic conductivity.
  • the conductive film provided on the electrode is peeled off from the current collector, and the ionic conductivity between the current collector and the active material layer is lowered.
  • the inorganic solid electrolyte breaks through (breaks) the conductive film, or the electrode active material breaks through the conductive film provided on the counter electrode, and a short circuit occurs.
  • the present invention has an inorganic solid electrolyte layer closely packed with an inorganic solid electrolyte, it is possible to ensure the adhesion between the current collector and the conductive film and further prevent the occurrence of a short circuit. It is an object to provide a secondary battery and a manufacturing method thereof. Moreover, this invention makes it a subject to provide the electrode sheet for all-solid-state secondary batteries used suitably for the said all-solid-state secondary battery, and its manufacturing method.
  • the term “closely packed with an inorganic solid electrolyte” means that a fine void having no substance such as a binder (binder) between particles of the inorganic solid electrolyte substantially reduces ionic conductivity.
  • the level that does not have a substantial effect cannot be uniquely determined. For example, when the cross section (63 ⁇ m ⁇ 48 ⁇ m) of the all-solid-state secondary battery is observed with a scanning microscope at a magnification of 3000 times, It can be set to such an extent that voids originating from the interface (which cannot be uniquely determined, but usually have a diameter or major axis length of 1 ⁇ m or more) cannot be confirmed.
  • the present inventors examined the effect on the battery when a pressure load was applied.
  • the conductive film was formed into a thin film by vapor deposition or the like, In addition to this, by setting the surface of the current collector on which the conductive film is provided to a specific surface morphology, the interaction between the conductive film and the surface of the current collector is enhanced, and pressure is applied. It has been found that even when a load acts, high adhesion between the current collector and the conductive film can be secured, and occurrence of a short circuit can be prevented.
  • the present invention has been further studied based on these findings and has been completed.
  • An all solid state secondary battery comprising: The surface of the current collector of the positive electrode has an arithmetic average roughness Ra of 0.24 to 0.38 ⁇ m, and 10 to 80 recesses / 100 ⁇ m 2 having an average opening diameter of 0.3 to 3.0 ⁇ m. All-solid secondary battery.
  • the negative electrode has a conductive film and a negative electrode active material layer in this order on the surface of the current collector,
  • the surface of the current collector of the negative electrode has an arithmetic average roughness Ra of 0.24 to 0.38 ⁇ m, and 10 to 80 concave portions with an average opening diameter of 0.3 to 3.0 ⁇ m / 100 ⁇ m 2.
  • the all-solid-state secondary battery as described in ⁇ 1>.
  • ⁇ 3> The all-solid secondary according to ⁇ 1> or ⁇ 2>, wherein the surface has an arithmetic average roughness Ra of 0.25 to 0.31, and the number of recesses is 40 to 70/100 ⁇ m 2 battery.
  • ⁇ 4> The all-solid-state secondary battery according to any one of ⁇ 1> to ⁇ 3>, wherein the conductive film is a film of a metal, a metal oxide, or a carbonaceous material.
  • the conductive film is a film of a metal, a metal oxide, or a carbonaceous material.
  • a current collector having a surface having an arithmetic average roughness Ra of 0.24 to 0.38 ⁇ m and 10 to 80 concave portions with an average opening diameter of 0.3 to 3.0 ⁇ m / 100 ⁇ m 2
  • An electrode sheet for an all-solid-state secondary battery having a conductive film and an active material layer in this order on the surface.
  • a current collector having a surface having an arithmetic average roughness Ra of 0.24 to 0.38 ⁇ m and a recess having an average opening diameter of 0.3 to 3.0 ⁇ m of 10 to 80/100 ⁇ m 2
  • the manufacturing method of the electrode sheet for all-solid-state secondary batteries which forms a conductive film on the surface and then forms an active material layer.
  • ⁇ 8> The method for producing an electrode sheet for an all-solid-state secondary battery according to ⁇ 6> or ⁇ 7>, wherein the conductive film is formed by a vapor deposition method or a coating method using a metal, a metal oxide, or a carbonaceous material.
  • a method for producing an all-solid secondary battery including the method for producing an electrode sheet for an all-solid secondary battery according to any one of ⁇ 6> to ⁇ 8>.
  • 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 when “acryl” is simply described, it means methacryl and / or acryl.
  • the all-solid-state secondary battery of the present invention has an inorganic solid electrolyte layer closely packed with an inorganic solid electrolyte, it can ensure the adhesion between the current collector and the conductive film, and further, the occurrence of a short circuit. Can also be prevented.
  • the electrode sheet for all-solid-state secondary batteries of this invention can be used suitably for the all-solid-state secondary battery which has said outstanding characteristic.
  • the all solid state secondary battery of the present invention has a positive electrode, a negative electrode facing the positive electrode, and a solid electrolyte layer between the positive electrode and the negative electrode.
  • the positive electrode has a positive electrode conductive film and a positive electrode active material layer in this order on the surface of the positive electrode current collector.
  • the negative electrode has a negative electrode active material layer on the negative electrode current collector, and may have a negative electrode conductive film on the surface of the negative electrode current collector on which the negative electrode active material layer is formed.
  • the positive electrode current collector forming the positive electrode has a specific surface form (uneven structure) described later.
  • the surface on which the negative electrode conductive film is formed preferably has the same surface form as the positive electrode current collector.
  • 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 includes a negative electrode current collector 1, a negative electrode conductive film 7, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode conductive film as viewed from the negative electrode side. 8. It has a structure in which the positive electrode current collector 5 is laminated in this order, and adjacent layers are in direct contact with each other.
  • the positive electrode current collector 5 and the negative electrode current collector 1 are preferably electronic conductors. In the present invention, either or both of the positive electrode current collector and the negative electrode current collector may be simply referred to as a current collector.
  • a material for forming the positive electrode current collector aluminum, aluminum alloy, stainless steel, nickel, titanium and the like are preferable, and among them, aluminum and aluminum alloy are more preferable.
  • aluminum, copper, copper alloy, stainless steel, nickel, and titanium are preferable, and aluminum, copper, and copper alloy are more preferable.
  • the shape of the current collector is usually a film sheet, but if a conductive film can be formed, the net, punched, lath, porous, foam, and fiber group are formed.
  • the body can also be used.
  • the thickness of the current collector is not particularly limited, but is preferably 1 to 500 ⁇ m.
  • the positive electrode current collector has the following surface form on the surface on which the positive electrode conductive film is formed.
  • Arithmetic mean roughness Ra is 0.24 to 0.38 ⁇ m
  • the number of recesses having an average opening diameter of 0.3 to 3.0 ⁇ m is 10 to 80/100 ⁇ m 2
  • the arithmetic average roughness Ra is 0.24 to 0.38 ⁇ m.
  • the arithmetic average roughness Ra is smaller than 0.24 ⁇ m, the adhesion between the positive electrode current collector and the positive electrode conductive film is not sufficient, and the positive electrode conductive film may be peeled off from the positive electrode current collector.
  • the arithmetic average roughness Ra is larger than 0.38 ⁇ m, the all solid state secondary battery may be short-circuited. Further, the positive electrode conductive film may be peeled off.
  • Arithmetic average roughness Ra is preferably 0.25 to 0.37 ⁇ m, more preferably 0.25 to 0.31 ⁇ m, in terms of adhesion between the positive electrode current collector and the positive electrode conductive film and prevention of occurrence of short circuit. preferable.
  • the arithmetic average roughness Ra is an arithmetic average roughness measured according to JIS B0601: 2010 using a stylus type surface roughness meter (for example, a surface roughness measuring machine SJ-401 manufactured by Mitutoyo Corporation). .
  • the positive electrode current collector has a recess on its surface.
  • the concave portion is not particularly limited with respect to the average opening diameter, but the concave portion having an average opening diameter of 0.3 to 3.0 ⁇ m includes the adhesion between the positive electrode current collector and the positive electrode conductive film, And it is important in terms of preventing the occurrence of short circuits.
  • the average opening diameter of the recesses is preferably 0.8 to 3.0 ⁇ m.
  • the surface of the positive electrode current collector has 10 to 80 recesses having an average opening diameter of 0.3 to 3.0 ⁇ m per surface area of 100 ⁇ m 2 .
  • the number of concave portions with the average opening diameter per unit surface area (sometimes referred to as the number of concave portions) is less than 10, the adhesion between the positive electrode current collector and the positive electrode conductive film is not sufficient, and the positive electrode current collector In some cases, the positive electrode conductive film may peel off.
  • the number of recesses is more than 80, the peripheral edge of each opening becomes a protrusion, and the short circuit may increase during a pressure load.
  • the number of recesses is preferably 15 to 70, more preferably 20 to 70, and still more preferably 40 to 70.
  • the interaction with the positive electrode conductive film formed on the thin film is increased, and a pressure load force is applied during and after production. Even if the inorganic solid electrolyte is closely packed, the adhesion between the positive electrode current collector and the positive electrode conductive film and the occurrence of a short circuit can be achieved at a high level.
  • the opening diameter of a recessed part means the opening diameter of a recessed part, and the average opening diameter of a recessed part is the average value.
  • SEM scanning electron microscope
  • the surface of the positive electrode current collector was photographed at a magnification of 2000 times from directly above, and in the obtained SEM image, the periphery (“the opening of the recess was defined).
  • At least 50 concave portions having a substantially circular shape (annular shape) are extracted, and the diameter is read as an opening diameter to calculate an average opening diameter.
  • one recessed part overlaps with another recessed part, it does not extract as a recessed part.
  • a recess having an opening diameter of 0.3 to 3.0 ⁇ m existing in a 10 ⁇ m ⁇ 10 ⁇ m region (arbitrary three regions) (limited to a recess in which the edge of the opening is continuous in an annular shape) Is counted for each region, and the average value is calculated as the number of recesses (pieces / 100 ⁇ m 2 ).
  • the surface form of the negative electrode current collector is not particularly limited, it is preferable that the negative electrode current collector has a surface form satisfying the above (1) and (2) as in the positive electrode current collector. In this case, the surface forms of the positive electrode current collector and the negative electrode current collector may be the same or different.
  • the conductive film (positive electrode conductive film) 8 forming the positive electrode may be any film formed of a conductive material.
  • the conductive material include conductive particles such as metals, metal oxides, and carbonaceous materials.
  • the metal include copper, nickel, chromium, aluminum, platinum, silver, zinc, titanium, indium, antimony, bismuth, cobalt, tungsten, molybdenum, and alloys thereof.
  • the metal oxide the said metal oxide is mentioned, for example.
  • As a carbonaceous material the carbonaceous material demonstrated with the conductive support agent mentioned later is mentioned, for example.
  • metals or carbonaceous materials are preferable, carbonaceous materials are more preferable, and graphite or carbon nanotubes (CNT) are more preferable.
  • the film thickness of the positive electrode conductive film is not particularly limited, but is preferably 0.05 to 50 ⁇ m, more preferably 0.1 to 30 ⁇ m in terms of adhesion to the positive electrode current collector, stress relaxation under pressure load, and the like. preferable.
  • the positive electrode conductive film is not a solid fine particle of a conductive material, but is formed into a thin film by a coating (printing) method, a vapor deposition method, a plating method, or the like, and has an adhesive property with a positive electrode current collector and a conductive material. From the viewpoint of improving the property, it is preferable.
  • This positive electrode conductive film preferably has a low volume resistivity because of its characteristics, and those having a volume resistivity of 0.5 ⁇ -cm or less, for example, 1 ⁇ 10 ⁇ 1 to 1 ⁇ 10 ⁇ 5 ⁇ -cm are used. it can.
  • the volume resistivity is preferably 5 ⁇ 10 ⁇ 2 to 5 ⁇ 10 ⁇ 5 ⁇ -cm, more preferably 1 ⁇ 10 ⁇ 2 to 1 ⁇ 10 ⁇ 4 ⁇ -cm.
  • the negative electrode conductive film is synonymous with the positive electrode conductive film, and preferable ones are also the same.
  • the type and thickness of the material having conductivity may be the same as or different from those of the positive electrode conductive film.
  • either or both of the positive electrode conductive film and the negative electrode conductive film may be simply referred to as a conductive film.
  • 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. Considering general battery dimensions, the thickness of each of the above layers 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.
  • the solid electrolyte layer 3 contains an inorganic solid electrolyte, and preferably contains a binder from the viewpoint of improving the binding between solid particles and between layers.
  • the solid electrolyte layer usually does not contain a positive electrode active material and / or a negative electrode active material.
  • the positive electrode active material layer 4 and the negative electrode active material layer 2 each contain a positive electrode active material or a negative electrode active material, and preferably contain a solid electrolyte from the viewpoint of improving ion conductivity.
  • Each active material layer preferably contains a binder from the viewpoint of improving the binding between the solid particles, the active material layer-solid electrolyte layer, and the active material layer-conductive film.
  • the inorganic solid electrolyte and the binder contained in the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 may be the same or different from each other.
  • one or both of the positive electrode active material and the negative electrode active material may be simply referred to as an active material or an electrode active material.
  • One or both of the positive electrode active material layer and the negative electrode active material layer may be simply referred to as an active material layer.
  • the inorganic solid electrolyte is an inorganic solid electrolyte, and the solid electrolyte is a solid electrolyte capable of moving ions inside. Since it does not contain organic substances as the main ion conductive material, organic solid electrolytes (polymer electrolytes typified by polyethylene oxide (PEO), etc., organics typified by lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), etc. It is clearly distinguished from the electrolyte salt). Further, since the inorganic solid electrolyte is solid in a steady state, it is not dissociated or released into cations and anions.
  • organic solid electrolytes polymer electrolytes typified by polyethylene oxide (PEO), etc.
  • LiTFSI lithium bis (trifluoromethanesulfonyl) imide
  • inorganic electrolyte salts LiPF 6 , LiBF 4 , lithium bis (fluorosulfonyl) imide (LiFSI), LiCl, etc.
  • LiPF 6 lithium bis (fluorosulfonyl) imide
  • LiFSI lithium bis (fluorosulfonyl) imide
  • LiCl 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 inorganic solid electrolyte has ion conductivity of a metal element belonging to Group 1 or Group 2 of the periodic table.
  • the inorganic solid electrolyte preferably has an ionic conductivity of lithium ions.
  • a solid electrolyte material usually used for an all-solid secondary battery can be appropriately selected and used.
  • Typical examples of inorganic solid electrolytes include (i) sulfide-based inorganic solid electrolytes and (ii) oxide-based inorganic solid electrolytes.
  • a sulfide-based inorganic solid electrolyte is preferably used from the viewpoint that a better interface can be formed between the active material and the inorganic solid electrolyte.
  • Sulfide-based 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 what has electronic insulation is preferable.
  • the sulfide-based inorganic solid electrolyte preferably contains at least Li, S, and P as elements and has lithium ion conductivity. However, depending on the purpose or the case, other than Li, S, and P may be used. An element may be included.
  • a lithium ion conductive inorganic solid electrolyte that satisfies the composition represented by the following formula (A) can be mentioned and is preferable.
  • L represents an element selected from Li, Na and K, and Li is preferred.
  • M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge. Among these, B, Sn, Si, Al, or Ge is preferable, and Sn, Al, or Ge is more preferable.
  • A represents I, Br, Cl or F, preferably I or Br, and particularly preferably I.
  • L, M, and A can each be one or more of the above elements.
  • a1 to e1 indicate the composition ratio of each element, and a1: b1: c1: d1: e1 satisfies 1 to 12: 0 to 1: 1: 2 to 12: 0 to 5.
  • a1 is further preferably 1 to 9, and more preferably 1.5 to 4.
  • b1 is preferably 0 to 0.5.
  • d1 is preferably 3 to 7, and more preferably 3.25 to 4.5.
  • e1 is preferably 0 to 3, more preferably 0 to 1.
  • the composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based inorganic solid electrolyte.
  • the sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass ceramic), or only a part may be crystallized.
  • glass glass
  • glass ceramic glass ceramic
  • Li—PS system glass containing Li, P, and S or Li—PS system glass ceramics containing Li, P, and S can be used.
  • the sulfide-based inorganic solid electrolyte includes [1] lithium sulfide (Li 2 S) and phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), [2] lithium sulfide and at least one of simple phosphorus and simple sulfur, Or [3] It can be produced by the reaction of lithium sulfide, phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), at least one of elemental phosphorus and elemental sulfur.
  • the ratio of Li 2 S to P 2 S 5 in the Li—PS system glass and Li—PS system glass ceramic is a molar ratio of Li 2 S: P 2 S 5 , preferably 65:35 to 85:15, more preferably 68:32 to 77:23.
  • the lithium ion conductivity can be further increased.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 ⁇ 4 S / cm or more, more preferably 1 ⁇ 10 ⁇ 3 S / cm or more. Although there is no particular upper limit, it is practical that it is 1 ⁇ 10 ⁇ 1 S / cm or less.
  • the sulfide-based inorganic solid electrolyte include, for example, those using a raw material composition containing Li 2 S and a sulfide of an element belonging to Group 13 to Group 15. it can. 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 —G
  • Examples of a method for synthesizing a sulfide-based inorganic solid electrolyte material using such a raw material composition include an amorphization method.
  • Examples of the amorphization method include a mechanical milling method 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 element belonging to Group 1 or Group 2 of the periodic table, And what has electronic insulation is preferable.
  • the oxide-based inorganic solid electrolyte preferably has an ionic conductivity of 1 ⁇ 10 ⁇ 6 S / cm or more, more preferably 5 ⁇ 10 ⁇ 6 S / cm or more, and 1 ⁇ 10 ⁇ 5 S. / Cm or more is particularly preferable.
  • the upper limit is not particularly limited, but it is practical that it is 1 ⁇ 10 ⁇ 1 S / cm or less.
  • Li xa La ya TiO 3 [xa satisfies 0.3 ⁇ xa ⁇ 0.7, and ya satisfies 0.3 ⁇ ya ⁇ 0.7.
  • LLT Li xb La yb Zr zb M bb mb Onb
  • M bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In and Sn
  • Xb satisfies 5 ⁇ xb ⁇ 10
  • yb satisfies 1 ⁇ yb ⁇ 4
  • zb satisfies 1 ⁇ zb ⁇ 4
  • mb satisfies 0 ⁇ mb ⁇ 2
  • nb satisfies 5 ⁇ nb ⁇ 20.
  • Li xc B yc M cc zc Onc (M cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In and Sn.
  • Xc is 0 ⁇ xc ⁇ 5
  • Yc satisfies 0 ⁇ yc ⁇ 1,
  • zc satisfies 0 ⁇ zc ⁇ 1,
  • nc satisfies 0 ⁇ nc ⁇ 6
  • Li xd (Al, Ga) yd (Ti, Ge) zd Si ad P md Ond (xd satisfies 1 ⁇ xd ⁇ 3, yd Satisfies 0 ⁇ yd ⁇ 1, zd satisfies 0 ⁇ zd ⁇ 2, ad satisfies 0 ⁇ ad ⁇ 1, md satisfies 1 ⁇ md ⁇ 7, and nd satisfies 3 ⁇
  • Li, P and O Phosphorus compounds containing Li, P and O are also desirable.
  • lithium phosphate Li 3 PO 4
  • LiPON obtained by substituting a part of oxygen of lithium phosphate with nitrogen
  • LiPOD 1 (D 1 is preferably Ti, V, Cr, Mn, Fe, Co, Ni, And at least one element selected from Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt, and Au.
  • LiA 1 ON (A 1 is one or more elements selected from Si, B, Ge, Al, C, and Ga) can be preferably used.
  • LLT Li xb La yb Zr zb M bb mb O 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 Li xd, yd, zd, ad, md and nd are as defined above.
  • These may be used alone or in combination of two or more.
  • the inorganic solid electrolyte is preferably a particle.
  • the volume average particle diameter of the particulate inorganic solid electrolyte is not particularly limited, but is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more. As an upper limit, it is preferable that it is 100 micrometers or less, and it is more preferable that it is 50 micrometers or less.
  • the measurement of the volume average particle diameter of an inorganic solid electrolyte is performed in the following procedures.
  • the inorganic solid electrolyte particles are prepared by diluting a 1 mass% dispersion in a 20 mL sample bottle using water (heptane in the case of a substance unstable to water).
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes and used immediately after that.
  • a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA)
  • data was acquired 50 times using a quartz cell for measurement at a temperature of 25 ° C., Obtain the volume average particle size.
  • JISZ8828 2013 “Particle Size Analysis—Dynamic Light Scattering Method” is referred to as necessary. Five samples are prepared for each level, and the average value is adopted.
  • the content of the solid component in the inorganic solid electrolyte layer of the inorganic solid electrolyte is 5% by mass or more at 100% by mass of the solid component when considering both the battery performance and the effect of reducing and maintaining the interface resistance. Is more preferable, 70% by mass or more is more preferable, and 90% by mass or more is particularly preferable. As an upper limit, it is preferable that it is 99.9 mass% or less from the same viewpoint, It is more preferable that it is 99.5 mass% or less, It is especially preferable that it is 99 mass% or less.
  • the content of the inorganic solid electrolyte in the positive electrode active material layer or the negative electrode active material layer is preferably such that the total content of the positive electrode active material or the negative electrode active material and the inorganic solid electrolyte is in the above range.
  • the solid component refers to a component that does not volatilize or evaporate when dried at 170 ° C. for 6 hours. Typically, it refers to components other than the dispersion medium described below.
  • An inorganic solid electrolyte may be used individually by 1 type, or may be used in combination of 2 or more type.
  • each layer (that is, a negative electrode active material layer, a solid electrolyte layer and / or a positive electrode active material layer, the same shall apply hereinafter) preferably contains a binder.
  • the binder that can be 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), and a copolymer of polyvinylidene fluoride and hexafluoropropylene (PVdF-HFP).
  • hydrocarbon-based thermoplastic resin examples include polyethylene, polypropylene, styrene butadiene rubber (SBR), hydrogenated styrene butadiene rubber (HSBR), butylene rubber, acrylonitrile butadiene rubber, polybutadiene, polyisoprene, and polyisoprene latex.
  • 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.
  • urethane resin examples include polyurethane.
  • copolymers with other vinyl monomers are also preferably used. Examples thereof include a poly (meth) methyl acrylate-polystyrene copolymer, a poly (meth) methyl acrylate-acrylonitrile copolymer, and a poly (meth) butyl acrylate-acrylonitrile-styrene copolymer.
  • PVdF-HFP or HSBR is preferably used. These may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the polymer constituting the binder that can be 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 gel permeation chromatography (GPC). The measuring method is based on the measuring method in the examples described later.
  • the eluent used is THF (tetrahydrofuran), and is selected from chloroform, NMP (N-methyl-2-pyrrolidone), and m-cresol / chloroform (manufactured by Shonan Wako Pure Chemical Industries, Ltd.). be able to.
  • the content of the binder in the layer is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and 1% by mass or more. Is more preferable.
  • 10 mass% or less is preferable from a viewpoint of a battery characteristic, 8 mass% or less is more preferable, 6 mass% or less is further more preferable, and 5 mass% or less is especially preferable.
  • the mass ratio of the total mass (total amount) of the inorganic solid electrolyte and the active material to the mass of the binder [(mass of the inorganic solid electrolyte + mass of the active material) / mass of the binder] is preferably in the range of 1,000 to 1. This ratio is more preferably 500 to 2, and further preferably 100 to 10.
  • Each layer also preferably contains a lithium salt.
  • the lithium salt is preferably a lithium salt usually used for an all-solid secondary battery, and is not particularly limited. For example, lithium salts described in paragraphs 0082 to 0085 of JP-A-2015-088486 are preferable.
  • the content of the lithium salt is preferably 0 part by mass or more and 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.
  • Each layer, particularly the active material layer, may contain a conductive additive used for improving the electronic conductivity of the active material.
  • a general conductive auxiliary 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 or carbon nanotube, which are electron conductive materials
  • Carbon fibers such as graphene, carbonaceous materials such as graphene or 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.
  • the content of the conductive assistant in the layer is not particularly limited and can be appropriately set in consideration of battery characteristics and the like.
  • Dispersant In the present invention, it is preferable to contain a dispersant in any of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer.
  • a dispersant By adding a dispersant, even when the concentration of either the electrode active material or the inorganic solid electrolyte is high, aggregation can be suppressed, and a uniform electrode layer (active material layer) and solid electrolyte layer can be formed. It is effective for improvement.
  • the dispersant those usually used for all-solid secondary batteries can be appropriately selected and used.
  • the content of the dispersant in the layer is not particularly limited and can be appropriately set in consideration of battery characteristics and the like.
  • the positive electrode active material is preferably one that can reversibly insert and / or release lithium ions.
  • the material is not particularly limited, and may be a transition metal oxide or an element that can be complexed with Li such as sulfur.
  • the positive electrode active material it is preferable to use a transition metal oxide, and a transition metal oxide having a transition metal element M a (one or more elements selected from Co, Ni, Fe, Mn, Cu, and V). More preferred.
  • this transition metal oxide includes an element M b (an element of the first (Ia) group of the metal periodic table other than lithium, an element of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Elements such as Sb, Bi, Si, P, and B) may be mixed.
  • the mixing amount 0 ⁇ 30 mol% relative to the amount of the transition metal element M a is preferable.
  • Those synthesized by mixing so that the molar ratio of Li / Ma is 0.3 to 2.2 are more preferable.
  • transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt structure, (MB) a transition metal oxide having a spinel structure, (MC) a lithium-containing transition metal phosphate compound, (MD And lithium-containing transition metal halide phosphate compounds, (ME) lithium-containing transition metal silicate compounds, and the like.
  • transition metal oxide having a layered rock salt structure LiCoO 2 (lithium cobaltate [LCO]), LiNi 2 O 2 (lithium nickelate), LiNi 0.85 Co 0.10 Al 0. 05 O 2 (nickel cobalt lithium aluminum oxide [NCA]), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (nickel manganese lithium cobalt oxide [NMC]), LiNi 0.5 Mn 0.5 O 2 ( Lithium manganese nickelate).
  • transition metal oxide having an (MB) spinel structure include LiCoMnO 4 , Li 2 FeMn 3 O 8 , Li 2 CuMn 3 O 8 , Li 2 CrMn 3 O 8 , and Li 2 NiMn 3 O 8. .
  • Examples of (MC) lithium-containing transition metal phosphate compounds include olivine-type iron phosphate salts such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , LiCoPO 4 and the like. And monoclinic Nasicon type vanadium phosphate salts such as Li 3 V 2 (PO 4 ) 3 (vanadium lithium phosphate).
  • the (MD) lithium-containing transition metal halogenated phosphate compound for example, Li 2 FePO 4 F such fluorinated phosphorus iron salt, Li 2 MnPO 4 hexafluorophosphate manganese salts such as F, Li 2 CoPO 4 F Cobalt fluorophosphates such as
  • Examples of the (ME) lithium-containing transition metal silicate compound include Li 2 FeSiO 4 , Li 2 MnSiO 4 , Li 2 CoSiO 4, and the like.
  • a transition metal oxide having a (MA) layered rock salt structure is preferable, and LCO is more preferable.
  • the shape of the positive electrode active material is not particularly limited, but is preferably particulate.
  • the volume average particle diameter (sphere conversion average particle diameter) of the positive electrode active material is not particularly limited.
  • the thickness can be 0.1 to 50 ⁇ m.
  • an ordinary pulverizer or classifier may be used.
  • the positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
  • the volume average particle diameter (sphere-converted average particle diameter) of the positive electrode active material particles can be measured using a laser diffraction / scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA).
  • the content of the positive electrode active material in the positive electrode active material layer is not particularly limited, preferably 10 to 95% by mass, more preferably 20 to 90% by mass, further preferably 30 to 85% by mass, and 50 to 80% by mass. Particularly preferred.
  • the mass (mg) (weight per unit area) of the positive electrode active material per unit area (cm 2 ) of the positive electrode active material layer is not particularly limited. It can be arbitrarily determined according to the designed battery capacity.
  • the positive electrode active materials may be used alone or in combination of two or more.
  • the negative electrode active material is preferably one that can reversibly insert and / or release lithium ions.
  • 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.
  • a carbonaceous material or a lithium composite oxide is preferably used from the viewpoint of reliability.
  • the metal composite oxide is preferably capable of inserting and extracting lithium.
  • the material is not particularly limited, but preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
  • the carbonaceous material used as the negative electrode active material is a material substantially made of carbon.
  • various synthetics such as petroleum pitch, carbon black such as acetylene black (AB), graphite (natural graphite, artificial graphite such as vapor-grown graphite), PAN (polyacrylonitrile) resin or furfuryl alcohol resin, etc.
  • the carbonaceous material which baked resin can be mentioned.
  • 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.
  • carbonaceous materials can be divided into non-graphitizable carbonaceous materials and graphite-based carbonaceous materials according to the degree of graphitization.
  • the carbonaceous material preferably has a face spacing or density and crystallite size described in JP-A-62-222066, JP-A-2-6856, and 3-45473.
  • the carbonaceous material does not have to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, or the like is used. You can also.
  • an amorphous oxide is particularly preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used. It is done.
  • amorphous as used herein means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering band having a peak in the region of 20 ° to 40 ° in terms of 2 ⁇ , and is a crystalline diffraction line. You may have.
  • the strongest intensity of crystalline diffraction lines seen from 2 ° to 40 ° to 70 ° is 100 times the diffraction line intensity at the peak of the broad scattering band seen from 2 ° to 20 °. It is preferable that it is 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.
  • the amorphous oxide of the metalloid element and the chalcogenide are more preferable, and elements of Groups 13 (IIIB) to 15 (VB) of the periodic table, Al , Ga, Si, Sn, Ge, Pb, Sb, Bi alone or in combination of two or more thereof, and chalcogenide are particularly preferable.
  • preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , SiO, GeO, SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 8 i 2 O 3 , Bi 2 O 4 , SnSiO 3 , GeS, SnS, SnS 2 , PbS, PbS 2 , Sb 2 S 3 , Sb 2 S 5 , SnSiS 3 is preferred.
  • 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 occlusion and release of lithium ions, and the deterioration of the electrode 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]
  • hard carbon or graphite is preferably used, and graphite is more preferably used.
  • the carbonaceous materials may be used singly or in combination of two or more.
  • the shape of the negative electrode active material is not particularly limited, but is preferably particulate.
  • the average particle size of the negative electrode active material is preferably 0.1 to 60 ⁇ m.
  • an ordinary 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.
  • pulverizing wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary.
  • classification is preferably performed.
  • the classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be used both dry and wet.
  • the average particle diameter of the negative electrode active material particles can be measured by the same method as the above-described method for measuring the volume average particle diameter of the positive electrode active material.
  • the content of the negative electrode active material in the negative electrode active material layer is not particularly limited, is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and more preferably 30 to 85% by mass. More preferably, it is 40 to 80% by mass.
  • the mass (mg) (weight per unit area) of the negative electrode active material per unit area (cm 2 ) of the negative electrode active material layer is not particularly limited. It can be arbitrarily determined according to the designed battery capacity.
  • the said negative electrode active material may be used individually by 1 type, or may be used in combination of 2 or more type.
  • a functional layer or a member is appropriately interposed or disposed between or outside each of the negative electrode conductive film, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode conductive film. May be.
  • each said layer and electrical power collector may be comprised by the single layer, or may be comprised by the multilayer.
  • the basic structure of the all-solid-state secondary battery can be manufactured by arranging each of the above layers. Depending on the application, it may be used as an all-solid secondary battery as it is, but in order to form a dry battery, it is further enclosed in a suitable housing.
  • the housing may be metallic or made of resin (plastic). When using a metallic thing, the thing made from an aluminum alloy or stainless steel can be mentioned, for example.
  • the metallic housing is preferably divided into a positive-side housing and a negative-side housing, and electrically connected to the positive current collector and the negative current collector, respectively.
  • the casing on the positive electrode side and the casing on the negative electrode side are preferably joined and integrated through a gasket for preventing a short circuit.
  • Electrode sheet for all-solid-state secondary battery (hereinafter simply referred to as “electrode sheet of the present invention”) is an electrode sheet having a conductive film and an active material layer in this order on a current collector, It can use suitably for the all-solid-state secondary battery of this invention.
  • This electrode sheet is usually a sheet having a current collector and an active material layer provided with a conductive film, but an embodiment having a current collector with a conductive film, an active material layer and a solid electrolyte layer in this order, and The aspect which has a collector with an electroconductive film, an active material layer, a solid electrolyte layer, and an active material layer in this order is also included.
  • the configuration and the layer thickness of each layer constituting the electrode sheet are the same as the configuration and the layer thickness of each layer described in the all solid state secondary battery of the present invention.
  • the all-solid-state secondary battery and the electrode sheet for the all-solid-state secondary battery can be produced by a conventional method. This will be described in detail below.
  • the all-solid-state secondary battery and the all-solid-state secondary battery electrode sheet of the present invention form a conductive film on a metal foil serving as a current collector, and then apply the solid electrolyte composition to form a coating film. It can be manufactured by forming.
  • a positive electrode conductive film is formed on a metal foil that is a positive electrode current collector, a positive electrode material (positive electrode composition) is applied to form a positive electrode active material layer, and a positive electrode sheet for an all-solid-state secondary battery is formed. Make it.
  • a solid electrolyte composition for forming a solid electrolyte layer is applied on the positive electrode active material layer of the sheet to form a solid electrolyte layer.
  • a negative electrode material negative electrode composition
  • a solid electrolyte layer was sandwiched between the positive electrode active material layer and the negative electrode active material layer by superimposing a negative electrode current collector (metal foil) provided with a negative electrode conductive film as necessary on the negative electrode active material layer.
  • An all-solid secondary battery having a structure can be obtained. If necessary, this can be enclosed in a housing to obtain a desired all-solid secondary battery. Further, by reversely forming each layer, a negative electrode active material layer, a solid electrolyte layer, and a positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collector with the positive electrode conductive film is stacked, A solid secondary battery can also be manufactured.
  • Another method includes the following method. That is, a positive electrode sheet for an all-solid secondary battery is produced as described above. Further, a negative electrode conductive film is formed on a metal foil as a negative electrode current collector, and a negative electrode material (a composition for negative electrode layer) is applied to form a negative electrode active material layer. A sheet is produced. Next, a solid electrolyte layer is formed on one of the active material layers of these sheets as described above. Furthermore, the other of the positive electrode sheet for an all solid secondary battery and the negative electrode sheet for an all solid secondary battery is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other. In this way, an all-solid secondary battery can be manufactured. Another method includes the following method.
  • a positive electrode sheet for an all-solid secondary battery and a negative electrode sheet for an all-solid secondary battery are produced.
  • a solid electrolyte composition is applied to a substrate to produce a solid electrolyte sheet composed of a solid electrolyte layer. Furthermore, it laminates
  • An all-solid-state secondary battery can also be manufactured by a combination of the above forming methods. For example, as described above, a positive electrode sheet for an all-solid secondary battery, a negative electrode sheet for an all-solid secondary battery, and a solid electrolyte sheet are respectively produced. Then, after laminating the solid electrolyte layer peeled off from the base material on the negative electrode sheet for an all solid secondary battery, an all solid secondary battery can be produced by pasting the positive electrode sheet for the all solid secondary battery. it can. In this method, the solid electrolyte layer can be laminated on the positive electrode sheet for an all-solid secondary battery, and bonded to the negative electrode sheet for an all-solid secondary battery. In the said manufacturing method, it can replace with the said negative electrode sheet for all-solid-state secondary batteries, and can also use the sheet
  • the positive electrode current collector used in the above production method is provided with a positive electrode conductive film on the surface thereof.
  • the negative electrode current collector is provided with a negative electrode conductive film on the surface thereof as necessary.
  • the surface of the current collector is roughened as necessary, and the current collector is set to the surface form.
  • the method for roughening the surface of the current collector is not particularly limited, and a normal method can be employed. For example, when producing a current collector by rolling, a method of transferring the surface state of a rolling roll can be mentioned. Further, a method of roughening the surface of the current collector by a sandblast method or the like can be mentioned.
  • the surface form can be appropriately set according to the conditions of the material, shape, particle size, spraying pressure, spraying speed, and spraying time of the sand used.
  • a method of subjecting the current collector to an electrochemical surface roughening treatment (also referred to as an electrolytic surface roughening treatment) is also included.
  • electrolytic surface roughening is preferred.
  • an electrolytic surface-roughening method will be described by taking a current collector made of aluminum as an example.
  • the surface form of the current collector can be appropriately set by subjecting the current collector formed of a material other than aluminum to the same electrolytic surface roughening.
  • the aluminum forming the current collector subjected to the electrolytic surface roughening treatment is not particularly limited, and a normal aluminum foil can be used.
  • the aluminum foil is a metal foil mainly composed of aluminum.
  • alloy numbers 1085, 1N30, and 3003 described in Japanese Industrial Standard (JIS Standard) H4000 can be used.
  • the thickness of the aluminum foil may be the same as the thickness of the current collector, but is preferably 100 ⁇ m or less, preferably 5 to 80 ⁇ m, and more preferably 10 to 50 ⁇ m.
  • the electrochemical roughening treatment of the aluminum foil may include various treatments or steps other than the electrochemical roughening treatment as long as it includes at least the electrochemical roughening treatment.
  • an electrochemical surface-roughening method for obtaining the above surface form for example, if necessary, an aluminum foil is subjected to an alkali etching treatment, followed by an acid desmutting treatment and an electrochemical surface-roughening treatment using an electrolytic solution in sequence. Examples of the method include a method of performing an alkali etching treatment, an acid desmutting treatment on an aluminum foil, and an electrochemical surface roughening treatment using different electrolytic solutions a plurality of times, but the present invention is not limited thereto. In these methods, after the electrochemical surface roughening treatment, an alkali etching treatment and an acid desmutting treatment may be further performed. Hereinafter, each process of the surface treatment will be described in detail.
  • an electrolytic solution used for the electrochemical surface roughening treatment using a normal alternating current can be used.
  • an electrolytic solution mainly composed of hydrochloric acid or nitric acid because the above-described surface shape can be easily obtained.
  • Electrolytic surface roughening can be performed according to, for example, the electrochemical grain method (electrolytic grain method) described in Japanese Patent Publication No. 48-28123 and British Patent No. 896,563.
  • This electrolytic grain method uses a sinusoidal alternating current, but it may be performed using a special waveform as described in JP-A-52-58602. Further, the waveform described in JP-A-3-79799 can also be used.
  • the methods described in JP-A-3-267400 and JP-A-1-141094 can also be applied.
  • JP-A-52-58602, JP-A-52-152302, JP-A-53-12738, JP-A-53-12739, JP-A-53-32821, JP-A-53-32222, JP 53-32833, JP 53-32824, JP 53-32825, JP 54-85802, JP 55-122896, JP 55-13284, JP 48-28123, JP-B-51-7081, JP-A-52-13338, JP-A-52-133840, JP-A-52-133844, JP-A-52-133845, JP-A-53- Nos. 149135 and 54-146234 can also be used.
  • the concentration of the acidic solution is preferably 0.5 to 2.5% by mass, but it is particularly preferably 0.7 to 2.0% by mass in consideration of use in the smut removal treatment.
  • the liquid temperature is preferably 20 to 80 ° C., more preferably 30 to 60 ° C.
  • An aqueous solution mainly composed of hydrochloric acid or nitric acid is an aqueous solution of hydrochloric acid or nitric acid having a concentration of 1 to 100 g / L. At least one of the hydrochloric acid compounds having hydrochloric acid ions can be used by adding in a range from 1 g / L to saturation. Moreover, the metal contained in aluminum alloys, such as iron, copper, manganese, nickel, titanium, magnesium, a silica, may melt
  • the compound capable of forming a complex with Cu include ammonia; hydrogen atom of ammonia such as methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, cyclohexylamine, triethanolamine, triisopropanolamine, EDTA (ethylenediaminetetraacetic acid). And amines obtained by substituting with a hydrocarbon group (aliphatic, aromatic, etc.); metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate and the like.
  • ammonium salts such as ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium phosphate, and ammonium carbonate are also included.
  • the temperature is preferably 10 to 60 ° C, more preferably 20 to 50 ° C.
  • the AC power wave used for the electrochemical surface roughening treatment is not particularly limited, and a sine wave, a rectangular wave, a trapezoidal wave, a triangular wave or the like is used, but a rectangular wave or a trapezoidal wave is preferable, and a trapezoidal wave is particularly preferable.
  • the time (TP) until the current reaches a peak from zero is preferably 0.5 to 3 msec. If it is less than 0.5 msec, processing irregularities such as chatter marks that occur perpendicular to the traveling direction of the aluminum foil are likely to occur.
  • TP exceeds 3 msec, especially when a nitric acid electrolyte is used, it is easily affected by trace components in the electrolyte typified by ammonium ions and the like that spontaneously increase by electrolytic treatment, and uniform graining is performed. It becomes hard to be broken.
  • a trapezoidal wave AC duty ratio of 1: 2 to 2: 1 can be used. However, as described in Japanese Patent Laid-Open No. 5-195300, in an indirect power feeding method that does not use a conductor roll for aluminum. A duty ratio of 1: 1 is preferable.
  • a trapezoidal AC frequency of 0.1 to 120 Hz can be used, but 50 to 70 Hz is preferable in terms of equipment. When the frequency is lower than 50 Hz, the carbon electrode of the main electrode is easily dissolved, and when the frequency is higher than 70 Hz, it is easily affected by an inductance component on the power supply circuit, and the power supply cost is increased.
  • One or more AC power supplies can be connected to the electrolytic cell.
  • an auxiliary anode is installed, It is preferable to divert part of the alternating current.
  • An anodic reaction that acts on the aluminum foil facing the main electrode by diverting a part of the current value as a direct current to an auxiliary anode provided in a separate tank from the two main electrodes via a rectifier or switching element It is possible to control the ratio between the current value for the current and the current value for the cathode reaction.
  • the ratio of the amount of electricity involved in the cathode reaction and the anodic reaction is preferably 0.3 to 0.95.
  • an electrolytic cell usually used for surface treatment such as a vertical type, a flat type, and a radial type can be used.
  • a radial type electrolytic cell as described in JP-A-5-195300 is particularly preferable.
  • the electrolytic solution passing through the electrolytic cell may be parallel to the traveling direction of the aluminum web or may be a counter.
  • the arithmetic average roughness Ra and the number of recesses are set in the above range by electrochemical surface roughening treatment (hereinafter also referred to as “nitric acid electrolysis”) using an electrolytic solution mainly composed of nitric acid.
  • nitric acid electrolysis since nitric acid electrolysis enables formation of a uniform and high-density recess, alternating current is used, the peak current density (peak value of current density) is set to 15 A / dm 2 or more, and the average current density (average value). ) Is preferably 13 A / dm 2 or more, and the amount of electricity is preferably 100 c / dm 2 or more.
  • the peak current density is preferably 100 A / dm 2 or less, and more preferably 68 A / dm 2 or less. Further, the average current density is preferably 40 A / dm 2 or less, and more preferably 31.0 A / dm 2 or less.
  • the amount of electricity is preferably 400 c / dm 2 or less.
  • the concentration or temperature of the electrolytic solution in nitric acid electrolysis is not particularly limited, and electrolysis is performed at 30 to 60 ° C. using a nitric acid electrolytic solution having a high concentration, for example, a nitric acid concentration of 15 to 35% by mass, or a nitric acid concentration of 0.1%. Electrolysis can be carried out at a high temperature, for example, at 80 ° C. or higher, using a 7-2 mass% nitric acid electrolyte.
  • the arithmetic average roughness Ra and the number of recesses are set in the above range also by electrochemical surface roughening treatment (hereinafter, also referred to as “hydrochloric acid electrolysis”) using an electrolytic solution mainly composed of hydrochloric acid. can do.
  • hydrochloric acid electrolysis for the reason that uniform and high-density recesses can be formed, an alternating current is used, the peak current density is 30 A / dm 2 or more, the average current density is 13 A / dm 2 or more, and The electrolytic treatment is preferably performed under the condition that the amount of electricity is 150 c / dm 2 or more.
  • the peak current density is preferably 100 A / dm 2 or less, the average current density is preferably 40 A / dm 2 or less, and the amount of electricity is preferably 400 c / dm 2 or less.
  • pickling is preferably performed to remove dirt (smut) remaining on the surface.
  • the acid used include nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, and borohydrofluoric acid.
  • the desmutting treatment is performed, for example, by bringing the aluminum foil into contact with an acidic solution (containing aluminum ions of 0.01 to 5% by mass) having a concentration of 0.5 to 30% by mass such as hydrochloric acid, nitric acid, and sulfuric acid. .
  • the method of bringing the aluminum foil into contact with the acidic solution examples include a method of passing the aluminum foil through the acidic solution bath, a method of immersing the aluminum foil in the acidic solution bath, and spraying the acidic solution onto the surface of the aluminum foil.
  • the acid solution is mainly composed of an aqueous solution mainly composed of nitric acid or an aqueous solution mainly composed of hydrochloric acid discharged in the above-described electrolytic surface-roughening treatment, or sulfuric acid discharged in an anodic oxidation process described later. It is possible to use a waste solution of an aqueous solution.
  • the temperature of the desmut treatment is preferably 25 to 90 ° C.
  • the processing time is preferably 1 to 180 seconds.
  • Aluminum and aluminum alloy components may be dissolved in the acidic solution used for the desmut treatment.
  • an alkali etching treatment can be performed before and / or after the electrolytic surface roughening treatment.
  • the alkali etching treatment is a treatment for dissolving the surface layer by bringing the aluminum foil into contact with an alkali solution. This treatment is performed for the purpose of removing the rolling oil, dirt, natural oxide film, etc. on the surface of the aluminum foil or dissolving the smut generated in the acidic electrolyte.
  • the alkali etching treatment can be performed by applying normal conditions without particular limitation.
  • the aluminum foil treated as described above can be anodized as necessary from the viewpoint of preventing corrosion.
  • the anodizing treatment can be performed by a usual method and conditions.
  • the sealing process which seals the micropore which exists in an anodic oxide film can also be performed as needed.
  • the sealing treatment can be performed by a usual method and conditions.
  • a normal method and conditions can be adopted for each treatment in the electrochemical surface roughening treatment method. For example, each process (method or condition) described in JP-A-2015-53240 can be referred to as appropriate.
  • -Washing treatment- it is preferable to carry out water washing after completion of the above-described processes.
  • pure water, well water, tap water, or the like can be used.
  • a nip device may be used to prevent the processing liquid from being brought into the next process.
  • the method for forming the conductive film on the surface of the current collector having the above surface form is not particularly limited.
  • CVD chemical vapor deposition
  • BVD physical vapor deposition
  • sputtering using the above-described conductive particles examples include a deposition method such as phosphorus, a plating method such as electroplating, and an application (printing) method in which a coating composition in which the above-described conductive particles are dispersed in a binder is applied (printed) to the surface of the current collector and dried. It is done.
  • a method of forming a conductive film by the vapor deposition method or the coating method using the above-described conductive particles is preferable.
  • the solid electrolyte composition for forming the solid electrolyte layer contains an inorganic solid electrolyte.
  • the composition for positive electrodes for forming a positive electrode active material layer contains a positive electrode active material, and also contains an inorganic solid electrolyte.
  • the negative electrode composition for forming the negative electrode active material layer preferably contains a negative electrode active material and further contains an inorganic solid electrolyte.
  • the solid electrolyte composition for forming the solid electrolyte layer, the positive electrode composition, and the negative electrode composition are combined.
  • a solid electrolyte composition sometimes referred to as a solid electrolyte composition.
  • the solid electrolyte composition contains an inorganic solid electrolyte, and may contain a positive electrode active material or a negative electrode active material, and further a binder, a lithium salt, a conductive additive, a dispersant, and a dispersion medium.
  • the inorganic solid electrolyte, the positive electrode active material, the negative electrode active material, the binder, the lithium salt, the conductive assistant and the dispersant are as described above.
  • Examples of the dispersion medium include the following, which are preferable.
  • the dispersion medium only needs to disperse each of the above components, and examples thereof include various organic solvents.
  • Specific examples of the dispersion medium include the following.
  • Examples of the alcohol compound solvent include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, Examples include 2-methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-butanediol.
  • ether compound solvents examples include alkylene glycol alkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene.
  • alkylene glycol alkyl ethers ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene.
  • Glycol monomethyl ether tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.), dialkyl ethers (dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, etc.), cyclic ethers (tetrahydrofuran, geo Sun (1,2-, 1,3- and each isomer 1,4), etc.), and the like.
  • Examples of the amide compound solvent include N, N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ⁇ -caprolactam, formamide, N -Methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.
  • Examples of the amino compound solvent include triethylamine, diisopropylethylamine, tributylamine and the like.
  • Examples of the ketone compound solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • Examples of the aromatic compound solvent include benzene, toluene, xylene and the like.
  • Examples of the aliphatic compound solvent include hexane, heptane, octane, decane, and the like.
  • Examples of the nitrile compound solvent include acetonitrile, propyronitrile, isobutyronitrile, and the like.
  • Examples of the ester compound solvent include ethyl acetate, butyl acetate, propyl acetate, butyl butyrate, and butyl pentanoate.
  • Examples of the non-aqueous dispersion medium include the above aromatic compound solvents and aliphatic compound solvents.
  • 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.
  • the content of the dispersion medium in the solid electrolyte composition is preferably 10 to 95 parts by weight, more preferably 15 to 90 parts by weight, and particularly preferably 20 to 85 parts by weight with respect to 100 parts by weight as a whole.
  • the said dispersion medium may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the solid electrolyte composition of the present invention can be produced by mixing an inorganic solid electrolyte, a binder and a dispersion medium, and if necessary, other components using, for example, various mixers.
  • the method for applying the solid electrolyte composition is not particularly limited, and can be appropriately selected. Examples thereof include coating (preferably wet coating), spray coating, spin coating coating, dip coating, slit coating, stripe coating, and bar coating coating.
  • the solid electrolyte composition may be dried after being applied, or may be dried 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.
  • each layer or all-solid secondary battery After producing the applied solid electrolyte composition or all-solid-state secondary battery. Moreover, it may pressurize in the state which laminated
  • An example of the pressurizing method is a hydraulic cylinder press.
  • the applied pressure is not particularly limited and is generally preferably in the range of 50 to 1500 MPa.
  • the heating temperature is not particularly limited, and is generally in the range of 30 to 300 ° C. It is also possible to press at a temperature higher than the glass transition temperature of the inorganic solid electrolyte. On the other hand, when the inorganic solid electrolyte and the binder coexist, pressing can be performed at a temperature higher than the glass transition temperature of the binder. However, in general, the temperature does not exceed the melting point of the binder.
  • the pressurization may be performed in a state where the coating solvent or the dispersion medium is previously dried, or may be performed in a state where the solvent or the dispersion medium remains.
  • the atmosphere during pressurization is not particularly limited, and may be any of the following: air, dry air (dew point of ⁇ 20 ° C. or lower), inert gas (for example, argon gas, helium gas, nitrogen gas).
  • the pressing time may be a high pressure in a short time (for example, within several hours), or a medium pressure may be applied for a long time (1 day or more).
  • all-solid-state secondary battery other than the electrode sheet or the solid electrolyte sheet for an all-solid-state secondary battery for example, in order to keep applying moderate pressure, all-solid-state secondary battery restraints (screw tightening pressure, etc.) It can also be used.
  • the pressing pressure may be uniform or different with respect to the pressed part such as the sheet surface.
  • the pressing pressure can be changed according to the area or film thickness of the pressed part. Also, the same part can be changed stepwise with different pressures.
  • the press surface may be smooth or roughened.
  • the all solid state secondary battery manufactured as described above is preferably initialized after manufacture or before use.
  • the initialization is not particularly limited, and can be performed, for example, by performing initial charging / discharging in a state where the press pressure is increased, and then releasing the pressure until the general use pressure of the all-solid secondary battery is reached.
  • the all solid state secondary battery of the present invention can be applied to various uses. 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, minidisc, electric shaver, transceiver, electronic notebook, calculator, memory card, portable tape recorder, radio, backup power supply, memory card, etc. It is done.
  • Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military purposes and space. Moreover, it can also combine with a solar cell.
  • An all-solid secondary battery is 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 secondary battery that uses the above-described Li—PS, LLT, LLZ, or the like. It is divided into 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 particles.
  • the inorganic solid electrolyte is distinguished from the above-described electrolyte (polymer electrolyte) using a polymer compound such as polyethylene oxide as an ion conductive medium, and the inorganic compound serves as an ion conductive medium. Specific examples include Li—PS, LLT, and LLZ.
  • the inorganic solid electrolyte itself does not release cations (Li ions) but exhibits an ion transport function.
  • a material that is added to the electrolytic solution or the solid electrolyte layer and serves as a source of ions that release cations is sometimes called an electrolyte, but it is distinguished from the electrolyte as the ion transport material.
  • electrolyte salt or “supporting electrolyte”.
  • the electrolyte salt include LiTFSI (lithium bistrifluoromethanesulfonylimide).
  • composition means a mixture in which two or more components are uniformly mixed. However, as long as the uniformity is substantially maintained, aggregation or uneven distribution may partially occur within a range in which a desired effect is achieved.
  • a solid electrolyte composition when it is referred to as a solid electrolyte composition, it basically refers to a composition (typically a paste) that is a material for forming a solid electrolyte layer or the like, and an electrolyte layer or the like formed by curing the composition. Shall not be included in this.
  • Li 2 S lithium sulfide
  • P 2 S 5 diphosphorus pentasulfide
  • a zirconia 45 mL container (manufactured by Fritsch) was charged with 66 zirconia beads having a diameter of 5 mm, and then the entire amount of the mixture of lithium sulfide and diphosphorus pentasulfide was charged, and the container was completely sealed under an argon atmosphere. .
  • This container is set in a planetary ball mill P-7 (trade name, manufactured by Fritsch), mechanical milling is performed at a temperature of 25 ° C. and a rotation speed of 510 rpm for 20 hours, and a yellow powder of Li—PS system glass (sulfide inorganic) 6.20 g of solid electrolyte) was obtained.
  • the AC power supply waveform is subjected to electrochemical surface roughening using a carbon electrode as a counter electrode, using a trapezoidal rectangular wave alternating current with a time TP of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1. It was. Ferrite was used for the auxiliary anode. The current density was 60A / dm 2 at the peak current, and a 28.1A / dm 2 in average, also the quantity of electricity in the aluminum foil of the electric quantity during anodic sum at 120c / dm 2 there were. Then, water washing by spraying was performed. Table 1 below shows the conditions for electrochemical surface roughening.
  • the current collector AL-1 was produced in the same manner as the current collector AL-1, except that the electrochemical roughening treatment conditions were changed to the treatment conditions shown in Table 1 below.
  • Body AL-2 to 5 and current collector C-AL-1 to 3 for comparison were prepared.
  • Example 1 ⁇ Preparation of each composition> -Preparation of solid electrolyte composition- 180 pieces of zirconia beads having a diameter of 5 mm are put into a 45 mL container (manufactured by Fritsch) made of zirconia, 9.5 g of the Li—PS system glass synthesized above, 0.5 g of PVdF—HFP, and 1,4 as a dispersion medium. -15.0 g of dioxane was charged. Thereafter, this container was set in a planetary ball mill P-7 (trade name, 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 solid electrolyte composition.
  • the PVdF-HFP was measured by GPC under the following conditions, and the mass average molecular weight was 70,000.
  • composition for positive electrode- 180 zirconia beads having a diameter of 5 mm are put into a 45 mL container (manufactured by Fritsch) made of zirconia, 1.5 g of the Li—PS system glass synthesized above, 0.5 g of PVdF—HFP, and 1,4 as dispersion media.
  • This container was set in a planetary ball mill P-7 (manufactured by Fritsch), and machine dispersion was continued for 2 hours under the conditions of a temperature of 25 ° C. and a rotation speed of 300 rpm.
  • composition for negative electrode- 180 pieces of zirconia beads having a diameter of 5 mm are put into a 45 mL container (manufactured by Fritsch) made of zirconia, and 8 parts by mass of graphite (spheroidized graphite powder manufactured by Nippon Graphite Industries, Ltd., described as “graphite” in Table 2 below) , 2 parts by mass of the Li—PS glass synthesized above, 0.3 part by mass of binder (HSBR, hydrogenated styrene butadiene rubber, JSR product name: Dynalon 1321P), and 10 parts by mass of heptane as a dispersion medium did.
  • HSBR hydrogenated styrene butadiene rubber
  • Dynalon 1321P Dynalon 1321P
  • This container was set on a planetary ball mill P-7 (trade name, manufactured by Fritsch), and mechanical dispersion was continued for 90 minutes at a temperature of 25 ° C. and a rotation speed of 360 rpm to prepare a composition for a negative electrode.
  • the mass average molecular weight of the HSBR measured by GPC was 200,000, and Tg was ⁇ 50 ° C.
  • the negative electrode composition prepared above was applied onto a conductive film provided on a copper foil by an applicator (trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.) with adjustable clearance, and 80 After heating at 1 ° C. for 1 hour, the composition was further heated at 110 ° C. for 1 hour to dry the negative electrode composition. Then, using a heat press, the dried negative electrode composition is heated (110 ° C.) while being pressurized (605 MPa, 1 minute), and has a negative electrode active material layer with a thickness of 100 ⁇ m. A sheet was produced.
  • SA-201 Baker type applicator manufactured by Tester Sangyo Co., Ltd.
  • the solid electrolyte composition prepared above was applied onto the negative electrode active material layer by the above-described Baker type applicator, and the solid electrolyte composition was heated at 80 ° C. for 1 hour, and further heated at 110 ° C. for 6 hours.
  • the sheet having the solid electrolyte layer formed on the negative electrode active material layer was pressurized (605 MPa, 1 minute) while being heated (120 ° C.) using a heat press, and the total film thickness with the negative electrode active material layer was 150 ⁇ m.
  • a negative electrode sheet for an all-solid secondary battery with a solid electrolyte layer was produced.
  • the film thickness of the solid electrolyte layer was 50 ⁇ m.
  • the positive electrode composition prepared above was applied onto the positive electrode conductive film by the above-mentioned Baker type applicator, heated at 80 ° C. for 1 hour, and further heated at 110 ° C. for 1 hour to dry the positive electrode composition. did. Then, using a heat press, the dried positive electrode composition is pressurized (605 MPa, 1 minute) while heating (120 ° C.), and has a positive electrode active material layer with a film thickness of 100 ⁇ m. A sheet was produced.
  • An all-solid secondary battery shown in FIG. 2 was produced.
  • the negative electrode sheet for an all solid secondary battery with the solid electrolyte layer produced above was cut out into a disk shape with a diameter of 10 mm, and the positive electrode sheet for an all solid secondary battery was cut out into a disk shape with a diameter of 10 mm.
  • the cut-out negative electrode sheet piece for an all-solid-state secondary battery with a solid electrolyte layer and the positive-electrode sheet piece for an all-solid-state secondary battery are attached by pressing at 605 MPa so that the solid electrolyte layer and the positive electrode active material layer face each other.
  • all-solid-state secondary battery (coin battery) 13 was manufactured by placing it in a stainless steel 2032 type coin case 11 incorporating a spacer and washer (both not shown in FIG. 2) and applying a restraining pressure from the outside.
  • 12 shows the laminated body of the electrode sheet for all-solid-state secondary batteries which laminated
  • the layer configuration of the all-solid secondary battery manufactured in this way has the layer configuration shown in FIG.
  • Examples 2 to 5 and Comparative Examples 1 to 3 In the production of the all-solid secondary battery of Example 1, except that the current collector AL-1 was changed to the current collector shown in Table 2, the same as the production of the all-solid secondary battery of Example 1, The all solid state secondary batteries of Examples 2, 4, 5 and Comparative Examples 1 to 3 were produced, respectively. Further, in the production of the all-solid-state secondary battery of Example 1, the current collector AL-1 was changed to the current collector shown in Table 2, and further replaced with a graphite positive electrode conductive film as follows. An all-solid secondary battery of Example 3 was produced in the same manner as in the production of the all-solid secondary battery of Example 1 except that a positive electrode conductive film (thickness 4 ⁇ m) of carbon nanotubes was formed.
  • the all-solid-state secondary batteries of Examples 1 to 5 in which the conductive film is formed on the surface of the current collector having a specific surface form in which the arithmetic average roughness Ra and the number of recesses are within a predetermined range are inorganic It was shown that fine voids could not be confirmed in the solid electrolyte layer, the adhesion between the current collector and the conductive film was high, and no short circuit occurred. On the other hand, in the all-solid-state secondary batteries of Comparative Examples 1 to 3 in which a conductive film is formed on the surface of the current collector that does not have the specific surface form, fine voids are confirmed in the inorganic solid electrolyte layer. Although it was not possible, it was shown that the conductive film peeled off from the current collector or a short circuit occurred.
  • Examples 6 to 10 In Examples 1 to 5, the same procedure as in Examples 1 to 5 except that the current collectors AL-1 to AL-5 used in each example were used instead of the copper foil as the negative electrode current collector.
  • Each solid secondary battery was manufactured. About each manufactured all-solid-state secondary battery, the presence or absence of the space

Abstract

L'invention concerne une pile rechargeable tout solide, son procédé de fabrication, une feuille d'électrode pour pile rechargeable tout solide et son procédé de fabrication, ladite pile étant pourvue d'une cathode qui comporte un film électroconducteur et une couche de matériau actif de cathode dans l'ordre indiqué sur la surface d'un collecteur, d'une anode qui comporte une couche de matériau actif d'anode, et d'une couche d'électrolyte solide inorganique entre la couche de matériau actif de cathode et la couche de matériau actif d'anode ; la surface du collecteur présentant une rugosité moyenne arithmétique Ra de 0,24 à 0,38 µm, et de 10 à 80 alvéoles par 100 µm2 ; et lesdites alvéoles présentant un diamètre d'ouverture moyen de 0,3 à 3,0 µm.
PCT/JP2016/086820 2015-12-14 2016-12-09 Pile rechargeable tout solide, feuille d'électrode pour pile rechargeable tout solide, et procédé de fabrication desdites pile et feuille WO2017104583A1 (fr)

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CN112864454A (zh) * 2019-11-27 2021-05-28 郑州宇通集团有限公司 一种多层固态电解质及其制备方法、固态锂电池
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CN112864454A (zh) * 2019-11-27 2021-05-28 郑州宇通集团有限公司 一种多层固态电解质及其制备方法、固态锂电池
WO2022176796A1 (fr) * 2021-02-16 2022-08-25 株式会社クレハ Solution de liant, suspension, couche d'électrolyte solide, électrode et batterie tout solide

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