WO2022172945A1 - Batterie et procédé de fabrication de batterie - Google Patents

Batterie et procédé de fabrication de batterie Download PDF

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Publication number
WO2022172945A1
WO2022172945A1 PCT/JP2022/005058 JP2022005058W WO2022172945A1 WO 2022172945 A1 WO2022172945 A1 WO 2022172945A1 JP 2022005058 W JP2022005058 W JP 2022005058W WO 2022172945 A1 WO2022172945 A1 WO 2022172945A1
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active material
solid electrolyte
electrode active
battery
material layer
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PCT/JP2022/005058
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English (en)
Japanese (ja)
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哲也 上野
長 鈴木
崇将 向井
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Tdk株式会社
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Publication of WO2022172945A1 publication Critical patent/WO2022172945A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a battery and a method of manufacturing a battery.
  • This application claims priority based on Japanese Patent Application No. 2021-020429 filed in Japan on February 12, 2021, the content of which is incorporated herein.
  • a sintering method and a powder molding method are examples of methods for manufacturing an all-solid-state battery.
  • a negative electrode, a solid electrolyte layer, and a positive electrode are laminated and then sintered to form an all-solid battery.
  • the powder molding method after laminating a negative electrode, a solid electrolyte layer, and a positive electrode, pressure is applied to form an all-solid battery.
  • Materials that can be used for the solid electrolyte layer vary depending on the manufacturing method.
  • Known solid electrolytes include oxide-based solid electrolytes, sulfide-based solid electrolytes, complex hydride-based solid electrolytes (such as LiBH4 ), and the like.
  • Patent Document 1 discloses a solid electrolyte secondary battery having a positive electrode, a negative electrode, and a solid electrolyte composed of a compound represented by the general formula Li 3-2X M X In 1-Y M' Y L 6-Z L' Z. disclosed.
  • M and M' are metal elements
  • L and L' are halogen elements.
  • X, Y and Z independently satisfy 0 ⁇ X ⁇ 1.5, 0 ⁇ Y ⁇ 1 and 0 ⁇ Z ⁇ 6.
  • the positive electrode also includes a positive electrode layer containing a positive electrode active material containing Li element and a positive electrode current collector.
  • the negative electrode also includes a negative electrode layer containing a negative electrode active material and a negative electrode current collector.
  • Patent Document 2 discloses a solid electrolyte material represented by the following compositional formula (1). Li 6-3Z Y Z X 6 Formula (1) Here, 0 ⁇ Z ⁇ 2 is satisfied, and X is Cl or Br. Further, Patent Document 2 describes a battery in which at least one of a negative electrode and a positive electrode contains the solid electrolyte material.
  • Patent Literature 3 describes an all-solid battery including an electrode active material layer having a first solid electrolyte material and a second solid electrolyte material.
  • the first solid electrolyte material is a single-phase electron-ion mixed conductor, and is a material having an active material and an anion component in contact with the active material and different from the anion component of the active material.
  • the second solid electrolyte material is an ionic conductor that is in contact with the first solid electrolyte material, has the same anion component as the first solid electrolyte material, and does not have electronic conductivity.
  • the first solid electrolyte material is Li2ZrS3 .
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a battery with high charge/discharge efficiency and a method for manufacturing the same.
  • a battery according to a first aspect includes a battery element comprising a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer. At least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer includes a solid electrolyte represented by the following formula (1).
  • E is at least one element selected from the group consisting of Al, Sc, Y, Zr, Hf, and lanthanides
  • G is Na, K, Rb, Cs, Mg, Ca
  • Bi is an element
  • D is at least one element selected from the group consisting of CO 3 , SO 4 , BO 3 , PO 4 , NO 3 , SiO 3 , OH and O 2
  • X is F, Cl and Br
  • the amount of water contained in the battery element may be 0.01 mg/g or more and 1 mg/g or less per unit mass.
  • the battery according to the above aspect may further include an exterior body covering the battery element, and a water content in an accommodation space between the battery element and the exterior body may be 400 ppmv or less.
  • a method for manufacturing a battery according to the second aspect includes an element manufacturing step of sandwiching a solid electrolyte layer between a positive electrode active material layer and a negative electrode active material layer and pressure-molding them to manufacture a battery element; a housing step of housing the battery element in an exterior body, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer is represented by the above formula (1).
  • a solid electrolyte is included, and the dew point in the device fabrication process is lower than -30°C and higher than -90°C.
  • the battery according to the above aspect is excellent in charge/discharge efficiency.
  • FIG. 1 is a perspective view of an all-solid-state battery according to an embodiment
  • FIG. 1 is a cross-sectional view of an all-solid-state battery according to an embodiment
  • FIG. 1 is a perspective view of an all-solid-state battery 100 according to this embodiment.
  • An all-solid-state battery 100 shown in FIG. 1 includes a power storage element 10 and an exterior body 20 .
  • the power storage element 10 is housed in the housing space K inside the exterior body 20 .
  • FIG. 1 shows a state immediately before the storage element 10 is housed in the exterior body 20 .
  • the storage element 10 has external terminals 12 and 14 electrically connected to the outside.
  • the exterior body 20 has, for example, a metal foil 22 and resin layers 24 laminated on both sides of the metal foil 22 (see FIG. 2).
  • the exterior body 20 is a metal laminate film in which a metal foil 22 is coated from both sides with polymer films (resin layers).
  • the metal foil 22 is, for example, aluminum foil.
  • the resin layer 24 is, for example, a polymer film such as polypropylene.
  • the resin layer 24 may be the same or different on the inside and outside.
  • a polymer with a high melting point such as polyethylene terephthalate (PET), polyamide (PA), etc.
  • PE polyethylene
  • PP polypropylene
  • PVC polyvinyl chloride
  • FEP fluoroethylene propylene resin
  • CTFE trifluoroethylene chloride resin
  • PVF vinylidene fluoride resin
  • PFA perfluorinated alkoxy resin
  • Materials having high heat resistance, oxidation resistance, reduction resistance, corrosion resistance, and weather resistance can be used. From the viewpoint of further improving heat resistance, oxidation resistance, reduction resistance, corrosion resistance, and weather resistance, a resin layer obtained by molding two or more kinds of resins into a matrix or a resin layer having a multilayer structure of two or more layers is used. You can use it.
  • FIG. 2 is a cross-sectional view of the all-solid-state battery 100 according to this embodiment.
  • the all-solid battery 100 has a positive electrode 11 , a negative electrode 13 , a solid electrolyte layer 15 , external terminals 12 and 14 , and an exterior body 20 .
  • the positive electrode 11 , the negative electrode 13 , the solid electrolyte layer 15 and the external terminals 12 and 14 constitute the storage element 10 .
  • a housing space K is provided between the storage element 10 and the exterior body 20 .
  • the positive electrode 11 has a positive electrode current collector 11A and a positive electrode active material layer 11B.
  • the negative electrode 13 has a negative electrode current collector 13A and a negative electrode active material layer 13B.
  • the solid electrolyte layer 15 is, for example, between the positive electrode active material layer 11B and the negative electrode active material layer 13B.
  • the battery element EL is composed of a positive electrode active material layer 11B, a solid electrolyte layer 15, and a negative electrode active material layer 13B.
  • the all-solid-state battery 100 is charged or discharged by giving and receiving electrons through the positive electrode current collector 11A and the negative electrode current collector 13A and by giving and receiving lithium ions through the solid electrolyte layer 15 .
  • a laminated body in which the all-solid-state battery 100, the positive electrode 11, the negative electrode 13, and the solid electrolyte layer 15 are laminated, or a wound body thereof may be used.
  • the all-solid-state battery 100 is used, for example, as a laminate battery, a prismatic battery, a cylindrical battery, a coin-shaped battery, a button-shaped battery, and the like.
  • the amount of water contained in the battery element EL is 0.01 mg/g or more and 1 mg/g or less per unit mass.
  • the amount of water contained in the battery element EL is preferably 0.01 mg/g or more and 0.5 mg/g or less per unit mass.
  • the amount of water per unit mass contained in the battery element EL is obtained by dividing the weight of the water contained in the battery element EL by the weight of the battery element EL.
  • the amount of water contained in the battery element EL can be measured using, for example, the Karl Fischer method.
  • the water content per unit mass contained in the battery element EL is 0.01 mg/g or more and 1 mg/g or less, particles constituting the battery element EL flow during pressure molding, and cracks occur in the battery element EL. can be suppressed.
  • the charge/discharge efficiency of the all-solid-state battery 100 is improved. This is because the flow of current and lithium ions that circumvents cracks is less likely to occur, and local non-uniformity in charge and discharge reactions can be suppressed.
  • the amount of water in the accommodation space K is, for example, 400 ppmv or less. It is preferable that the water content in the housing space K is, for example, 0.5 ppmv or more and 120 ppmv or less. If the amount of water in the accommodation space K is within the above range, it is possible to suppress the generation of halogenated gas due to the reaction between the solid electrolyte and water.
  • the halogenated gas corrodes metal parts (current collectors, conductive aids, storage containers, etc.) of the battery element 10, and is one of the factors that lower the current collecting function. When the generation of halogenated gas is suppressed, it is possible to suppress the electrochemical reaction from becoming locally non-uniform, and the charge/discharge efficiency of the all-solid-state battery 100 is further improved.
  • Solid electrolyte layer 15 contains a solid electrolyte.
  • the solid electrolyte layer 15 contains, for example, a solid electrolyte represented by the following formula (1). Li 3+ ae E 1-b G b D c X de (1)
  • E is a trivalent or tetravalent element.
  • E is, for example, at least one element selected from the group consisting of Al, Sc, Y, Zr, Hf, and lanthanides.
  • Lanthanides are La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
  • E preferably contains Sc or Zr, particularly preferably Zr.
  • E contains Sc or Zr, the ionic conductivity of the solid electrolyte increases.
  • G is an element that is contained as necessary.
  • G is Na, K, Rb, Cs, Mg, Ca, Sr, Ba, B, Si, Al, Ti, Cu, Sc, Y, Zr, Nb, Ag, In, Sn, Sb, Hf, Ta, W , Au, and Bi.
  • the amount of lithium ions, which are carrier ions increases or decreases, the ionic conductivity increases, and the potential window on the reduction side widens.
  • G in formula (1) may be a monovalent element selected from Na, K, Rb, Cs, and Ag among the above.
  • G is a monovalent element, the resulting solid electrolyte has high ionic conductivity and a wide potential window on the reduction side.
  • G is particularly preferably Na and/or Cs.
  • G in formula (1) may be a divalent element selected from Mg, Ca, Ba, Sr, Cu, and Sn among the above.
  • G is a divalent element, carrier ions increase, resulting in a solid electrolyte with high ionic conductivity and a wide potential window on the reduction side.
  • G is particularly preferably Mg and/or Ca.
  • G in formula (1) may be trivalent selected from Al, Y, In, Au, and Bi among the above.
  • G is a trivalent element, the number of carrier ions increases, resulting in a solid electrolyte with high ionic conductivity.
  • G is preferably any one selected from the group consisting of In, Au, and Bi.
  • G in formula (1) may be Zr, Hf, or Sn, which are tetravalent elements among the above.
  • G is a tetravalent element
  • the solid electrolyte has high ionic conductivity.
  • G particularly preferably contains Hf and/or Zr.
  • G in formula (1) may be a pentavalent element selected from Nb, Sb, and Ta among the above.
  • G is a pentavalent element, holes are formed to facilitate movement of carrier ions, resulting in a solid electrolyte with high ionic conductivity.
  • G particularly preferably contains Sb and/or Ta.
  • G in formula (1) may be W, which is a hexavalent element among the above.
  • the solid electrolyte has high ionic conductivity.
  • D in formula (1) is included as necessary.
  • D is at least one element selected from the group consisting of CO3 , SO4 , BO3 , PO4, NO3 , SiO3, OH and O2 .
  • the potential window on the reduction side of the solid electrolyte becomes wide.
  • D is preferably at least one group selected from the group consisting of SO 4 and CO 3 , particularly preferably SO 4 . The stronger the covalent bond between D and E, the stronger the ionic bond between E and X. Therefore, it is presumed that the E in the compound is difficult to be reduced and the compound has a wide potential window on the reduction side.
  • X in formula (1) is an essential element.
  • X is at least one selected from the group consisting of F, Cl, Br and I;
  • X has a large ionic radius per valence.
  • Including X in the solid electrolyte increases the conductivity of lithium ions in the solid electrolyte.
  • X preferably contains Cl.
  • X preferably contains F in order to improve the balance between oxidation resistance and reduction resistance of the solid electrolyte.
  • X preferably contains I in order to increase the resistance to reduction of the solid electrolyte.
  • a is the above numerical value determined according to the valence of G.
  • b is 0 or more and less than 0.5.
  • the solid electrolyte represented by formula (1) contains E as an essential element, but may not contain G. If b is 0.1 or more, the effect obtained by including G in the solid electrolyte can be sufficiently obtained. Moreover, when b is less than 0.5, it is possible to suppress a decrease in the ionic conductivity of the solid electrolyte due to an excessive G content. b is preferably 0.45 or less.
  • c is 0 or more and 5 or less. Therefore, D does not have to be contained in the solid electrolyte.
  • c is preferably 0.1 or more.
  • c is 0.1 or more, the effect of improving the ionic conductivity due to the inclusion of D can be sufficiently obtained.
  • c is 5 or less, preferably 2.5 or less so that the ionic conductivity of the solid electrolyte does not decrease due to the excessive D content.
  • d is greater than 0 and less than or equal to 7.1.
  • d is 7.1 or less, it is possible to suppress a decrease in the ionic conductivity of the solid electrolyte due to an excessive X content.
  • e is 0 or more and 2 or less. Also, 0 ⁇ de.
  • formula (1) satisfies 0 ⁇ e ⁇ 2 and 0 ⁇ de, the Li content and X content contained in the compound represented by formula (1) are appropriate, and the content of X is too high. As a result, the binding force to carrier ions is suppressed, and the ionic conductivity of the solid electrolyte increases.
  • the solid electrolyte represented by Formula (1) preferably has Zr as E and Cl as X.
  • the compound represented by the formula ( 1 ) serves as a solid electrolyte having a good balance between the ionic conductivity and the potential window . is preferred.
  • Solid electrolyte layer 15 may contain other substances in addition to the solid electrolyte represented by formula (1).
  • the ionic conductivity of the solid electrolyte layer 15 increases. Although the details of the reason are unknown, it is considered as follows.
  • the above other substances have the function of helping the ionic connection between the particles of the solid electrolyte represented by formula (1). It is presumed that this reduces the grain boundary resistance between particles of the solid electrolyte represented by the formula (1) and increases the ionic conductivity of the solid electrolyte layer 15 as a whole.
  • the content of other substances in the solid electrolyte layer 15 is, for example, 0.1% by mass or more and 1.0% by mass or less from the viewpoint of obtaining the effect of reducing the grain boundary resistance between particles. Moreover, when the content of other substances exceeds 1.0% by mass or more, the solid electrolyte layer 15 is likely to crack, thereby hindering ionic connection between particles.
  • the solid electrolyte layer 15 may contain a binder.
  • the solid electrolyte layer 15 is made of, for example, fluorine-based resins such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), imide-based resins such as cellulose, styrene-butadiene rubber, ethylene-propylene rubber, polyimide resin, and polyamide-imide resin. It may also contain a resin, an ion conductive polymer, and the like.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • imide-based resins such as cellulose, styrene-butadiene rubber, ethylene-propylene rubber, polyimide resin, and polyamide-imide resin. It may also contain a resin, an ion conductive polymer, and the like.
  • Ion-conductive polymers are, for example, monomers of polymer compounds (polyether polymer compounds such as polyethylene oxide and polypropylene oxide, polyphosphazenes, etc.) and lithium salts such as LiClO 4 , LiBF 4 , LiPF 6 and LiTFSI. Alternatively, it is a compound obtained by combining an alkali metal salt mainly composed of lithium.
  • the content of the binder is preferably 0.1% by volume or more and 30% by volume or less of the entire solid electrolyte layer 15 .
  • the binder helps maintain good bonding between the solid electrolytes of the solid electrolyte layer 15, prevents cracks between the solid electrolytes, and suppresses a decrease in ionic conductivity and an increase in grain boundary resistance. .
  • the positive electrode 11 has, for example, a positive electrode current collector 11A and a positive electrode active material layer 11B containing a positive electrode active material.
  • the positive electrode current collector 11A preferably has high conductivity.
  • metals such as silver, palladium, gold, platinum, aluminum, copper, nickel, titanium, stainless steel, alloys thereof, or conductive resins can be used.
  • the positive electrode current collector 11A may be in the form of powder, foil, punched, or expanded. From the viewpoint of not degrading the current collecting function of the positive electrode current collector 11A, the positive electrode current collector 11A is stored in a glove box in which argon gas is circulated, using a dehydrated glass bottle or an aluminum laminate bag by heat vacuum drying or the like. preferably.
  • the dew point in the glove box is, for example, lower than -30°C and higher than -90°C.
  • the positive electrode active material layer 11B is formed on one side or both sides of the positive electrode current collector 11A.
  • the positive electrode active material layer 11B contains a positive electrode active material.
  • the positive electrode active material layer 11B may contain, for example, the solid electrolyte represented by the above formula (1).
  • the positive electrode active material layer 11B may also contain a conductive aid and a binder.
  • the positive electrode mixture used for the positive electrode active material layer 11B is produced by mixing, for example, in a glove box in which argon gas is circulated, using an agate mortar, pot mill, blender, hybrid mixer, or the like. From the viewpoint of good pressure molding of the battery element EL, the dew point in the glove box is preferably lower than -30°C and higher than -90°C.
  • the oxygen concentration in the glove box is, for example, 1 ppm or less.
  • the positive electrode active material contained in the positive electrode active material layer 11B includes, for example, lithium-containing transition metal oxides, transition metal fluorides, polyanions, transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, and transition metal oxynitrides. is.
  • the positive electrode active material is not particularly limited as a positive electrode active material as long as it can reversibly progress lithium ion release and absorption, and lithium ion desorption and insertion, and is used in known lithium ion secondary batteries. can be used.
  • the positive electrode active material used for the positive electrode active material layer 11B is stored in a glass bottle or an aluminum laminate bag that has been dehydrated by heat vacuum drying or the like in a glove box in which argon gas is circulated, from the viewpoint of good pressure molding. good to do
  • the dew point in the glove box is preferably ⁇ 30° C. or lower and ⁇ 90° C. or higher.
  • a positive electrode active material that does not contain lithium can be used by starting the battery from discharging.
  • positive electrode active materials include lithium-free metal oxides ( MnO2 , V2O5 , etc.), lithium-free metal sulfides (MoS2, etc.), lithium - free fluorides ( FeF3 , VF3 , etc.). ) and the like.
  • the negative electrode 13 has, for example, a negative electrode current collector 13A and a negative electrode active material layer 13B containing a negative electrode active material.
  • the negative electrode current collector 13A preferably has high conductivity. For example, it is preferable to use metals such as silver, palladium, gold, platinum, aluminum, copper, nickel, stainless steel, iron, alloys thereof, or conductive resins.
  • the negative electrode current collector 13A may be in the form of powder, foil, punched, or expanded.
  • the negative electrode current collector 13A is stored in a glove box in which argon gas is circulated, using a glass bottle or an aluminum laminate bag dehydrated by heat vacuum drying or the like. good to do
  • the dew point in the glove box is preferably lower than -30°C and higher than -90°C.
  • the negative electrode active material layer 13B is formed on one side or both sides of the negative electrode current collector 13A.
  • the negative electrode active material layer 13B contains a negative electrode active material.
  • the negative electrode active material layer 13B may contain, for example, the solid electrolyte represented by the above formula (1). Further, the negative electrode active material layer 13B may contain a conductive aid and a binder.
  • the negative electrode mixture used for the negative electrode active material layer 13B is prepared, for example, by mixing in a glove box in which argon gas is circulated, using an agate mortar, pot mill, blender, hybrid mixer, or the like.
  • the dew point in the glove box is preferably lower than -30°C and higher than -90°C from the viewpoint of good pressure molding of the battery element EL.
  • the oxygen concentration in the glove box is, for example, 1 ppm or less.
  • the negative electrode active material contained in the negative electrode active material layer 13B may be any compound that can occlude and release mobile ions, and negative electrode active materials used in known lithium ion secondary batteries can be used.
  • the negative electrode active material include carbon materials such as simple alkali metals, alkali metal alloys, graphite (natural graphite, artificial graphite), carbon nanotubes, non-graphitizable carbon, easily graphitizable carbon, low-temperature fired carbon, aluminum, silicon, Metals that can combine with metals such as alkali metals such as tin, germanium and their alloys, SiO x (0 ⁇ x ⁇ 2), oxides such as iron oxide, titanium oxide, tin dioxide, lithium titanate (Li 4 Ti 5 O 12 ) and other lithium metal oxides.
  • the negative electrode active material used for the negative electrode active material layer 13B is stored in a glove box in which argon gas is circulated, using a glass bottle or an aluminum laminate bag dehydrated by heat vacuum drying or the like from the viewpoint of good pressure molding. good.
  • the dew point in the glove box is preferably lower than -30°C and higher than -90°C.
  • the conductive aid is not particularly limited as long as it improves the electron conductivity of the positive electrode active material layer 11B and the negative electrode active material layer 13B, and known conductive aids can be used.
  • Conductive agents include, for example, carbon-based materials such as graphite, carbon black, graphene, and carbon nanotubes, metals such as gold, platinum, silver, palladium, aluminum, copper, nickel, stainless steel, iron, and conductive oxides such as ITO. or mixtures thereof.
  • the conductive aid may be in the form of powder or fiber.
  • the conductive aid in a glass bottle or an aluminum laminate bag dehydrated by heat vacuum drying or the like in a glove box in which argon gas is circulated.
  • the dew point in the glove box is preferably lower than -30°C and higher than -90°C.
  • the binders are the positive electrode current collector 11A and the positive electrode active material layer 11B, the negative electrode current collector 13A and the negative electrode active material layer 13B, the positive electrode active material layer 11B, the negative electrode active material layer 13B and the solid electrolyte layer 15, and the positive electrode active material.
  • Various materials forming the layer 11B and various materials forming the negative electrode active material layer 13B are joined.
  • the binder is preferably used within a range that does not impair the functions of the positive electrode active material layer 11B and the negative electrode active material layer 13B.
  • Any binding material may be used as long as the above bonding is possible, and examples thereof include fluororesins such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • the binder for example, cellulose, styrene/butadiene rubber, ethylene/propylene rubber, polyimide resin, polyamideimide resin, or the like may be used.
  • a conductive polymer having electronic conductivity or an ion-conductive polymer having ionic conductivity may be used as the binder.
  • Examples of conductive polymers having electronic conductivity include polyacetylene. In this case, it is not necessary to add a conductive additive because the binder also exhibits the function of the conductive additive particles.
  • the ion-conductive polymer having ion conductivity for example, one that conducts lithium ions can be used, and polymer compounds (polyether-based polymer compounds such as polyethylene oxide and polypropylene oxide, polyphosphazene etc.) with a lithium salt such as LiClO 4 , LiBF 4 , LiPF 6 or an alkali metal salt mainly composed of lithium.
  • Polymerization initiators used for compositing include, for example, photopolymerization initiators or thermal polymerization initiators compatible with the above monomers. Properties required for the binder include oxidation/reduction resistance and good adhesiveness.
  • the content of the binder in the positive electrode active material layer 11B is not particularly limited, it is preferably 0.5 to 30% by volume of the positive electrode active material layer from the viewpoint of lowering the resistance of the positive electrode active material layer 11B. From the viewpoint of improving the energy density, the content of the binder in the positive electrode active material layer 11B is preferably 0% by volume.
  • the content of the binder in the negative electrode active material layer 13B is not particularly limited, it is preferably 0.5 to 30% by volume of the negative electrode active material layer from the viewpoint of lowering the resistance of the negative electrode active material layer 13B. From the viewpoint of improving the energy density, the content of the binder in the positive electrode active material layer 11B is preferably 0% by volume.
  • At least one of the positive electrode active material layer 11B, the negative electrode active material layer 13B, and the solid electrolyte layer 15 contains a non-aqueous electrolyte, an ionic liquid, or a gel electrolyte for the purpose of improving rate characteristics, which are one of battery characteristics. May be mixed.
  • a method for producing the solid electrolyte represented by Formula (1) will be described.
  • a solid electrolyte is obtained by mixing and reacting raw material powders at a predetermined molar ratio so as to obtain a desired composition. Any reaction method can be used, and mechanochemical milling, sintering, melting, liquid phase, solid phase, and the like can be used.
  • a solid electrolyte can be produced, for example, by a mechanochemical milling method.
  • a planetary ball mill device is prepared.
  • a planetary ball mill device is a device that puts media (hard balls to promote grinding or mechanochemical reaction) and materials into a dedicated container, rotates and revolves, and grinds materials or causes mechanochemical reactions between materials. be.
  • a predetermined amount of zirconia balls are prepared in a zirconia container in a glove box in which argon gas is circulated.
  • the dew point in the glove box is preferably lower than -30°C and higher than -90°C.
  • the oxygen concentration in the glove box is, for example, 1 ppm or less.
  • predetermined raw materials are prepared in a zirconia container at a predetermined molar ratio so as to obtain the desired composition, and the container is sealed with a zirconia lid.
  • the raw material may be powder or liquid.
  • titanium chloride (TiCl 4 ) and tin chloride (SnCl 4 ) are liquid at room temperature.
  • a mechanochemical reaction occurs.
  • a powdery solid electrolyte composed of a compound having a desired composition can be obtained.
  • the all-solid-state battery 100 has, for example, an element manufacturing process for manufacturing the storage element 10 and a housing process for housing the storage element 10 in the exterior body 20 .
  • the battery element EL according to this embodiment is manufactured using, for example, a powder molding method.
  • the powder compaction process is carried out in an environment with a dew point lower than -30°C and higher than -90°C.
  • the powder forming method is preferably carried out in an environment with a dew point of -50°C or lower and -85°C or higher.
  • the powder forming method is performed by adjusting the dew point in the glove box, for example.
  • a resin holder having a through hole in the center, a lower punch, and an upper punch are prepared.
  • a metal holder made of die steel may be used instead of the resin holder in order to improve moldability.
  • the diameter of the through hole of the resin holder is, for example, 10 mm, and the diameters of the lower and upper punches are, for example, 9.99 mm.
  • a lower punch is inserted from below the through-hole of the resin holder, and a solid electrolyte in powder form is introduced from the opening side of the resin holder.
  • an upper punch is inserted onto the charged powdery solid electrolyte, placed on a pressing machine, and pressed.
  • the press pressure is, for example, 373 MPa.
  • the powdered solid electrolyte is pressed by an upper punch and a lower punch in a resin holder to form the solid electrolyte layer 15 .
  • the upper punch is once removed, and the material for the positive electrode active material layer is put on the upper punch side of the solid electrolyte layer 15 . After that, the upper punch is inserted again and pressed.
  • the press pressure is, for example, 373 MPa.
  • the material of the positive electrode active material layer becomes the positive electrode active material layer 11B by pressing.
  • the lower punch is temporarily removed, and the material for the negative electrode active material layer is put on the lower punch side of the solid electrolyte layer 15 .
  • the sample is turned upside down, and the material for the negative electrode active material layer is put on the solid electrolyte layer 15 so as to face the positive electrode active material layer 11B.
  • the lower punch is inserted again and pressed.
  • the press pressure is, for example, 373 MPa.
  • the material of the negative electrode active material layer becomes the negative electrode active material layer 13B by pressing.
  • the metal holder is divided, and the battery element EL composed of the positive electrode active material layer 11B, the solid electrolyte layer 15, and the negative electrode active material layer 13B is taken out. Through the above procedure, the battery element EL of this embodiment is obtained.
  • the accommodation step is performed, for example, in a glove box in which argon gas is circulated.
  • the dew point inside the glove box shall be -30°C or lower and -90°C or higher.
  • the dew point in the glove box is preferably ⁇ 50° C. or lower and ⁇ 85° C. or higher.
  • the oxygen concentration in the glove box is, for example, 1 ppm or less.
  • the positive electrode current collector 11A is attached to one end of the external terminal 12 (the portion to be inserted into the exterior body 20) using ultrasonic welding or the like to form a positive electrode current collector unit.
  • the negative electrode current collector 13A is attached to one end of the external terminal 14 (the portion to be inserted into the exterior body 20) using ultrasonic welding or the like to form a negative electrode current collector unit.
  • the positive electrode current collector unit and the negative electrode current collector unit are temporarily heat-bonded to the opening of the exterior body with a gap left between the external terminals 12 and 14 so as not to cause a short circuit.
  • the positive electrode current collector 11A and the negative electrode current collector 13A are arranged so as to overlap each other in plan view.
  • the battery element EL is wrapped so that the positive electrode current collector 11A and the positive electrode active material layer 11B of the battery element EL are connected, and the negative electrode current collector 13A and the negative electrode active material layer 13B of the battery element EL are connected. 20. Finally, the all-solid-state battery 100 is obtained by heat-sealing the opening. The exterior body 20 improves the weather resistance of the all-solid-state battery 100 .
  • stainless steel plates and bakelite plates having screw holes at the four corners may be prepared. good.
  • the stainless steel plate/bakelite plate/all-solid-state battery 100/bakelite plate/stainless steel plate are stacked in this order, and these are attached to the all-solid-state battery 100 by tightening the screws at the four corners.
  • the powder molding method has been described as an example of the method for manufacturing the electric storage device 10 described above, it may also be manufactured by a sheet molding method containing a resin.
  • the sheet molding method is also made in the glove box.
  • the sheet molding method is also carried out in an environment where the dew point is lower than -30°C and higher than -90°C.
  • the sheet molding method is preferably carried out in an environment with a dew point of -50°C or lower and -85°C or higher.
  • the sheet molding method is performed by adjusting the dew point in the glove box, for example.
  • a solid electrolyte paste containing a powdery solid electrolyte is prepared.
  • the solid electrolyte layer 15 is fabricated by applying the prepared solid electrolyte paste to a PET film, a fluororesin film, or the like, drying, preforming, and peeling.
  • the positive electrode 11 is manufactured by applying a positive electrode active material paste containing a positive electrode active material onto the positive electrode current collector 11A, drying it, and temporarily molding it to form a positive electrode active material layer 11B.
  • the negative electrode 13 is manufactured by applying a paste containing a negative electrode active material onto the negative electrode current collector 13A, drying it, and temporarily molding it to form the negative electrode active material layer 13B.
  • the positive electrode 11, the negative electrode 13, and the solid electrolyte layer 15 can be punched into the required size and shape.
  • the solid electrolyte layer 15 is sandwiched between the positive electrode 11 and the negative electrode 13 so that the positive electrode active material layer 11B and the negative electrode active material layer 13B face each other, and the whole is pressed and bonded.
  • the electric storage device 10 of the present embodiment is obtained.
  • the all-solid-state battery 100 according to the present embodiment is manufactured in an environment in which the amount of water is adjusted, and cracks are less likely to occur in the battery element EL.
  • cracks in the battery element EL are suppressed, cracks are bypassed between the positive electrode active material layer 11B and the solid electrolyte layer 15, between the negative electrode active material layer 13B and the solid electrolyte layer 15, and within the solid electrolyte layer 15. This reduces the movement of undesired charges and lithium ions, thereby preventing local unevenness in charging and discharging.
  • the electrochemical reaction of the all-solid-state battery 100 becomes uniform.
  • the all-solid-state battery 100 according to this embodiment has few cracks in the battery element EL, and is excellent in charging and discharging efficiency.
  • Example 1 Synthesis of solid electrolyte-
  • a solid electrolyte was synthesized in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
  • the weighed raw material powder was placed in a Zr container together with Zr balls having a diameter of 5 mm, and mechanochemical milling was performed using a planetary ball mill. The treatment was carried out by mixing for 24 hours at a rotation speed of 500 rpm and then sieving through a 200 ⁇ m mesh. As a result, Li 2 ZrSO 4 Cl 4 powder was obtained as a solid electrolyte.
  • the positive electrode mixture was weighed and mixed in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm, in which argon gas was circulated.
  • Lithium cobaltate (LiCoO 2 ):Li 2 ZrSO 4 Cl 4 :carbon black 77:18:5 parts by weight, and mixed for 3 minutes in an agate mortar to obtain a positive electrode mixture.
  • a battery element composed of a positive electrode active material layer/solid electrolyte layer/negative electrode active material layer was produced by powder molding using the above solid electrolyte, positive electrode mixture, and negative electrode mixture.
  • the battery element was fabricated in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
  • a split holder (metal holder) with a through hole (molding part) with a diameter of 10 mm in the center and a lower punch and an upper punch with a diameter of 9.99 mm were prepared with SKD11 die steel.
  • the metal holder consisted of two metal plates fixed at the four corners with hexagonal screws.
  • the metal holder, lower punch, and upper punch are mirror-finished.
  • a DLC (diamond-like carbon) coating was applied to the molded portion of the metal holder to prevent short circuits during molding and to facilitate removal after molding.
  • a lower punch was inserted from below the metal holder, and 110 mg of solid electrolyte was added through the opening of the metal holder.
  • the upper punch was then inserted over the solid electrolyte.
  • This first unit was placed on a press and pressed at a pressure of 373 MPa to form a solid electrolyte layer. The first unit was removed from the press and the upper punch removed.
  • the fabricated battery element had a diameter of 10 mm, a thickness of 0.7 mm, and 132 mg.
  • the outer periphery of the fabricated battery element was observed with an optical microscope (100x objective lens) to confirm the number of cracks, and the number of cracks per unit area was obtained from the number of cracks/battery element radius x thickness.
  • the water content of the battery element was measured using the Karl Fischer method (coulometric titration method).
  • Ten battery elements (1.32 g) were set in a sample chamber of a moisture vaporizer (VA-300) and heated to 170.degree. Nitrogen gas was used as the carrier gas and adjusted to 0.15 mL/min, and the moisture content was measured using a moisture analyzer (CA-310). Measurements were performed in a glove box filled with nitrogen gas (G1 grade).
  • the obtained battery element was housed in an outer package.
  • the battery elements were housed in a glove box having a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
  • An aluminum laminate bag with a length of 5 cm and a width of 5 cm was prepared as an outer package for enclosing the battery element.
  • an aluminum foil width 4 mm, length 40 mm, thickness 100 ⁇ m
  • maleic anhydride-grafted polypropylene (PP) was placed over a positive electrode current collector ( ⁇ 10 mm, thickness 20 um, aluminum foil).
  • a positive electrode current collector unit was produced by sonic welding. The one to which the positive electrode current collector was not welded was used as an external terminal.
  • a nickel foil (width 4 mm, length 40 mm, thickness 100 ⁇ m) wrapped around the center with maleic anhydride-grafted polypropylene (PP) was placed over the negative electrode current collector ( ⁇ 10 mm, thickness 10 um, copper foil).
  • PP maleic anhydride-grafted polypropylene
  • a space is provided so that the positive electrode current collector and the negative electrode current collector overlap in plan view and a short circuit does not occur between the external terminals, and the external terminals are outside.
  • stainless steel plates and bakelite plates of 10 cm length, 10 cm width, and 5 mm thickness with screw holes at the four corners were prepared, and stacked in the order of stainless steel plate/bakelite plate/all-solid-state battery/bakelite plate/stainless steel plate, and placed in the four corners.
  • a charge-discharge test was performed with the screws of the battery tightened.
  • the charge/discharge test was performed in a constant temperature bath at 25°C. Charging was carried out at 0.1C to 2.8V with constant current and constant voltage (referred to as CCCV). Charging was terminated until the current became 1/20C. The discharge was a constant current discharge at 0.1C to 1.3V. Then, the initial charge/discharge efficiency was calculated from the following formula (2).
  • Example 1 The results of Example 1 are summarized in Tables 1 to 4 described later.
  • Example 2 to 11 Comparative Examples 1 to 3
  • the dew point when synthesizing the solid electrolyte, or the dew point and mixing time when mixing the positive electrode mixture and the negative electrode mixture were used to examine the amount of water contained in the battery element. , and the dew point at the time of molding are changed.
  • Other conditions were the same as in Example 1, and the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
  • the results of Examples 2-11 and Comparative Examples 1-3 are summarized in Table 1 below.
  • Example 12 the solid electrolyte was synthesized in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
  • LiCl and ZrCl 4 as raw material powders were weighed so that the molar ratio was 2:1.
  • the weighed raw material powder was placed in a Zr container together with Zr balls having a diameter of 5 mm, and mechanochemical milling was performed using a planetary ball mill. The treatment was carried out by mixing for 24 hours at a rotation speed of 500 rpm and then sieving through a 200 ⁇ m mesh. Li 2 ZrCl 6 was thus obtained as a solid electrolyte.
  • Example 12 differs from Example 1 in that the composition of the solid electrolyte was changed. Other conditions were the same as in Example 1, and the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
  • Example 13-22 Comparative Examples 4-6
  • the dew point when synthesizing the solid electrolyte, or the dew point and mixing time when mixing the positive electrode mixture and the negative electrode mixture were used to examine the amount of water contained in the battery element. , and the dew point at the time of molding are changed.
  • Other conditions were the same as in Example 12, and the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
  • the results of Examples 13-22 and Comparative Examples 4-6 are summarized in Table 1 below.
  • Example 39 the solid electrolyte was synthesized in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
  • Li 2 O and ZrCl 4 were weighed as raw material powder so that the molar ratio was 1:1.
  • the weighed raw material powder was placed in a Zr container together with Zr balls having a diameter of 5 mm, and mechanochemical milling was performed using a planetary ball mill. The treatment was carried out by mixing for 24 hours at a rotation speed of 500 rpm and then sieving through a 200 ⁇ m mesh. Li 2 ZrOCl 4 was thus obtained as a solid electrolyte.
  • Example 39 differs from Example 1 in that the composition of the solid electrolyte was changed. Other conditions were the same as in Example 1, and the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
  • Examples 40-49, Comparative Examples 7-9 In Examples 40 to 49 and Comparative Examples 7 to 9, the dew point when synthesizing the solid electrolyte, or the dew point and mixing time when mixing the positive electrode mixture and the negative electrode mixture were used to examine the amount of water contained in the battery element. , and the dew point at the time of molding are changed. Other conditions were the same as in Example 39, and the crack occurrence rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured. The results of Examples 40-49 and Comparative Examples 7-9 are summarized in Table 2 below.
  • Example 58 the solid electrolyte was synthesized in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
  • the weighed raw material powder was placed in a Zr container together with Zr balls having a diameter of 5 mm, and mechanochemical milling was performed using a planetary ball mill. The treatment was carried out by mixing for 24 hours at a rotation speed of 500 rpm and then sieving through a 200 ⁇ m mesh.
  • Example 58 differs from Example 1 in that the composition of the solid electrolyte was changed. Other conditions were the same as in Example 1, and the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
  • Example 59-68, Comparative Examples 10-12 In Examples 59 to 68 and Comparative Examples 10 to 12, the dew point during synthesis of the solid electrolyte, or the dew point and mixing time during mixing of the positive electrode mixture and the negative electrode mixture were used to examine the amount of water contained in the battery element. , and the dew point at the time of molding were changed. Other conditions were the same as in Example 58, and the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured. The results of Examples 59-68 and Comparative Examples 10-12 are summarized in Table 2 below.
  • Example 77 the solid electrolyte was synthesized in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm, in which argon gas was circulated.
  • Example 77 differs from Example 1 in that the composition of the solid electrolyte was changed. Other conditions were the same as in Example 1, and the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
  • Example 78-87 Comparative Examples 13-15
  • the dew point during synthesis of the solid electrolyte, or the dew point and mixing time during mixing of the positive electrode mixture and the negative electrode mixture were used to examine the amount of water contained in the battery element. , and the dew point at the time of molding were changed.
  • Other conditions were the same as in Example 77, and the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
  • the results of Examples 78-87 and Comparative Examples 13-15 are summarized in Table 3 below.
  • Example 96 the solid electrolyte was synthesized in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
  • the weighed raw material powder was placed in a Zr container together with Zr balls having a diameter of 5 mm, and mechanochemical milling was performed using a planetary ball mill. The treatment was carried out by mixing for 24 hours at a rotation speed of 500 rpm and then sieving through a 200 ⁇ m mesh.
  • Example 96 differs from Example 1 in that the composition of the solid electrolyte was changed. Other conditions were the same as in Example 1, and the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
  • Example 97-106 Comparative Examples 16-18
  • the dew point at the time of synthesizing the solid electrolyte, or the dew point and the mixing time at the time of mixing the positive electrode mixture and the negative electrode mixture were used to examine the amount of water contained in the battery element. , and the dew point at the time of molding were changed.
  • Other conditions were the same as in Example 96, and the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
  • the results of Examples 97-106 and Comparative Examples 16-18 are summarized in Table 3 below.
  • Example 115 the solid electrolyte was synthesized in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
  • Li 3 PO 4 and ZrCl 4 Li 2 SO 4 as raw material powders were weighed so that the molar ratio was 1:3.
  • the weighed raw material powder was placed in a Zr container together with Zr balls having a diameter of 5 mm, and mechanochemical milling was performed using a planetary ball mill. The treatment was carried out by mixing for 24 hours at a rotation speed of 500 rpm and then sieving through a 200 ⁇ m mesh.
  • Example 115 differs from Example 1 in that the composition of the solid electrolyte was changed. Other conditions were the same as in Example 1, and the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
  • Example 116-125 Comparative Examples 19-21
  • the dew point when synthesizing the solid electrolyte, or the dew point and mixing time when mixing the positive electrode mixture and the negative electrode mixture were used to examine the amount of water contained in the battery element. , and in that the dew point at the time of molding was changed.
  • Other conditions were the same as in Example 115, and the crack occurrence rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
  • the results of Examples 116-125 and Comparative Examples 19-21 are summarized in Table 4 below.
  • Example 134 a solid electrolyte was synthesized in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
  • Li 3 PO 4 and YCl 3 as raw material powders were weighed so that the molar ratio was 1:3.
  • the weighed raw material powder was placed in a Zr container together with Zr balls having a diameter of 5 mm, and mechanochemical milling was performed using a planetary ball mill. The treatment was carried out by mixing for 24 hours at a rotation speed of 500 rpm and then sieving through a 200 ⁇ m mesh.
  • Example 134 differs from Example 1 in that the composition of the solid electrolyte was changed. Other conditions were the same as in Example 1, and the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
  • Examples 135-144, Comparative Examples 22-24 In Examples 135 to 144 and Comparative Examples 22 to 24, the dew point at the time of synthesizing the solid electrolyte, or the dew point and the mixing time at the time of mixing the positive electrode mixture and the negative electrode mixture were used to examine the amount of water contained in the battery element. , and the dew point at the time of molding were changed. Other conditions were the same as in Example 134, and the crack occurrence rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured. The results of Examples 135-144 and Comparative Examples 22-24 are summarized in Table 4 below.
  • Examples 23 to 30 are the same as in Example 4, except that the cell elements are housed at a dew point of ⁇ 20° C. or less and ⁇ 85° C. or more in which argon gas is circulating, and in a glove box with an oxygen concentration of 1 ppm. Then, the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured. In addition, the moisture content in the housing space K was measured using a capacitive transmitter (EasidewOnline, +ED Transmitter-99J, manufactured by Michelle). The results of Examples 23-30 are summarized in Table 5 below.
  • Examples 31 to 28 were the same as in Example 15, except that the cell elements were housed at a dew point of ⁇ 20° C. or less and ⁇ 85° C. or more in which argon gas was circulating, and were carried out in a glove box with an oxygen concentration of 1 ppm. Then, the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured. In addition, the moisture content in the housing space K was measured using a capacitive transmitter (EasidewOnline, +ED Transmitter-99J, manufactured by Michelle). The results of Examples 31-38 are summarized in Table 5 below.
  • Examples 50 to 57 are the same as in Example 42, except that the cell elements are housed at a dew point of ⁇ 20° C. or less and ⁇ 85° C. or more in which argon gas is circulating, and in a glove box with an oxygen concentration of 1 ppm. Then, the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured. In addition, the moisture content in the housing space K was measured using a capacitive transmitter (EasidewOnline, +ED Transmitter-99J, manufactured by Michelle). The results of Examples 50-57 are summarized in Table 6 below.
  • Examples 69 to 76 are the same as in Example 61, except that the battery elements are housed at a dew point of ⁇ 20° C. or less and ⁇ 85° C. or more in which argon gas is circulating, and in a glove box with an oxygen concentration of 1 ppm. Then, the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured. In addition, the moisture content in the housing space K was measured using a capacitive transmitter (EasidewOnline, +ED Transmitter-99J, manufactured by Michelle). The results of Examples 69-76 are summarized in Table 6 below.
  • Examples 88 to 95 are the same as in Example 80, except that the cell elements are housed at a dew point of ⁇ 20° C. or less and ⁇ 85° C. or more in which argon gas is circulating, and in a glove box with an oxygen concentration of 1 ppm. Then, the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured. In addition, the moisture content in the housing space K was measured using a capacitive transmitter (EasidewOnline, +ED Transmitter-99J, manufactured by Michelle). The results of Examples 88-95 are summarized in Table 7 below.
  • Examples 107 to 114 are the same as in Example 99, except that the cell elements are housed at a dew point of ⁇ 20° C. or less and ⁇ 85° C. or more in which argon gas is circulating, and in a glove box with an oxygen concentration of 1 ppm. Then, the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured. In addition, the moisture content in the housing space K was measured using a capacitive transmitter (EasidewOnline, +ED Transmitter-99J, manufactured by Michelle). The results of Examples 107-114 are summarized in Table 7 below.
  • Examples 126 to 133 are the same as in Example 118, except that the battery elements are housed at a dew point of ⁇ 20° C. or less and ⁇ 85° C. or more in which argon gas is circulating, and in a glove box with an oxygen concentration of 1 ppm. Then, the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured. In addition, the moisture content in the housing space K was measured using a capacitive transmitter (EasidewOnline, +ED Transmitter-99J, manufactured by Michelle). The results of Examples 126-133 are summarized in Table 8 below.
  • Examples 145 to 152 are the same as in Example 137, except that the battery elements are housed at a dew point of ⁇ 20° C. or less and ⁇ 85° C. or more in which argon gas is circulating, and in a glove box with an oxygen concentration of 1 ppm. Then, the crack generation rate of the battery element, the water content of the battery element, and the initial charge/discharge efficiency of the all-solid-state battery were measured. In addition, the moisture content in the housing space K was measured using a capacitive transmitter (EasidewOnline, +ED Transmitter-99J, manufactured by Michelle). The results of Examples 145-152 are summarized in Table 8 below.
  • All-solid-state batteries according to Examples 1 to 22, Examples 39 to 49, Examples 58 to 68, Examples 77 to 87, Examples 96 to 106, Examples 115 to 125, and Examples 134 to 144 were heated at 170°C.
  • the water content measured by Karl Fischer is 0.01 mg / g or more and 1 mg / g or less, the generation of cracks is suppressed, and the charge / discharge efficiency is better than the all-solid-state batteries according to Comparative Examples 1 to 24. Met.
  • the all-solid-state batteries according to Example 4 and Examples 23-28 had a water content of 400 ppmv or less in the housing space K, and had better charge-discharge efficiency than the all-solid-state batteries according to Examples 29 and 30. .
  • the all-solid-state batteries according to Examples 15 and 31 to 36 had a water content of 400 ppmv or less in the housing space K, and had better charge-discharge efficiency than the all-solid-state batteries according to Examples 37 and 38. .
  • the all-solid-state batteries according to Examples 42 and 50-55 had a water content of 400 ppmv or less in the housing space K, and had better charge-discharge efficiencies than the all-solid-state batteries according to Examples 56 and 57. .
  • the all-solid-state batteries according to Examples 61 and 69-74 had a water content of 400 ppmv or less in the housing space K, and had better charge-discharge efficiencies than the all-solid-state batteries according to Examples 75 and 76. .
  • the all-solid-state batteries according to Examples 80 and 88-93 had a water content of 400 ppmv or less in the housing space K, and had better charge-discharge efficiencies than the all-solid-state batteries according to Examples 94 and 95. .
  • the all-solid-state batteries according to Examples 99 and 107 to 112 had a water content of 400 ppmv or less in the housing space K, and had better charge-discharge efficiencies than the all-solid-state batteries according to Examples 113 and 114. .
  • the all-solid-state batteries according to Examples 118 and 126 to 131 had a water content of 400 ppmv or less in the housing space K, and had better charge-discharge efficiency than the all-solid-state batteries according to Examples 132 and 133. .
  • the all-solid-state batteries according to Examples 137 and 145 to 150 had a water content of 400 ppmv or less in the housing space K, and had better charge-discharge efficiencies than the all-solid-state batteries according to Examples 151 and 152. .

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

Cette batterie comprend un élément de batterie comprenant une couche de matériau actif d'électrode positive, une couche de matériau actif d'électrode négative et une couche d'électrolyte solide disposée entre la couche de matériau actif d'électrode positive et la couche de matériau actif d'électrode négative. Un électrolyte solide représenté par (1) : Li3+a-eE1-bGbDcXd-e est contenu dans au moins l'une parmi la couche de matériau actif d'électrode positive, la couche de matériau actif d'électrode négative et la couche d'électrolyte solide. La quantité d'eau contenue dans l'élément de batterie va de 0,01 à 1 mg/g par unité de masse.
PCT/JP2022/005058 2021-02-12 2022-02-09 Batterie et procédé de fabrication de batterie WO2022172945A1 (fr)

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JP2021020429A JP2024097093A (ja) 2021-02-12 2021-02-12 電池及び電池の製造方法
JP2021-020429 2021-02-12

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009181920A (ja) * 2008-01-31 2009-08-13 Ohara Inc 固体電池
JP2013020881A (ja) * 2011-07-13 2013-01-31 Toyota Motor Corp 電池
WO2020070955A1 (fr) * 2018-10-01 2020-04-09 パナソニックＩｐマネジメント株式会社 Matériau d'électrolyte solide à base d'halogénure et batterie l'utilisant
WO2021024785A1 (fr) * 2019-08-07 2021-02-11 Tdk株式会社 Électrolyte solide, couche d'électrolyte solide et pile à électrolyte solide
WO2021024876A1 (fr) * 2019-08-07 2021-02-11 Tdk株式会社 Électrolyte solide, couche d'électrolyte solide et batterie à électrolyte solide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009181920A (ja) * 2008-01-31 2009-08-13 Ohara Inc 固体電池
JP2013020881A (ja) * 2011-07-13 2013-01-31 Toyota Motor Corp 電池
WO2020070955A1 (fr) * 2018-10-01 2020-04-09 パナソニックＩｐマネジメント株式会社 Matériau d'électrolyte solide à base d'halogénure et batterie l'utilisant
WO2021024785A1 (fr) * 2019-08-07 2021-02-11 Tdk株式会社 Électrolyte solide, couche d'électrolyte solide et pile à électrolyte solide
WO2021024876A1 (fr) * 2019-08-07 2021-02-11 Tdk株式会社 Électrolyte solide, couche d'électrolyte solide et batterie à électrolyte solide

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