WO2021199677A1 - 固体電解質材料、それを用いた電池、および固体電解質材料の製造方法 - Google Patents

固体電解質材料、それを用いた電池、および固体電解質材料の製造方法 Download PDF

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WO2021199677A1
WO2021199677A1 PCT/JP2021/004428 JP2021004428W WO2021199677A1 WO 2021199677 A1 WO2021199677 A1 WO 2021199677A1 JP 2021004428 W JP2021004428 W JP 2021004428W WO 2021199677 A1 WO2021199677 A1 WO 2021199677A1
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solid electrolyte
electrolyte material
material according
examples
smcl
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English (en)
French (fr)
Japanese (ja)
Inventor
敬太 水野
敬 久保
真志 境田
哲也 浅野
章裕 酒井
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to CN202180021695.XA priority Critical patent/CN115298754A/zh
Priority to EP21779961.8A priority patent/EP4131502A4/en
Priority to JP2022511604A priority patent/JP7664539B2/ja
Publication of WO2021199677A1 publication Critical patent/WO2021199677A1/ja
Priority to US17/956,379 priority patent/US20230040104A1/en
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
    • C01F17/36—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 halogen being the only anion, e.g. NaYF4
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • 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

Definitions

  • the present disclosure relates to a solid electrolyte material, a battery using the solid electrolyte material, and a method for producing the solid electrolyte material.
  • the solid electrolyte materials of the present disclosure include Li, DC, Y, Sm, and X.
  • DC is at least one selected from the group consisting of Mg, Ca, Sr, Ba, and Zn.
  • X is at least one selected from the group consisting of F, Cl, Br, and I.
  • the present disclosure provides a new solid electrolyte material with high usefulness.
  • FIG. 1 shows a cross-sectional view of the battery 1000 according to the second embodiment.
  • FIG. 2 is a flowchart showing an example of the manufacturing method according to the third embodiment.
  • FIG. 3 is a flowchart showing an example of the manufacturing method according to the third embodiment.
  • FIG. 4 is a flowchart showing an example of the manufacturing method according to the third embodiment.
  • FIG. 5 shows a schematic view of a pressure forming die 300 used for evaluating the ionic conductivity of a solid electrolyte material.
  • FIG. 6 is a graph showing a Core-Cole plot obtained by measuring the impedance of the solid electrolyte material according to Example 1.
  • FIG. 1 shows a cross-sectional view of the battery 1000 according to the second embodiment.
  • FIG. 2 is a flowchart showing an example of the manufacturing method according to the third embodiment.
  • FIG. 3 is a flowchart showing an example of the manufacturing method according to the third embodiment.
  • FIG. 4 is a flowchart showing an example of the
  • FIG. 7 is a graph showing X-ray diffraction patterns according to Examples 1 to 6, Example 10 to Example 15, Comparative Example 1, and Comparative Example 2.
  • FIG. 8 is a graph showing X-ray diffraction patterns according to Examples 7, 9, 1, and 2.
  • FIG. 9 is a graph showing the initial discharge characteristics of the battery according to the first embodiment.
  • the solid electrolyte material according to the first embodiment includes Li, DC, Y, Sm, and X.
  • DC is at least one selected from the group consisting of Mg, Ca, Sr, Ba, and Zn.
  • X is at least one selected from the group consisting of F, Cl, Br, and I.
  • the solid electrolyte material according to the first embodiment can have, for example, practical lithium ion conductivity, for example, high lithium ion conductivity.
  • the high lithium ion conductivity is, for example, 1 ⁇ 10 -5 S / cm or more in the vicinity of room temperature. That is, the solid electrolyte material according to the first embodiment can have, for example, an ionic conductivity of 1 ⁇ 10 -5 S / cm or more.
  • the solid electrolyte material according to the first embodiment may substantially consist of Li, DC, Y, Sm, and X.
  • the solid electrolyte material according to the first embodiment is substantially composed of Li, DC, Y, Sm, and X
  • the ratio means the amount of substance of all the elements constituting the solid electrolyte material according to the first embodiment. It means that the ratio (that is, mole fraction) of the total amount of substance of Li, DC, Y, Sm, and X to the total of is 90% or more. As an example, the ratio may be 95% or more.
  • the solid electrolyte material according to the first embodiment may consist only of Li, DC, Y, Sm, and X.
  • DC may be Ca in order to increase the ionic conductivity of the solid electrolyte material.
  • the solid electrolyte material according to the first embodiment may be a material represented by the following composition formula (1).
  • the following four formulas 0 ⁇ a ⁇ 0.25, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 6 and 0 ⁇ d ⁇ 0.05, Is satisfied.
  • the material represented by the composition formula (1) has high ionic conductivity.
  • the mathematical formula: 0.01 ⁇ a ⁇ 0.15 may be satisfied in the composition formula (1).
  • the upper and lower limits of the range of a in the composition formula (1) are more than 0 (ie, 0 ⁇ a), 0.01, 0.1, 0.15, 0.125, 0.15, and 0. It may be specified by any combination selected from the numerical values of 25.
  • the upper and lower limits of the range b in the composition formula (1) are more than 0, 0.01, 0.1, 0.15, 0.2, 0.3, 0.5, 0.7, 0. It may be defined by any combination chosen from numbers 9 and less than 1 (ie b ⁇ 1).
  • the upper and lower limits of the range of c in the composition formula (1) are arbitrary selected from the numerical values of 0, 1.5, 2.5, 3, 3.5, 4, 4.5, 5, and 6. It may be specified by a combination.
  • the X-ray diffraction pattern of the solid electrolyte material in the first embodiment is X by the ⁇ -2 ⁇ method using Cu—K ⁇ rays (wavelengths 1.5405 ⁇ and 1.5444 ⁇ , that is, wavelengths 0.15405 nm and 0.15444 nm). It can be obtained by linear diffraction measurement.
  • the obtained X-ray diffraction pattern at least one peak exists in the range of the diffraction angle 2 ⁇ of 29.0 ° or more and 32.0 ° or less, and the times of 14.0 ° or more and 18.0 ° or less. At least two peaks may be present in the range of the angle 2 ⁇ .
  • a crystal phase having such a peak is called a first crystal phase.
  • the solid electrolyte material containing the first crystal phase has high ionic conductivity. When the solid electrolyte material contains the first crystal phase, a pathway for diffusion of lithium ions is likely to be formed. Therefore, the ionic conductivity is further improved.
  • the first crystal phase belongs to the trigonal system.
  • the crystal phase belonging to the trigonal system has a crystal structure similar to Li 3 ErCl 6 disclosed in ICSD (Inorganic Crystal Structure Database) Collection Code 50151, and has an X-ray diffraction pattern peculiar to this structure.
  • a crystal phase having such a peak is called a second crystal phase.
  • the solid electrolyte material containing the second crystal phase has high ionic conductivity. When the solid electrolyte material contains the second crystal phase, a pathway for diffusion of lithium ions is likely to be formed. Therefore, the ionic conductivity is further improved.
  • the second crystal phase has at least two peaks in the range of the diffraction angle 2 ⁇ of 26.0 ° or more and 35.0 ° or less, and 13.7 ° or more and 16.0 °. At least one peak may be present in the range of the following diffraction angles 2 ⁇ .
  • Such solid electrolyte materials have higher ionic conductivity. When the solid electrolyte material contains a crystal phase having the above peak, a pathway for diffusion of lithium ions is more likely to be formed. Therefore, the ionic conductivity is further improved.
  • the second crystal phase belongs to the monoclinic system.
  • the crystal phase belonging to the monoclinic system has a crystal structure similar to Li 3 ErBr 6 disclosed in ICSD (Inorganic Crystal Structure Database) Collection Code 50182, and has an X-ray diffraction pattern peculiar to this structure.
  • the solid electrolyte material according to the first embodiment may further contain a third crystal phase different from the first crystal phase and the second crystal phase. That is, the solid electrolyte material according to the first embodiment may further contain a third crystal phase having a peak other than the above-mentioned range of the diffraction angle 2 ⁇ .
  • the third crystal phase may be interposed between the first crystal phase and the second crystal phase.
  • the solid electrolyte material according to the first embodiment may be crystalline or amorphous.
  • the shape of the solid electrolyte material according to the first embodiment is not limited. Examples of such shapes are needle-shaped, spherical, or elliptical spherical.
  • the solid electrolyte material according to the first embodiment may be particles.
  • the solid electrolyte material according to the first embodiment may be formed to have the shape of a pellet or a plate.
  • FIG. 1 shows a cross-sectional view of the battery 1000 according to the second embodiment.
  • the positive electrode 201 contains the positive electrode active material particles 204 and the solid electrolyte particles 100.
  • the electrolyte layer 202 contains an electrolyte material.
  • the electrolyte material is, for example, a solid electrolyte material.
  • the negative electrode 203 contains negative electrode active material particles 205 and solid electrolyte particles 100.
  • the ratio of the volume of the positive electrode active material particle 204 to the total volume of the positive electrode active material particle 204 and the volume of the solid electrolyte particle 100 is 0.30 or more and 0.95. It may be as follows.
  • the positive electrode 201 may have a thickness of 10 ⁇ m or more and 500 ⁇ m or less.
  • the electrolyte layer 202 contains an electrolyte material.
  • the electrolyte material is, for example, the solid electrolyte material according to the first embodiment.
  • the electrolyte layer 202 may be a solid electrolyte layer.
  • X' is at least one selected from the group consisting of F, Cl, Br, and I.
  • the solid electrolyte material according to the first embodiment is referred to as the first solid electrolyte material.
  • a solid electrolyte material different from the solid electrolyte material according to the first embodiment is called a second solid electrolyte material.
  • the electrolyte layer 202 may contain not only the first solid electrolyte material but also the second solid electrolyte material. In the electrolyte layer 202, the first solid electrolyte material and the second solid electrolyte material may be uniformly dispersed. The layer made of the first solid electrolyte material and the layer made of the second solid electrolyte material may be laminated along the stacking direction of the battery 1000.
  • the electrolyte layer 202 may have a thickness of 1 ⁇ m or more and 1000 ⁇ m or less. When the electrolyte layer 202 has a thickness of 1 ⁇ m or more, the positive electrode 201 and the negative electrode 203 are less likely to be short-circuited. When the electrolyte layer 202 has a thickness of 1000 ⁇ m or less, the battery can operate at high output.
  • the negative electrode 203 contains a material capable of occluding and releasing metal ions such as lithium ions.
  • the material is, for example, a negative electrode active material (for example, negative electrode active material particles 205).
  • Examples of negative electrode active materials are metal materials, carbon materials, oxides, nitrides, tin compounds, or silicon compounds.
  • the metal material may be a simple substance metal or an alloy.
  • Examples of metallic materials are lithium metals or lithium alloys.
  • Examples of carbon materials are natural graphite, coke, developing carbon, carbon fibers, spheroidal carbon, artificial graphite, or amorphous carbon. From the point of view of capacitance density, suitable examples of the negative electrode active material are silicon (ie, Si), tin (ie, Sn), a silicon compound, or a tin compound.
  • the negative electrode active material particles 205 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less. When the negative electrode active material particles 205 have a median diameter of 0.1 ⁇ m or more, the dispersed state of the negative electrode active material particles 205 and the solid electrolyte particles 100 becomes good in the negative electrode 203. This improves the charge / discharge characteristics of the battery. When the negative electrode active material particles 205 have a median diameter of 100 ⁇ m or less, the lithium diffusion rate in the negative electrode active material particles 205 is improved. This allows the battery to operate at high output.
  • the ratio of the volume of the negative electrode active material particles 205 to the total volume of the negative electrode active material particles 205 and the volume of the solid electrolyte particles 100 is 0.30 or more and 0.95. It may be as follows.
  • At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 contains a second solid electrolyte material for the purpose of enhancing ionic conductivity, chemical stability, and electrochemical stability. May be.
  • the second solid electrolyte material may be a halide solid electrolyte.
  • halide solid electrolyte Li 2 MgX '4, Li 2 FeX' 4, Li (Al, Ga, In) X '4, Li 3 (Al, Ga, In) X' 6, or LiI.
  • X' is at least one selected from the group consisting of F, Cl, Br, and I.
  • the second solid electrolyte material may be a sulfide solid electrolyte.
  • Examples of sulfide solid electrolytes are Li 2 SP 2 S 5 , Li 2 S-SiS 2 , Li 2 SB 2 S 3 , Li 2 S-GeS 2 , Li 3.25 Ge 0.25 P 0.75 S 4 , or It is Li 10 GeP 2 S 12 .
  • the second solid electrolyte material may be an oxide solid electrolyte.
  • a solid oxide electrolyte is (I) NASICON type solid electrolytes such as LiTi 2 (PO 4 ) 3 or elemental substituents thereof, (Ii) Perovskite-type solid electrolytes such as (LaLi) TiO 3, (Iii) Lithium-type solid electrolytes such as Li 14 ZnGe 4 O 16 , Li 4 SiO 4 , LiGeO 4 or elemental substituents thereof, (Iv) a garnet-type solid electrolyte such as Li 7 La 3 Zr 2 O 12 or an elemental substituent thereof, or (v) Li 3 PO 4 or an N-substituted product thereof.
  • NASICON type solid electrolytes such as LiTi 2 (PO 4 ) 3 or elemental substituents thereof
  • Perovskite-type solid electrolytes such as (LaLi) TiO 3
  • Lithium-type solid electrolytes such as Li 14 ZnGe 4 O 16 , Li 4 SiO 4 , LiGe
  • the second solid electrolyte material may be an organic polymer solid electrolyte.
  • organic polymer solid electrolytes examples include polymer compounds and lithium salt compounds.
  • the polymer compound may have an ethylene oxide structure. Since the polymer compound having an ethylene oxide structure can contain a large amount of lithium salts, the ionic conductivity can be further enhanced.
  • lithium salt LiPF 6, LiBF 4, LiSbF 6, LiAsF 6, LiSO 3 CF 3, LiN (SO 2 CF 3) 2, LiN (SO 2 C 2 F 5) 2, LiN (SO 2 CF 3) (SO 2 C 4 F 9 ) or LiC (SO 2 CF 3 ) 3 .
  • One lithium salt selected from these may be used alone. Alternatively, a mixture of two or more lithium salts selected from these may be used.
  • At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 is a non-aqueous electrolyte solution, a gel electrolyte, or ions for the purpose of facilitating the transfer of lithium ions and improving the output characteristics of the battery. It may contain a liquid.
  • the non-aqueous electrolyte solution contains a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
  • non-aqueous solvents examples include cyclic carbonate solvents, chain carbonate solvents, cyclic ether solvents, chain ether solvents, cyclic ester solvents, chain ester solvents, or fluorine solvents.
  • cyclic carbonate solvents are ethylene carbonate, propylene carbonate, or butylene carbonate.
  • chain carbonate solvents are dimethyl carbonate, ethyl methyl carbonate, or diethyl carbonate.
  • Examples of cyclic ether solvents are tetrahydrofuran, 1,4-dioxane, or 1,3-dioxolane.
  • chain ether solvents are 1,2-dimethoxyethane or 1,2-diethoxyethane.
  • An example of a cyclic ester solvent is ⁇ -butyrolactone.
  • An example of a chain ester solvent is methyl acetate.
  • fluorine solvents are fluoroethylene carbonate, methyl fluoropropionate, fluorobenzene, fluoroethyl methyl carbonate, or fluorodimethylene carbonate.
  • One non-aqueous solvent selected from these may be used alone. Alternatively, a mixture of two or more non-aqueous solvents selected from these may be used.
  • lithium salt LiPF 6, LiBF 4, LiSbF 6, LiAsF 6, LiSO 3 CF 3, LiN (SO 2 CF 3) 2, LiN (SO 2 C 2 F 5) 2, LiN (SO 2 CF 3) (SO 2 C 4 F 9 ) or LiC (SO 2 CF 3 ) 3 .
  • One lithium salt selected from these may be used alone. Alternatively, a mixture of two or more lithium salts selected from these may be used.
  • the concentration of the lithium salt is, for example, 0.5 mol / liter or more and 2 mol / liter or less.
  • a polymer material impregnated with a non-aqueous electrolyte solution can be used.
  • polymer materials are polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethylmethacrylate, or polymers with ethylene oxide bonds.
  • cations contained in ionic liquids are (I) Aliphatic chain quaternary salts such as tetraalkylammonium or tetraalkylphosphonium, (Ii) Aliphatic cyclic ammonium such as pyrrolidiniums, morpholiniums, imidazoliniums, tetrahydropyrimidiniums, piperaziniums, or piperidiniums, or (iii) nitrogen-containing heteros such as pyridiniums or imidazoliums. It is a ring aromatic cation.
  • anion contained in the ionic liquid PF 6 -, BF 4 - , SbF 6 -, AsF 6 -, SO 3 CF 3 -, N (SO 2 CF 3) 2 -, N (SO 2 C 2 F 5 ) 2 -, N (SO 2 CF 3) (SO 2 C 4 F 9) -, or C (SO 2 CF 3) 3 - a.
  • the ionic liquid may contain a lithium salt.
  • At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a binder for the purpose of improving the adhesion between the particles.
  • binders are polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylic nitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, Polyacrylic acid hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinylidene acetate, polyvinylpyrrolidone, polyether, polyether sulfone, hexafluoropolypropylene, styrene butadiene rubber , Or carboxymethyl cellulose.
  • Copolymers can also be used as binders.
  • binders are tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid.
  • a copolymer of two or more materials selected from the group consisting of hexadiene A mixture of two or more selected from the above materials may be used as a binder.
  • a conductive aid is (I) Graphites such as natural graphite or artificial graphite, (Ii) Carbon blacks such as acetylene black or ketjen black, (Iii) Conductive fibers such as carbon fibers or metal fibers, (Iv) Carbon Fluoride, (V) Metal powders such as aluminum, (Vi) Conductive whiskers, such as zinc oxide or potassium titanate, (Vii) A conductive metal oxide such as titanium oxide, or (viii) a conductive polymer compound such as polyaniline, polypyrrole, or polythiophene.
  • the conductive auxiliary agent (i) or (ii) described above may be used.
  • Examples of the shape of the battery according to the second embodiment are coin type, cylindrical type, square type, sheet type, button type, flat type, or laminated type.
  • a material for forming a positive electrode, a material for forming an electrolyte layer, and a material for forming a negative electrode are prepared, and the positive electrode, the electrolyte layer, and the negative electrode are arranged in this order by a known method. It may be manufactured by producing the laminated body.
  • FIG. 2 is a flowchart showing an example of the manufacturing method according to the third embodiment.
  • the manufacturing method according to the third embodiment includes a firing step S1000.
  • the mixed material is fired in an inert gas atmosphere.
  • the mixed material fired in the firing step S1000 includes a halide containing Li, a halide containing Y, a halide containing Sm, and a halide containing DC.
  • DC is at least one selected from the group consisting of Mg, Ca, Sr, and Ba.
  • the solid electrolyte material according to the first embodiment can be produced by the production method according to the third embodiment.
  • the manufacturing method according to the third embodiment is an industrially highly productive method.
  • An industrially productive method is, for example, a method that can be mass-produced at low cost. That is, the production method according to the third embodiment includes Li, DC, Y, and Sm by a simple production method, that is, firing in an inert gas atmosphere, without using a vacuum sealing tube and a planetary ball mill. Solid electrolyte materials can be produced.
  • the powder of the mixed material may be placed in a container (for example, a crucible) and fired in a heating furnace.
  • the mixed material may be fired at 200 ° C. or higher and 650 ° C. or lower.
  • the solid electrolyte material can be produced by a highly productive method.
  • the firing temperature By setting the firing temperature to 200 ° C. or higher, the mixed materials can be sufficiently reacted.
  • the mixed material may be fired at 400 ° C. or higher and 650 ° C. or lower in order to produce a solid electrolyte material having higher ionic conductivity by an industrially productive method. By setting the firing temperature to 400 ° C. or higher, the mixed materials can be sufficiently reacted.
  • the mixed material may be fired in 1 minute or more and 3600 minutes or less when the firing temperature is 400 ° C. or higher.
  • the solid electrolyte material can be produced by an industrially highly productive method.
  • the firing time By setting the firing time to 1 minute or more, the mixed material can be sufficiently reacted.
  • the firing time By setting the firing time to 3600 minutes or less, volatilization of the fired product can be suppressed. That is, a solid electrolyte material having a desired composition ratio or a composition close to the desired one can be obtained.
  • the mixed material may be fired for 180 minutes or less (eg, 1 minute or more and 180 minutes or less) in order to produce a solid electrolyte material having higher ionic conductivity by an industrially productive method.
  • the firing time By setting the firing time to 180 minutes or less, the volatilization of the solid electrolyte material as the fired product can be further suppressed.
  • a solid electrolyte material having a desired composition ratio or a composition close to the desired one can be obtained (that is, composition deviation can be further suppressed).
  • the inert gas for example, helium, nitrogen, or argon can be used.
  • the mixed material may be a material in which Li ⁇ , Y ⁇ 3 , Sm ⁇ 3 , and DC ⁇ 2 are mixed.
  • ⁇ , ⁇ , ⁇ , and ⁇ are at least one independently selected from the group consisting of F, Cl, Br, and I, respectively. This makes it possible to easily produce a solid electrolyte material containing Li, DC, Y, and Sm.
  • the mixed material may be a material in which Me X f is further mixed.
  • M is selected from the group consisting of Na, K, In, Sn, Bi, La, Ce, Pr, Nd, Pm, Gd, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
  • X is at least one selected from the group consisting of F, Cl, Br, and I. e> 0 and f> 0 are satisfied. Thereby, the characteristics (for example, ionic conductivity) of the produced solid electrolyte material can be improved.
  • ⁇ , ⁇ , ⁇ , and ⁇ may be at least one independently selected from the group consisting of Cl and Br, respectively. Thereby, the characteristics (for example, ionic conductivity) of the produced solid electrolyte material can be further improved.
  • At least one selected from the group consisting of Li ⁇ , Y ⁇ 3 , Sm ⁇ 3 , and DC ⁇ 2 contained in the mixed material is a cation in which a part of the cations (that is, Li, Y, Sm, and DC) is another cation. It may be replaced by (for example, M described above).
  • FIG. 3 is a flowchart showing an example of the manufacturing method according to the third embodiment.
  • a halide containing Li, a halide containing Y, a halide containing Sm, and a halide containing DC may be prepared and mixed so as to have a desired molar ratio.
  • a known mixing device eg, mortar, blender, or ball mill
  • mortar, blender, or ball mill may be used to mix the ingredients.
  • the mixing step S1100 powders of each raw material may be prepared and mixed. At this time, in the firing step S1000, the powdered mixed material may be fired.
  • the powdery mixed material obtained in the mixing step S1100 may be formed into pellets by pressurization. Alternatively, in the firing step S1000, the pellet-shaped mixed material may be fired.
  • a raw material containing Li ⁇ as a main component, a raw material containing Y ⁇ 3 as a main component, a raw material containing Sm ⁇ 3 as a main component, and a raw material containing DC ⁇ 2 as a main component may be mixed.
  • the main component is the component contained most in the molar ratio.
  • materials such as Li ⁇ , Y ⁇ 3 , Sm ⁇ 3 , or DC ⁇ 2 may be synthesized.
  • a known commercially available product for example, a material having a purity of 99% or more may be used.
  • At least one selected from the group consisting of prepared Li ⁇ , Y ⁇ 3 , Sm ⁇ 3 , and DC ⁇ 2 is one in which some of the cations (ie, Li, Y, Sm, and DC) are different cations (eg, Li, Y, Sm, and DC). , May be replaced by M) above.
  • Example 1> Preparation of solid electrolyte material
  • dry argon atmosphere LiBr, LiCl, CaCl 2 , YCl 3 , and SmCl 3 are used as raw material powders
  • LiBr: LiCl: CaCl 2 : YCl 3 : SmCl 3 2: 0.8: 0.1: 0.8: 0.2 was prepared so as to have a molar ratio.
  • These raw material powders were crushed and mixed in an agate mortar. The obtained mixed powder was placed in an alumina crucible and calcined at 500 ° C.
  • FIG. 5 shows a schematic view of the pressure forming die 300 used to evaluate the ionic conductivity of the solid electrolyte material.
  • the pressure forming die 300 included a punch upper part 301, a frame type 302, and a punch lower part 303. Both the upper punch 301 and the lower punch 303 were made of electron-conducting stainless steel.
  • the frame 302 was made of insulating polycarbonate.
  • the upper punch 301 and the lower punch 303 were connected to a potentiostat (Princeton Applied Research, VersaSTAT4) equipped with a frequency response analyzer.
  • the upper part 301 of the punch was connected to the working electrode and the terminal for measuring the potential.
  • the lower part of the punch 303 was connected to the counter electrode and the reference electrode.
  • the impedance of the solid electrolyte material was measured at room temperature by an electrochemical impedance measurement method.
  • FIG. 6 is a graph showing a Core-Cole plot obtained by measuring the impedance of the solid electrolyte material according to Example 1.
  • the real value of the impedance at the measurement point where the absolute value of the phase of the complex impedance is the smallest was regarded as the resistance value of the solid electrolyte material to ionic conduction. See the arrow R SE shown in FIG. 6 for the real value.
  • the ionic conductivity was calculated based on the following mathematical formula (2).
  • ⁇ (R SE ⁇ S / t) -1 ...
  • ⁇ represents ionic conductivity.
  • S represents the contact area of the solid electrolyte material with the punch upper portion 301. That is, S is equal to the cross-sectional area of the hollow portion of the frame mold 302 in FIG.
  • R SE represents the resistance value of the solid electrolyte material in impedance measurement.
  • t represents the thickness of the solid electrolyte material. That is, t is equal to the thickness of the layer formed from the powder 101 of the solid electrolyte material in FIG.
  • the ionic conductivity of the solid electrolyte material according to Example 1 measured at 24 ° C. was 2.86 ⁇ 10 -3 S / cm.
  • FIG. 7 is a graph showing an X-ray diffraction pattern of the solid electrolyte material of Example 1. The results shown in FIG. 7 were measured by the following methods.
  • the X-ray diffraction pattern of the solid electrolyte material according to Example 1 was measured using an X-ray diffractometer (Rigaku, MiniFlex600) in a dry environment having a dew point of ⁇ 50 ° C. or lower.
  • Cu-K ⁇ rays (wavelengths 1.5405 ⁇ and 1.5444 ⁇ ) were used as the X-ray source, and the X-ray diffraction pattern was measured by the ⁇ -2 ⁇ method.
  • the metal In (thickness 200 ⁇ m), the metal Li (thickness 200 ⁇ m), and the metal In (thickness 200 ⁇ m) were laminated in this order on the solid electrolyte layer.
  • a pressure of 80 MPa was applied to the obtained laminate to form a second electrode.
  • a current collector made of stainless steel was attached to the first electrode and the second electrode, and a current collector lead was attached to the current collector.
  • the battery according to Example 1 was charged until a voltage of 3.68 V was reached at a current density of 78 ⁇ A / cm 2.
  • the current density corresponds to a 0.05 C rate.
  • Example 2 The battery according to Example 1 was then discharged until a voltage of 1.88 V was reached at a current density of 78 ⁇ A / cm 2.
  • the battery according to Example 1 had an initial discharge capacity of 1.2 mAh.
  • Example 2 (Preparation of solid electrolyte material)
  • LiBr, LiCl, CaCl 2 , YCl 3 , and SmCl 3 were used as raw material powders
  • LiBr: LiCl: CaCl 2 : YCl 3 : SmCl 3 2: 0.8: 0.1: 0.9. It was prepared to have a molar ratio of: 0.1.
  • Example 26 to 46 the solid electrolyte materials according to Examples 26 to 46 were obtained in the same manner as in Example 1 except for the firing time and temperature.
  • the firing temperature and firing time are shown in Table 1-2.
  • FIG. 7 is a graph showing the X-ray diffraction pattern of the solid electrolyte material according to Examples 1 to 6, 10 to 12, 14 and 16 to 19. The angles of the observed diffraction peaks are shown in Table 2-1. All of the solid electrolyte materials shown in FIG. 7 had a first crystal phase.
  • FIG. 8 is a graph showing the X-ray diffraction pattern of the solid electrolyte material according to Examples 7 to 9, 13, and 15. The angles of the observed diffraction peaks are shown in Table 2-2. All of the solid electrolyte materials shown in FIG. 8 had a second crystal phase. Examples 8, 9, and 15 had a first crystal phase as well as a second crystal phase.
  • the solid electrolyte material according to Examples 1 to 46 has a higher ionic conductivity of 1 ⁇ 10 -5 S / cm or more near room temperature.
  • the solid electrolyte material has high ionic conductivity if the DC is at least one selected from the group consisting of Ca, Mg, and Sr. As is apparent when Example 1 is compared with Examples 16 and 17, if the DC is Ca, the solid electrolyte material has higher ionic conductivity.
  • the solid electrolyte material has high ionic conductivity.
  • the solid electrolyte material has higher ionic conductivity when the firing temperature is 450 ° C. or higher and 650 ° C. or lower. Have. It is considered that this is because the solid electrolyte material has higher crystallinity. As will be apparent when comparing Examples 1, 26 to 28, 35, and 40 with Examples 26 and 27, the solid electrolyte material will have even higher ionic conductivity if the firing temperature is 450 ° C. or higher and 550 ° C. or lower. Have. It is considered that this is because the occurrence of thermal decomposition at high temperature, that is, the occurrence of composition deviation of the solid electrolyte material can be suppressed.
  • the solid electrolyte material has higher ionic conductivity. It is considered that this is because the thermal decomposition (that is, the composition deviation of the solid electrolyte material) due to the long-time firing can be suppressed.
  • the solid electrolyte material according to the present disclosure is suitable for providing a battery having high lithium ion conductivity and being able to be charged and discharged well. Further, the method for producing a solid electrolyte material according to the present disclosure is an industrially highly productive method capable of easily producing a solid electrolyte material having high ionic conductivity.
  • the solid electrolyte material of the present disclosure and the method for producing the same are used in, for example, a battery (for example, an all-solid-state lithium ion secondary battery).

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PCT/JP2021/004428 2020-03-31 2021-02-05 固体電解質材料、それを用いた電池、および固体電解質材料の製造方法 Ceased WO2021199677A1 (ja)

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EP4186862A4 (en) * 2020-07-22 2024-02-21 Panasonic Intellectual Property Management Co., Ltd. SOLID ELECTROLYTE MATERIAL AND BATTERY THEREOF

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EP4325615A4 (en) * 2021-04-13 2025-08-06 Panasonic Ip Man Co Ltd BATTERY

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