WO2023013305A1 - 正極材料、それを用いた電池、および電池の充電方法 - Google Patents

正極材料、それを用いた電池、および電池の充電方法 Download PDF

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WO2023013305A1
WO2023013305A1 PCT/JP2022/025777 JP2022025777W WO2023013305A1 WO 2023013305 A1 WO2023013305 A1 WO 2023013305A1 JP 2022025777 W JP2022025777 W JP 2022025777W WO 2023013305 A1 WO2023013305 A1 WO 2023013305A1
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positive electrode
solid electrolyte
battery
active material
material according
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French (fr)
Japanese (ja)
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真志 境田
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Panasonic Intellectual Property Management Co Ltd
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Priority to JP2023539705A priority Critical patent/JPWO2023013305A1/ja
Priority to EP22852731.3A priority patent/EP4383362A4/en
Priority to CN202280049810.9A priority patent/CN117751464A/zh
Publication of WO2023013305A1 publication Critical patent/WO2023013305A1/ja
Priority to US18/418,294 priority patent/US20240250291A1/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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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 positive electrode material, a battery using the same, and a battery charging method.
  • Patent Document 1 discloses an all-solid battery using a halide solid electrolyte.
  • Patent Document 2 discloses an all-solid battery using a sulfide solid electrolyte.
  • An object of the present disclosure is to provide a positive electrode material suitable for use in a high operating potential range.
  • the positive electrode material of the present disclosure is including a positive electrode active material and a halide solid electrolyte,
  • the halide solid electrolyte contains F
  • the positive electrode active material is capable of intercalating and deintercalating lithium ions at greater than 4.3 V vs. lithium.
  • the present disclosure provides cathode materials suitable for use in the high operating potential range.
  • FIG. 1 shows a cross-sectional view of a cathode material 1000 according to a first embodiment.
  • FIG. 2 shows a cross-sectional view of a battery 1100 according to the first embodiment.
  • FIG. 3 is a graph showing initial charge/discharge characteristics of batteries according to Examples 1-2 and Comparative Examples 1-2.
  • a cathode material according to the first embodiment includes a cathode active material and a halide solid electrolyte.
  • the halide solid electrolyte contains F.
  • the positive electrode active material is capable of intercalating and deintercalating lithium ions at greater than 4.3 V vs. lithium.
  • One way to increase the energy density of a battery is to increase the operating potential range of the positive electrode. That is, the current 4.3 V vs.
  • One is to operate the cell at potentials higher than Li/Li + .
  • Patent Literature 1 discloses a halide solid electrolyte.
  • a halide solid electrolyte containing Cl, Br, or I as a halogen element is 4.3 V vs.
  • oxidative decomposition occurs.
  • the charge/discharge characteristics of the battery deteriorate.
  • Patent Document 2 discloses a sulfide solid electrolyte. Since the sulfide solid electrolyte has low oxidation resistance, the positive electrode is applied at 4.3 V vs. Good charge/discharge characteristics cannot be obtained when operated at potentials higher than Li/Li + .
  • the halide solid electrolyte contained in the positive electrode material according to the first embodiment contains F, it can have high oxidation resistance. This is because F has a high redox potential. Therefore, if the positive electrode material according to the first embodiment is used, 4.3 V vs. Even if the battery is operated at a potential higher than Li/Li + , it is possible to realize a battery with excellent charge-discharge efficiency.
  • the upper limit of the operating potential range of the battery is not particularly limited, for example, 6.0 V vs. Li/Li + or less.
  • the positive electrode material according to the first embodiment is suitable for use in a high operating potential range, that is, the operating potential range of the positive electrode can be increased. Therefore, the positive electrode material according to the first embodiment can increase the energy density of the battery.
  • the halide solid electrolyte may contain anions other than F in order to increase the ion conductivity of the positive electrode material.
  • anions are Cl, Br, I, O, S or Se.
  • the ratio of the amount of F substance to the total amount of the anions constituting the halide solid electrolyte may be 0.50 or more and 1.0 or less.
  • the halide solid electrolyte may contain at least one selected from the group consisting of Ti, Zr, and Al, Li, and F in order to increase the ion conductivity of the positive electrode material.
  • the halide solid electrolyte may consist essentially of Li, M, Al, and F.
  • M is at least one selected from the group consisting of Ti and Zr.
  • the phrase "the halide solid electrolyte consists essentially of Li, M, Al, and F" means that Li, M, Al, and It means that the total ratio (ie, mole fraction) of the substance amount of F is 90% or more. As an example, the ratio (ie, mole fraction) may be 95% or greater.
  • the halide solid electrolyte may consist of Li, M, Al, and F only.
  • the halide solid electrolyte may contain elements that are unavoidably mixed. Examples of such elements are hydrogen, oxygen or nitrogen. Such elements can be present in the raw powder of the solid electrolyte material or in the atmosphere for manufacturing or storing the solid electrolyte material.
  • the halide solid electrolyte may be represented by the following compositional formula (1).
  • M is at least one selected from the group consisting of Ti and Zr.
  • 0 ⁇ x ⁇ 1 and 0 ⁇ b ⁇ 1.5 are satisfied.
  • Such a halide solid electrolyte represented by formula (1) has high ionic conductivity.
  • the upper and lower limits of the range of x in formula (1) are 0.01, 0.2, 0.4, 0.5, 0.5, 0.7, 0.8, 0.95, and 0 It can be defined by any combination of numbers selected from 0.99.
  • the upper and lower limits of the range of b in formula (1) are 0.7, 0.8, 0.9, 0.96, 1, 1.04, 1.1, 1.2, and 1.3. can be defined by any combination selected from the numerical values of
  • M may be Zr.
  • M may be Ti.
  • the halide solid electrolyte may be Li2.8Zr0.2Al0.8F6 or Li2.7Ti0.3Al0.7F6 .
  • the halogenated solid electrolyte may be crystalline or amorphous.
  • the halogenated solid electrolyte may contain a crystalline phase represented by Formula (1).
  • the shape of the halide solid electrolyte is not limited. Examples of such shapes are acicular, spherical, or ellipsoidal.
  • the halide solid electrolyte may be particles.
  • the halide solid electrolyte may have the shape of pellets or plates.
  • the solid electrolyte may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less, and a median diameter of 0.5 ⁇ m or more and 10 ⁇ m. It may have a median diameter of: This allows the halide solid electrolyte and other materials (eg, active materials) to be well dispersed.
  • the median diameter means the particle size at which the cumulative deposition is 50% in the volume-based particle size distribution.
  • the volume-based particle size distribution is measured by, for example, a laser diffraction measurement device or an image analysis device.
  • Examples of positive electrode active materials are lithium-containing transition metal oxides, transition metal fluorides, polyanions, fluorinated polyanion materials, transition metal oxyfluorides, transition metal oxysulfides, or transition metal oxynitrides.
  • Examples of lithium-containing transition metal oxides are Li(Ni,Co,Al) O2 , Li(Ni,Co,Mn) O2 or Li(Ni,Mn) O2 .
  • Li(Ni,Co,Mn) O2 may be, for example, LiCoO2 .
  • Li(Ni,Mn) O2 may be , for example, Li( Ni0.5Mn1.5 ) O2 .
  • a lithium-containing transition metal oxide or a lithium-containing transition metal oxyfluoride may be used as a positive electrode active material that operates particularly at a high potential.
  • Examples of the crystal structure of the positive electrode active material are a layered rocksalt structure, a rocksalt structure, or a spinel structure.
  • the positive electrode material according to the first embodiment may contain at least one selected from the group consisting of lithium-containing transition metal oxides and lithium-containing transition metal oxyfluorides as a positive electrode active material.
  • the positive electrode active material may have at least one crystal structure selected from the group consisting of a layered rocksalt structure, a rocksalt structure, and a spinel structure.
  • the positive electrode active material may contain Ni in order to increase the operating potential of the battery.
  • Li(Ni 0.5 Mn 1.5 )O 2 having a spinel structure may be used as the positive electrode active material.
  • FIG. 1 is a cross-sectional view showing a positive electrode material 1000 according to the first embodiment.
  • a positive electrode material 1000 according to the first embodiment includes a positive electrode active material 204 and a halide solid electrolyte 100 .
  • the halide solid electrolyte 100 contains F.
  • the shape of the positive electrode active material 204 is not limited to a specific shape.
  • the cathode active material 204 may be particles.
  • the positive electrode active material 204 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less. When the positive electrode active material 204 has a median diameter of 0.1 ⁇ m or more, the positive electrode active material 204 and other materials (eg, the halide solid electrolyte 100) can be well dispersed. This improves the charge/discharge characteristics of the battery. When the positive electrode active material 204 has a median diameter of 100 ⁇ m or less, the diffusion rate of lithium in the positive electrode active material 204 is improved. This allows the battery to operate at high output.
  • the positive electrode active material 204 may have a median diameter larger than that of the halide solid electrolyte 100 . Thereby, the positive electrode active material 204 and the halide solid electrolyte 100 can be well dispersed.
  • a coating layer may be formed on at least part of the surface of the positive electrode active material 204 .
  • a coating layer can be formed on the surface of the positive electrode active material 204, for example, before mixing with the conductive aid and the binder.
  • coating materials contained in the coating layer are sulfide solid electrolytes or oxide solid electrolytes.
  • FIG. 2 shows a cross-sectional view of the battery 1100 according to the first embodiment.
  • a battery 1100 according to the second embodiment includes a positive electrode 201 , an electrolyte layer 202 and a negative electrode 203 .
  • Electrolyte layer 202 is provided between positive electrode 201 and negative electrode 203 .
  • the positive electrode 201 contains the positive electrode material according to the first embodiment (eg, positive electrode material 1000).
  • the energy density of the battery can be improved.
  • the battery charging method according to the second embodiment may include, for example, charging the battery such that the charging potential of the positive electrode 201 exceeds 4.3 V with respect to lithium.
  • the positive electrode 201 contains a positive electrode active material 204 and a solid electrolyte 110 .
  • Solid electrolyte 110 is, namely, the halide solid electrolyte described in the first embodiment.
  • the electrolyte layer 202 contains an electrolyte material.
  • the negative electrode 203 contains a negative electrode active material 205 and a solid electrolyte 110 .
  • the solid electrolyte 110 included in the electrolyte layer 202 may be the halide solid electrolyte described in the first embodiment.
  • the ratio of the volume of the positive electrode active material 204 to the total volume of the positive electrode active material 204 and the volume of the solid electrolyte 110 is 0.30 or more and 0.95. It may be below.
  • 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, a solid electrolyte material.
  • the electrolyte layer 202 may be a solid electrolyte layer.
  • the solid electrolyte material included in the electrolyte layer 202 may be the halide solid electrolyte described in the first embodiment.
  • Examples of solid electrolytes contained in the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 include, in addition to the halide solid electrolytes described in the first embodiment, sulfide solid electrolytes, oxide solid electrolytes, halide solid electrolytes, Or an organic polymer solid electrolyte.
  • sulfide solid electrolytes are Li 2 SP 2 S 5 , Li 2 S-SiS 2 , Li 2 S-B 2 S 3 , Li 2 S-GeS 2 , Li 3.25 Ge 0.25 P 0.75 S 4 , or Li10GeP2S12 . _
  • oxide solid electrolytes are (i) NASICON-type solid electrolytes such as LiTi2 ( PO4 ) 3 or elemental substitutions thereof; (ii) perovskite-type solid electrolytes such as (LaLi) TiO3 ; (iii) LISICON -type solid electrolytes such as Li14ZnGe4O16 , Li4SiO4 , LiGeO4 or elemental substitutions thereof ; (iv) garnet- type solid electrolytes such as Li7La3Zr2O12 or its elemental substitutions, or ( v) Li3PO4 or its N substitutions, is.
  • NASICON-type solid electrolytes such as LiTi2 ( PO4 ) 3 or elemental substitutions thereof
  • perovskite-type solid electrolytes such as (LaLi) TiO3 ;
  • LISICON -type solid electrolytes such as Li14ZnGe4O16 , Li4SiO4 , LiGeO4
  • halide solid electrolytes are Li2MgX4 , Li2FeX4 , Li(Al,Ga,In) X4 , Li3 ( Al ,Ga,In) X6 , or LiI.
  • X is at least one selected from the group consisting of F, Cl, Br and I.
  • halide solid electrolyte material is the compound represented by LiaMebYcZ6 .
  • Me is at least one selected from the group consisting of metal elements other than Li and Y and metalloid elements.
  • Z is at least one selected from the group consisting of F, Cl, Br and I;
  • m represents the valence of Me.
  • m represents the valence of Me.
  • Temimetallic elements are B, Si, Ge, As, Sb, and Te.
  • Metallic element means all elements contained in Groups 1 to 12 of the periodic table (excluding hydrogen), and all elements contained in Groups 13 to 16 of the periodic table (however, B , Si, Ge, As, Sb, Te, C, N, P, O, S, and Se).
  • Me is the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb to improve the ionic conductivity of the halide solid electrolyte. It may be at least one selected from.
  • the halide solid electrolyte may be Li3YCl6 or Li3YBr6 .
  • organic polymer solid electrolytes examples include polymeric compounds and lithium salt compounds.
  • the polymer compound may have an ethylene oxide structure. Since a polymer compound having an ethylene oxide structure can contain a large amount of lithium salt, the ionic conductivity can be further increased.
  • lithium salts are LiPF6 , LiBF4 , LiSbF6, LiAsF6 , LiSO3CF3 , LiN ( SO2CF3 ) 2 , LiN( SO2C2F5 ) 2 , LiN( SO2CF3 ) . ( SO2C4F9 ) , or LiC ( SO2CF3 )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 electrolyte layer 202 may contain two or more solid electrolyte materials. Two or more solid electrolyte materials may be uniformly dispersed in the electrolyte layer 202 . A layer made of the first solid electrolyte material and a layer made of the second solid electrolyte material may be stacked along the stacking direction of battery 1100 .
  • the battery according to the second embodiment may include the positive electrode 201, the second electrolyte layer, the first electrolyte layer, and the negative electrode 203 in this order.
  • the solid electrolyte material contained in the first electrolyte layer may have a lower reduction potential than the solid electrolyte material contained in the second electrolyte layer.
  • the solid electrolyte material contained in the second electrolyte layer can be used without being reduced. As a result, the charging and discharging efficiency of the battery can be improved.
  • the electrolyte layer 202 may have a thickness of 1 ⁇ m or more and 1000 ⁇ m or less.
  • the negative electrode 203 contains a material capable of intercalating and deintercalating metal ions (eg, lithium ions).
  • the material is, for example, the negative electrode active material 205 .
  • Examples of the negative electrode active material 205 are metal materials, carbon materials, oxides, nitrides, tin compounds, or silicon compounds.
  • the metallic material may be a single metal or an alloy.
  • Examples of metallic materials are lithium metal or lithium alloys.
  • Examples of carbon materials are natural graphite, coke, ungraphitized carbon, carbon fibers, spherical carbon, artificial graphite, or amorphous carbon. From the viewpoint of capacity density, suitable examples of negative electrode active materials are silicon (ie, Si), tin (ie, Sn), silicon compounds, or tin compounds.
  • the shape of the negative electrode active material 205 is not limited to a specific shape.
  • the negative electrode active material 205 may be particles.
  • the negative electrode active material 205 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less.
  • negative electrode active material 205 and solid electrolyte 110 can be well dispersed in negative electrode 203 . Thereby, the charge/discharge characteristics of the battery 1100 are improved.
  • the negative electrode active material 205 has a median diameter of 100 ⁇ m or less, the diffusion rate of lithium in the negative electrode active material 205 is improved. This allows battery 1100 to operate at high output.
  • the negative electrode active material 205 may have a larger median diameter than the solid electrolyte 110 . Thereby, the negative electrode active material 205 and the solid electrolyte 110 can be dispersed satisfactorily in the negative electrode 203 .
  • the ratio of the volume of negative electrode active material 205 to the sum of the volume of negative electrode active material 205 and the volume of solid electrolyte 110 is 0.30 or more and 0.95. It may be below.
  • the negative electrode 203 may have a thickness of 10 ⁇ m or more and 500 ⁇ m or less.
  • At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 is composed of a non-aqueous electrolyte liquid, a gel electrolyte, or an ion in order to facilitate the transfer of lithium ions and improve the output characteristics of the battery. It may contain liquids.
  • the non-aqueous electrolyte 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.
  • linear 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 linear ester solvent is methyl acetate.
  • fluorosolvents 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 combination of two or more non-aqueous solvents selected from these may be used.
  • lithium salts are LiPF6 , LiBF4 , LiSbF6, LiAsF6 , LiSO3CF3 , LiN ( SO2CF3 ) 2 , LiN( SO2C2F5 ) 2 , LiN( SO2CF3 ) . ( SO2C4F9 ) , or LiC ( SO2CF3 )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 lithium salt concentration is, for example, in the range of 0.5 mol/L or more and 2 mol/L or less.
  • a polymer material impregnated with a non-aqueous electrolyte can be used as the gel electrolyte.
  • examples of polymeric materials are polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, or polymers with ethylene oxide linkages.
  • ionic liquids examples include (i) aliphatic chain quaternary salts such as tetraalkylammonium or tetraalkylphosphonium; (ii) aliphatic cyclic ammoniums such as pyrrolidiniums, morpholiniums, imidazoliniums, tetrahydropyrimidiniums, piperaziniums, or piperidiniums; or (iii) nitrogen-containing heteroatoms such as pyridiniums or imidazoliums ring aromatic cations, is.
  • aliphatic chain quaternary salts such as tetraalkylammonium or tetraalkylphosphonium
  • aliphatic cyclic ammoniums such as pyrrolidiniums, morpholiniums, imidazoliniums, tetrahydropyrimidiniums, piperaziniums, or piperidiniums
  • nitrogen-containing heteroatoms such as pyridin
  • Examples of anions contained in the ionic liquid are 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 ( SO2CF3 ) ( SO2C4F9 )- , or C( SO2CF3 ) 3- .
  • 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 in order to improve adhesion between particles.
  • binders include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, 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, polyvinyl 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 ethers, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid , and hexadiene.
  • a mixture of two or more materials selected from these may be used as the binder.
  • At least one selected from the positive electrode 201 and the negative electrode 203 may contain a conductive aid in order to improve electronic conductivity.
  • Examples of conductive aids are (i) graphites such as natural or artificial graphite; (ii) carbon blacks such as acetylene black or ketjen black; (iii) conductive fibers such as carbon 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 polymeric compound such as polyaniline, polypyrrole, or polythiophene; is.
  • the conductive aid (i) or (ii) may be used.
  • Examples of the shape of the battery according to the second embodiment are coin-shaped, cylindrical, rectangular, sheet-shaped, button-shaped, flat-shaped, and laminated.
  • 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 made by making laminated laminates.
  • Example 1> Preparation of Halide Solid Electrolyte
  • a molar ratio of 2:0.8 was prepared.
  • These raw powders were ground and mixed in a mortar. The obtained mixed powder was put into a ball mill pod together with ⁇ -butyrolactone as an organic solvent. Then, using a planetary ball mill, milling was performed at 500 rpm for 12 hours.
  • the solid content ratio was set to 50%, and balls with a diameter of 1 mm were used.
  • the solid content ratio is calculated by ⁇ (mass of input raw material)/(mass of input raw material+mass of input solvent) ⁇ 100.
  • the balls were separated to obtain a slurry.
  • the resulting slurry was dried at 200° C. for 1 hour under nitrogen flow using a mantle heater.
  • a powder of the halide solid electrolyte of Example 1 was obtained by pulverizing the resulting solid in a mortar.
  • the halide solid electrolyte material of Example 1 had a composition represented by Li2.8Zr0.2Al0.8F6 .
  • Example 1 (Production of battery) In a dry argon atmosphere, the halide solid electrolyte of Example 1 and the active material Li(Ni 0.5 Mn 1.5 )O 2 were prepared in a volume ratio of 40:60. These ingredients were mixed in an agate mortar. Thus, the positive electrode material of Example 1 was obtained.
  • Example 1 In an insulating cylinder having an inner diameter of 9.5 mm, Li 3 PS 4 (57.41 mg), the halide solid electrolyte of Example 1 (26 mg), and the positive electrode material of Example 1 (9.9 mg) Laminated in this order.
  • a pressure of 720 MPa was applied to the obtained laminate to form a first electrolyte layer, a second electrolyte layer, and a positive electrode. That is, the second electrolyte layer was sandwiched between the first electrolyte layer and the positive electrode.
  • the thicknesses of the first electrolyte layer and the second electrolyte layer were 450 ⁇ m and 150 ⁇ m, respectively.
  • metal Li (thickness: 200 ⁇ m) was laminated on the first electrolyte layer. A pressure of 10 MPa was applied to the obtained laminate to form a negative electrode.
  • current collectors made of stainless steel were attached to the positive and negative electrodes, and current collecting leads were attached to the current collectors.
  • Example 1 a battery according to Example 1 was obtained.
  • FIG. 3 is a graph showing the initial discharge characteristics of the battery according to Example 1.
  • FIG. Initial charge/discharge characteristics were measured by the following method.
  • the voltage on the vertical axis shown in FIG. 3 is the voltage with respect to lithium, that is, it corresponds to "electrode potential [V vs. Li/Li + ]".
  • the battery according to Example 1 was placed in a constant temperature bath at 85°C.
  • a cell according to Example 1 was charged at a current density of 18 ⁇ A/cm 2 until a voltage of 5.0 V was reached. This current density corresponds to a 0.01C rate.
  • Example 1 The cell according to Example 1 was then discharged at a current density of 18 ⁇ A/cm 2 until a voltage of 3.5 V was reached.
  • the battery according to Example 1 had an initial charge/discharge efficiency of 83.7%.
  • Example 2 (Preparation of Halide Solid Electrolyte)
  • These raw powders were ground and mixed in a mortar.
  • the obtained mixed powder was milled at 500 rpm for 12 hours using a planetary ball mill.
  • the powder of the halide solid electrolyte of Example 2 was obtained.
  • the halide solid electrolyte of Example 2 had a composition represented by Li2.7Ti0.3Al0.7F6 .
  • Example 2 (Production of battery) In a dry argon atmosphere, the halide solid electrolyte of Example 2 and the active material Li(Ni 0.5 Mn 1.5 )O 2 were prepared in a volume ratio of 40:60. These ingredients were mixed in an agate mortar. Thus, the positive electrode material of Example 2 was obtained.
  • a battery of Example 2 was obtained in the same manner as in Example 1 except for the above items.
  • Example 1 A charge/discharge test was performed in the same manner as in Example 1 except that Li 3 PS 4 was used instead of the halide solid electrolyte of Example 1. However, the battery was produced without using the first electrolyte layer. Also, the thickness of the second electrolyte layer was set to 600 ⁇ m. That is, in the battery of Comparative Example 1, a Li 3 PS 4 layer having a thickness of 600 ⁇ m was provided as an electrolyte layer between the positive electrode and the negative electrode.
  • LiCl and YCl 3 were prepared as raw powders in a molar ratio of 2.7:1.1.
  • the raw material powder mixture was fired at 550° C. for 1 hour in an argon atmosphere.
  • a solid electrolyte Li 2.7 Y 1.1 Cl 6 was obtained.
  • Example 1 A charge/discharge test was performed in the same manner as in Example 1 except that Li 2.7 Y 1.1 Cl 6 was used instead of the halide solid electrolyte of Example 1.
  • the battery using the positive electrode material according to the present disclosure is 4.3 V vs. Good charge/discharge characteristics were exhibited even in a high potential operating range exceeding Li/Li + .
  • the positive electrode material of the present disclosure is used, for example, in all-solid lithium ion secondary batteries.

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PCT/JP2022/025777 2021-08-06 2022-06-28 正極材料、それを用いた電池、および電池の充電方法 Ceased WO2023013305A1 (ja)

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WO2024176982A1 (ja) * 2023-02-24 2024-08-29 パナソニックＩｐマネジメント株式会社 正極及びそれを用いた電池
WO2025069384A1 (ja) * 2023-09-29 2025-04-03 国立大学法人名古屋工業大学 電池
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WO2024176982A1 (ja) * 2023-02-24 2024-08-29 パナソニックＩｐマネジメント株式会社 正極及びそれを用いた電池
WO2025069384A1 (ja) * 2023-09-29 2025-04-03 国立大学法人名古屋工業大学 電池
WO2025069383A1 (ja) 2023-09-29 2025-04-03 国立大学法人名古屋工業大学 電池
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