WO2022254956A1 - Matériau d'électrolyte solide et batterie l'utilisant - Google Patents

Matériau d'électrolyte solide et batterie l'utilisant Download PDF

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WO2022254956A1
WO2022254956A1 PCT/JP2022/016861 JP2022016861W WO2022254956A1 WO 2022254956 A1 WO2022254956 A1 WO 2022254956A1 JP 2022016861 W JP2022016861 W JP 2022016861W WO 2022254956 A1 WO2022254956 A1 WO 2022254956A1
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solid electrolyte
electrolyte material
negative electrode
positive electrode
battery
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English (en)
Japanese (ja)
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智康 横山
恒星 大浦
卓弥 成瀬
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パナソニックＩｐマネジメント株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/04—Binary compounds including binary selenium-tellurium compounds
    • 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
    • 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
    • H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
    • 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

Definitions

  • the present disclosure relates to solid electrolyte materials and batteries using the same.
  • Patent Document 1 discloses solid-phase electrolytes Li 8 N 2 Te and Li 7.75 N 1.75 Te 1.25 containing tellurium charged to ⁇ 2 valences, Li 7.75 N 1.75 Se 1.25 containing selenium charged to ⁇ 2 valences, and Li 8 N 2 S and Li 7.75 N 1.75 S 1.25 containing negatively charged sulfur are disclosed.
  • Non-Patent Document 1 discloses a solid-phase electrolyte Li 9 NS 3 containing -2-charged sulfur.
  • An object of the present disclosure is to provide a novel solid electrolyte material with lithium ion conductivity.
  • This disclosure is contains lithium and chalcogen elements, The valence of the chalcogen element is greater than -2 and less than 0, A solid electrolyte material is provided.
  • the present disclosure can provide a novel solid electrolyte material with lithium ion conductivity.
  • FIG. 1 shows a cross-sectional view of a battery 1000 according to a second embodiment.
  • FIG. 2 shows a schematic diagram of a pressure forming die 300 used to evaluate the ionic conductivity of solid electrolyte materials.
  • FIG. 3 is a graph showing Cole-Cole plots obtained by impedance measurement of solid electrolyte materials according to Example 2 and Comparative Example 2.
  • FIG. 4 is a graph showing the initial charge/discharge characteristics of the battery according to Example 1.
  • FIG. 1 shows a cross-sectional view of a battery 1000 according to a second embodiment.
  • FIG. 2 shows a schematic diagram of a pressure forming die 300 used to evaluate the ionic conductivity of solid electrolyte materials.
  • FIG. 3 is a graph showing Cole-Cole plots obtained by impedance measurement of solid electrolyte materials according to Example 2 and Comparative Example 2.
  • FIG. 4 is a graph showing the initial charge/discharge characteristics of the battery according to Example 1.
  • the solid electrolyte material of the present embodiment contains lithium and chalcogen elements.
  • the valence of the chalcogen element is greater than -2 and less than 0.
  • a solid electrolyte material is a solid electrolyte material suitable for improving lithium ion conductivity.
  • Solid electrolyte materials for example, have high lithium ion conductivity. Therefore, solid electrolyte materials can be used to obtain batteries with excellent charge-discharge characteristics.
  • An example of such a battery is an all-solid secondary battery.
  • an example of high lithium ion conductivity is, for example, 4.0 ⁇ 10 ⁇ 5 S/cm or more near room temperature.
  • the solid electrolyte material can have, for example, an ionic conductivity of 4.0 ⁇ 10 ⁇ 5 S/cm or higher.
  • Room temperature is, for example, 25°C.
  • chalcogen elements mean oxygen, sulfur, selenium, and tellurium.
  • Chalcogen elements that is, group 16 elements
  • sulfur, selenium, and tellurium have strong covalent bonding properties, so they can stably adopt a state having a higher valence than -2, that is, a weakly negatively charged state.
  • the weakening of the negative charge of the anion weakens the Coulomb interaction between the anion and the lithium ion, thereby improving the ionic conductivity of the solid electrolyte material.
  • the valence of the chalcogen element is -1.5, -1 or -0.5, and may be -1 or -0.5 in particular.
  • XPS measurement can be used to evaluate the chargeability of elements.
  • the binding energy obtained by XPS measurement is higher than the single metal and lower than the chalcogen element charged to -2 valence
  • the chalcogen element to be measured is less than 0 valence, and a valence greater than -2. can be determined to be charged.
  • the valence of the chalcogen element is greater than -2 and less than 0.
  • valence in this specification means the formal charge amount, that is, the "formal valence", not the charge amount actually charged on the ion.
  • Lithium and nitrogen have strong ionicity, so that lithium takes a constant formal valence of +1 and nitrogen takes a constant formal valence of -3 in any compositional region. Then, the formal valence of the chalcogen element is calculated so that the entire composition formula is neutral.
  • the solid electrolyte material may contain elements that are unavoidably mixed.
  • An example of such an element is hydrogen.
  • 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.
  • Elements that are unavoidably mixed in the solid electrolyte material are, for example, 1 mol % or less.
  • the solid electrolyte material according to the first embodiment may further contain nitrogen in order to increase the ionic conductivity of the solid electrolyte material.
  • the solid electrolyte material according to the first embodiment may consist of lithium, chalcogen elements, and nitrogen.
  • Composed of lithium, chalcogen elements, and nitrogen means that no other elements are intentionally added except for inevitable impurities. For example, it means that the molar ratio (that is, molar fraction) of the total substance amount of lithium, chalcogen element, and nitrogen to the total substance amount of all elements constituting the solid electrolyte material is 95% or more.
  • the solid electrolyte material may be a material represented by the following compositional formula (1).
  • Ch is at least one selected from the group consisting of S, Se, and Te.
  • the solid electrolyte material represented by compositional formula (1) has high ionic conductivity.
  • Ch may contain Te in order to increase the ionic conductivity of the solid electrolyte material.
  • Ch may be Te.
  • Ch may contain Se in order to increase the ionic conductivity of the solid electrolyte material.
  • Ch may be Se.
  • Ch may contain S in the composition formula (1).
  • Ch may be S.
  • composition formula (1) 0.01 ⁇ x ⁇ 0.99 and 0.1 ⁇ y ⁇ 0.9 may be satisfied, and 0.2 ⁇ x ⁇ 0.8 and 0.3 ⁇ y ⁇ 0.6 may be satisfied.
  • the shape of the solid electrolyte material is not limited. Examples of such shapes are acicular, spherical, or ellipsoidal.
  • the solid electrolyte material may be particles.
  • the solid electrolyte material may have the shape of pellets or plates.
  • the solid electrolyte material When the shape of the solid electrolyte material is particulate (for example, spherical), the solid electrolyte material may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less, or a median diameter of 0.5 ⁇ m or more and 10 ⁇ m or less. diameter. This allows good dispersion of the solid electrolyte material and other materials.
  • median particle size is meant the particle size for which the cumulative deposition in the volume-based particle size distribution is equal to 50%.
  • the volume-based particle size distribution is measured by, for example, a laser diffraction measurement device or an image analysis device.
  • a solid electrolyte material is manufactured, for example, by the following method.
  • raw material powders of single chalcogen elements are mixed so as to have the desired composition.
  • the target composition is Li 7 N 2 Te
  • the raw powders may be mixed in pre-adjusted molar ratios to compensate for possible compositional variations in the synthesis process.
  • lithium metal sulfur, selenium, or tellurium metal may be used.
  • a mixture of raw material powders is mechanochemically reacted with each other in a mixing device such as a planetary ball mill to obtain a reactant. That is, the raw material powders are reacted with each other using the method of mechanochemical milling.
  • the reactants may be fired in vacuum or in an inert atmosphere.
  • a mixture of raw material powders may be fired in vacuum or in an inert atmosphere to obtain a reactant.
  • inert atmospheres include helium atmosphere, argon atmosphere, and nitrogen atmosphere.
  • the solid electrolyte material according to the first embodiment is obtained.
  • a battery according to the second embodiment includes a positive electrode, an electrolyte layer, and a negative electrode.
  • An electrolyte layer is disposed between the positive and negative electrodes.
  • At least one selected from the group consisting of the positive electrode, the electrolyte layer, and the negative electrode contains the solid electrolyte material according to the first embodiment.
  • the battery according to the second embodiment contains the solid electrolyte material according to the first embodiment, it has excellent charge/discharge characteristics.
  • FIG. 1 shows a cross-sectional view of a battery 1000 according to the second embodiment.
  • a battery 1000 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 .
  • a positive electrode 201 contains a positive electrode active material 204 and a solid electrolyte 100 .
  • the negative electrode 203 contains a negative electrode active material 205 and a solid electrolyte 100 .
  • the solid electrolyte 100 includes the solid electrolyte material according to the first embodiment.
  • the solid electrolyte 100 may be particles containing the solid electrolyte material according to the first embodiment as a main component.
  • a particle containing the solid electrolyte material according to the first embodiment as a main component means a particle in which the component contained in the largest molar ratio is the solid electrolyte material according to the first embodiment.
  • the solid electrolyte 100 may be particles made of the solid electrolyte material according to the first embodiment.
  • the positive electrode 201 contains a material capable of intercalating and deintercalating metal ions such as lithium ions.
  • the material is, for example, the positive electrode active material 204 .
  • positive electrode active materials are lithium-containing transition metal oxides, transition metal fluorides, polyanion materials, fluorinated polyanion materials, transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, or transition metal oxynitrides.
  • lithium-containing transition metal oxides are Li(Ni,Co,Mn) O2 , Li(Ni,Co,Al) O2 or LiCoO2 .
  • (A, B, C) means "at least one selected from the group consisting of A, B, and C.”
  • 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.
  • positive electrode active material 204 and solid electrolyte 100 can be well dispersed in positive electrode 201 . Thereby, the charge/discharge characteristics of the battery 1000 are improved.
  • 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 battery 1000 to operate at high output.
  • the positive electrode active material 204 may have a larger median diameter than the solid electrolyte 100 . Thereby, the positive electrode active material 204 and the solid electrolyte 100 can be well dispersed.
  • 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 100 is 0.30 or more and 0.95 or less.
  • 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 electrolyte layer 202 may contain the solid electrolyte material according to the first embodiment.
  • the electrolyte layer 202 may contain 50% by mass or more of the solid electrolyte material according to the first embodiment.
  • the electrolyte layer 202 may contain 70% by mass or more of the solid electrolyte material according to the first embodiment.
  • the electrolyte layer 202 may contain 90% by mass or more of the solid electrolyte material according to the first embodiment.
  • the electrolyte layer 202 may consist only of the solid electrolyte material according to the first embodiment.
  • the solid electrolyte material according to the first embodiment is hereinafter referred to as the first solid electrolyte material.
  • a solid electrolyte material different from the first solid electrolyte material is referred to as 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. 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 1000 .
  • the electrolyte layer 202 may consist only of the second solid electrolyte material.
  • 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 short circuit between the positive electrode 201 and the negative electrode 203 is less likely to occur. If the electrolyte layer 202 has a thickness of 1000 ⁇ m or less, the battery 1000 can operate at high power.
  • the negative electrode 203 contains a material capable of intercalating and deintercalating metal ions such as 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.
  • suitable examples of negative electrode active material 205 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 100 can be well dispersed in negative electrode 203 . Thereby, the charge/discharge characteristics of the battery 1000 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 1000 to operate at high output.
  • the negative electrode active material 205 may have a larger median diameter than the solid electrolyte 100 . Thereby, the negative electrode active material 205 and the solid electrolyte 100 can be well dispersed.
  • the ratio of the volume of the negative electrode active material 205 to the total volume of the negative electrode active material 205 and the volume of the solid electrolyte 100 is 0.30 or more and 0.95 or less.
  • 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 positive electrode 201, electrolyte layer 202, and negative electrode 203 contains a second solid electrolyte material for the purpose of enhancing ion conductivity, chemical stability, and electrochemical stability. may be
  • the second solid electrolyte material may be a halide solid electrolyte.
  • halide solid electrolytes are Li 2 MgX' 4 , Li 2 FeX' 4 , Li(Al,Ga,In)X' 4 or Li 3 (Al,Ga,In)X' 6 .
  • X' is at least one selected from the group consisting of F, Cl, Br and I.
  • halide solid electrolyte is the compound represented by LipMeqYrZ6 .
  • Me is at least one element selected from the group consisting of metal elements other than Li and Y and metalloid elements.
  • the value of m' represents the valence of Me.
  • Simetallic 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 ( , B, Si, Ge, As, Sb, Te, C, N, P, O, S, and Se).
  • Z is at least one selected from the group consisting of F, Cl, Br and I;
  • Me is selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb. may be at least one.
  • the second solid electrolyte material may be a sulfide 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 . _
  • the second solid electrolyte material may be an oxide solid electrolyte.
  • oxide solid electrolytes examples include (i) NASICON-type solid electrolytes such as LiTi2 ( PO4 ) 3 or elemental substitutions thereof, (ii) perovskite-type solid electrolytes such as (LaLi) TiO3 , and (iii) LISICON-type solid electrolytes such as Li14ZnGe4O16 , Li4SiO4 , LiGeO4 or elemental substitutions thereof , (iv) garnet - type solid electrolytes such as Li7La3Zr2O12 or elemental substitutions thereof or ( v) Li3PO4 or its N-substitution.
  • 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 or elemental
  • the second solid electrolyte material may be an organic polymer solid electrolyte.
  • organic polymer solid electrolytes are 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.
  • 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 electrolyte for the purpose of facilitating the transfer of lithium ions and improving 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.
  • linear 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 mixture 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, 0.5 mol/liter or more and 2 mol/liter 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) pyrrolidiniums, morpholiniums, imidazoliniums, tetrahydropyrimidiniums , piperaziniums, or aliphatic cyclic ammoniums such as piperidiniums, or (iii) nitrogen-containing heterocyclic aromatic cations such as pyridiniums or imidazoliums.
  • aliphatic chain quaternary salts such as tetraalkylammonium or tetraalkylphosphonium
  • pyrrolidiniums morpholiniums, imidazoliniums, tetrahydropyrimidiniums , piperaziniums, or aliphatic cyclic ammoniums such as piperidiniums
  • nitrogen-containing heterocyclic aromatic cations such as pyri
  • 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 for the purpose of improving 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 selected from the above materials 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 for the purpose of increasing electronic conductivity.
  • conductive aids include (i) graphites such as natural or artificial graphite, (ii) carbon blacks such as acetylene black or ketjen black, (iii) conductive materials 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) conductive metal oxides such as titanium oxide. or (viii) a conductive polymeric compound such as polyaniline, polypyrrole, or polythiophene. For cost reduction, 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.
  • Example 1 Preparation of raw materials
  • dry argon atmosphere an argon atmosphere having a dew point of ⁇ 60° C. or less
  • These raw powders were ground and mixed in a mortar. Thus, a mixed powder was obtained.
  • the mixed powder was calcined at 500° C. for 1 hour in a dry argon atmosphere.
  • the obtained powder was pulverized in a mortar to obtain a Li 2 Te powder.
  • Li 3 N manufactured by Sigma-Aldrich
  • Li 2 Te and Te as raw material powders in a dry argon atmosphere
  • a molar ratio of 2:0.75:0.25 Li 3 N:Li 2 Te:Te.
  • prepared as These raw powders were ground and mixed in a mortar. Thus, a mixed powder was obtained.
  • the mixed powder was milled at 500 rpm for 12 hours using a planetary ball mill.
  • the solid electrolyte material powder according to Example 1 was obtained.
  • the solid electrolyte material according to Example 1 had a composition represented by Li7.5N2Te .
  • FIG. 2 is a schematic diagram showing a pressure molding die 300 used to evaluate the ionic conductivity of solid electrolyte materials.
  • the pressure forming die 300 had a punch upper part 301 , a frame mold 302 and a punch lower part 303 . Both the punch upper portion 301 and the punch lower portion 303 were made of electronically conductive stainless steel.
  • the frame mold 302 was made of insulating polycarbonate.
  • the ionic conductivity of the solid electrolyte material according to Example 1 was measured by the following method.
  • the solid electrolyte material powder according to Example 1 (that is, the solid electrolyte material powder 101 in FIG. 2) was filled inside the pressure molding die 300 . Inside the pressing die 300, a pressure of 300 MPa was applied to the solid electrolyte material powder 101 according to Example 1 using an upper punch 301 and a lower punch 303. As shown in FIG.
  • the upper punch 301 and lower punch 303 were connected to a potentiostat (Princeton Applied Research, VersaSTAT4) equipped with a frequency response analyzer.
  • the punch upper part 301 was connected to the working electrode and the terminal for potential measurement.
  • the punch bottom 303 was connected to the counter and reference electrodes.
  • the impedance of the solid electrolyte material was measured by electrochemical impedance measurement at room temperature.
  • FIG. 3 is a graph showing Cole-Cole plots obtained by impedance measurement of solid electrolyte materials according to Example 2 and Comparative Example 2.
  • FIG. 3 is a graph showing Cole-Cole plots obtained by impedance measurement of solid electrolyte materials according to Example 2 and Comparative Example 2.
  • the real value of the impedance at the measurement point where the absolute value of the phase of the complex impedance was the smallest was regarded as the resistance to ion conduction of the solid electrolyte material. See the arrow R se shown in FIG. 3 for the real value.
  • the ionic conductivity was calculated based on the following formula (2) using the resistance value.
  • ⁇ represents ionic conductivity.
  • S represents the contact area of the solid electrolyte material with the punch upper part 301 .
  • 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.
  • t represents the thickness of the layer formed from the solid electrolyte material powder 101 in FIG.
  • Li 6 PS 5 Cl 80 mg
  • the solid electrolyte material according to Example 1 (30 mg)
  • the above mixture are placed in this order. laminated.
  • the amount of mixture was such that it contained 4 mg of graphite.
  • a pressure of 740 MPa was applied to this laminate to form a solid electrolyte layer and a first electrode.
  • current collectors made of stainless steel were attached to the first electrode and the second electrode, and current collecting leads were attached to the current collectors.
  • Example 1 a battery according to Example 1 was obtained.
  • (Charging and discharging test) 4 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 battery according to Example 1 was placed in a constant temperature bath at 25°C.
  • Example 1 The cell according to Example 1 was then discharged at a current density of 74.5 ⁇ A/cm 2 until a voltage of 0.5 V was reached.
  • the battery according to Example 1 had an initial discharge capacity of 119 mAh/g.
  • Example 2 to 6 Preparation of solid electrolyte material
  • Example 6 Se and Li 2 Se were used as raw material powders instead of Te and Li 2 Te.
  • Li 2 Se and Se were provided in a molar ratio of Li 2 Se:Se of (1 ⁇ x):x.
  • Li 3 N and Li 2-2x Se were also provided in a molar ratio of Li 3 N:Li 2-2x Se of (1 ⁇ y):y.
  • Batteries according to Examples 2 to 5 were obtained in the same manner as in Example 1, using the solid electrolyte materials according to Examples 2 to 6.
  • Comparative Examples 1 to 2 Preparation of solid electrolyte material
  • Li 3 N and Li 2 Te were prepared as raw material powders so that the molar ratio of Li 3 N:Li 2 Te was (1-y):y.
  • the solid electrolyte materials according to Examples 1 to 6 have a high ionic conductivity of 4.0 ⁇ 10 ⁇ 5 S/cm or more around room temperature. Therefore, a solid electrolyte material containing lithium and a chalcogen element, in which the chalcogen element is charged to a valence of less than 0 and greater than ⁇ 2, has high ionic conductivity.
  • the valence of the chalcogen element was -1.5, -1 or -0.5.
  • the solid electrolyte material tended to exhibit high ionic conductivity. It is believed that the weakened negative charge of the chalcogen element, which is an anion, weakened the Coulomb interaction between the chalcogen element and the lithium ion, further improving the ion conductivity of the solid electrolyte material.
  • the solid electrolyte material according to the present disclosure is a material that can improve lithium ion conductivity, and is suitable for providing batteries that can be charged and discharged satisfactorily.
  • the solid electrolyte material of the present disclosure is used, for example, in batteries (eg, all-solid lithium ion secondary batteries).

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  • Electrochemistry (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

Un matériau d'électrolyte solide (100) selon la présente invention contient du lithium et un élément chalcogène ; et la valence de l'élément chalcogène est supérieure à -2 mais inférieure à 0. Une batterie (1000) selon la présente invention est pourvue d'une électrode positive (201), d'une électrode négative (203) et d'une couche d'électrolyte (202) qui est disposée entre l'électrode positive (201) et l'électrode négative (203) ; et au moins un composant choisi dans le groupe constitué de l'électrode positive (201), l'électrode négative (203) et la couche d'électrolyte (202) contient le matériau d'électrolyte solide (100) décrit ci-dessus selon la présente invention.
PCT/JP2022/016861 2021-06-02 2022-03-31 Matériau d'électrolyte solide et batterie l'utilisant WO2022254956A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170047610A1 (en) * 2015-08-14 2017-02-16 Samsung Electronics Co., Ltd. Sulfide barrier coating or solid electrolyte
WO2017156130A1 (fr) * 2016-03-11 2017-09-14 Northwestern University Revêtements d'anode de protection pour batteries à haute énergie
JP2018174130A (ja) * 2017-03-31 2018-11-08 国立大学法人東京工業大学 固体電解質材料およびその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170047610A1 (en) * 2015-08-14 2017-02-16 Samsung Electronics Co., Ltd. Sulfide barrier coating or solid electrolyte
WO2017156130A1 (fr) * 2016-03-11 2017-09-14 Northwestern University Revêtements d'anode de protection pour batteries à haute énergie
JP2018174130A (ja) * 2017-03-31 2018-11-08 国立大学法人東京工業大学 固体電解質材料およびその製造方法

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