WO2021199676A1 - 固体電解質材料およびそれを用いた電池 - Google Patents

固体電解質材料およびそれを用いた電池 Download PDF

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Publication number
WO2021199676A1
WO2021199676A1 PCT/JP2021/004427 JP2021004427W WO2021199676A1 WO 2021199676 A1 WO2021199676 A1 WO 2021199676A1 JP 2021004427 W JP2021004427 W JP 2021004427W WO 2021199676 A1 WO2021199676 A1 WO 2021199676A1
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Prior art keywords
solid electrolyte
electrolyte material
less
material according
positive electrode
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PCT/JP2021/004427
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English (en)
French (fr)
Japanese (ja)
Inventor
洋平 林
航輝 上野
和秀 市川
哲也 浅野
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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 EP21781260.1A priority Critical patent/EP4131288A4/en
Priority to CN202180021698.3A priority patent/CN115315757A/zh
Priority to JP2022511603A priority patent/JP7724437B2/ja
Publication of WO2021199676A1 publication Critical patent/WO2021199676A1/ja
Priority to US17/946,536 priority patent/US20230021952A1/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
    • C01F7/00—Compounds of aluminium
    • C01F7/48—Halides, with or without other cations besides aluminium
    • C01F7/56—Chlorides
    • 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
    • C01F7/00—Compounds of aluminium
    • C01F7/48—Halides, with or without other cations besides aluminium
    • C01F7/64—Bromides
    • 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
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • 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
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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 and a battery using the same.
  • Patent Document 1 discloses an all-solid-state battery in which a sulfide solid electrolyte material is used.
  • the purpose of the present disclosure is to provide a new solid electrolyte material with high usefulness.
  • the solid electrolyte material of the present disclosure is represented by the following composition formula (1).
  • the values of a, b, c, and d are all greater than 0, and
  • X is at least one selected from the group consisting of Cl and Br.
  • 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 graph showing an X-ray diffraction pattern of the solid electrolyte material according to Examples 1 to 17.
  • FIG. 3 shows a schematic view of a pressure forming die 300 used for evaluating the ionic conductivity of a solid electrolyte material.
  • FIG. 4 is a graph showing a Core-Cole plot obtained by measuring the impedance of the solid electrolyte material according to Example 1.
  • FIG. 5 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 is represented by the following composition formula (1).
  • the values of a, b, c, and d are all greater than 0, and
  • X is at least one selected from the group consisting of Cl and Br.
  • 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. 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 can be used to obtain a battery having excellent charge / discharge characteristics.
  • An example of such a battery is an all-solid-state battery.
  • the all-solid-state battery may be a primary battery or a secondary battery.
  • the solid electrolyte material according to the first embodiment contains substantially no sulfur.
  • the fact that the solid electrolyte material according to the first embodiment substantially does not contain sulfur means that the solid electrolyte material does not contain sulfur as a constituent element except for sulfur which is unavoidably mixed as an impurity.
  • the amount of sulfur mixed as an impurity in the solid electrolyte material is, for example, 1 mol% or less. It is more desirable that the solid electrolyte material according to the first embodiment does not contain sulfur.
  • the sulfur-free solid electrolyte material is excellent in safety because hydrogen sulfide is not generated even when exposed to the atmosphere.
  • the sulfide solid electrolyte disclosed in Patent Document 1 can generate hydrogen sulfide when exposed to the atmosphere.
  • X may contain Cl in the solid electrolyte material according to the first embodiment. Desirably, X may be Cl.
  • the X-ray diffraction pattern of the solid electrolyte material according to the first embodiment can be measured by the ⁇ -2 ⁇ method using Cu—K ⁇ rays (wavelengths 1.5405 ⁇ and 1.5444 ⁇ ) as X-ray sources.
  • the solid electrolyte material according to the first embodiment may contain the first crystal phase.
  • a peak exists in the range of the diffraction angle 2 ⁇ of 28 ° or more and 32 ° or less, 33 ° or more and 37 ° or less, and 48 ° or more and 52 ° or less.
  • the solid electrolyte material containing the first crystal phase has high ionic conductivity.
  • the shape of the peak existing within the above-mentioned diffraction angle 2 ⁇ in the X-ray diffraction pattern of the first crystal phase may be broad. That is, when the appearance of a peak is confirmed in each range of the above-mentioned diffraction angle 2 ⁇ in the X-ray diffraction pattern, it is recognized that the peak exists in the above-mentioned range of the diffraction angle 2 ⁇ .
  • the peaks existing in the range of each diffraction angle may also be broad.
  • the solid electrolyte material according to the first embodiment may contain a second crystal phase.
  • the X-ray diffraction pattern of the second crystal phase at least one peak exists in the range of the diffraction angle 2 ⁇ of 26 ° or more and less than 28.5 °, and in the range of the diffraction angle 2 ⁇ of 28.5 ° or more and 33 ° or less. There are at least three peaks.
  • the solid electrolyte material containing the second crystal phase has high ionic conductivity.
  • the solid electrolyte material containing such a crystal phase has high ionic conductivity.
  • the solid electrolyte material according to the first embodiment may contain a third crystal phase.
  • a third crystal phase In the X-ray diffraction pattern of the third crystal phase, 11.5 ° or more and 14 ° or less, 14.5 ° or more and 17 ° or less, 23 ° or more and 25.5 ° or less, and 29.5 ° or more and 33 ° or less times.
  • At least one peak exists in the range of the folding angle 2 ⁇ , and at least two peaks exist in the range of the diffraction angle 2 ⁇ of 19.5 ° or more and 23 ° or less.
  • the solid electrolyte material containing the third crystal phase has high ionic conductivity.
  • the solid electrolyte material according to the first embodiment contains at least two selected from the group consisting of the first crystal phase, the second crystal phase, and the third crystal phase. May be.
  • the solid electrolyte material according to the first embodiment may further contain a first crystal phase, a second crystal phase, and a crystal phase having a crystal structure different from that of the third crystal phase.
  • the mathematical formula: b / (a + b)> 0.4 may be satisfied in the formula (1).
  • the amount of lithium contained in the crystal does not become excessive, so that lithium is easily dissolved in the crystal. That is, a stable crystal structure is realized.
  • b / (a + b) ⁇ 0.95 may be satisfied in the formula (1).
  • a sufficient amount of lithium ions are present in the crystal, so that the lithium ions are easily conducted.
  • 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.
  • the solid electrolyte material may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less, which is desirable. May have a median diameter of 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the solid electrolyte material according to the first embodiment has higher ionic conductivity.
  • the solid electrolyte material according to the first embodiment is mixed with another material such as an active material, the dispersed state of the solid electrolyte material and the other material according to the first embodiment becomes good.
  • the median diameter means the particle size when the cumulative volume in the volume-based particle size distribution is equal to 50%.
  • the volume-based particle size distribution is measured, for example, by a laser diffraction measuring device or an image analyzer.
  • the solid electrolyte material according to the first embodiment is produced, for example, as follows.
  • Raw material powder is prepared and mixed so as to have the desired composition.
  • the raw material powder may be, for example, a halide or an oxide.
  • the target composition is LiAlOCl 2
  • the LiCl raw material powder, the AlCl 3 raw material powder and the Al 2 O 3 raw material powder are mixed so as to have a molar ratio of 0.600: 0.200: 0.200.
  • the raw material powders may be mixed in a pre-adjusted molar ratio so as to offset possible compositional changes during the synthesis process.
  • the raw material powders are mechanically reacted with each other in a mixing device such as a planetary ball mill (that is, using the method of mechanochemical milling) to obtain a mixture.
  • a mixing device such as a planetary ball mill (that is, using the method of mechanochemical milling) to obtain a mixture.
  • the solid electrolyte material according to the first embodiment can be obtained.
  • the battery according to the second embodiment includes a positive electrode, an electrolyte layer, and a negative electrode.
  • the electrolyte layer is arranged between the positive electrode and the negative electrode.
  • At least one selected from the group consisting of a positive electrode, an electrolyte layer, and a negative electrode contains the solid electrolyte material according to the first embodiment. Since the battery according to the second embodiment contains the solid electrolyte material according to the first embodiment, it has high charge / discharge characteristics.
  • FIG. 1 shows a cross-sectional view of the battery 1000 according to the second embodiment.
  • the battery 1000 includes a positive electrode 201, an electrolyte layer 202, and a negative electrode 203.
  • the positive electrode 201 contains the positive electrode active material particles 204 and the solid electrolyte particles 100.
  • the electrolyte layer 202 is arranged between the positive electrode 201 and the negative electrode 203.
  • the electrolyte layer 202 contains an electrolyte material (for example, a solid electrolyte material).
  • the negative electrode 203 contains negative electrode active material particles 205 and solid electrolyte particles 100.
  • the solid electrolyte particle 100 is a particle containing the solid electrolyte material according to the first embodiment as a main component.
  • the particles containing the solid electrolyte material according to the first embodiment as a main component mean the particles in which the component contained most in the molar ratio is the solid electrolyte material according to the first embodiment.
  • the solid electrolyte particles 100 may be particles made of the solid electrolyte material according to the first embodiment.
  • the positive electrode 201 contains a material capable of occluding and releasing metal ions (for example, lithium ions).
  • the material is, for example, a positive electrode active material (for example, positive electrode active material particles 204).
  • Examples of positive electrode active materials are lithium-containing transition metal oxides, transition metal fluorides, polyanionic materials, fluorinated polyanionic materials, transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, or transition metal oxynitrides. be.
  • Examples of lithium-containing transition metal oxides are Li (Ni, Co, Al) O 2 , LiCo O 2 , or Li (Ni, Co, Mn) O 2 .
  • a preferable example of the positive electrode active material is Li (Ni, Co, Mn) O 2 .
  • Li (Ni, Co, Mn) O 2 can be charged and discharged at a potential of 4 V or higher.
  • “(A, B, C)" represents "at least one selected from the group consisting of A, B, and C.”
  • A, B, and C all represent elements.
  • the positive electrode active material particles 204 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less. When the positive electrode active material particles 204 have a median diameter of 0.1 ⁇ m or more, the positive electrode active material particles 204 and the solid electrolyte particles 100 can be satisfactorily dispersed in the positive electrode 201. This improves the charge / discharge characteristics of the battery. When the positive electrode active material particles 204 have a median diameter of 100 ⁇ m or less, the lithium diffusion rate in the positive electrode active material particles 204 is improved. This allows the battery to operate at high output.
  • the positive electrode active material particles 204 may have a median diameter larger than that of the solid electrolyte particles 100. As a result, the positive electrode active material particles 204 and the solid electrolyte particles 100 can be well dispersed.
  • the ratio of the volume of the positive electrode active material particles 204 to the total volume of the positive electrode active material particles 204 and the volume of the solid electrolyte particles 100 is 0.30 or more and 0. It may be 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 solid electrolyte material contained in the electrolyte layer 202 may contain the solid electrolyte material according to the first embodiment.
  • the electrolyte layer 202 may be composed of only the solid electrolyte material according to the first embodiment.
  • the electrolyte layer 202 may be composed only of a solid electrolyte material different from the solid electrolyte material according to the first embodiment.
  • a solid electrolyte material different from the solid electrolyte material according to the first embodiment.
  • Li 2 MgX '4, Li 2 FeX' 4 Li (Al, Ga, In) X '4, Li 3 (Al, Ga, In ) is X '6, or LiX'.
  • 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.
  • 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 100 ⁇ 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 100 ⁇ m or less, the battery can operate at high output.
  • the negative electrode 203 contains a material capable of occluding and releasing metal ions (for example, 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 single metal material 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.
  • 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 negative electrode active material particles 205 may have a median diameter larger than that of the solid electrolyte particles 100. As a result, in the negative electrode 203, the dispersed state of the negative electrode active material particles 205 and the solid electrolyte particles 100 becomes good.
  • 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. It may be 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 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 are a sulfide solid electrolyte, an oxide solid electrolyte, a halide solid electrolyte, or an organic polymer solid electrolyte.
  • Examples of the sulfide solid electrolyte Li 2 S-P 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 Li 10 GeP 2 S 12 .
  • 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
  • halide solid electrolyte as described above, Li 2 MgX '4, Li 2 FeX' 4, Li (Al, Ga, In) X '4, Li 3 (Al, Ga, In) X' 6, Or LiX'.
  • halides solid electrolyte is a compound represented by Li p Me q Y r Z 6 .
  • Me is at least one element 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.
  • Metalloid elements are B, Si, Ge, As, Sb, and Te.
  • Metallic elements are 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 composed of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb. It may be at least one selected.
  • 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 increased.
  • 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 may be, 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, tetrahydropyrimidiums, 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 in order to enhance 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 the binder.
  • At least one selected from the group consisting of the positive electrode 201 and the negative electrode 203 may contain a conductive auxiliary agent in order to enhance electron conductivity.
  • 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, It is a conductive metal oxide such as (vii) titanium oxide, or a conductive polymer compound such as (vii) polyaniline, polypyrrole, or polythiophene. In order to reduce the cost, 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.
  • Example 1 Preparation of solid electrolyte material
  • dry argon atmosphere LiCl, AlCl 3 , and Al 2 O 3 were used as raw material powders at 0.429: 0.214: 0. It was prepared to have a molar ratio of 357.
  • These raw material powders were mixed and milled at 500 rpm for 12 hours using a planetary ball mill. In this way, the powder of the solid electrolyte material according to Example 1 was obtained.
  • the solid electrolyte material according to Example 1 had a composition of Li 0.462 AlO 1.15 Cl 1.15.
  • FIG. 2 is a graph showing an X-ray diffraction pattern of the solid electrolyte material according to Example 1.
  • 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 atmosphere having a dew point of ⁇ 30 ° C. or lower. Cu-K ⁇ rays were used as the X-ray source.
  • FIG. 3 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.
  • the frame 302 was made of insulating polycarbonate.
  • the upper punch 301 and the lower punch 303 were made of electron-conducting stainless steel.
  • the ionic conductivity of the solid electrolyte material according to Example 1 was measured by the following method.
  • the powder of the solid electrolyte material according to Example 1 (that is, the powder 101 of the solid electrolyte material in FIG. 3) was filled inside the pressure forming die 300. Inside the pressure forming die 300, a pressure of 360 MPa was applied to the powder of the solid electrolyte material according to Example 1 using the punch upper part 301 and the punch lower part 303.
  • the upper punch 301 and the lower punch 303 were connected to a potentiostat (Biological, VSP-300) 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 ionic conductivity of the solid electrolyte material was measured at room temperature by an electrochemical impedance measurement method.
  • FIG. 4 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 to the ionic conductivity of the solid electrolyte material. See the arrow R SE shown in FIG. 4 for the real value.
  • the ionic conductivity was calculated based on the following mathematical formula (2).
  • ⁇ (R SE ⁇ S / t) -1 ...
  • R SE represents the resistance value of the solid electrolyte material in impedance measurement.
  • t represents the thickness of the solid electrolyte material to which the pressure is applied. 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 25 ° C. was 1.94 ⁇ 10 -4 S / cm.
  • Example 1 [Battery production]
  • the solid electrolyte material and the positive electrode active material Li (Ni, Co, Mn) O 2 (hereinafter referred to as “NCM”) according to Example 1 have a mass ratio of 24:76. prepared. These materials were mixed in an agate mortar to give the positive electrode mixture according to Example 1.
  • a sulfide solid electrolyte Li 2 SP 2 S 5 (hereinafter referred to as “LPS”) (60 mg), and a solid electrolyte material according to Example 1 (24 mg). ) are laminated in order to obtain a laminated body. A pressure of 160 MPa was applied to this laminate to form a solid electrolyte layer.
  • Example 2 the positive electrode mixture (9.2 mg) according to Example 1 was laminated on the solid electrolyte layer formed from the solid electrolyte material according to Example 1, and a laminate was obtained. A pressure of 360 MPa was applied to this laminate to form a positive electrode.
  • the metal In foil (thickness 200 ⁇ m), the metal Li foil (thickness 300 ⁇ m), and the metal In foil (thickness 200 ⁇ m) were laminated in this order on the solid electrolyte layer formed from the LPS to obtain a laminated body. rice field. A pressure of 80 MPa was applied to this laminate to form a negative electrode.
  • a current collector made of stainless steel was placed on the positive electrode and the negative electrode, and a current collector lead was attached to the current collector.
  • FIG. 5 is a graph showing the initial discharge characteristics of the battery according to the first embodiment.
  • the battery according to Example 1 was placed in a constant temperature bath at 25 ° C.
  • the battery according to Example 1 was charged at a current density of 98.8 ⁇ A / cm 2 until the positive electrode reached a voltage of 3.68 V with respect to the negative electrode.
  • the current density corresponds to a 0.05 C rate (20 hour rate) with respect to the theoretical capacity of the battery.
  • Charging is a state in which a current flows in the direction in which lithium ions move from the positive electrode mixture containing NCM to the In—Li alloy (that is, the negative electrode).
  • the battery according to Example 1 was discharged until the positive electrode reached a voltage of 1.88 V with respect to the negative electrode.
  • the current density corresponds to a 0.05 C rate (20 hour rate) with respect to the theoretical capacity of the battery.
  • the discharge is a state in which a current flows in the direction in which Li lithium ions move from the In—Li alloy (that is, the negative electrode) to the positive electrode mixture mixture containing NCM.
  • the battery according to Example 1 had an initial discharge capacity of 1.24 mAh.
  • Example 2 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.471: 0.243: 0.286.
  • Example 3 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.553: 0.184: 0.263.
  • Example 4 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.346: 0.269: 0.385.
  • Example 5 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.563: 0.125: 0.313.
  • Example 6 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.500: 0.167: 0.333.
  • Example 7 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have molar ratios of 0.600, 0.200, and 0.200.
  • Example 8 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.522: 0.261: 0.217.
  • Example 9 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.545: 0.227: 0.227.
  • Example 10 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.512: 0.244: 0.244.
  • Example 11 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.474: 0.263: 0.263.
  • Example 12 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.429: 0.286: 0.286.
  • Example 13 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.375: 0.313: 0.313.
  • Example 14 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.310: 0.345: 0.345.
  • Example 15 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.136: 0.409: 0.455.
  • Example 16 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.231: 0.385: 0.385.
  • Example 17 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.250: 0.333: 0.417.
  • Example 18 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.667: 0.148: 0.185.
  • Example 19 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.429: 0.333: 0.238.
  • Example 20 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.176: 0.529: 0.294.
  • Example 21 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.588: 0.235: 0.176.
  • Example 22 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.577: 0.269: 0.154.
  • Example 23 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.612: 0.163: 0.224.
  • Example 24 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.625: 0.125: 0.250.
  • Example 25 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.375: 0.500: 0.125.
  • Example 26 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.355: 0.225: 0.420.
  • Example 27 LiCl, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.266: 0.405: 0.329.
  • Example 28 LiCl, LiBr, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.480: 0.120: 0.200: 0.200.
  • Example 29 LiCl, LiBr, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.360: 0.240: 0.200: 0.200.
  • Example 30 LiCl, LiBr, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.240: 0.360: 0.200: 0.200.
  • Example 31 LiCl, LiBr, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.120: 0.480: 0.200: 0.200.
  • Example 32 LiBr, AlCl 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.600: 0.200: 0.200.
  • Example 33 LiBr, AlBr 3 , and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.600: 0.200: 0.200.
  • Comparative Example 1 Li 2 O and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.500: 0.500.
  • Comparative Example 3 AlCl 3 and Al 2 O 3 were prepared as raw material powders so as to have a molar ratio of 0.500: 0.500.
  • Comparative Example 4 LiCl and AlCl 3 were prepared as raw material powders so as to have a molar ratio of 0.500: 0.500. These raw material powders were mixed and milled at 500 rpm for 15 hours using a planetary ball mill. In this way, the solid electrolyte material according to Comparative Example 4 was obtained.
  • FIG. 2 is a graph showing an X-ray diffraction pattern of the solid electrolyte material according to Examples 2 to 17. The observed peak angles are shown in Table 3.
  • Example 7 when the solid electrolyte material contains Cl, the ionic conductivity is further increased.
  • Example 7 and 21 to 23 are compared with Example 24, when the molar ratio of O to Li is 0.80 or more and 1.10 or less, the ionic conductivity of the solid electrolyte material is further increased. It gets higher.
  • the solid electrolyte materials according to Examples 1 to 12 have 28 ° or more and 32 ° or less, 33 ° or more and 37 ° or less, and 48 ° or more and 52 ° in the X-ray diffraction pattern obtained by X-ray diffraction measurement using Cu—K ⁇ rays. It had a peak in the range of diffraction angle 2 ⁇ below °. That is, the solid electrolyte materials according to Examples 1 to 12 contained the first crystal phase.
  • the solid electrolyte materials according to Examples 8 to 14 had peaks in the X-ray diffraction pattern in the range of the diffraction angle 2 ⁇ of 26 ° or more and less than 28.5 ° and 47 ° or more and 50 ° or less.
  • the solid electrolyte material according to Examples 8 to 14 further has two or more peaks in the range of the diffraction angle 2 ⁇ of 17 ° or more and 21 ° or less, and further has a diffraction angle of 2 ⁇ of 28.5 ° or more and 33 ° or less. Had three or more peaks. That is, the solid electrolyte materials according to Examples 8 to 14 contained the second crystal phase. All of the solid electrolyte materials containing the second crystal phase had a high ionic conductivity of 1.0 ⁇ 10 -4 S / cm or more.
  • the solid electrolyte materials according to Examples 7 and 15 to 17 have 11.5 ° or more and 14 ° or less, 14.5 ° or more and 17 ° or less, 23 ° or more and 25.5 ° or less, and 29 in the X-ray diffraction pattern. It had a peak in the range of a diffraction angle of 2.5 ° or more and 33 ° or less, and had two or more peaks in the range of a diffraction angle of 19.5 ° or more and 23 ° or less. That is, the solid electrolyte materials according to Examples 7 and 15 to 17 contained the third crystal phase.
  • the solid electrolyte material according to Example 1 showed good discharge characteristics in a battery using NCM as the positive electrode active material. Therefore, the solid electrolyte material of the present disclosure can be used together with a positive electrode active material that can be charged and discharged at a potential of 4 V or higher. As a result, the solid electrolyte material of the present disclosure can improve the energy density of the battery.
  • the solid electrolyte material of the present disclosure is suitable for providing a battery that does not contain rare earth elements and sulfur, has practical ionic conductivity, and can be charged and discharged well.
  • the solid electrolyte material of the present disclosure is used, for example, in an all-solid-state lithium ion secondary battery.

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