WO2024257600A1 - 固体電解質材料、固体電解質材料の製造方法、正極材料および電池 - Google Patents

固体電解質材料、固体電解質材料の製造方法、正極材料および電池 Download PDF

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WO2024257600A1
WO2024257600A1 PCT/JP2024/019515 JP2024019515W WO2024257600A1 WO 2024257600 A1 WO2024257600 A1 WO 2024257600A1 JP 2024019515 W JP2024019515 W JP 2024019515W WO 2024257600 A1 WO2024257600 A1 WO 2024257600A1
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solid electrolyte
electrolyte material
positive electrode
battery
material according
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English (en)
French (fr)
Japanese (ja)
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勇祐 西尾
和史 宮武
真志 境田
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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 CN202480037434.0A priority Critical patent/CN121359221A/zh
Priority to EP24823220.9A priority patent/EP4726740A1/en
Priority to JP2025527630A priority patent/JPWO2024257600A1/ja
Publication of WO2024257600A1 publication Critical patent/WO2024257600A1/ja
Priority to US19/404,056 priority patent/US20260100413A1/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
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/05—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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • 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

  • This disclosure relates to solid electrolyte materials, methods for producing solid electrolyte materials, positive electrode materials, and batteries.
  • Patent Document 1 discloses an all-solid-state battery that uses a sulfide solid electrolyte.
  • Patent Document 2 discloses coating the surface of lithium nickel oxide with lithium fluoride.
  • the objective of this disclosure is to provide a solid electrolyte material that is suitable for lithium ion conduction and has improved contact with other materials.
  • the present disclosure relates to A solid electrolyte material, Li, Al, and X; X is an anion containing F, The specific surface area of the solid electrolyte material is 16 m 2 /g or more.
  • a solid electrolyte material is provided.
  • the present disclosure provides a solid electrolyte material that is suitable for lithium ion conduction and has improved contact with other materials.
  • FIG. 1 shows a cross-sectional view of a battery 1000 according to a second embodiment.
  • FIG. 2 shows a schematic diagram of a pressing die 300 used to evaluate the ionic conductivity of a solid electrolyte material.
  • FIG. 3 is a graph showing a Cole-Cole plot obtained by impedance measurement of the solid electrolyte material according to Example 1.
  • FIG. 4 is a graph showing the initial discharge characteristics of the battery according to Example 1.
  • the solid electrolyte material according to the first embodiment is composed of Li, Al, and X.
  • X is an anion containing F.
  • the specific surface area of the solid electrolyte material according to the first embodiment is greater than 16 m 2 /g.
  • the specific surface area of the solid electrolyte material in the present disclosure means the specific surface area determined by the BET (Brunauer-Emmett-Teller) method.
  • Consisting of Li, Al, and X means that elements other than Li, Al, and X are not actively used in the raw materials of the solid electrolyte material. It is permissible for the solid electrolyte material to contain unavoidable impurities. Examples of elements contained as unavoidable impurities are hydrogen, oxygen, and nitrogen. These elements are present in the raw powder of the solid electrolyte material, or in the atmosphere in which the solid electrolyte material is manufactured or stored. Impurities may also be mixed into the solid electrolyte material from the container used to synthesize the solid electrolyte material.
  • the solid electrolyte material according to the first embodiment is suitable for lithium ion conduction and has good contact with other materials. Therefore, the solid electrolyte material according to the first embodiment can reduce the resistance at the interface with other materials.
  • the other materials are, for example, active materials.
  • polycrystalline bodies are used as active materials for lithium-ion secondary batteries.
  • the surface of the active material is not flat, and often has small grooves or depressions or other irregularities.
  • the solid electrolyte it is desirable to improve the contact between the active material and the solid electrolyte in order to reduce the resistance of the battery.
  • the solid electrolyte must be deformed by compression or other means to match the uneven shape of the active material.
  • the surface of the solid electrolyte is flat and the particle size of the solid electrolyte is large, the pressure during pressing is concentrated on the convex parts of the surface of the active material.
  • the particle size of the solid electrolyte is smaller than the concave parts of the surface of the active material, pressure is applied with the solid electrolyte in the concave parts, so good contact between the active material and the solid electrolyte can be obtained.
  • the surface of the solid electrolyte is uneven, the solid electrolyte can easily enter the concave parts of the surface of the active material compared to when the surface is flat, making it easier to achieve good contact between the active material and the solid electrolyte.
  • a small particle size and an uneven surface mean a large specific surface area. In other words, a solid electrolyte with a large specific surface area is more likely to achieve good contact with the active material. As a result, the resistance of the battery can be reduced, and for example, the charge/discharge characteristics of the battery can be improved.
  • the solid electrolyte material according to the first embodiment can be used, for example, to obtain a battery with excellent charge/discharge characteristics.
  • An example of such a battery is a solid-state battery.
  • the solid electrolyte material according to the first embodiment is suitable as a material for a solid-state battery.
  • the solid-state battery may be a primary battery or a secondary battery.
  • the solid-state battery may be an all-solid-state battery.
  • the solid electrolyte material according to the first embodiment desirably does not contain sulfur.
  • a solid electrolyte material that does not contain sulfur is safe because it does not generate hydrogen sulfide even when exposed to the atmosphere.
  • the sulfide solid electrolyte disclosed in Patent Document 1 may generate hydrogen sulfide when exposed to the atmosphere.
  • the solid electrolyte material according to the first embodiment contains F, and therefore can have high oxidation resistance. This is because F has a high redox potential. On the other hand, F has a high electronegativity, and therefore the bond between F and Li is relatively strong. As a result, the lithium ion conductivity of the solid electrolyte material containing Li and F is usually low. For example, the conductivity of LiF disclosed in Patent Document 2 is so high that it cannot be measured by the AC impedance method. In contrast, the solid electrolyte material according to the first embodiment can have an ion conductivity of, for example, 1.2 ⁇ 10 ⁇ 10 S/cm or more by containing Al in addition to Li and F.
  • This value is a conductivity sufficient for lithium ions to move over a very short distance.
  • lithium ions can permeate the layer of the solid electrolyte material.
  • the specific surface area of the solid electrolyte material according to the first embodiment may be smaller than 100 m 2 /g, may be smaller than 60 m 2 /g, or may be 44.6 m 2 /g or less. With such a configuration, the above-mentioned effects can be sufficiently obtained.
  • the specific surface area of the solid electrolyte material according to the first embodiment may be 32.4 m 2 /g or more. With this configuration, the above-mentioned effects can be sufficiently obtained.
  • the solid electrolyte material according to the first embodiment may further contain at least one anion other than F.
  • anion other than F examples include Cl, Br, I, O, or Se.
  • the ratio of the amount of substance of F to the total amount of substances of the anions constituting the solid electrolyte material according to the first embodiment may be 0.50 or more and 1.0 or less.
  • the anion constituting the solid electrolyte material according to the first embodiment may be only F.
  • the ratio of the amounts of substances may be 1.0.
  • the solid electrolyte material according to the first embodiment has a composition formula (1) Li 6-3a Al a F 6 ...(1) (wherein 0 ⁇ a ⁇ 1.5 is satisfied)
  • a solid electrolyte material containing a phase having such a composition has high ionic conductivity.
  • the upper and lower limits of the range of a in formula (1) can be defined by any combination selected from the numerical values of 0.7, 0.8, 0.9, 0.96, 1, 1.04, 1.1, 1.2, and 1.3.
  • the solid electrolyte material according to the first embodiment may contain Li 3 AlF 6 or may be Li 3 AlF 6. Li 3 AlF 6 has excellent oxidation resistance.
  • the solid electrolyte material according to the first embodiment may be crystalline or amorphous.
  • the solid electrolyte material according to the first embodiment may include a phase represented by formula (1).
  • the shape of the solid electrolyte material according to the first embodiment is not limited. Examples of the shape are needle-like, spherical, or elliptical.
  • the solid electrolyte material according to the first embodiment may be in the form of particles.
  • the solid electrolyte material according to the first embodiment may have the shape of a pellet or a plate.
  • the solid electrolyte material according to the first embodiment is produced, for example, by the following method.
  • the raw powders of multiple halides are mixed with an organic solvent in a mixing device while being finely pulverized.
  • LiF and AlF3 are prepared in a molar ratio of about 3:1.
  • the raw material powder may be prepared in a pre-adjusted molar ratio to offset composition changes that may occur in the synthesis process.
  • the raw material powder and an organic solvent are put into a mixing device such as a planetary ball mill and mixed while being pulverized. That is, a treatment is performed using a wet ball mill.
  • the raw material powder may be mixed before being put into the mixing device.
  • the balls After mixing, the balls are separated to obtain a slurry with dispersed particles.
  • the slurry is dried at a temperature depending on the boiling point of the organic solvent used to obtain a solid.
  • the reactant is obtained by grinding this solid in a mortar.
  • the particle size of the product can be reduced.
  • the specific surface area of the solid electrolyte material can be improved.
  • the solid obtained by drying the above slurry can be expected to have a further reduced particle size by dissolving it in an organic solvent and recrystallizing it.
  • the raw powder of the solid electrolyte material can be dissolved in an organic solvent and recrystallized to reduce the particle size, and then processed using a wet ball mill.
  • the solid obtained by drying the above slurry may be calcined in a vacuum or in an inert atmosphere. Calcination is carried out, for example, at 100°C or higher and 300°C or lower for 1 hour or more. To suppress composition changes during calcination, calcination may be carried out in a sealed container such as a quartz tube.
  • the solid electrolyte material according to the first embodiment is obtained by performing wet grinding to grind a mixture containing a raw material composition containing the constituent components of the solid electrolyte material and a solvent.
  • the raw material composition containing the constituent components of the solid electrolyte material is raw material powder of multiple halides.
  • the solvent is typically an organic solvent.
  • the particle size of the balls used in the wet ball mill may be reduced.
  • the amount of balls used in the wet ball mill may be increased.
  • the processing time in the wet ball mill may be extended.
  • the solvent used in the wet ball mill may include at least one selected from the group consisting of ⁇ -butyrolactone, propylene carbonate, butyl acetate, ethanol, dimethyl sulfoxide, and tetralin.
  • the solid electrolyte material according to the first embodiment can be manufactured.
  • NMP N-methyl-2-pyrrolidone
  • the battery according to the second embodiment includes a positive electrode, an electrolyte layer, and a negative electrode.
  • the electrolyte layer is provided between the positive electrode and the negative electrode.
  • 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 has excellent charge/discharge characteristics because it contains the solid electrolyte material according to the first embodiment.
  • FIG. 1 shows a cross-sectional view of a battery 1000 according to the second embodiment.
  • the battery 1000 according to the second embodiment includes a positive electrode 201, an electrolyte layer 202, and a negative electrode 203.
  • the electrolyte layer 202 is provided between the positive electrode 201 and the negative electrode 203.
  • the positive electrode 201 contains a positive electrode active material 204 and a solid electrolyte 100.
  • the electrolyte layer 202 contains an electrolyte material.
  • the negative electrode 203 contains a negative electrode active material 205 and a solid electrolyte 100.
  • the solid electrolyte 100 includes, for example, 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.
  • Particles containing the solid electrolyte material according to the first embodiment as a main component refer to particles in which the component contained most abundantly in terms of 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 absorbing and releasing metal ions (e.g., lithium ions).
  • the material is, for example, the positive electrode active material 204.
  • Examples of the positive electrode active material 204 include lithium-containing metal oxides such as lithium-containing transition metal oxides, lithium-containing transition metal phosphates, transition metal fluorides, polyanions, fluorinated polyanion materials, transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, or transition metal oxynitrides.
  • the transition metal may be in the range not including d 10 elements (Zn, Cd, and Hg in group 12), lanthanides (excluding La (5d 1 6s 2 )), and actinides (excluding Ac (6d 1 7S 2 )) according to the definition described in, for example, the IUPAC "Gold Book” and "Red Book".
  • Examples of lithium-containing transition metal oxides are Li(Ni,Co,Mn)O 2 , Li(Ni,Co,Al)O 2 , or LiCoO 2 .
  • (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 positive electrode 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 the solid electrolyte 100 can be well dispersed in the positive electrode 201. This improves the charge and discharge characteristics of the battery 1000. When the positive electrode active material 204 has a median diameter of 100 ⁇ m or less, the lithium diffusion rate in the positive electrode active material 204 improves. This allows the battery 1000 to operate at a high output.
  • the positive electrode active material 204 may have a median diameter larger than that of the solid electrolyte 100. This allows the positive electrode active material 204 and the solid electrolyte 100 to be well dispersed in the positive electrode 201.
  • the ratio of the volume of the positive electrode active material 204 to the sum of the volume of the positive electrode active material 204 and the volume of the solid electrolyte 100 may be 0.30 or more and 0.95 or less.
  • a coating layer may be formed on at least a portion of the surface of the positive electrode active material 204.
  • the coating layer may be formed on the surface of the positive electrode active material 204, for example, before mixing with the conductive assistant and the binder.
  • coating materials included in the coating layer include a sulfide solid electrolyte, an oxide solid electrolyte, or a halide solid electrolyte.
  • the coating material may contain the solid electrolyte material according to the first embodiment in order to suppress oxidative decomposition of the sulfide solid electrolyte.
  • the coating material may contain an oxide solid electrolyte in order to suppress oxidative decomposition of the solid electrolyte material.
  • Lithium niobate which has excellent stability at high potentials, may be used as the oxide solid electrolyte. By suppressing oxidative decomposition, the overvoltage rise of the battery 1000 can be suppressed.
  • the sulfide solid electrolyte is a solid electrolyte containing Li and S.
  • a material described later such as Li 2 S-P 2 S 5
  • the positive electrode active material 204 is coated with the solid electrolyte material according to the first embodiment, oxidative decomposition of the solid electrolyte 100 containing Li and S can be suppressed.
  • 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 solid electrolyte material may include the solid electrolyte material according to the first embodiment.
  • the electrolyte layer 202 may be a solid electrolyte layer.
  • 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 will be referred to as the first solid electrolyte material.
  • a solid electrolyte material different from the first solid electrolyte material will be referred to as the 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 the battery 1000.
  • the battery according to the second embodiment may include a positive electrode 201, a second electrolyte layer, a first electrolyte layer, and a 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. This allows the solid electrolyte material contained in the second electrolyte layer to be used without being reduced. As a result, the charge/discharge efficiency of the battery 1000 can be improved.
  • the first electrolyte layer may contain a sulfide solid electrolyte in order to suppress the reductive decomposition of the solid electrolyte material. This allows the charge/discharge efficiency of the battery 1000 to be improved.
  • the second electrolyte layer may contain the first solid electrolyte material. Since the first solid electrolyte material has high oxidation resistance, a battery with excellent charge/discharge characteristics can be realized.
  • 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. If 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 short-circuit. If the electrolyte layer 202 has a thickness of 1000 ⁇ m or less, the battery 1000 can operate at high power.
  • Examples of the second solid electrolyte material are Li2MgX4 , Li2FeX4 , Li(Al,Ga,In) X4 , Li3 (Al,Ga,In) X6 , or LiI, where X is at least one selected from the group consisting of F, Cl, Br, and I.
  • 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 absorbing and releasing metal ions (e.g., 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 metal material may be a single metal or an alloy.
  • Examples of the metal material are lithium metal or lithium alloys.
  • Examples of the carbon material are natural graphite, coke, partially graphitized carbon, carbon fiber, spherical carbon, artificial graphite, or amorphous carbon. From the viewpoint of capacity density, suitable examples of the negative electrode active material are silicon (i.e., Si), tin (i.e., Sn), silicon compounds, or tin compounds.
  • the negative electrode active material 205 may be selected in consideration of the reduction resistance of the solid electrolyte material contained in the negative electrode 203.
  • the negative electrode active material 205 may be a material capable of absorbing and releasing lithium ions at 0.27 V or more relative to lithium.
  • examples of such negative electrode active materials are titanium oxide, indium metal, or lithium alloy.
  • examples of titanium oxide are Li4Ti5O12 , LiTi2O4 , or TiO2 .
  • 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.
  • the negative electrode active material 205 and the solid electrolyte 100 can be well dispersed in the negative electrode 203. This improves the charge and discharge characteristics of the battery 1000.
  • the negative electrode active material 205 has a median diameter of 100 ⁇ m or less, the lithium diffusion rate in the negative electrode active material 205 improves. This allows the battery 1000 to operate at a high output.
  • the negative electrode active material 205 may have a median diameter larger than that of the solid electrolyte 100. This allows the negative electrode active material 205 and the solid electrolyte 100 to be well dispersed in the negative electrode 203.
  • the ratio of the volume of the negative electrode active material 205 to the sum of the volume of the negative electrode active material 205 and the volume of the solid electrolyte 100 may be 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 the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a second solid electrolyte material for the purpose of increasing ionic conductivity, chemical stability, and electrochemical stability.
  • the second solid electrolyte material may be a sulfide solid electrolyte.
  • Examples of sulfide solid electrolytes are Li2S - P2S5 , Li2S - SiS2 , Li2S - B2S3 , Li2S - GeS2 , Li3.25Ge0.25P0.75S4 , or Li10GeP2S12 .
  • the negative electrode 203 may contain a sulfide solid electrolyte to suppress reductive decomposition of the solid electrolyte material.
  • the negative electrode active material By covering the negative electrode active material with an electrochemically stable sulfide solid electrolyte, it is possible to suppress contact between the first solid electrolyte material and the negative electrode active material. As a result, the internal resistance of the battery 1000 can be reduced.
  • the second solid electrolyte material may be an oxide solid electrolyte.
  • oxide solid electrolytes include: (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) a garnet-type solid electrolyte such as Li7La3Zr2O12 or its elemental substitutions, or (v) Li3PO4 or its N - substituted derivatives ; It is.
  • the second solid electrolyte material may be a halide solid electrolyte.
  • halide solid electrolytes are Li2MgX4 , Li2FeX4 , Li(Al,Ga,In) X4 , Li3 (Al,Ga,In) X6 , or LiI, where X is at least one selected from the group consisting of F, Cl, Br, and I.
  • halide solid electrolyte is a compound represented by Li a Me b Y c Z 6.
  • 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.
  • Metalloid elements are B, Si, Ge, As, Sb, and Te.
  • Metal elements are all elements included in Groups 1 to 12 of the periodic table (excluding hydrogen), and all elements included in Groups 13 to 16 of the periodic table (excluding B, Si, Ge, As, Sb, Te, C, N, P, O, S, and Se).
  • Me may be at least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb.
  • the halide solid electrolyte may be Li3YCl6 or Li3YBr6 .
  • the second solid electrolyte material may be an organic polymer solid electrolyte.
  • organic polymer solid electrolytes examples include polymer compounds and lithium salt compounds.
  • the polymer compound may have an ethylene oxide structure.
  • a polymer compound having an ethylene oxide structure can contain a large amount of lithium salt, and therefore can further increase the ionic conductivity.
  • lithium salt examples include 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 may contain a non-aqueous electrolyte solution, a gel electrolyte, or an ionic liquid to facilitate the transfer of lithium ions and improve the output characteristics of the battery.
  • 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.
  • 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 type of non-aqueous solvent selected from these may be used alone. Alternatively, a combination of two or more types of non-aqueous solvents selected from these may be used.
  • lithium salt examples include LiPF6 , LiBF4 , LiSbF6, LiAsF6 , LiSO3CF3 , LiN ( SO2CF3 ) 2 , LiN ( SO2C2F5 ) 2 , LiN( SO2CF3 )(SO2C4F9), or LiC( SO2CF3 ) 3 .
  • One type of lithium salt selected from these may be used alone. Alternatively, a mixture of two or more types of lithium salts selected from these may be used.
  • the concentration of the lithium salt 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 may be used.
  • polymer materials are polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, or a polymer having an ethylene oxide bond.
  • cations contained in ionic liquids are: (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 heterocyclic aromatic cations such as pyridiniums or imidazoliums, It is.
  • Aliphatic chain quaternary salts such as tetraalkylammonium or tetraalkylphosphonium
  • aliphatic cyclic ammoniums such as pyrrolidiniums, morpholiniums, imidazoliniums, tetrahydropyrimidiniums, piperaziniums, or piperidiniums
  • nitrogen-containing heterocyclic aromatic cations
  • Examples of anions contained in the ionic liquid are PF6- , BF4- , SbF6- , AsF6- , SO3CF3- , N ( SO2CF3 ) 2- , N ( SO2C2F5 ) 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 to improve adhesion between particles.
  • binders are 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, polyethersulfone, hexafluoropolypropylene, styrene butadiene rubber, or carboxymethylcellulose.
  • Copolymers may also be used as binders.
  • binders are copolymers of two or more materials selected from the group consisting of tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene.
  • a mixture of two or more of these materials may be used as a binder.
  • At least one selected from the positive electrode 201 and the negative electrode 203 may contain a conductive additive to improve electronic conductivity.
  • Examples of the conductive additive include: (i) graphites, such as natural or synthetic graphite; (ii) Carbon blacks such as acetylene black or ketjen black; (iii) conductive fibers, such as carbon or metal fibers; (iv) fluorocarbons, (v) metal powders such as aluminum; (vi) conductive whiskers such as zinc oxide or potassium titanate; (vii) a conductive metal oxide, such as titanium oxide; or (viii) a conductive polymer, such as polyaniline, polypyrrole, or polythiophene.
  • the conductive assistant i) or (ii) above may be used.
  • Examples of the shape of the battery according to the second embodiment include a coin type, a cylindrical type, a rectangular type, a sheet type, a button type, a flat type, or a laminated type.
  • the battery according to the second embodiment may be manufactured, for example, by preparing a material for forming a positive electrode, a material for forming an electrolyte layer, and a material for forming a negative electrode, and producing a laminate in which the positive electrode, electrolyte layer, and negative electrode are arranged in this order using a known method.
  • This disclosure makes it possible to provide a solid electrolyte material that is suitable for lithium ion conduction and has improved contact with other materials.
  • the solid electrolyte material is represented by the composition formula (1) Li 6-3x Al x F 6 ...(1) (wherein 0 ⁇ x ⁇ 1.5 is satisfied)
  • the solid electrolyte material according to Technology 1 includes a phase represented by the formula:
  • the solid electrolyte material including a phase having such a composition has high ionic conductivity.
  • a positive electrode material comprising the solid electrolyte material according to any one of claims 1 to 7, and a positive electrode active material coated with the solid electrolyte material.
  • a battery comprising a positive electrode containing the positive electrode material according to technology 10 and an electrolyte layer. According to the present disclosure, a battery in which an increase in overvoltage is suppressed can be obtained.
  • the battery according to the present disclosure is a solid-state battery.
  • Example 1 Preparation of solid electrolyte material
  • These raw material powders were charged into a 45cc planetary ball mill pod together with a 1mm ⁇ ball (25g).
  • ⁇ -butyrolactone (GBL) was dropped into the pod as an organic solvent so that the solid content ratio was 30%.
  • the solid content ratio is calculated by ⁇ (mass of input raw material)/(mass of input raw material + mass of input solvent) ⁇ x 100.
  • the milling process was performed for 12 hours at 500 rpm using a planetary ball mill. After the milling process, the balls were separated to obtain a slurry. The obtained slurry was dried at 270°C for 1 hour under nitrogen flow using a mantle heater. The obtained solid matter was crushed in a mortar to obtain a powder of the solid electrolyte material according to Example 1.
  • the solid electrolyte material according to Example 1 had a composition represented by Li 3 AlF 6 .
  • FIG. 2 shows a schematic diagram of a pressing die 300 used to evaluate the ionic conductivity of the solid electrolyte material.
  • the pressure molding die 300 had an upper punch 301, a frame 302, and a lower punch 303.
  • the frame 302 was made of insulating polycarbonate.
  • the upper punch 301 and the lower punch 303 were made of electronically conductive stainless steel.
  • the ionic conductivity of the solid electrolyte material of Example 1 was evaluated by the following method using the pressure molding die 300 shown in Figure 2.
  • the powder of the solid electrolyte material according to Example 1 was filled into the inside of the pressure molding die 300. Inside the pressure molding die 300, a pressure of 400 MPa was applied to the solid electrolyte material according to Example 1 using the upper punch 301 and the lower punch 303.
  • the upper punch 301 and the lower punch 303 were connected to a potentiostat (VSP300, manufactured by BioLogic) equipped with a frequency response analyzer.
  • the upper punch 301 was connected to a working electrode and a terminal for measuring potential.
  • the lower punch 303 was connected to a counter electrode and a reference electrode.
  • the impedance of the solid electrolyte material was measured by electrochemical impedance measurement at room temperature.
  • Figure 3 is a graph showing the Cole-Cole plot obtained by impedance measurement of the solid electrolyte material of Example 1.
  • ⁇ represents ionic conductivity.
  • S represents the contact area of the solid electrolyte material with the punch upper portion 301. That is, S is equal to the cross-sectional area of the hollow portion of the frame mold 302 in FIG. 3.
  • R SE represents the resistance value of the solid electrolyte material in impedance measurement.
  • t represents the thickness of the solid electrolyte material. That is, t represents the thickness of the layer formed from the powder 101 of the solid electrolyte material in FIG. 3.
  • the ionic conductivity of the solid electrolyte material of Example 1 measured at 25° C. was 1.4 ⁇ 10 ⁇ 10 S/cm.
  • the specific surface area was measured using a specific surface area/pore distribution measuring device (BELSORP MINI X, manufactured by MicrotrackBell Co., Ltd.)
  • BELSORP MINI X manufactured by MicrotrackBell Co., Ltd.
  • the specific surface area obtained using this device will be referred to as the BET specific surface area.
  • powder of the solid electrolyte material from Example 1 (approximately 1 g) was placed in a dedicated test tube.
  • the material was vacuum dried at 80°C for 1 hour.
  • the mass added was calculated from the difference between the weight of the test tube containing the sample after pretreatment and the weight of the test tube before the sample was added.
  • the BET specific surface area was measured using the pretreated test tube, and the specific surface area of the solid electrolyte material of Example 1 was found to be 16.0 m 2 /g.
  • NCA Li(Ni,Co,Al) O2
  • a coating layer made of LAF was formed on the surface of the NCA.
  • the coating layer was formed by a compression shear treatment using a particle composite device (NOB-MINI, manufactured by Hosokawa Micron Corporation). Specifically, the NCA and LAF were weighed out to have a volume ratio of 98.9:1.1, and treated under the following conditions: blade clearance: 2 mm, rotation speed: 8000 rpm, and treatment time: 30 min. This resulted in the coated active material of Example 1 being obtained.
  • LPS 50 mg
  • the above-mentioned positive electrode mixture 10 mg
  • a pressure of 300 MPa was applied to the resulting stack to form an electrolyte layer and a positive electrode.
  • the thickness of the electrolyte layer was 400 ⁇ m.
  • current collectors made of stainless steel were attached to the positive and negative electrodes, and current collecting leads were attached to the current collectors.
  • (Charge/discharge test) 4 is a graph showing the initial discharge characteristics of the battery according to Example 1. The initial charge/discharge characteristics were measured by the following method.
  • the battery according to Example 1 was placed in a thermostatic chamber at 25°C.
  • the battery according to Example 1 was charged at a current density of 125 ⁇ A/cm 2 until a voltage of 4.3 V was reached, which corresponds to a 0.1 C rate.
  • Example 1 The cell according to Example 1 was then discharged at a current density of 125 ⁇ A/cm 2 until a voltage of 3.1 V was reached.
  • the battery of Example 1 had an initial discharge capacity of 1,340 ⁇ Ah.
  • Example 2 to 4 (Preparation of solid electrolyte material)
  • the batteries according to Examples 2 to 4 were used to carry out charge and discharge tests in the same manner as in Example 1. As a result, the batteries according to Examples 2 to 4 were successfully charged and discharged in the same manner as the battery according to Example 1.
  • the solid electrolyte material of Reference Example 1 was produced by dry ball milling without using an organic solvent.
  • the ionic conductivity measured at 25° C. was 8.3 ⁇ 10 ⁇ 8 S/cm.
  • the measured specific surface area was 3.1 m 2 /g.
  • LiF was used as the solid electrolyte material, and the ionic conductivity was measured in the same manner as in Example 1. As a result, the ionic conductivity could not be measured at 25°C.
  • the solid electrolyte materials of Examples 1 to 4 have an ionic conductivity of 1.2 ⁇ 10 S/cm or more at room temperature and a specific surface area of 16 m /g or more, whereas the specific surface area of the solid electrolyte material of Reference Example 1 produced by a dry ball mill was a small value of 3.1 m /g.
  • the batteries according to Examples 1 to 4 were all charged and discharged at 25°C.
  • the solid electrolyte material disclosed herein has high lithium ion conductivity and is suitable for providing a battery that can be charged and discharged well.
  • results shown in this example are believed to be obtainable when using a positive electrode active material other than NCA, particularly a lithium-containing transition metal oxide.
  • the solid electrolyte material with a high specific surface area penetrates into the recesses on the surface of the active material, improving the contact between the solid electrolyte material and the active material. This effect is obtainable regardless of the composition of the positive electrode active material. This effect is particularly noticeable when the particles of the positive electrode active material are secondary particles.
  • the solid electrolyte material disclosed herein is used, for example, in lithium-ion secondary batteries.
  • Solid electrolyte 101 Powder of solid electrolyte material 201 Positive electrode 202 Electrolyte layer 203 Negative electrode 204 Positive electrode active material 205 Negative electrode active material 300 Pressure molding die 301 Upper punch part 302 Frame 303 Lower punch part 1000 Battery

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PCT/JP2024/019515 2023-06-12 2024-05-28 固体電解質材料、固体電解質材料の製造方法、正極材料および電池 Ceased WO2024257600A1 (ja)

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JP2011129312A (ja) 2009-12-16 2011-06-30 Toyota Motor Corp 硫化物固体電解質材料の製造方法、硫化物固体電解質材料およびリチウム電池
JP2012084547A (ja) 2003-12-05 2012-04-26 Nissan Motor Co Ltd 非水電解質リチウムイオン電池用正極材料およびこれを用いた電池
JP2023009668A (ja) * 2021-07-07 2023-01-20 株式会社サムスン日本研究所 非水電解質二次電池用被覆正極活物質及び該被覆正極活物質を含有する非水電解質二次電池。
WO2023042560A1 (ja) * 2021-09-15 2023-03-23 パナソニックＩｐマネジメント株式会社 固体電解質材料およびそれを用いた電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012084547A (ja) 2003-12-05 2012-04-26 Nissan Motor Co Ltd 非水電解質リチウムイオン電池用正極材料およびこれを用いた電池
JP2011129312A (ja) 2009-12-16 2011-06-30 Toyota Motor Corp 硫化物固体電解質材料の製造方法、硫化物固体電解質材料およびリチウム電池
JP2023009668A (ja) * 2021-07-07 2023-01-20 株式会社サムスン日本研究所 非水電解質二次電池用被覆正極活物質及び該被覆正極活物質を含有する非水電解質二次電池。
WO2023042560A1 (ja) * 2021-09-15 2023-03-23 パナソニックＩｐマネジメント株式会社 固体電解質材料およびそれを用いた電池

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