WO2023199629A1 - 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
WO2023199629A1
WO2023199629A1 PCT/JP2023/007416 JP2023007416W WO2023199629A1 WO 2023199629 A1 WO2023199629 A1 WO 2023199629A1 JP 2023007416 W JP2023007416 W JP 2023007416W WO 2023199629 A1 WO2023199629 A1 WO 2023199629A1
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Prior art keywords
solid electrolyte
electrolyte material
material according
positive electrode
negative electrode
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PCT/JP2023/007416
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English (en)
French (fr)
Japanese (ja)
Inventor
敬 久保
和史 宮武
良明 田中
隆平 片山
晃暢 宮崎
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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 JP2024514835A priority Critical patent/JPWO2023199629A1/ja
Publication of WO2023199629A1 publication Critical patent/WO2023199629A1/ja
Priority to US18/904,155 priority patent/US20250030045A1/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
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G35/00—Compounds of tantalum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G35/00—Compounds of tantalum
    • C01G35/006—Compounds containing tantalum, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G35/00—Compounds of tantalum
    • C01G35/02—Halides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a solid electrolyte material and a battery using the same.
  • Patent Document 1 discloses a solid electrolyte material containing Li, M, O, and X.
  • M is at least one element selected from the group consisting of Nb and Ta
  • X is at least one element selected from the group consisting of Cl, Br, and I.
  • An object of the present disclosure is to provide a solid electrolyte material that can suppress a decrease in ionic conductivity due to heat.
  • the solid electrolyte material of the present disclosure includes: Contains Li, M, O, and X,
  • M is at least one selected from the group consisting of Nb and Ta
  • X is at least one selected from the group consisting of F, Cl, Br, and I
  • the average value of the aspect ratio (L/W) between length (L) and width (W) in the columnar crystal is 5 or more, and the average length is 20 ⁇ m or less.
  • the present disclosure provides a solid electrolyte material that can suppress a decrease in ionic conductivity due to heat.
  • FIG. 1 is a flowchart illustrating an example of a method for manufacturing a solid electrolyte material according to the first embodiment.
  • FIG. 2 shows a cross-sectional view of a battery 1000 according to a second embodiment.
  • FIG. 3 shows a cross-sectional view of an electrode material 1100 according to a second embodiment.
  • FIG. 4 shows a SEM image of the solid electrolyte material according to Example 1.
  • FIG. 5 shows a schematic diagram of a pressure molding die 300 used to evaluate the ionic conductivity of a solid electrolyte material.
  • the solid electrolyte material according to the first aspect of the present disclosure is Contains Li, M, O, and X,
  • M is at least one selected from the group consisting of Nb and Ta
  • X is at least one selected from the group consisting of F, Cl, Br, and I
  • the average value of the aspect ratio (L/W) between length (L) and width (W) in the columnar crystal is 5 or more, and the average length is 20 ⁇ m or less.
  • the solid electrolyte material according to the first aspect In the solid electrolyte material according to the first aspect, a path for lithium ions to diffuse is easily formed, and at the same time, evaporation of constituent elements due to heat is suppressed. Therefore, reduction in ionic conductivity due to heat can be suppressed.
  • the solid electrolyte material according to the first aspect has improved ionic conductivity and heat resistance.
  • X may include Cl.
  • the solid electrolyte material according to the second aspect has improved ionic conductivity and heat resistance.
  • M may include Ta.
  • the solid electrolyte material according to the third aspect has improved ionic conductivity and heat resistance.
  • the molar ratio of Li to M may be 0.60 or more and 3.0 or less.
  • the solid electrolyte material according to the fourth aspect has improved ionic conductivity and heat resistance.
  • the molar ratio of O to X may be 0.05 or more and 0.4 or more.
  • the solid electrolyte material according to the fifth aspect has improved ionic conductivity and heat resistance.
  • the battery according to the sixth aspect of the present disclosure includes: positive electrode, a negative electrode, and an electrolyte layer disposed between the positive electrode and the negative electrode; Equipped with At least one selected from the group consisting of the positive electrode, the negative electrode, and the electrolyte layer contains the solid electrolyte material according to any one of the first to fifth aspects.
  • the battery according to the sixth aspect operates stably even in an environment with temperature changes and can have excellent charge/discharge characteristics. Further, even if heat treatment is performed at high temperature in the battery manufacturing process, it can have excellent charge/discharge characteristics.
  • the manufacturing method according to the seventh aspect of the present disclosure includes: A method for producing a solid electrolyte material according to any one of the first to fifth aspects, comprising: synthesizing a compound containing Li, M, O, and X; columnarizing the compound, M is at least one selected from the group consisting of Nb and Ta; X is at least one selected from the group consisting of F, Cl, Br, and I;
  • the columnarization includes a post-annealing process and a crushing process, The pulverization process is performed after the post-annealing process.
  • the manufacturing method according to the seventh aspect can manufacture a solid electrolyte material that can suppress a decrease in ionic conductivity due to heat.
  • the solid electrolyte material according to the first embodiment includes Li, M, O, and X, where M is at least one selected from the group consisting of Nb and Ta, and X is F, Cl, At least one selected from the group consisting of Br and I.
  • the solid electrolyte material according to the first embodiment includes columnar crystals.
  • the solid electrolyte material according to the first embodiment can reduce the decrease in ionic conductivity due to heat by including columnar crystals. More specifically, in a solid electrolyte material containing columnar crystals containing Li, M, O, and X, evaporation of constituent elements against heat is suppressed. As a result, the solid electrolyte material according to the first embodiment can also reduce the decrease in ionic conductivity due to heat. Moreover, according to the above configuration, a path for lithium ions to diffuse is easily formed. As a result, the solid electrolyte material according to the first embodiment can have practical ionic conductivity, for example, high lithium ion conductivity and It can have excellent heat resistance.
  • An example of high lithium ion conductivity is 0.1 mS/cm or more near room temperature. Room temperature is, for example, 22°C.
  • the solid electrolyte material according to the first embodiment may have an ionic conductivity of 0.1 mS/cm or more, for example.
  • the solid electrolyte material according to the first embodiment can also have an ionic conductivity of 1.5 mS/cm or more, for example.
  • the term "columnar crystal” refers to a crystal that has grown in one direction, and means one in which the aspect ratio (L/W) between the length (L) and width (W) of the crystal is greater than 2. Aspect ratio is the ratio of length (L) to width (W) of a crystal.
  • the length and width of a columnar crystal mean the length of the long side and the length of the short side of the columnar crystal, respectively.
  • the length of the long side is the longest diameter of the crystal in a plane image of the crystal observed with a scanning electron microscope
  • the length of the short side is the maximum value of the diameter in the direction perpendicular to the longest diameter.
  • the shape of the tip of the crystal is not limited, and the term “columnar crystal” includes needle-shaped crystals.
  • the solid electrolyte material according to the first embodiment may be a powder, and the powder may contain crystalline columnar particles or acicular particles.
  • the battery's positive electrode, electrolyte layer, and negative electrode require a high-temperature heat treatment process for densification and bonding.
  • the temperature in the heat treatment step is, for example, about 200°C to 300°C. Even when heat treatment is performed at about 300° C., the ionic conductivity of the solid electrolyte material according to the first embodiment is unlikely to decrease or does not decrease. Thus, the solid electrolyte material according to the first embodiment has excellent heat resistance.
  • the solid electrolyte material according to the first embodiment suppresses a decrease in ionic conductivity in the expected battery operating temperature range (for example, -30°C to 80°C), and has sufficient lithium ion conductivity for battery operation. can be maintained. Therefore, the battery using the solid electrolyte material according to the first embodiment can operate stably even in an environment with temperature changes.
  • the solid electrolyte material according to the first embodiment can be used because it has excellent charge and discharge characteristics.
  • An example of a battery is an all-solid-state battery.
  • the battery may be a primary battery or a secondary battery.
  • the solid electrolyte material according to the first embodiment contains substantially no sulfur.
  • the solid electrolyte material according to the first embodiment does not substantially contain sulfur, which means that the solid electrolyte material does not contain sulfur as a constituent element, except for sulfur that is unavoidably mixed as an impurity.
  • the amount of sulfur mixed as an impurity into the solid electrolyte material is, for example, 1 mol % or less.
  • the solid electrolyte material according to the first embodiment does not contain sulfur. Solid electrolyte materials that do not contain sulfur do not generate hydrogen sulfide even when exposed to the atmosphere, so they are highly safe.
  • the solid electrolyte material according to the first embodiment may consist essentially of Li, M, O, and X.
  • the solid electrolyte material according to the first embodiment substantially consists of Li, M, O, and X
  • the ratio of the total amount of Li, M, O, and X to the total amount of substances is 90% or more. As an example, the ratio may be 95% or more.
  • the solid electrolyte material according to the first embodiment may consist only of Li, M, O, and X.
  • X may contain Cl in order to improve the ionic conductivity and heat resistance of the solid electrolyte material.
  • X may be Cl.
  • M may include Ta in the solid electrolyte material according to the first embodiment.
  • M may be Ta.
  • the molar ratio of Li to M (hereinafter referred to as "Li/M molar ratio”) is 0.60. It may be greater than or equal to 3.0.
  • the molar ratio of O to X (hereinafter referred to as "O/X molar ratio”) may be 0.05 or more and 0.4 or less.
  • the Li/M molar ratio may be 0.60 or more and 3.0 or less, and the O/X molar ratio may be 0.05 or more and 0.4 or less.
  • the Li/M molar ratio may be 1.5 or more and 3.0 or less, and 2.4 or more. It may be 2.7 or less.
  • the O/X molar ratio may be 0.27 or more and 0.4 or less, or 0.3 or more and 0.4 or less.
  • the Li/M molar ratio may be 1.5 or more and 3.0 or less, and the O/X molar ratio may be 0.27 or more and 0.4 or less.
  • the Li/M molar ratio may be 2.4 or more and 2.7 or less, and the O/X molar ratio may be 0.3 or more and 0.4 or less.
  • the Li/M molar ratio is 2.6, and the O/X molar ratio is 0.38. It may be.
  • the average value of the aspect ratio (L/W) between the length (L) and the width (W) of the columnar crystals is 5 or more, and the average length of the columnar crystals is It is 20 ⁇ m or less.
  • the average length-to-width aspect ratio (L/W) of the columnar crystals may be 5 or more and 100 or less, and the average length of the columnar crystals may be 3 ⁇ m or more and 20 ⁇ m or less.
  • the average value and average length of the aspect ratio of the columnar crystals are calculated as the average value of the aspect ratio and length of 10 columnar crystals selected from 3 ⁇ m or more in length measured from an electron microscope image.
  • the shape and size of the solid electrolyte material can be measured with a scanning electron microscope (SEM) or an image analysis device.
  • SEM scanning electron microscope
  • FIG. 1 is a flowchart illustrating an example of a method for manufacturing a solid electrolyte material according to the first embodiment.
  • the method for manufacturing a solid electrolyte material according to the first embodiment includes synthesizing a compound containing Li, M, O, and X (S01) and forming the synthesized compound into columns (S02).
  • the process of synthesizing a compound will be referred to as a synthesis process
  • the process of forming a synthesized compound into a columnar structure will be referred to as a columnarization process.
  • M is at least one selected from the group consisting of Nb and Ta
  • X is at least one selected from the group consisting of F, Cl, Br, and I.
  • the columnarization step S02 includes a post-annealing process and a pulverizing process, and the pulverizing process is performed after the post-annealing process.
  • the synthesis step S01 and the columnarization step S02 are performed in this order.
  • raw material powder is first prepared so as to have the desired composition.
  • raw material powders are oxides, hydroxides, halides, or acid halides.
  • the element types of M and X are determined.
  • the mixing ratio of the raw materials the molar ratios of Li/M and O/X are determined.
  • the raw material powders may be mixed in a pre-adjusted molar ratio to offset compositional changes that may occur during the synthesis process.
  • a reactant is obtained by firing the mixture of raw material powders.
  • a mixture of raw material powders may be sealed in an airtight container made of quartz glass or borosilicate glass and fired under vacuum or an inert gas atmosphere.
  • the inert gas atmosphere is, for example, an argon atmosphere or a nitrogen atmosphere.
  • a mixture of raw material powders may be mechanochemically reacted with each other in a mixing device such as a planetary ball mill to obtain a reactant. That is, the raw materials may be mixed and reacted using a mechanochemical milling method.
  • a solid electrolyte material consisting of Li, M, O, and X can be obtained by these methods.
  • the solid electrolyte material produced in the synthesis step S01 is columnarized.
  • the post-annealing process may be, for example, baking for 30 minutes or more and 240 minutes or less.
  • the firing temperature is, for example, 150°C or higher and 300°C or lower.
  • the pulverization process is, for example, a wet pulverization process.
  • an organic solvent and a solid electrolyte material are mixed.
  • the mixing method There are no particular limitations on the mixing method. Further, the blending ratio of the organic solvent and the solid electrolyte material may be appropriately selected.
  • solid electrolyte composition a solution consisting of an organic solvent and a solid electrolyte material.
  • Grinding media is used for wet grinding.
  • the shape of the grinding media is not limited. Examples of the shape of the grinding media are spherical or bale-shaped.
  • the size of the grinding media largely depends on the size of the solid electrolyte material after it is columnarized. For example, it is desirable to use grinding media that is spherical and has a diameter of 1.0 mm or less.
  • the wet pulverization process is performed, for example, by using a roll mill, a pot mill, or a planetary ball mill, in which a container containing an organic solvent, a solid electrolyte material, and a pulverizing media is rotated and pulverized.
  • a bead mill may be used, in which a solution containing an organic solvent and a solid electrolyte is passed through a grinding chamber equipped with a rotor containing grinding media, and the rotor is rotated at high speed.
  • a sieve is used to separate the solid electrolyte composition after pulverization from the pulverization media.
  • the pulverization conditions may be appropriately set according to each device.
  • the organic solvent is removed from the solid electrolyte composition.
  • the organic solvent may be removed by reduced pressure drying or vacuum drying. Drying under reduced pressure refers to removing an organic solvent from a solid electrolyte composition in a pressure atmosphere lower than atmospheric pressure.
  • the pressure atmosphere lower than atmospheric pressure may be a gauge pressure of -0.01 MPa or less, for example.
  • the solid electrolyte composition may be heated to 50°C or higher and 250°C or lower.
  • Vacuum drying refers to, for example, removing the organic solvent from the solid electrolyte composition at a temperature that is 20° C. lower than the boiling point of the organic solvent and at a vapor pressure or lower.
  • the organic solvent may be removed by heating the solid electrolyte composition in an environment with an inert gas flow.
  • inert gases are nitrogen or argon.
  • the heating temperature is, for example, 50°C or higher and 250°C or lower.
  • the composition of the solid electrolyte material can be determined, for example, by inductively coupled plasma (ICP) emission spectroscopy, ion chromatography, or inert gas fusion-infrared absorption.
  • ICP inductively coupled plasma
  • the compositions of Li and M can be determined by ICP emission spectroscopy
  • the composition of X can be determined by ion chromatography
  • O can be measured by inert gas fusion-infrared absorption.
  • the battery according to the second embodiment includes a positive electrode, an electrolyte layer, and a negative electrode.
  • An electrolyte layer is disposed between the positive 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 contains the solid electrolyte material according to the first embodiment, excellent charge and discharge characteristics can be maintained even when the battery is exposed to high temperatures. Batteries, for example, are heat treated at high temperatures during manufacture.
  • FIG. 2 shows a cross-sectional view of a battery 1000 according to the second embodiment.
  • the battery 1000 includes a positive electrode 201, an electrolyte layer 202, and a negative electrode 203. Electrolyte layer 202 is arranged between positive electrode 201 and negative electrode 203.
  • the positive electrode 201 contains positive electrode active material particles 204 and solid electrolyte particles 100.
  • the electrolyte layer 202 contains an electrolyte material.
  • the electrolyte material is, for example, a solid electrolyte material.
  • the negative electrode 203 contains negative electrode active material particles 205 and solid electrolyte particles 100.
  • the solid electrolyte particles 100 are particles containing the solid electrolyte material according to the first embodiment.
  • the solid electrolyte particles 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 in the largest 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 that can insert and release metal ions such as lithium ions.
  • the positive electrode 201 contains, for example, a positive electrode active material (for example, positive electrode active material particles 204).
  • positive electrode active materials are lithium-containing transition metal oxides, transition metal fluorides, polyanionic materials, fluorinated polyanionic materials, transition metal sulfides, transition metal oxysulfides, or transition metal oxynitrides.
  • lithium-containing transition metal oxides are Li(Ni,Co,Al) O2 , Li(Ni,Co,Mn) O2 , or LiCoO2 .
  • (A, B, C) means "at least one selected from the group consisting of A, B, and C.”
  • lithium phosphate may be used as the positive electrode active material.
  • lithium iron phosphate may be used as the positive electrode active material.
  • the solid electrolyte material according to the first embodiment containing I is easily oxidized.
  • the oxidation reaction of the solid electrolyte material is suppressed. That is, formation of an oxide layer having low lithium ion conductivity is suppressed. As a result, the battery has high charge/discharge efficiency.
  • the positive electrode 201 may contain not only the solid electrolyte material according to the first embodiment but also a transition metal oxyfluoride as a positive electrode active material. Even when the solid electrolyte material according to the first embodiment is fluorinated with a transition metal fluoride, a resistance layer is hardly formed. As a result, the battery has high charge/discharge efficiency.
  • Transition metal oxyfluorides contain oxygen and fluorine.
  • the transition metal oxyfluoride may be a compound represented by the composition formula Lip Me q O m F n .
  • Me is Mn, Co, Ni, Fe, Al, Cu, V, Nb, Mo, Ti, Cr, Zr, Zn, Na, K, Ca, Mg, Pt, Au, Ag, Ru, W, At least one selected from the group consisting of B, Si, and P, and the formula: 0.5 ⁇ p ⁇ 1.5, 0.5 ⁇ q ⁇ 1.0, 1 ⁇ m ⁇ 2, and 0 ⁇ n ⁇ 1 is satisfied.
  • An example of such a transition metal oxyfluoride is Li 1.05 (Ni 0.35 Co 0.35 Mn 0.3 ) 0.95 O 1.9 F 0.1 .
  • 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 well dispersed in the positive electrode 201. This improves the charging and discharging 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 within 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 larger median diameter than the solid electrolyte particles 100. Thereby, in the positive electrode 201, 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.
  • FIG. 3 shows a cross-sectional view of an electrode material 1100 according to the second embodiment.
  • Electrode material 1100 is included in positive electrode 201, for example.
  • a coating layer 216 may be formed on the surface of the electrode active material particles 206. Thereby, an increase in reaction overvoltage of the battery can be suppressed.
  • the coating material included in the coating layer 216 are a sulfide solid electrolyte, an oxide solid electrolyte, or a halide solid electrolyte.
  • the coating material may be the solid electrolyte material according to the first embodiment, and X may be at least one selected from the group consisting of Cl and Br.
  • the solid electrolyte material according to the first embodiment is less likely to be oxidized than the sulfide solid electrolyte. As a result, an increase in reaction overvoltage of the battery can be suppressed.
  • the coating material is the solid electrolyte material according to the first embodiment, and X is from the group consisting of Cl and Br. It may be at least one selected.
  • the solid electrolyte material according to the first embodiment that does not contain I is less likely to be oxidized than the solid electrolyte material according to the first embodiment that contains I. As a result, the battery has high charge/discharge efficiency.
  • the coating material may include an oxide solid electrolyte.
  • the oxide solid electrolyte may be lithium niobate, which has excellent stability even at high potentials. As a result, the battery has high charge/discharge efficiency.
  • the positive electrode 201 may consist of a first positive electrode layer containing a first positive electrode active material and a second positive electrode layer containing a second positive electrode active material.
  • the second positive electrode layer is disposed between the first positive electrode layer and the electrolyte layer 202, the first positive electrode layer and the second positive electrode layer contain the solid electrolyte material according to the first embodiment including I, and A coating layer 216 is formed on the surface of the second positive electrode active material.
  • the solid electrolyte material according to the first embodiment included in the electrolyte layer 202 can be prevented from being oxidized by the second positive electrode active material. As a result, the battery has a high charging capacity.
  • Examples of the coating material included in the coating layer 216 are a sulfide solid electrolyte, an oxide solid electrolyte, a polymer solid electrolyte, or a halide solid electrolyte. However, when the coating material is a halide solid electrolyte, I is not included as a halogen element.
  • the first positive electrode active material may be the same material as the second positive electrode active material, or may be a different material from the second positive electrode active material.
  • 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.
  • Electrolyte layer 202 may be a solid electrolyte layer.
  • Electrolyte layer 202 may contain a solid electrolyte material according to the first embodiment.
  • the electrolyte layer 202 may be made only of the solid electrolyte material according to the first embodiment.
  • the electrolyte layer 202 may be made only of a solid electrolyte material different from the solid electrolyte material according to the first embodiment.
  • solid electrolyte materials different from the solid electrolyte material according to the first embodiment include Li 2 MgX' 4 , Li 2 FeX' 4 , Li (Al, Ga, In) X' 4 , Li 3 (Al, Ga, In) )X' 6 or LiI.
  • X' is at least one selected from the group consisting of F, Cl, Br, and I.
  • the solid electrolyte material according to the first embodiment will be referred to as a first solid electrolyte material.
  • a solid electrolyte material different from the solid electrolyte material according to the first embodiment is referred to as a second solid electrolyte material.
  • the electrolyte layer 202 may contain not only the first solid electrolyte material but also the second solid electrolyte material.
  • 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 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 power.
  • Another electrolyte layer may be further provided between the electrolyte layer 202 and the negative electrode 203.
  • the electrolyte layer 202 includes a first solid electrolyte material
  • a material that is electrochemically more stable than the first solid electrolyte material is used.
  • An electrolyte layer made of another solid electrolyte material may be further provided between electrolyte layer 202 and negative electrode 203.
  • the negative electrode 203 contains a material that can insert and release metal ions (for example, lithium ions).
  • the negative electrode 203 contains, 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 or an alloy.
  • An example of a metallic material is lithium metal or a lithium alloy.
  • Examples of carbon materials are natural graphite, coke, semi-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), a silicon compound, or a tin compound.
  • the negative electrode active material may be selected based on the reduction resistance of the solid electrolyte material included in the negative electrode 203.
  • a material capable of intercalating and deintercalating lithium ions at 0.27 V or higher relative to lithium may be used as the negative electrode active material. If the negative electrode active material is such a material, reduction of the first solid electrolyte material contained in the negative electrode 203 can be suppressed. As a result, the battery has high charge/discharge efficiency.
  • examples of such materials are titanium oxide, indium metal or lithium alloys.
  • titanium oxides are Li 4 Ti 5 O 12 , LiTi 2 O 4 or TiO 2 .
  • 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 negative electrode active material particles 205 and the solid electrolyte particles 100 can be well dispersed in the negative electrode 203. This improves the charging and discharging 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 within 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 larger median diameter than the solid electrolyte particles 100. Thereby, in the negative electrode 203, the negative electrode active material particles 205 and the solid electrolyte particles 100 can be well dispersed.
  • the ratio of the volume of the negative electrode active material particles 205 to the sum of the 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 electrode material 1100 shown in FIG. 3 may be contained in the negative electrode 203.
  • a coating layer 216 may be formed on the surface of the electrode active material particles 206.
  • the battery has high charge/discharge efficiency.
  • the coating material included in the coating layer 216 are a sulfide solid electrolyte, an oxide solid electrolyte, a polymer solid electrolyte, or a halide solid electrolyte.
  • the coating material may be a sulfide solid electrolyte, an oxide solid electrolyte, or a polymer solid electrolyte.
  • a sulfide solid electrolyte is Li 2 SP 2 S 5 .
  • An example of an oxide solid electrolyte is trilithium phosphate.
  • An example of a polymeric solid electrolyte is a composite compound of polyethylene oxide and lithium salt. An example of such a polymeric solid electrolyte is lithium bis(trifluoromethanesulfonyl)imide.
  • 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.
  • the second solid electrolyte material are a sulfide solid electrolyte, an oxide solid electrolyte, a halide solid electrolyte, or an organic polymer solid electrolyte.
  • sulfide solid electrolyte means a solid electrolyte containing sulfur.
  • Oxide solid electrolyte means a solid electrolyte containing oxygen.
  • the oxide solid electrolyte may contain anions other than oxygen (excluding sulfur anions and halogen anions).
  • Oxide solid electrolyte means a solid electrolyte that contains a halogen element and does not contain sulfur.
  • the halide solid electrolyte may contain not only a halogen element but also oxygen.
  • Examples of sulfide solid electrolytes are Li 2 SP 2 S 5 , Li 2 S-SiS 2 , Li 2 SB 2 S 3 , Li 2 S-GeS 2 , Li 3.25 Ge 0.25 P 0.75 S 4 , or It is Li 10 GeP 2 S 12 .
  • an oxide solid electrolyte is (i) NASICON type solid electrolyte such as LiTi 2 (PO 4 ) 3 or its elemental substitution product; (ii) a perovskite solid electrolyte such as (LaLi) TiO3 ; (iii) LISICON-type solid electrolytes such as Li 14 ZnGe 4 O 16 , Li 4 SiO 4 , LiGeO 4 or elemental substitutes thereof; (iv) a garnet-type solid electrolyte such as Li 7 La 3 Zr 2 O 12 or its elemental substitution product; or (v) Li 3 PO 4 or its N-substituted product.
  • NASICON type solid electrolyte such as LiTi 2 (PO 4 ) 3 or its elemental substitution product
  • a perovskite solid electrolyte such as (LaLi) TiO3 ;
  • LISICON-type solid electrolytes such as Li 14 ZnGe 4 O 16 , Li 4 SiO 4 , Li
  • 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 and metalloid elements other than Li and Y.
  • Z is at least one selected from the group consisting of F, Cl, Br, and I.
  • the value of m represents the valence of Me'.
  • Metalloid elements are B, Si, Ge, As, Sb, and Te.
  • Metallic elements include 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 selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb. It may be at least one selected from the following.
  • halide solid electrolytes are Li 3 YCl 6 or Li 3 YBr 6 .
  • the negative electrode 203 may contain a sulfide solid electrolyte.
  • the sulfide solid electrolyte which is electrochemically stable with respect to the negative electrode active material, prevents the first solid electrolyte material and the negative electrode active material from coming into contact with each other.
  • the battery has a low internal resistance.
  • organic polymer solid electrolytes examples include polymer compounds and lithium salt compounds.
  • the polymer compound may have an ethylene oxide structure. Since a polymer compound having an ethylene oxide structure can contain a large amount of lithium salt, it has higher ionic conductivity.
  • lithium salts are LiPF6 , LiBF4 , LiSbF6, LiAsF6 , LiSO3CF3 , LiN ( SO2CF3 ) 2 , LiN( SO2C2F5 ) 2 , LiN( SO2CF3 ) . (SO 2 C 4 F 9 ), or LiC(SO 2 CF 3 ) 3 .
  • One type of 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 made of a non-aqueous electrolyte, a gel electrolyte, or a non-aqueous electrolyte for the purpose of facilitating transfer of lithium ions and improving the output characteristics of the battery. It may contain liquid.
  • the non-aqueous electrolyte includes a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
  • nonaqueous solvents are cyclic carbonate solvents, chain carbonate solvents, cyclic ether solvents, chain ether solvents, cyclic ester solvents, chain ester solvents, or fluorine solvents.
  • cyclic carbonate solvents are ethylene carbonate, propylene carbonate, or butylene carbonate.
  • linear carbonate solvents are dimethyl carbonate, ethylmethyl carbonate, or diethyl carbonate.
  • cyclic ether solvents are tetrahydrofuran, 1,4-dioxane, or 1,3-dioxolane.
  • An example of a linear ether solvent is 1,2-dimethoxyethane or 1,2-diethoxyethane.
  • An example of a cyclic ester solvent is ⁇ -butyrolactone.
  • An example of a linear ester solvent is methyl acetate.
  • fluorine solvents are fluoroethylene carbonate, methyl fluoropropionate, fluorobenzene, fluoroethylmethyl carbonate, or fluorodimethylene carbonate.
  • One type of nonaqueous solvent selected from these may be used alone. Alternatively, a mixture of two or more nonaqueous solvents selected from these may be used.
  • lithium salts are LiPF6 , LiBF4 , LiSbF6, LiAsF6 , LiSO3CF3 , LiN ( SO2CF3 ) 2 , LiN( SO2C2F5 ) 2 , LiN( SO2CF3 ) . (SO 2 C 4 F 9 ), or LiC(SO 2 CF 3 ) 3 .
  • One type of lithium salt selected from these may be used alone. Alternatively, a mixture of two or more lithium salts selected from these may be used.
  • the concentration of the lithium salt is, for example, in a range of 0.5 mol/liter or more and 2 mol/liter or less.
  • a polymer material impregnated with a non-aqueous electrolyte may be used as the gel electrolyte.
  • examples of polymeric materials are polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, or polymers with ethylene oxide linkages.
  • ionic liquids examples include: (i) aliphatic chain quaternary salts such as tetraalkylammonium or tetraalkylphosphonium; (ii) aliphatic cyclic ammoniums such as pyrrolidiniums, morpholiniums, imidazoliniums, tetrahydropyrimidiniums, piperaziniums, or piperidiniums; or (iii) nitrogen-containing heteros such as pyridiniums or imidazoliums. ring aromatic cation, It is.
  • Examples of anions contained in ionic liquids are PF 6 - , BF 4 - , SbF 6 - , AsF 6 - , SO 3 CF 3 - , N(SO 2 CF 3 ) 2 - , N(SO 2 C 2 F 5 ) 2- , N ( SO2CF3 ) ( SO2C4F9 )- , or C( SO2CF3 ) 3- .
  • the ionic liquid may contain a lithium salt.
  • At least one selected from the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a binder for the purpose of improving adhesion between particles.
  • binders include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, Polyacrylic acid hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyether sulfone, hexafluoropolypropylene, styrene butadiene rubber , or carboxymethylcellulose.
  • Copolymers may be used as binders.
  • binders are tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and It is a copolymer of two or more materials selected from the group consisting of hexadiene. Mixtures of two or more selected from the above materials may also be used.
  • At least one selected from the positive electrode 201 and the negative electrode 203 may contain a conductive additive for the purpose of increasing electronic conductivity.
  • Examples of conductive aids are: (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) fluorinated carbon; (v) metal powders such as aluminum; (vi) conductive whiskers such as zinc oxide or potassium titanate; (vii) a conductive metal oxide such as titanium oxide, or (viii) a conductive polymer compound such as polyaniline, polypyrrole, or polythiophene.
  • the above-mentioned conductive aid (i) or (ii) may be used.
  • Examples of the shape of the battery according to the second embodiment are a coin shape, a cylindrical shape, a square shape, a sheet shape, a button shape, a flat shape, and a laminated shape.
  • 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 also be manufactured by producing a laminate.
  • Example 1 [Preparation of solid electrolyte material] (synthesis process)
  • dry argon atmosphere (hereinafter simply referred to as "dry argon atmosphere") having a dew point of -60°C or less
  • These materials were ground and mixed in an agate mortar.
  • the resulting mixture was placed in a quartz glass filled with argon gas and fired at 350° C. for 3 hours.
  • the obtained baked product was ground in an agate mortar.
  • Post-annealing was performed by placing the pulverized fired product in an alumina crucible and firing at 260°C for 2 hours. Thereby, the compound consisting of Ta and Cl was volatilized. In this way, a solid electrolyte material (hereinafter referred to as "LTOC") consisting of Li, Ta, O, and Cl was obtained.
  • LTOC solid electrolyte material
  • LTOC (4 g) and p-chlorotoluene (16 g) were placed in a planetary ball mill grinding pot and stirred with a spatula to prepare a solid electrolyte composition.
  • Zirconia grinding media (25 g) was placed in the planetary ball mill grinding pot.
  • the grinding media was spherical and had a diameter of 0.5 mm. Grinding was performed at 300 rpm for 60 minutes using a planetary ball mill (manufactured by Fritsch, PULVERISETTE 7). Thereafter, the grinding media and the solid electrolyte composition were separated using a sieve with an opening of 212 ⁇ m.
  • a solid electrolyte composition was placed in a closed glass beaker, nitrogen was flowed through it at a rate of 10 L/min, it was heated to 200°C, and p-chlorotoluene was removed over a period of 2 hours.
  • FIG. 4 shows a SEM image of the solid electrolyte material according to Example 1.
  • the solid electrolyte material according to Example 1 contained columnar crystals.
  • the average value of the aspect ratio (L/W) between length (L) and width (W) in the columnar crystals was 5 or more, and the average length was 20 ⁇ m or less.
  • the average value of the average length and aspect ratio was calculated as the average value of 10 columnar crystals with lengths of 3 ⁇ m or more measured by SEM images.
  • composition analysis of solid electrolyte material The Li and M contents of the solid electrolyte material were measured by high frequency inductively coupled plasma emission spectrometry using a high frequency inductively coupled plasma emission spectrometer (manufactured by ThermoFisher Scientific, iCAP7400).
  • the Cl content was measured by an ion chromatography method using an ion chromatography device (manufactured by Dionex, ICS-2000).
  • the O content was measured by inert gas melting-infrared absorption method using an oxygen analyzer (manufactured by Horiba, EMGA-930). From the measurement results, the molar ratios of Li/M and O/X were calculated.
  • the solid electrolyte material according to Example 1 had a Li/M molar ratio of 2.6 and an O/X molar ratio of 0.38.
  • FIG. 5 shows a schematic diagram of a pressure molding die 300 used to evaluate the ionic conductivity of a solid electrolyte material.
  • the pressure molding die 300 included a punch upper part 301, a frame mold 302, and a punch lower part 303.
  • the frame mold 302 was made of insulating polycarbonate.
  • Both the punch upper part 301 and the punch lower part 303 were made of electronically conductive stainless steel.
  • the ionic conductivity of the solid electrolyte material according to Example 1 was measured by the following method.
  • the solid electrolyte material powder according to Example 1 (that is, the solid electrolyte material powder 101 in FIG. 5) was filled into the pressure molding die 300. Inside the pressure molding die 300, a pressure of 300 MPa was applied to the solid electrolyte material according to Example 1 using the punch upper part 301.
  • the punch upper part 301 and the punch lower part 303 were connected to a potentiostat (Versa STAT 4, manufactured by Princeton Applied Research) equipped with a frequency response analyzer.
  • the punch upper part 301 was connected to a working electrode and a terminal for potential measurement.
  • Punch lower part 303 was connected to a counter electrode and a reference electrode.
  • the ionic conductivity of the solid electrolyte material according to Example 1 was measured at room temperature by electrochemical impedance measurement. As a result, the ionic conductivity measured at 22°C was 3.7 mS/cm.
  • the method for measuring ionic conductivity was the same as the method described in [Evaluation of ionic conductivity] above.
  • the ionic conductivity of the solid electrolyte material according to Example 1 after heat treatment measured at 22° C. was 1.7 mS/cm.
  • the rate of change in ionic conductivity of the solid electrolyte material due to heat treatment was -54%.
  • the rate of change in ionic conductivity is calculated by (ion conductivity after heat treatment ⁇ ion conductivity before heat treatment) ⁇ ion conductivity before heat treatment ⁇ 100.
  • Both Ta and Nb are Group 5 transition metal elements. Therefore, even if part or all of Ta is replaced with Nb, the reduction in ionic conductivity at the level of the example can be suppressed. Similarly, even if part or all of the halogen element Cl is replaced with at least one selected from the group consisting of F, Br, and I, suppression of the decrease in ionic conductivity at the level of the example can be achieved. .
  • the solid electrolyte material according to the present disclosure has practical ionic conductivity and can reduce the decrease in ionic conductivity due to heat. Therefore, the solid electrolyte material according to the present disclosure is suitable for providing a battery with excellent charge and discharge characteristics.
  • the solid electrolyte material of the present disclosure is used, for example, in an all-solid lithium ion secondary battery.
  • Solid electrolyte particles 101 Powder of solid electrolyte material 201 Positive electrode 202 Electrolyte layer 203 Negative electrode 204 Positive electrode active material particles 205 Negative electrode active material particles 206 Electrode active material particles 216 Covering layer 300 Pressure molding die 301 Punch upper part 302 Frame 303 Punch lower part 1000 Battery 1100 Electrode material

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WO2020137153A1 (ja) * 2018-12-28 2020-07-02 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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WO2020137153A1 (ja) * 2018-12-28 2020-07-02 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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