WO2022219847A1 - 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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WO2022219847A1
WO2022219847A1 PCT/JP2021/046672 JP2021046672W WO2022219847A1 WO 2022219847 A1 WO2022219847 A1 WO 2022219847A1 JP 2021046672 W JP2021046672 W JP 2021046672W WO 2022219847 A1 WO2022219847 A1 WO 2022219847A1
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solid electrolyte
electrolyte material
material according
positive electrode
negative electrode
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French (fr)
Japanese (ja)
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卓弥 成瀬
智康 横山
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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 JP2023514329A priority Critical patent/JPWO2022219847A1/ja
Priority to EP21937040.0A priority patent/EP4324791A4/en
Priority to CN202180096867.XA priority patent/CN117242531A/zh
Publication of WO2022219847A1 publication Critical patent/WO2022219847A1/ja
Priority to US18/469,587 priority patent/US20240021871A1/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
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M2300/0071—Oxides
    • 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 solid electrolyte materials and batteries using the same.
  • Patent Document 1 discloses a lithium ion conductive solid electrolyte material composed of Li, La, O, and X, and an all-solid-state battery using these materials.
  • X is at least one element from the group consisting of Cl, Br and I.
  • An object of the present disclosure is to provide a solid electrolyte material suitable for improving lithium ion conductivity.
  • Solid electrolyte materials of the present disclosure include Li, La, O, X, and hydrides, X is at least one selected from the group consisting of F, Cl, Br and I;
  • the present disclosure provides a solid electrolyte material suitable for improving lithium ion conductivity.
  • FIG. 1 shows a cross-sectional view of a battery 1000 according to a second embodiment.
  • FIG. 2 shows a cross-sectional view of an electrode material 1100 according to a second embodiment.
  • FIG. 3 shows a schematic diagram of a pressure forming die 300 used to evaluate the ionic conductivity of solid electrolyte materials.
  • 4 is a graph showing a Cole-Cole plot obtained by impedance measurement of the solid electrolyte material according to Example 1.
  • FIG. 5 is a graph showing initial charge/discharge characteristics of the battery according to Example 1.
  • FIG. 6 is a graph showing X-ray diffraction patterns of solid electrolyte materials according to Examples 1 to 5 and Comparative Example 1.
  • the solid electrolyte material according to the first embodiment contains Li, La, O, X, and hydrides.
  • X is at least one selected from the group consisting of F, Cl, Br and I;
  • the solid electrolyte material according to the first embodiment is a solid electrolyte material suitable for improving lithium ion conductivity.
  • the solid electrolyte material according to the first embodiment may for example have a practical lithium ion conductivity, for example a high lithium ion conductivity.
  • the high lithium ion conductivity is, for example, 3 ⁇ 10 ⁇ 5 S/cm or more near room temperature (eg, 25° C.). That is, the solid electrolyte material according to the first embodiment can have an ionic conductivity of, for example, 3 ⁇ 10 ⁇ 5 S/cm or more.
  • the solid electrolyte material according to the first embodiment can be used to obtain batteries with excellent charge/discharge characteristics.
  • An example of such a battery is an all solid state battery.
  • the all-solid battery may be a primary battery or a secondary battery.
  • the solid electrolyte material according to the first embodiment does not substantially contain sulfur.
  • the fact that the solid electrolyte material according to the first embodiment does not substantially contain sulfur means that the solid electrolyte material does not contain sulfur as a constituent element except sulfur that is unavoidably mixed as an impurity. In this case, sulfur mixed as an impurity in the solid electrolyte material is, for example, 1 mol % or less.
  • the solid electrolyte material according to the first embodiment does not contain sulfur.
  • a sulfur-free solid electrolyte material does not generate hydrogen sulfide even when exposed to the atmosphere, and is therefore excellent in safety.
  • the sulfide solid electrolyte disclosed in Patent Document 1 can generate hydrogen sulfide when exposed to the atmosphere.
  • the solid electrolyte material according to the first embodiment may consist essentially of Li, La, O, X, and hydrides.
  • the solid electrolyte material according to the first embodiment consists essentially of Li, La, O, X, and a hydride
  • the ratio of the total amount of Li, La, O, X and hydride substances to the total amount is 90% or more.
  • the molar ratio may be 95% or more.
  • the solid electrolyte material according to the first embodiment may consist only of Li, La, O, X, and hydrides.
  • the solid electrolyte material according to the first embodiment may contain elements that are unavoidably mixed.
  • An example of such an element is nitrogen.
  • Such elements can be present in the raw powder of the solid electrolyte material or in the atmosphere for manufacturing or storing the solid electrolyte material.
  • the elements that are unavoidably mixed as described above are, for example, 1 mol % or less.
  • the solid electrolyte material according to the first embodiment contains hydrides in addition to Li, La, O, and X.
  • the hydride is an ionic hydride containing an anion
  • the anion is believed to interact weakly with Li + compared to halide ions such as I ⁇ . Therefore, it is considered that the solid electrolyte material according to the first embodiment can improve the lithium ion conductivity because the hydride does not easily bind Li + and thus facilitates the conduction of Li + .
  • the ratio of the amount of substance of O to the total amount of substance of X and hydride may be less than one.
  • Such solid electrolyte materials have improved lithium ion conductivity.
  • the amount of the borohydride compound containing I and BH 4 - may be less than one.
  • the ratio of the amount of Li to the amount of La may be 0.75 or more and 2.0 or less.
  • the ratio of the amount of hydride to the amount of X may be more than 0 and 2.0 or less.
  • the ratio of the amount of hydride containing BH 4 ⁇ to the amount of I may be greater than 0 and 2.0 or less.
  • the hydride may contain, for example, boron atoms.
  • Such solid electrolyte materials have improved lithium ion conductivity.
  • a hydride containing a boron atom may contain, for example, at least one selected from the group consisting of a borohydride compound containing BH 4 - and a carborane.
  • a carborane is C2B10H12 .
  • Such solid electrolyte materials have improved lithium ion conductivity.
  • the hydride may include a borohydride compound containing BH4- .
  • the hydride may be a borohydride compound containing BH4- .
  • the hydride may be free of boron.
  • the hydride may contain nitrogen atoms, for example.
  • Examples of hydrides containing a nitrogen atom are amidides or imidides.
  • the amidide may be, for example, LiNH2 .
  • the imidide may be Li 2 NH, for example.
  • X may contain I in order to further improve the ionic conductivity of the solid electrolyte material.
  • X may be I.
  • the solid electrolyte material according to the first embodiment may be a composite material containing LaOX and hydride. Such solid electrolyte materials have improved ionic conductivity.
  • the solid electrolyte material according to the first embodiment may be a material represented by the following formula (1). That is, the solid electrolyte material according to the first embodiment may be a composite material containing LaOX and lithium borohydride (LiBH 4 ) as a hydride. 1.0LaOX+aLiX+bLiBH 4 (1) Here, 0 ⁇ a ⁇ 3.0 and 0 ⁇ b ⁇ 3.0 are satisfied.
  • LiBH 4 lithium borohydride
  • the solid electrolyte material represented by formula (1) above has improved lithium ion conductivity.
  • Li + constituting LiX is attracted to LaOX, and the Li + conducts, that is, Li + conducts at the interface between LiX and LaOX.
  • the solid electrolyte material represented by the above formula (1) also contains LiBH 4 as a hydride. LiBH 4 interacts weaker with Li + than with X. That is, Li + forming LiBH 4 is more likely to be attracted to the LaOX side. Therefore, it is considered that the solid electrolyte material represented by the above formula (1) containing LiBH 4 can improve the lithium ion conductivity.
  • 0 ⁇ a ⁇ 2.0 and 0 ⁇ b ⁇ 2.0 may be satisfied in the above formula (1).
  • a ⁇ b may be satisfied in the above formula (1).
  • the upper and lower limits of the range of a in the above formula (1) are defined by any combination selected from numerical values of 0, 0.4, 0.8, 1.2, 1.6, and 2.0. may
  • the upper and lower limits of the range of b in the above formula (1) are any combination selected from the numerical values of 0.4, 0.8, 1.0, 1.2, 1.6, and 2.0 may be specified.
  • X may be I in the above formula (1).
  • the solid electrolyte material according to the first embodiment may be crystalline or amorphous.
  • the shape of the solid electrolyte material according to the first embodiment is not limited. Examples of such shapes are acicular, spherical, or ellipsoidal.
  • the solid electrolyte material according to the first embodiment may be particles.
  • the solid electrolyte material according to the first embodiment may have the shape of pellets or plates.
  • the solid electrolyte material When the shape of the solid electrolyte material according to the first embodiment is particulate (for example, spherical), the solid electrolyte material may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less, and may have a median diameter of 0.5 ⁇ m or more. And it may have a median diameter of 10 ⁇ m or less. Thereby, the solid electrolyte material according to the first embodiment and other materials can be well dispersed.
  • the median diameter of particles means the particle diameter (d50) corresponding to 50% of the cumulative volume in the volume-based particle size distribution.
  • a volume-based particle size distribution can be measured by a laser diffraction measurement device or an image analysis device.
  • the solid electrolyte material according to the first embodiment can be manufactured by the following method.
  • Raw material powder is prepared so that it has the desired composition.
  • the composition ratio of the target solid electrolyte material is 1.0LaOI / 1.6LiI / 0.4LiBH4
  • the Li2O raw material powder , LiBH4 raw material powder, La2O3 raw material powder, and LaI 3 raw material powders are mixed in a molar ratio of 12:6:1:13.
  • the raw material powders may be mixed in a pre-adjusted molar ratio so as to compensate for composition changes that may occur during the synthesis process.
  • the raw material powders are mechanochemically reacted with each other (that is, using the method of mechanochemical milling) in a mixing device such as a planetary ball mill to obtain a reactant.
  • the solid electrolyte material according to the first embodiment is obtained.
  • the composition of the solid electrolyte material can be determined, for example, by ICP emission spectrometry, ion chromatography, inert gas fusion-infrared absorption, or EPMA (Electron Probe Micro Analyzer).
  • ICP emission spectrometry ion chromatography
  • I inert gas fusion-infrared absorption
  • EPMA Electro Probe Micro Analyzer
  • the composition of Li and La can be determined by ICP emission spectroscopy
  • the composition of I can be determined by ion chromatography
  • O can be measured by inert gas fusion-infrared absorption.
  • Hydrides can be analyzed and quantitatively evaluated, for example, by EPMA or XPS (X-ray photoelectron spectroscopy).
  • the second embodiment describes a battery using the solid electrolyte material according to the first embodiment.
  • a battery according to the second embodiment includes a positive electrode, a negative electrode, and an electrolyte layer.
  • An electrolyte layer is disposed between the positive and negative electrodes.
  • At least one selected from the group consisting of the positive electrode, the electrolyte layer, and the negative electrode contains the solid electrolyte material according to the first embodiment.
  • the battery according to the second embodiment contains the solid electrolyte material according to the first embodiment, it has excellent charge/discharge characteristics.
  • the battery may be an all solid state battery.
  • FIG. 1 shows a cross-sectional view of a battery 1000 according to the second embodiment.
  • a battery 1000 according to the second embodiment includes a positive electrode 201 , an electrolyte layer 202 and a negative electrode 203 .
  • Electrolyte layer 202 is disposed 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 contain 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.
  • a particle containing the solid electrolyte material according to the first embodiment as a main component means a particle in which the component contained in the largest molar ratio is the solid electrolyte material according to the first embodiment.
  • the solid electrolyte particles 100 may be particles made of the solid electrolyte material according to the first embodiment.
  • the solid electrolyte particles 100 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less, or may have a median diameter of 0.5 ⁇ m or more and 10 ⁇ m or less. In this case, the solid electrolyte particles 100 have higher ionic conductivity.
  • the positive electrode 201 contains a material capable of intercalating and deintercalating metal ions such as lithium ions.
  • the positive electrode 201 contains, for example, a positive electrode active material (eg, positive electrode active material particles 204).
  • positive electrode active materials are lithium-containing transition metal oxides, transition metal fluorides, polyanion materials, fluorinated polyanion materials, transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, or transition metal oxynitrides.
  • lithium-containing transition metal oxides are LiNi1 -dfCodAlfO2 (where 0 ⁇ d , 0 ⁇ f , and 0 ⁇ (d+f) ⁇ 1 ) or LiCoO2.
  • lithium phosphate may be used as the positive electrode active material.
  • the positive electrode 201 may contain a transition metal oxyfluoride as a positive electrode active material together with the solid electrolyte material according to the first embodiment. Even if the solid electrolyte material according to the first embodiment is fluorinated with a transition metal oxyfluoride, it is difficult for a resistance layer to be formed. As a result, the battery 1000 has high charge/discharge efficiency.
  • Transition metal oxyfluorides contain oxygen and fluorine.
  • the transition metal oxyfluoride may be a compound represented by Li p Me' q O m Fn .
  • Me' is Mn, Co, Ni, Fe, Al, Cu, V, Nb, Mo, Ti, Cr, Zr, Zn, Na, K, Ca, Mg, Pt, Au, Ag, Ru, W , B, Si, and P, and the formula: 0.5 ⁇ p ⁇ 1.5, 0.5 ⁇ q ⁇ 1.0, 1 ⁇ m ⁇ 2, and 0 ⁇ n ⁇ 1 are satisfied.
  • An example of such a transition metal oxyfluoride is Li1.05 ( Ni0.35Co0.35Mn0.3 ) 0.95O1.9F0.1 .
  • the positive electrode active material particles 204 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less. When positive electrode active material particles 204 have a median diameter of 0.1 ⁇ m or more, positive electrode active material particles 204 and solid electrolyte particles 100 can be well dispersed in positive electrode 201 . This improves the charge/discharge characteristics of the battery. When the positive electrode active material particles 204 have a median diameter of 100 ⁇ m or less, the diffusion rate of lithium in the positive electrode active material particles 204 is improved. This allows the battery to operate at high output.
  • the positive electrode active material particles 204 may have a larger median diameter than the solid electrolyte particles 100 . Thereby, 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 sum of the volume of the positive electrode active material particles 204 and the volume of the solid electrolyte particles 100 is 0.30 or more and 0.30. It may be 95 or less.
  • FIG. 2 shows a cross-sectional view of the electrode material 1100 according to the second embodiment.
  • Electrode material 1100 is included in, for example, positive electrode 201 .
  • a coating layer 216 may be formed on the surface of the electrode active material particles 206 to prevent the solid electrolyte particles 100 from reacting with the positive electrode active material (that is, the electrode active material particles 206). Thereby, an increase in the reaction overvoltage of the battery can be suppressed.
  • coating materials included in coating layer 216 are sulfide solid electrolytes, oxide solid electrolytes, or halide solid electrolytes.
  • the coating material may be lithium niobate, which has excellent stability even at high potentials.
  • 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 cathode layer is disposed between the first cathode layer and the electrolyte layer 202 .
  • the first positive electrode layer and the second positive electrode layer may contain the solid electrolyte material according to the first embodiment, and a coating layer may be formed on the surface of the second positive electrode active material. According to the above configuration, the solid electrolyte material according to the first embodiment included in the electrolyte layer 202 can be suppressed from being oxidized by the second positive electrode active material. As a result, the battery has a high charge capacity.
  • coating materials included in coating layer 216 are sulfide solid electrolytes, oxide solid electrolytes, polymer solid electrolytes, or halide solid electrolytes.
  • 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.
  • the electrolyte layer 202 may be a solid electrolyte layer.
  • the electrolyte layer 202 may contain the solid electrolyte material according to the first embodiment.
  • the electrolyte layer 202 may consist only of the solid electrolyte material according to the first embodiment.
  • the solid electrolyte material according to the first embodiment is hereinafter referred to as the first solid electrolyte material.
  • a solid electrolyte material different from the solid electrolyte material according to the first embodiment is called a second solid electrolyte material.
  • the electrolyte layer 202 may contain a second solid electrolyte material.
  • the electrolyte layer 202 may consist of only 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.
  • 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 short circuit between the positive electrode 201 and the negative electrode 203 is less likely to occur. If the electrolyte layer 202 has a thickness of 100 ⁇ m or less, the battery can operate at high power.
  • electrolyte layer 202 may be further provided between the electrolyte layer 202 and the negative electrode 203 .
  • the second electrolyte layer may be composed of another solid electrolyte material that is more electrochemically stable than the first solid electrolyte material.
  • the reduction potential of the solid electrolyte material forming the second electrolyte layer may be lower than the reduction potential of the first solid electrolyte material.
  • the negative electrode 203 contains a material capable of intercalating and deintercalating metal ions such as lithium ions.
  • the negative electrode 203 contains, for example, a negative electrode active material (eg, 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.
  • Examples of metallic materials are lithium metal or lithium alloys.
  • Examples of carbon materials are natural graphite, coke, ungraphitized carbon, carbon fibers, spherical carbon, artificial graphite, or amorphous carbon. From the viewpoint of capacity density, suitable examples of negative electrode active materials are silicon (ie, Si), tin (ie, Sn), silicon compounds, or tin compounds.
  • the negative electrode active material may be selected based on the reduction resistance of the solid electrolyte material contained in the negative electrode 203 .
  • a material capable of intercalating and deintercalating lithium ions at 0 V or higher with respect 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. Examples of titanium oxides are Li4Ti5O12 , LiTi2O4 , or TiO2 .
  • the negative electrode active material particles 205 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less. When negative electrode active material particles 205 have a median diameter of 0.1 ⁇ m or more, negative electrode active material particles 205 and solid electrolyte particles 100 can be well dispersed in negative electrode 203 . This improves the charge/discharge characteristics of the battery. When the negative electrode active material particles 205 have a median diameter of 100 ⁇ m or less, the diffusion rate of lithium in the negative electrode active material particles 205 is improved. This allows the battery to operate at high output.
  • the negative electrode active material particles 205 may have a larger median diameter than the solid electrolyte particles 100 . Thereby, 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 volumes of the negative electrode active material particles 205 and the solid electrolyte particles 100 is 0.30 or more and 0. 0.95 or less.
  • the electrode material 1100 shown in FIG. 2 may be included in the negative electrode 202 .
  • a coating layer 216 may be formed on the surface of the electrode active material particles 206 to prevent the solid electrolyte particles 100 from reacting with the negative electrode active material (that is, the electrode active material particles 206). Thereby, the battery has a high charge-discharge efficiency.
  • coating materials included in coating layer 216 are sulfide solid electrolytes, oxide solid electrolytes, polymer solid electrolytes, or halide solid electrolytes.
  • the coating material may be a sulfide solid electrolyte or a polymer solid electrolyte.
  • a sulfide solid electrolyte is Li 2 SP 2 S 5 .
  • polymer solid electrolytes are composite compounds of polyethylene oxide and lithium salts.
  • An example of such a polymer 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 positive electrode 201, electrolyte layer 202, and negative electrode 203 contains a second solid electrolyte material for the purpose of enhancing ion conductivity, chemical stability, and electrochemical stability.
  • a second solid electrolyte material for the purpose of enhancing ion conductivity, chemical stability, and electrochemical stability.
  • the second solid electrolyte material are sulfide solid electrolytes, oxide solid electrolytes, halide solid electrolytes, or organic polymer solid electrolytes.
  • 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 and halogen elements).
  • a "halide solid electrolyte” means a solid electrolyte containing a halogen element and not containing sulfur.
  • the halide solid electrolyte may contain not only halogen elements but also oxygen.
  • sulfide solid electrolytes are Li 2 SP 2 S 5 , Li 2 S-SiS 2 , Li 2 S-B 2 S 3 , Li 2 S-GeS 2 , Li 3.25 Ge 0.25 P 0.75 S 4 , or Li10GeP2S12 . _
  • oxide solid electrolytes are (i) NASICON - type solid electrolytes such as LiTi2(PO4)3 or elemental substitutions thereof; (ii) perovskite-type solid electrolytes such as (LaLi) TiO3 ; ( iii) LISICON - type solid electrolytes such as Li14ZnGe4O16 , Li4SiO4 , LiGeO4 or elemental substitutions thereof; ( iv ) garnet - type solid electrolytes such as Li7La3Zr2O12 or its elemental substitutions; or ( v) Li3PO4 or its N substitutions.
  • NASICON - type solid electrolytes such as LiTi2(PO4)3 or elemental substitutions thereof
  • perovskite-type solid electrolytes such as (LaLi) TiO3 ;
  • LISICON - type solid electrolytes such as Li14ZnGe4O16 , Li4SiO4 , LiGeO4 or
  • halide solid electrolyte material is the compound represented by LiaMebYcZ6 .
  • Me is at least one element selected from the group consisting of metal elements other than Li and Y and metalloid elements.
  • Z is at least one selected from the group consisting of F, Cl, Br and I;
  • the value of m represents the valence of Me.
  • “Semimetal elements” are B, Si, Ge, As, Sb, and Te.
  • Metallic elements are all elements contained in groups 1 to 12 of the periodic table (excluding hydrogen), and all elements contained in groups 13 to 16 of the periodic table (however, B, Si, Ge, As, Sb, Te, C, N, P, O, S, and Se).
  • Me is selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb. At least one may be selected.
  • Li 3 YCl 6 or Li 3 YBr 6 is used as the halide solid electrolyte.
  • 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, can suppress contact between the first solid electrolyte material and the negative electrode active material. As a result, the internal resistance of the battery is reduced.
  • organic polymer solid electrolytes are polymeric compounds and lithium salt compounds.
  • the polymer compound may have an ethylene oxide structure. Since a polymer compound having an ethylene oxide structure can contain a large amount of lithium salt, the ionic conductivity can be further increased.
  • lithium salts are LiPF6 , LiBF4 , LiSbF6 , LiAsF6 , LiSO3CF3, LiN(SO2CF3)2 , LiN ( SO2C2F5 ) 2 , LiN ( SO2CF3 ). ( SO2C4F9 ) , or LiC ( SO2CF3 ) 3 .
  • One lithium salt selected from these may be used alone. Alternatively, a mixture of two or more lithium salts selected from these may be used.
  • At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 is a non-aqueous electrolyte, a gel electrolyte, or an ion electrolyte for the purpose of facilitating the transfer of lithium ions and improving the output characteristics of the battery. It may contain liquids.
  • the non-aqueous electrolyte contains a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
  • non-aqueous solvents examples include cyclic carbonate solvents, chain carbonate solvents, cyclic ether solvents, chain ether solvents, cyclic ester solvents, chain ester solvents, or fluorine solvents.
  • cyclic carbonate solvents are ethylene carbonate, propylene carbonate, or butylene carbonate.
  • linear carbonate solvents are dimethyl carbonate, ethyl methyl carbonate, or diethyl carbonate.
  • examples of cyclic ether solvents are tetrahydrofuran, 1,4-dioxane, or 1,3-dioxolane.
  • linear ether solvents are 1,2-dimethoxyethane or 1,2-diethoxyethane.
  • An example of a cyclic ester solvent is ⁇ -butyrolactone.
  • An example of a linear ester solvent is methyl acetate.
  • fluorosolvents are fluoroethylene carbonate, methyl fluoropropionate, fluorobenzene, fluoroethyl methyl carbonate, or fluorodimethylene carbonate.
  • One non-aqueous solvent selected from these may be used alone. Alternatively, a mixture of two or more non-aqueous solvents selected from these may be used.
  • lithium salts are LiPF6 , LiBF4 , LiSbF6 , LiAsF6 , LiSO3CF3, LiN(SO2CF3)2 , LiN ( SO2C2F5 ) 2 , LiN ( SO2CF3 ). ( SO2C4F9 ) , or LiC ( SO2CF3 ) 3 .
  • One lithium salt selected from these may be used alone. Alternatively, a mixture of two or more lithium salts selected from these may be used.
  • the lithium salt concentration may be, for example, 0.5 mol/liter or more and 2 mol/liter or less.
  • a polymer material impregnated with a non-aqueous electrolyte can be used as the gel electrolyte.
  • examples of polymeric materials are polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, or polymers with ethylene oxide linkages.
  • ionic liquids examples include (i) aliphatic chain quaternary salts such as tetraalkylammonium or tetraalkylphosphonium; (ii) aliphatic cyclic ammoniums such as pyrrolidiniums, morpholiniums, imidazoliniums, tetrahydropyrimidiniums, piperaziniums, or piperidiniums, or (iii) nitrogen-containing heterogeneous compounds such as pyridiniums or imidazoliums ring aromatic cations, is.
  • aliphatic chain quaternary salts such as tetraalkylammonium or tetraalkylphosphonium
  • aliphatic cyclic ammoniums such as pyrrolidiniums, morpholiniums, imidazoliniums, tetrahydropyrimidiniums, piperaziniums, or piperidiniums
  • nitrogen-containing heterogeneous compounds such as
  • Examples of anions contained in the ionic liquid are PF 6 ⁇ , BF 4 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ , SO 3 CF 3 ⁇ , N(SO 2 CF 3 ) 2 ⁇ , N(SO 2 C 2 F 5 ) 2- , N( SO2CF3 ) ( SO2C4F9 ) - , or C ( SO2CF3 ) 3- .
  • the ionic liquid may contain lithium salts.
  • At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a binder for the purpose of improving adhesion between particles.
  • binders include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, Polyacrylic acid hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyether sulfone, hexafluoropolypropylene, styrene-butadiene rubber , or carboxymethyl cellulose.
  • a copolymer may be used as a binder.
  • binders include 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. A mixture of two or more selected from the above materials may be used as the binder.
  • At least one selected from the positive electrode 201 and the negative electrode 203 may contain a conductive aid for the purpose of increasing electronic conductivity.
  • Examples of conductive aids are (i) graphites such as natural or artificial graphite; (ii) carbon blacks such as acetylene black or ketjen black; (iii) conductive fibers such as carbon or metal fibers; (iv) carbon fluoride, (v) metal powders such as aluminum; (vi) conductive whiskers such as zinc oxide or potassium titanate; (vii) a conductive metal oxide such as titanium oxide, or (viii) a conductive polymeric compound such as polyaniline, polypyrrole, or polythiophene; is.
  • the conductive aid (i) or (ii) may be used.
  • Examples of the shape of the battery according to the second embodiment are coin-shaped, cylindrical, rectangular, sheet-shaped, button-shaped, flat-shaped, and laminated.
  • a material for forming a positive electrode, a material for forming an electrolyte layer, and a material for forming a negative electrode are prepared, and the positive electrode, the electrolyte layer, and the negative electrode are arranged in this order by a known method. It may also be manufactured by making laminated laminates.
  • Example 1 [Preparation of Solid Electrolyte Material] Li 2 O, LiBH 4 , La 2 O 3 and LaI 3 as raw material powders were mixed at a ratio of 12:6:1:13 in an argon atmosphere having a dew point of ⁇ 60° C. or lower (hereinafter referred to as “dry argon atmosphere”). was prepared to have a molar ratio of A mixture of these raw material powders was milled at 500 rpm for 30 hours using a planetary ball mill. Thus, the solid electrolyte material powder according to Example 1 was obtained. The solid electrolyte material according to Example 1 had a composition represented by 1.0LaOI.1.6LiI.0.4LiBH4 .
  • the composition here is a charge composition calculated from the charge amount.
  • the composition of the obtained solid electrolyte material was almost the same as the composition of the preparation, depending on the manufacturing method used in this example.
  • the solid electrolyte material was produced by milling treatment with a ball mill, and the X-ray diffraction pattern obtained by X-ray diffraction measurement of the obtained solid electrolyte material showed LaOI, LiI, and LiBH. Since a diffraction peak indicating the presence of 4 was confirmed, the obtained solid electrolyte material of Example 1 is considered to be a composite material containing LaOI, LiI, and LiBH 4 .
  • 6 is a graph showing an X-ray diffraction pattern of the solid electrolyte material according to Example 1.
  • FIG. 3 shows a schematic diagram of a pressure forming die 300 used to evaluate the ionic conductivity of solid electrolyte materials.
  • the pressure forming die 300 had a punch upper part 301 , a frame mold 302 and a punch lower part 303 .
  • the frame mold 302 was made of insulating polycarbonate. Both the punch upper portion 301 and the punch lower portion 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. 3) was filled inside the pressure molding die 300 . Inside the pressing die 300 , a pressure of 400 MPa was applied to the solid electrolyte material according to Example 1 using the punch upper part 301 .
  • the upper punch 301 and lower punch 303 were connected to a potentiostat (Bio-Logic Sciences Instruments, VMP-300) equipped with a frequency response analyzer.
  • the punch upper part 301 was connected to the working electrode and the terminal for potential measurement.
  • the punch bottom 303 was connected to the counter and reference electrodes.
  • the ionic conductivity of the solid electrolyte material according to Example 1 was measured at room temperature by an electrochemical impedance measurement method.
  • FIG. 4 is a graph showing a Cole-Cole plot obtained by impedance measurement of the solid electrolyte material according to Example 1.
  • the real value of the impedance at the measurement point where the absolute value of the phase of the complex impedance was the smallest was regarded as the resistance to ion conduction of the solid electrolyte material. See the arrow R se shown in FIG. 4 for the real value.
  • ⁇ represents ionic conductivity.
  • S represents the contact area of the solid electrolyte material with the punch upper part 301 (equal to the cross-sectional area of the hollow part 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 to which pressure is applied (equal to the thickness of the layer formed from the solid electrolyte material powder 101 in FIG. 3).
  • a metal In foil, a metal Li foil, and a metal In foil were laminated in this order on the solid electrolyte layer.
  • a pressure of 40 MPa was applied to this laminate to form a counter electrode.
  • a current collector made of stainless steel was attached to the electrode and the counter electrode, and a current collecting lead was attached to the current collector.
  • [Charging and discharging test] 4 is a graph showing the initial discharge characteristics of the battery according to Example 1.
  • FIG. Initial charge/discharge characteristics were measured by the following method.
  • the battery according to Example 1 was placed in a constant temperature bath at 25°C.
  • Example 1 A cell according to Example 1 was charged until a voltage of 0.58 V was reached at a current density of 17.1 ⁇ A/cm 2 . This current density corresponds to a 0.01C rate.
  • Example 1 The cell according to Example 1 was then discharged at a current density of 17.1 ⁇ A/cm 2 until a voltage of 1.0 V was reached. This current density corresponds to a 0.01C rate.
  • the battery according to Example 1 had an initial discharge capacity of 829 ⁇ Ah.
  • Comparative Example 1 Li 2 O and LaI 3 were prepared as raw material powders so as to have a molar ratio of 1:1.
  • Example 2 The solid electrolyte materials of Examples 2 to 5 and Comparative Example 1 were also subjected to X-ray diffraction measurements.
  • 6 is a graph showing X-ray diffraction patterns of solid electrolyte materials according to Examples 2 to 5 and Comparative Example 1.
  • FIG. 6 is a graph showing X-ray diffraction patterns of solid electrolyte materials according to Examples 2 to 5 and Comparative Example 1.
  • the battery according to Example 1 was charged and discharged at room temperature.
  • the solid electrolyte material according to the present disclosure can improve lithium ion conductivity while suppressing generation of hydrogen sulfide.
  • the solid electrolyte material of the present disclosure is suitable for providing well chargeable and dischargeable batteries.
  • the solid electrolyte material and manufacturing method thereof of the present disclosure are used, for example, in batteries (eg, all-solid lithium ion secondary batteries).

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PCT/JP2021/046672 2021-04-15 2021-12-17 固体電解質材料およびそれを用いた電池 Ceased WO2022219847A1 (ja)

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