Classifications

• • 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
  • C01G25/00—Compounds of zirconium
  • C01G25/006—Compounds containing zirconium, 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
  • C01G35/006—Compounds containing tantalum, with or without oxygen or hydrogen, and containing two or more other elements
• • 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
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/058—Construction or manufacture
  • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/50—Solid solutions
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/40—Electric properties
• • 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 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 reduces the amount of hydrogen halide gas generated.
• the solid electrolyte material of the present disclosure includes a solid electrolyte and an oxide material
• the solid electrolyte includes Li, M, O, and X
• M is at least one selected from the group consisting of Nb, Ta, and Zr
• X is at least one selected from the group consisting of F, Cl, Br, and I
• the oxide material includes at least one selected from the group consisting of oxides of divalent metal elements and oxides of trivalent metal elements
• a mass ratio of the oxide material to the solid electrolyte is 1% or more and 50% or less.
• the present disclosure provides a solid electrolyte material that reduces the amount of hydrogen halide gas generated.
• 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 molding die 300 used to evaluate the ionic conductivity of solid electrolyte materials.
• the solid electrolyte material according to the first embodiment includes a solid electrolyte and an oxide material.
• the solid electrolyte contains Li, M, O, and X.
• M is at least one selected from the group consisting of Nb, Ta, and Zr.
• X is at least one selected from the group consisting of F, Cl, Br, and I.
• the oxide material includes at least one selected from the group consisting of oxides of divalent metal elements and oxides of trivalent metal elements.
• the mass ratio of the oxide material to the solid electrolyte is 1% or more and 50% or less.
• the solid electrolyte material according to the first embodiment can reduce the amount of hydrogen halide gas generated. Further, the solid electrolyte material according to the first embodiment can have, for example, a practical ionic conductivity (for example, a practical ionic conductivity that can be used in batteries). Further, the solid electrolyte material according to the first embodiment can have, for example, high lithium ion conductivity. Here, the high lithium ion conductivity is, for example, 1 mS/cm or more.
• the present inventors have discovered that in solid electrolytes containing halogen and oxygen, hydrogen halide gas is generated when manufacturing batteries.
• the solid electrolyte material according to the first embodiment can reduce the amount of hydrogen halide gas generated. Therefore, the battery using the solid electrolyte material according to the first embodiment can be manufactured at a higher dew point temperature, and the manufacturing cost can be reduced.
• the solid electrolyte material according to the first embodiment may be a mixture of the solid electrolyte and the oxide material.
• the solid electrolyte may form a composite with the oxide material.
• the oxide material efficiently absorbs hydrogen chloride gas generated from the solid electrolyte. This makes it possible to reduce the amount of hydrogen halide gas released into the environment.
• hydrogen halide gas absorbed in an oxide material may react with the oxide material to generate a metal halide constituting the oxide and water.
• the oxide contained in the oxide material is, for example, an oxide different from the positive electrode active material. That is, the oxide material contained in the solid electrolyte material according to the first embodiment excludes, for example, the positive electrode active material.
• the oxide material may include at least one selected from the group consisting of ZnO, CaO, MgO, La 2 O 3 , and Fe 2 O 3 . According to the above configuration, hydrogen halide gas can be further reduced.
• the oxide material may contain ZnO.
• the mass ratio of the oxide material to the solid electrolyte may be 1.6% or more and 39.0% or less.
• the mass ratio of the oxide material to the solid electrolyte may be 25% or less.
• the oxide material When the shape of the oxide material is particulate (for example, spherical), the oxide material may have a median diameter of 1 ⁇ m or less, or may have a median diameter of 0.1 ⁇ m or less. good.
• the median diameter of particles means the particle diameter (d50) corresponding to 50% cumulative volume in the volume-based particle size distribution.
• Volume-based particle size distribution can be measured by a laser diffraction measurement device or an image analysis device.
• the particle size of the oxide material is small, the surface area per unit mass of the particles increases. As a result, more hydrogen halide gas can be absorbed.
• the solid electrolyte may consist essentially of Li, M, O, and X.
• the solid electrolyte consists essentially of Li, M, O, and X means that the amount of Li, M, O, and It means that the molar ratio of the total amount is 90% or more. As an example, the molar ratio may be 95% or more.
• the solid electrolyte may consist only of Li, M, O, and X.
• the solid electrolyte may have a composition represented by the following compositional formula (1).
• 0.1 ⁇ a ⁇ 7.0, 0.4 ⁇ b ⁇ 1.9, and 1.0 ⁇ c ⁇ 11 are satisfied.
• compositional formula (1) 0.3 ⁇ a ⁇ 5.0, 0.6 ⁇ b ⁇ 1.6, and 2.0 ⁇ c ⁇ 9.0 may be satisfied, and 0.6 ⁇ a ⁇ 3.0, 0.7 ⁇ b ⁇ 1.2, and 3.0 ⁇ c ⁇ 7.0 may be satisfied.
• X may contain Cl in the solid electrolyte.
• X may be Cl.
• the molar ratio of Li to M in the solid electrolyte may be 0.6 or more and 3.0 or less.
• the shape of the solid electrolyte is not limited. Examples of such shapes are needle-like, spherical, and oval-spherical.
• the solid electrolyte may be particles.
• the solid electrolyte may be formed to have the shape of a pellet or plate.
• the solid electrolyte When the shape of the solid electrolyte material is particulate (for example, spherical), the solid electrolyte may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less, or a median diameter of 0.5 ⁇ m or more and 10 ⁇ m or less. It may have a diameter. This allows the solid electrolyte and other materials to be well dispersed.
• the solid electrolyte can be manufactured by the method described below.
• Raw material powder is prepared so that it has the desired composition.
• Examples of raw material powders are oxides, hydroxides, halides, or acid halides.
• M is Ta and X is Cl
• the molar ratio Li/M and the molar ratio O/X at the time of mixing the raw materials are 1.0 and 0.2
• M and X are determined by the selection of raw material powder. By appropriately selecting the mixing ratio of the raw material powder, the molar ratios of Li/M and O/X can be adjusted.
• 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 atmosphere is, for example, an argon atmosphere or a nitrogen atmosphere.
• a mixture of raw material powders may be reacted with each other mechanochemically (by a method of mechanochemical milling) in a mixing device such as a planetary ball mill to obtain a reactant.
• the values of the molar ratio Li/M and the molar ratio O/X of the obtained solid electrolyte may be larger than the values calculated from the molar ratio of the prepared raw material powder.
• the molar ratio Li/M can be increased by about 20% to 70%
• the molar ratio O/X can be increased by about 40% to 75%.
• composition of the solid electrolyte is determined, for example, by ICP emission spectrometry, ion chromatography, inert gas melting-infrared absorption, or EPMA (Electron Probe Micro Analyzer) method.
• a solid electrolyte material is obtained by mixing the solid electrolyte with an oxide material.
• the mixing method may be mechanochemical milling or mortar mixing.
• Mortar mixing is a method in which powdered materials are placed in an agate mortar and stirred using a mortar and pestle.
• 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 has excellent charge and discharge characteristics.
• FIG. 1 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, solid electrolyte particles 100, and oxide particles 102.
• the electrolyte layer 202 contains an electrolyte material.
• the electrolyte material may be, for example, the solid electrolyte material according to the first embodiment.
• electrolyte layer 202 includes the solid electrolyte material according to the first embodiment, electrolyte layer 202 contains solid electrolyte particles 100 and oxide particles 102, as shown in FIG.
• the negative electrode 203 contains negative electrode active material particles 205, solid electrolyte particles 100, and oxide particles 102.
• the solid electrolyte particles 100 are particles containing a solid electrolyte included in the solid electrolyte material according to the first embodiment.
• the solid electrolyte particles 100 may be particles containing as a main component the solid electrolyte contained in the solid electrolyte material according to the first embodiment.
• Particles containing the solid electrolyte contained in the solid electrolyte material according to the first embodiment as a main component mean particles in which the largest component is the solid electrolyte contained in the solid electrolyte material according to the first embodiment.
• the solid electrolyte particles 100 may be particles made of a solid electrolyte included in the solid electrolyte material according to the first embodiment.
• the oxide particles 102 are particles containing an oxide material included in the solid electrolyte material according to the first embodiment.
• the oxide particles 102 may be particles containing as a main component the oxide material contained in the solid electrolyte material according to the first embodiment.
• Particles containing the oxide material contained in the solid electrolyte material according to the first embodiment as a main component mean particles in which the largest component is the oxide material contained in the solid electrolyte material according to the first embodiment.
• the oxide particles 102 may be particles made of an oxide material included in 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 , LiCoO2 , or Li(Ni,Co,Mn) O2 .
• (A, B, C) means "at least one selected from the group consisting of A, B, and C.”
• A, B, and C all represent elements.
• 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 contained in the solid electrolyte material according to the first embodiment containing I is easily oxidized.
• the oxidation reaction of the solid electrolyte 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 if the solid electrolyte contained in 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 element selected from the group consisting of B, Si, and P, and the following 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 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 form a good dispersion state 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, the positive electrode active material particles 204 and the solid electrolyte particles 100 can form a good dispersion state.
• 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. 2 shows a cross-sectional view of an electrode material 1100 according to a 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 is a solid electrolyte included in the solid electrolyte material according to the first embodiment, and X is at least one kind selected from the group consisting of Cl and Br. It may be an element.
• the solid electrolyte material contained in 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 a solid electrolyte contained in the solid electrolyte material according to the first embodiment, and X may be at least one element selected from the group consisting of Cl and Br.
• the solid electrolyte contained in the solid electrolyte material according to the first embodiment that does not contain I is less likely to be oxidized than the solid electrolyte contained in 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, and the first positive electrode layer and the second positive electrode layer are the solid electrolyte contained in the solid electrolyte material according to the first embodiment containing I.
• a coating layer 216 is formed on the surface of the second positive electrode active material. According to the above configuration, it is possible to suppress the solid electrolyte contained in the solid electrolyte material according to the first embodiment contained in the electrolyte layer 202 from being oxidized by the second positive electrode active material. As a result, the battery has a high charging capacity.
• the coating material included in the coating layer 206 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.
• 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 be made only of the solid electrolyte material according to the first embodiment.
• the solid electrolyte contained in the electrolyte layer 202 may be composed only of a solid electrolyte different from the solid electrolyte contained in the solid electrolyte material according to the first embodiment.
• solid electrolytes different from the solid electrolyte contained in 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 element selected from the group consisting of F, Cl, Br, and I.
• the solid electrolyte included in the solid electrolyte material according to the first embodiment will be referred to as a first solid electrolyte.
• a solid electrolyte different from the solid electrolyte contained in the solid electrolyte material according to the first embodiment is called a second solid electrolyte.
• the electrolyte layer 202 may contain not only the first solid electrolyte but also the second solid electrolyte.
• the first solid electrolyte and the second solid electrolyte 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 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.
• electrolyte layer 202 may be further provided between the electrolyte layer 202 and the negative electrode 203.
• the electrolyte layer 202 includes a first solid electrolyte, in order to more stably maintain the high ionic conductivity of the solid electrolyte, it may be composed of another solid electrolyte that is more electrochemically stable than the solid electrolyte.
• a further electrolyte layer may be provided.
• 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 contained 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 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 form a good dispersion state 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, the negative electrode active material particles 205 and the solid electrolyte particles 100 can form a good dispersion state.
• 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. 2 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 positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a second solid electrolyte for the purpose of increasing ionic conductivity.
• the second solid electrolyte 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 element 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' may be at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb. .
• 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 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. It is a ring aromatic cation.
• 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 in order to improve 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, or a stacked shape.
• Example 1 Preparation of solid electrolyte
• dry atmosphere a dry atmosphere having a dew point of -30°C or less
• the molar ratio Li/M was 2.0.
• the molar ratio Li/M was 0.9 and O/X was 0.19.
• the molar ratios Li/M and O/X were measured by ICP emission spectrometry for Li and M, ion chromatography for X, and inert gas melting-infrared absorption method for O.
• the devices used to measure the composition were an ICP emission spectrometer, an ion chromatograph, and an oxygen analyzer.
• the average particle diameter of ZnO was about 20 nm.
• FIG. 3 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. 3) 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 was connected via the upper punch 301 and the lower punch 303 to a potentiostat (VersaSTAT4, 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 5.1 mS/cm.
• Example 2 to 9 and Comparative Example 1 [Preparation of solid electrolyte material]
• solid electrolyte materials according to Examples 2 to 5 were obtained in the same manner as in Example 1 except for the mass ratio of ZnO to the solid electrolyte. The mass ratios are shown in Table 1.
• Example 6 La 2 O 3 was used instead of ZnO. The mass ratio of La 2 O 3 to the solid electrolyte was 20.1%. A solid electrolyte material according to Example 6 was obtained in the same manner as Example 1 except for the above matters.
• the average particle size of La 2 O 3 was about 100 nm.
• Example 7 CaO was used instead of ZnO.
• the mass ratio of CaO to the solid electrolyte was 10.3%.
• a solid electrolyte material according to Example 7 was obtained in the same manner as Example 1 except for the above matters.
• the average particle diameter of CaO was approximately 160 nm.
• Example 8 MgO was used instead of ZnO.
• the mass ratio of MgO to the solid electrolyte was 11.1%.
• a solid electrolyte material according to Example 8 was obtained in the same manner as Example 1 except for the above matters.
• the average particle diameter of MgO was about 50 nm.
• Example 9 Fe 2 O 3 was used instead of ZnO.
• the mass ratio of Fe 2 O 3 to the solid electrolyte was 16.2%.
• a solid electrolyte material according to Example 8 was obtained in the same manner as Example 1 except for the above matters.
• the average particle size of Fe 2 O 3 was about 50 nm.
• Comparative Example 1 no oxide material was used. That is, the solid electrolyte material according to Comparative Example 1 consists of the solid electrolyte according to Example 1.
• Example 10 and Comparative Example 2 [Preparation of solid electrolyte]
• These raw material powders were ground and mixed in a mortar to obtain a mixed powder.
• the obtained mixed powder was milled at 600 rpm for 24 hours using a planetary ball mill. In this way, a solid electrolyte according to Example 10 was obtained.
• the composition of the obtained solid electrolyte was analyzed in the same manner as in Example 1, and the molar ratio Li/M was determined from the analyzed composition. The molar ratio Li/M was 2.0.
• Example 10 the solid electrolyte according to Example 10 and ZnO were prepared such that the mass ratio of ZnO to the solid electrolyte was 12.3%.
• a solid electrolyte material according to Example 10 was obtained in the same manner as Example 1 except for the above matters.
• Comparative Example 2 no oxide material was used. That is, the solid electrolyte material according to Comparative Example 2 consists of the solid electrolyte according to Example 10.
• Example 10 when comparing Example 10 and Comparative Example 2, in which the constituent elements of the solid electrolyte are the same "Li, Zr, O, Cl", it is found that the solid electrolyte material according to Example 10, which contains an oxide material, The amount of hydrogen chloride gas generated was smaller than that of the solid electrolyte material according to Comparative Example 2, which did not contain any solid material.
• Example 3 As is clear from a comparison of Example 3 and Comparative Examples 1 and 2, the solid electrolyte material containing 17.3% by mass of ZnO generates less gas and has high ionic conductivity.
• the solid electrolyte material according to the present disclosure can reduce the amount of hydrogen halide gas generated and can also have higher lithium ion conductivity. Therefore, the solid electrolyte material according to the present disclosure is a suitable material for providing a battery with excellent charge and discharge characteristics at low manufacturing cost.
• the battery 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 102 Oxide particles 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 shape 303 Punch lower part 1000 Battery 1100 Electrode material

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