WO2024075618A1 - 硫化物固体電解質の製造方法 - Google Patents

硫化物固体電解質の製造方法 Download PDF

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WO2024075618A1
WO2024075618A1 PCT/JP2023/035340 JP2023035340W WO2024075618A1 WO 2024075618 A1 WO2024075618 A1 WO 2024075618A1 JP 2023035340 W JP2023035340 W JP 2023035340W WO 2024075618 A1 WO2024075618 A1 WO 2024075618A1
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solid electrolyte
sulfide solid
mixture
raw material
sulfide
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French (fr)
Japanese (ja)
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美勝 清野
安延 金子
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Priority to JP2024555759A priority Critical patent/JPWO2024075618A1/ja
Priority to KR1020257011114A priority patent/KR20250084288A/ko
Priority to CN202380070987.1A priority patent/CN119998896A/zh
Priority to EP23874745.5A priority patent/EP4600976A1/en
Publication of WO2024075618A1 publication Critical patent/WO2024075618A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/14—Sulfur, selenium, or tellurium compounds of phosphorus
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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 invention relates to a method for producing a sulfide solid electrolyte.
  • Methods for producing a solid electrolyte used in a solid electrolyte layer are roughly divided into a solid phase method and a liquid phase method.
  • the liquid phase method is further classified into a homogeneous method in which a solid electrolyte material is completely dissolved in a solvent, and a heterogeneous method in which a solid electrolyte material is not completely dissolved and a suspension in which solid and liquid coexist is formed.
  • a method is known in which raw materials such as lithium sulfide and diphosphorus pentasulfide are subjected to mechanical milling treatment using an apparatus such as a ball mill or a bead mill, and then heated as necessary to produce an amorphous or crystalline solid electrolyte (see, for example, Patent Document 1).
  • Patent Document 5 and Non-Patent Documents 2 and 3 disclose a method for producing an amorphous electrolyte having a Li 3 PS 4 composition by irradiating lithium sulfide and diphosphorus pentasulfide with microwaves in an organic solvent.
  • the present invention has been made in consideration of these circumstances, and aims to provide a method for producing a sulfide solid electrolyte that employs a liquid phase method, reduces the heating temperature, suppresses granulation due to heating, maintains particle size, and can efficiently produce a sulfide solid electrolyte of high quality.
  • the method for producing a sulfide solid electrolyte according to the present invention includes the steps of: A method for producing a sulfide solid electrolyte, comprising: a first step of mixing raw material components containing lithium atoms, phosphorus atoms, sulfur atoms, and halogen atoms in an organic solvent to obtain a mixture; a second step of irradiating the mixture with microwaves of 0.5 to 700 W/g to heat the mixture to 50 to 360°C; and a third step of cooling the mixture to 20 to 70°C, the second and third steps being repeated 2 to 50 times; It is.
  • the present invention provides a method for producing a sulfide solid electrolyte that employs a liquid phase method, reduces the heating temperature, suppresses granulation caused by heating, maintains particle size, and efficiently produces a sulfide solid electrolyte of high quality.
  • 1 is an X-ray diffraction spectrum of the sulfide solid electrolyte obtained in Example 1.
  • 1 is an X-ray diffraction spectrum of the sulfide solid electrolyte obtained in Example 2.
  • 1 is an X-ray diffraction spectrum of the sulfide solid electrolyte obtained in Example 3.
  • 1 is an X-ray diffraction spectrum of the sulfide solid electrolyte obtained in Example 4.
  • 1 is an X-ray diffraction spectrum of the sulfide solid electrolyte obtained in Comparative Example 1.
  • the present embodiment The following describes an embodiment of the present invention (hereinafter, may be referred to as “the present embodiment”). Note that in this specification, the upper and lower limit values of the numerical ranges “greater than or equal to,” “less than or equal to,” and “to” are values that can be combined in any way, and the numerical values in the examples can also be used as the upper and lower limit values.
  • the solid-phase method is centered on solid-phase reactions, and it is easy to obtain a solid electrolyte with high purity, so it is easy to realize high ionic conductivity, but it is characterized by being unsuitable for mass production.
  • efforts have been made to enlarge the size (mass production) for industrial production, and the liquid-phase method has attracted attention as a method that can be easily synthesized in large quantities in addition to its versatility and applicability.
  • firing is generally performed to improve the crystallinity of the sulfide solid electrolyte.
  • firing at a high temperature of about 400°C is required.
  • granulation occurs, making the particle size larger than before firing, and it may become necessary to perform a crushing process, which ultimately leads to higher costs for the sulfide solid electrolyte.
  • the need for firing at a high temperature can cause problems such as accelerated corrosion of the reaction equipment, which can lead to higher costs for the sulfide solid electrolyte due to increased equipment costs.
  • the inventors therefore conducted extensive research into the manufacturing method of sulfide solid electrolytes, particularly into the calcination process, and discovered that by irradiating a mixture of the raw material ingredients in an organic solvent with microwaves, the heating temperature can be kept low and granulation caused by heating can be suppressed. Reducing the heating temperature not only reduces the energy required for heating, but also reduces equipment costs, as mentioned above. Furthermore, being able to maintain particle size by suppressing granulation caused by heating eliminates the need for a crushing process after heating, which is extremely effective in improving manufacturing efficiency and reducing costs.
  • Patent Document 5 Non-Patent Documents 2 and 3 describe microwave irradiation in sulfide solid electrolytes.
  • microwave irradiation is adopted when manufacturing an electrolyte (lithium thiophosphate) having a composition of Li 3 PS 4 using Li 2 S and P 2 S 5 , and microwave irradiation is not performed on those containing halogen atoms.
  • Patent Document 5 and Non-Patent Document 2 describe the production of an amorphous sulfide solid electrolyte by microwave irradiation, but do not produce a crystalline sulfide solid electrolyte, such as one having an argyrodite crystal structure.
  • Non-Patent Document 3 describes that while microwave irradiation is performed as described above, high-temperature firing is also performed. Therefore, in view of conventional manufacturing methods, it is a surprising phenomenon that a sulfide solid electrolyte having a reduced heating temperature and a maintained particle size can be produced by a very simple operation of performing microwave irradiation instead of the firing operation in conventional manufacturing methods, while suppressing granulation due to heating.
  • solid electrolyte refers to an electrolyte that maintains a solid state at 25°C under a nitrogen atmosphere.
  • the “sulfide solid electrolyte” obtained by the manufacturing method of this embodiment refers to a solid electrolyte that contains alkali metal atoms, sulfur atoms, phosphorus atoms, and halogen atoms, and has ionic conductivity due to alkali metal atoms such as lithium atoms.
  • the above-mentioned “sulfide solid electrolyte” may also contain metal atoms such as Ge, Na, K, Mg, Ca, Al, Si, Sb, Ti, and Zr.
  • sulfide solid electrolyte includes both crystalline sulfide solid electrolytes and amorphous sulfide solid electrolytes.
  • crystalline sulfide solid electrolyte refers to a solid electrolyte in which a peak derived from a solid electrolyte is observed in the X-ray diffraction pattern in an X-ray diffraction measurement, and it does not matter whether or not there is a peak derived from the raw material of the solid electrolyte.
  • the crystalline sulfide solid electrolyte includes a crystal structure derived from a solid electrolyte, and may be a crystal structure derived from the solid electrolyte in part or entirely. And, as long as the crystalline sulfide solid electrolyte has the above-mentioned X-ray diffraction pattern, it may include an amorphous sulfide solid electrolyte (also called a "glass component") in part. Therefore, the crystalline sulfide solid electrolyte includes so-called glass ceramics obtained by heating an amorphous solid electrolyte (glass component) to a temperature above the crystallization temperature.
  • an amorphous sulfide solid electrolyte refers to one in which the X-ray diffraction pattern in an X-ray diffraction measurement is a halo pattern in which no peaks other than those derived from the material are observed, and it does not matter whether or not there are peaks derived from the raw materials of the solid electrolyte.
  • a method for producing a sulfide solid electrolyte according to a first embodiment of the present invention includes the steps of: A method for producing a sulfide solid electrolyte, comprising: a first step of mixing raw material components containing lithium atoms, phosphorus atoms, sulfur atoms, and halogen atoms in an organic solvent to obtain a mixture; a second step of irradiating the mixture with microwaves of 0.5 to 700 W/g to heat the mixture to 50 to 360°C; and a third step of cooling the mixture to 20 to 70°C, the second and third steps being repeated 2 to 50 times; It is.
  • Heating by microwave irradiation is a method of increasing the temperature of a target substance by irradiating the target substance with microwaves.
  • the inventors of the present invention have considered whether it is possible to suppress the temperature of the reaction system as a whole by selectively heating and reacting the raw material contents containing the raw material of the sulfide solid electrolyte by utilizing the characteristic of heating the target substance by microwave irradiation. Then, they considered whether it is possible to suppress the temperature of the reaction system as a whole by selectively heating the raw material contents by microwave irradiation in an organic solvent, so that the heat of the raw material contents can be absorbed by the organic solvent.
  • the inventors also discovered that simply maintaining the temperature of the raw material inclusions high does not sufficiently promote the reaction between the solid electrolyte raw materials contained in the raw material inclusions, and that the reaction between the solid electrolyte raw materials is promoted while the raw material inclusions are irradiated with specific high-power microwaves, leading to the present invention.
  • the manufacturing method of this embodiment is a manufacturing method that not only produces a sulfide solid electrolyte while reducing the heating temperature, but also suppresses granulation due to heating, maintains the particle size, and produces a high-quality sulfide solid electrolyte, simply by performing the extremely simple operation of irradiating microwaves at a specific output. Reducing the heating temperature not only leads to a reduction in equipment costs, but also reduces the energy consumption required for heating. Furthermore, suppressing granulation due to heating and maintaining the particle size eliminates the need for a crushing process after heating. As a result, the manufacturing method of this embodiment improves the efficiency of sulfide solid electrolyte manufacturing, reduces costs, and produces a high-quality sulfide solid electrolyte.
  • a method for producing a sulfide solid electrolyte according to a second embodiment of the present invention includes the steps of: a method for producing a sulfide solid electrolyte according to the first embodiment, comprising a heat-retaining step of irradiating the mixture with microwaves and maintaining the mixture at a temperature of 80 to 360° C. for 1 to 300 minutes after carrying out the second step, and then carrying out the third step; It is.
  • a method for producing a sulfide solid electrolyte according to a third embodiment of the present invention includes the steps of: The method for producing a sulfide solid electrolyte according to the first or second aspect, wherein the organic solvent has a dielectric loss factor of 10.0 or less at 25° C. It is. In the third embodiment, an organic solvent having a predetermined dielectric loss factor is used.
  • the energy loss when a substance is placed in an electromagnetic field irradiated with microwaves is the sum of conductive loss, dielectric loss, and magnetic loss.
  • dielectric loss occurs, and the energy of the electric field is converted into thermal energy, generating heat.
  • the lower the dielectric loss the more efficiently the energy from microwave irradiation can be consumed by the raw material contents.
  • the dielectric loss factor is a loss factor that is proportional to the dielectric loss, and the dielectric loss factor and the dielectric loss have the following relationship.
  • Dielectric loss ⁇ f ⁇ 0 ⁇ ′′
  • the dielectric loss factor is an index of the ease of heating by microwaves, and the smaller the dielectric loss factor, the smaller the dielectric loss. Therefore, if the dielectric loss factor of the organic solvent used in the manufacturing method of this embodiment is 10.0 or less, the raw material contents can be heated more selectively, making it possible to more efficiently manufacture a sulfide solid electrolyte.
  • a method for producing a sulfide solid electrolyte according to a fourth embodiment of the present invention includes the steps of: The method for producing a sulfide solid electrolyte according to any one of the first to third aspects, wherein the boiling point of the organic solvent is 50° C. or higher. It is.
  • the fourth embodiment is to employ an organic solvent having a predetermined boiling point.
  • the higher the boiling point of the organic solvent the more the amount of organic solvent that evaporates when the raw material contents are selectively heated can be reduced, and the raw material contents can be more uniformly retained in the organic solvent. This makes it easier to selectively heat the raw material contents, and also makes it possible to reduce the amount of organic solvent used.
  • a method for producing a sulfide solid electrolyte according to a fifth embodiment of the present invention includes the steps of: The method for producing a sulfide solid electrolyte according to any one of the first to fourth aspects, wherein the organic solvent is an aromatic solvent. It is.
  • the fifth embodiment is to employ an aromatic solvent, that is, an organic solvent having an aromatic ring, as the organic solvent.
  • Aromatic solvents which are organic solvents having an aromatic ring, tend to satisfy the properties in the second and third forms described above, i.e., the dielectric loss factor and boiling point. This makes it possible to produce sulfide solid electrolytes more efficiently.
  • a method for producing a sulfide solid electrolyte according to a sixth embodiment of the present invention includes the steps of: The method for producing a sulfide solid electrolyte according to any one of the first to fifth aspects, wherein the content of the raw material contained in the mixture is 1 mass% or more and 20 mass% or less. It is.
  • the sixth embodiment is one in which the content of the raw material contained in the mixture is within a predetermined range. This allows the amount of organic solvent used to be reduced, making it possible to produce a sulfide solid electrolyte more efficiently.
  • a method for producing a sulfide solid electrolyte according to a seventh aspect of the present embodiment includes the steps of: The method for producing a sulfide solid electrolyte according to any one of the first to sixth aspects, wherein in the second step, the mixture is irradiated with microwaves of 130 to 700 W/g; It is.
  • the microwave output irradiated in the second step is set to a predetermined range. According to the seventh embodiment, the reaction between the solid electrolyte raw materials is efficiently promoted, and a sulfide solid electrolyte of higher quality is obtained.
  • a method for producing a sulfide solid electrolyte according to an eighth embodiment of the present invention includes the steps of: The method for producing a sulfide solid electrolyte according to any one of the first to seventh aspects, wherein in the second step, the mixture is heated to 150 to 360° C.; It is.
  • a method for producing a sulfide solid electrolyte according to a ninth aspect of this embodiment includes the steps of: The method for producing a sulfide solid electrolyte according to any one of the second to eighth aspects, wherein the mixture is heated to 150 to 360° C. in the heat-retaining step. It is.
  • the eighth embodiment is to heat the mixture to a temperature within a predetermined range.
  • the ninth embodiment is to keep the mixture at a temperature within a predetermined range.
  • conventional manufacturing methods require firing at a high temperature of about 400° C.
  • a method for producing a sulfide solid electrolyte according to a tenth aspect of this embodiment includes the steps of: The method for producing a sulfide solid electrolyte according to any one of the first to ninth aspects, wherein the mixture is maintained at the temperature for 1 to 240 minutes in the heat-retaining step. It is.
  • the time during which the temperature of the mixture is maintained within the range in the heat retention step is set to a predetermined range.
  • a method for producing a sulfide solid electrolyte according to an eleventh aspect of this embodiment includes the steps of: The method for producing a sulfide solid electrolyte according to any one of the first to tenth aspects, wherein the second and third steps are repeated 2 to 20 times. It is.
  • the number of times the second and third steps are repeated is set within a predetermined range from the viewpoint of achieving both productivity and quality of the sulfide solid electrolyte.
  • a method for producing a sulfide solid electrolyte according to a twelfth aspect of this embodiment includes the steps of: The method for producing a sulfide solid electrolyte according to any one of the first to eleventh aspects, wherein the sulfide solid electrolyte is a crystalline sulfide solid electrolyte having an argyrodite-type crystal structure; It is.
  • the obtained sulfide solid electrolyte has an argyrodite crystal structure.
  • a sulfide solid electrolyte having an argyrodite crystal structure requires firing at a high temperature of about 400°C according to conventional manufacturing methods.
  • the manufacturing method of the present embodiment includes mixing raw material ingredients including lithium atoms, phosphorus atoms, sulfur atoms, and halogen atoms in an organic solvent to obtain a mixture.
  • raw material ingredients including lithium atoms, phosphorus atoms, sulfur atoms, and halogen atoms in an organic solvent.
  • the raw material ingredients will be described to obtain the mixture.
  • the raw material inclusions include lithium atoms, phosphorus atoms, sulfur atoms, and halogen atoms.
  • the raw material inclusions are not particularly limited as long as they contain these atoms, and may be a material containing at least one atom selected from these atoms, either singly or in combination as a raw material. It is preferable that the inclusions include two or more substances selected from substances containing at least one atom selected from lithium atoms, phosphorus atoms, sulfur atoms, and halogen atoms. Therefore, the sulfide solid electrolyte obtained by the manufacturing method of this embodiment contains lithium atoms, phosphorus atoms, sulfur atoms, and halogen atoms.
  • Substances that can be used as raw materials contain at least one atom of lithium, phosphorus, sulfur, and halogen atoms, and more specifically, alkali metal sulfides such as lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide; alkali metal halides such as lithium halides such as lithium fluoride, lithium chloride, lithium bromide, and lithium iodide, and sodium halides such as sodium iodide, sodium fluoride, sodium chloride, and sodium bromide; phosphorus sulfides such as diphosphorus trisulfide (P 2 S 3 ) and diphosphorus pentasulfide (P 2 S 5 ); phosphorus halides such as various phosphorus fluorides (PF 3 , PF 5 ), various phosphorus chlorides (PCl 3 , PCl 5 , P 2 Cl 4 ), various phosphorus bromides (PBr
  • Examples of compounds that can be used as raw materials other than those mentioned above include compounds containing at least one atom selected from the above four types of atoms and containing atoms other than the four types of atoms, more specifically, lithium compounds such as lithium oxide, lithium hydroxide, and lithium carbonate; metal sulfides such as silicon sulfide, germanium sulfide, boron sulfide, gallium sulfide, tin sulfide (SnS, SnS 2 ), aluminum sulfide, and zinc sulfide; phosphate compounds such as sodium phosphate and lithium phosphate; metal halides such as aluminum halides, silicon halides, germanium halides, arsenic halides, selenium halides, tin halides, antimony halides, tellurium halides, and bismuth halides; phosphorus oxyhalides such as phosphorus oxychloride (POCl 3 ) and phosphorus
  • the halogen atom may vary depending on the sulfide solid electrolyte to be obtained, but from the viewpoint of more easily obtaining a sulfide solid electrolyte having high ionic conductivity, a chlorine atom, a bromine atom, or an iodine atom is preferred among the halogen atoms. These atoms may be used alone or in combination of two or more kinds.
  • bromine atoms and iodine atoms are more preferred, and when attempting to obtain a sulfide solid electrolyte having an argyrodite type crystal structure, chlorine atoms and bromine atoms are more preferred.
  • preferred substances that can be used as raw materials among the above include alkali metal sulfides such as lithium sulfide and sodium sulfide, phosphorus sulfides such as diphosphorus trisulfide (P 2 S 3 ) and diphosphorus pentasulfide (P 2 S 5 ), halogen elements such as fluorine (F 2 ), chlorine (Cl 2 ), bromine (Br 2 ), and iodine (I 2 ), and lithium halides such as lithium fluoride, lithium chloride, lithium bromide, and lithium iodide.
  • alkali metal sulfides lithium sulfide is preferred, and of the phosphorus sulfides, diphosphorus pentasulfide is preferred.
  • the raw material containing halogen atoms may vary depending on the sulfide solid electrolyte to be obtained, so it cannot be generalized, but among the halogen elements, chlorine (Cl 2 ), bromine (Br 2 ), and iodine (I 2 ) are preferable, and among the lithium halides, lithium chloride, lithium bromide, and lithium iodide are preferable. Furthermore, when attempting to obtain a sulfide solid electrolyte having a thiolicon region II type crystal structure, the halogen elements are more preferable, bromine (Br 2 ) and iodine (I 2 ), and the lithium halides are more preferable, lithium bromide and lithium iodide.
  • the halogen elements are more preferable, chlorine (Cl 2 ) and bromine (Br 2 ), and the lithium halides are more preferable, lithium chloride and lithium bromide.
  • the combination of materials that can be used as raw materials is lithium sulfide, phosphorus sulfide, and lithium halide, or lithium sulfide, phosphorus sulfide, and a halogen element, and more preferably lithium sulfide, phosphorus sulfide, and lithium halide.
  • phosphorus pentasulfide is preferable as phosphorus sulfide
  • the lithium halide and halogen element can be selected according to the sulfide solid electrolyte to be obtained, as described above.
  • preferred examples of compounds that can be used as raw materials include sulfide solid electrolytes such as Li 3 PS 4 containing PS 4 units.
  • sulfide solid electrolytes such as Li 3 PS 4 containing PS 4 units.
  • the composition ratio of the structure can be increased, that is, the PS 4 fraction can be improved, and high ionic conductivity can be obtained, compared to the case where a sulfide solid electrolyte is formed while being synthesized by a reaction between compounds using a compound such as lithium sulfide as a raw material.
  • examples of the sulfide solid electrolyte that can be used as a compound used as a raw material include an amorphous sulfide solid electrolyte having a molecular structure of Li 3 PS 4 (also referred to as “amorphous Li 3 PS 4 "), a crystalline sulfide solid electrolyte (also referred to as “crystalline Li 3 PS 4 "), and the like.
  • an amorphous sulfide solid electrolyte having a structure containing halogen atoms, or a crystalline sulfide solid electrolyte, or a precursor equivalent thereto can also be used as the "amorphous sulfide solid electrolyte".
  • the raw sulfide solid electrolyte is preferably an amorphous or crystalline sulfide solid electrolyte that does not contain a Li 4 P 2 S 7 structure.
  • raw sulfide solid electrolytes can be produced by conventional production methods such as mechanical milling, slurry, and melt quenching, and commercially available products can also be used.
  • those produced by a solution method in which the raw materials are completely dissolved and synthesized can also be used.
  • the sulfide solid electrolyte used as a raw material may be amorphous or crystalline, or may contain both amorphous and crystalline materials.
  • raw sulfide solid electrolyte may be amorphous or crystalline, or may contain both amorphous and crystalline materials.
  • the dispersibility of the halogen atoms is improved, and bonding between the halogen atoms and the lithium atoms, sulfur atoms, and phosphorus atoms in the solid electrolyte is facilitated, resulting in a sulfide solid electrolyte with higher ionic conductivity.
  • the lithium sulfide when lithium sulfide is used as the raw material, the lithium sulfide is preferably in the form of particles.
  • the average particle size (D 50 ) of the lithium sulfide particles is preferably 10 ⁇ m or more and 2000 ⁇ m or less, more preferably 30 ⁇ m or more and 1500 ⁇ m or less, and even more preferably 50 ⁇ m or more and 1000 ⁇ m or less.
  • the average particle size (D 50 ) is the particle size at which the particle size distribution cumulative curve is drawn and the particle size is accumulated from the smallest particle size to reach 50% of the whole, and the volume distribution is, for example, the average particle size that can be measured using a laser diffraction/scattering type particle size distribution measuring device.
  • the solid raw materials preferably have an average particle size of the same order as that of the lithium sulfide particles, that is, preferably within the same range as the average particle size of the lithium sulfide particles.
  • the particle size of the raw material compound may be adjusted by pulverization or the like as necessary.
  • the ratio of lithium sulfide to the total of lithium sulfide and diphosphorus pentasulfide cannot be generalized because it varies depending on the sulfide solid electrolyte to be obtained, but from the viewpoint of obtaining higher chemical stability and high ionic conductivity, it is preferably 60 mol% or more, more preferably 65 mol% or more, and even more preferably 68 mol% or more, with the upper limit being preferably 85 mol% or less, more preferably 83 mol% or less, and even more preferably 80 mol% or less.
  • the content of lithium sulfide and diphosphorus pentasulfide relative to the total of these is preferably 55 mol% or more, more preferably 58 mol% or more, and even more preferably 60 mol% or more, with the upper limit being preferably 100 mol% or less, more preferably 90 mol% or less, even more preferably 80 mol% or less, and even more preferably 70 mol% or less.
  • the ratio of lithium bromide to the total of lithium bromide and lithium iodide is preferably 1 mol % or more, more preferably 20 mol % or more, even more preferably 40 mol % or more, still more preferably 50 mol % or more, and the upper limit is preferably 99 mol % or less, more preferably 90 mol % or less, even more preferably 80 mol % or less, and still more preferably 70 mol % or less.
  • the ratio of lithium bromide to the total of lithium bromide and lithium chloride is the same as the ratio of lithium bromide to the total of lithium bromide and lithium iodide described above.
  • the raw material ingredients are mixed in an organic solvent.
  • organic solvents various solvents widely called organic solvents can be used.
  • solvents that have traditionally been used in the production of solid electrolytes can be used as the solvent, including, for example, hydrocarbon solvents such as aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, and aromatic hydrocarbon solvents.
  • aliphatic hydrocarbons examples include saturated aliphatic hydrocarbons such as pentane, hexane, 2-ethylhexane, heptane, octane, decane, undecane, dodecane, and tridecane, as well as unsaturated aliphatic hydrocarbons corresponding to the above-mentioned saturated aliphatic hydrocarbons such as pentene and hexene.
  • alicyclic hydrocarbons examples include saturated alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, as well as unsaturated aliphatic hydrocarbons corresponding to the above-mentioned saturated alicyclic hydrocarbons such as cyclohexene and methylcyclohexene.
  • aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, ethylbenzene, tert-butylbenzene, biphenyl, naphthalene, tetrahydronaphthalene (tetralin, cyclohexylbenzene), anthracene, and the like.
  • examples of the solvent include solvents containing atoms other than carbon and hydrogen atoms, such as heteroatoms, for example, nitrogen atoms, oxygen atoms, sulfur atoms, and halogen atoms.
  • Preferred examples of the solvent containing an oxygen atom as a heteroatom include ether solvents, ester solvents, as well as alcohol solvents, aldehyde solvents, and ketone solvents.
  • ether solvents include aliphatic ethers such as dimethyl ether, diethyl ether, tert-butyl methyl ether, dimethoxymethane, dimethoxyethane, diethylene glycol dimethyl ether (diglyme), triethylene oxide glycol dimethyl ether (triglyme), diethylene glycol, and triethylene glycol; alicyclic ethers such as ethylene oxide, propylene oxide, tetrahydrofuran, tetrahydropyran, dimethoxytetrahydrofuran, cyclopentyl methyl ether, and dioxane; heterocyclic ethers such as furan, benzofuran, and benzopyran; and aromatic ethers such as methyl phenyl ether (anisole), ethyl phenyl ether, dibenzyl ether, and diphenyl ether (diphenyl oxide).
  • aliphatic ethers such as dimethyl ether, diethyl
  • ester solvents include methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate; aliphatic esters such as methyl propionate, ethyl propionate, dimethyl oxalate, diethyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, and diethyl succinate; alicyclic esters such as methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, and dimethyl cyclohexanedicarboxylate; heterocyclic esters such as methyl pyridinecarboxylate, methyl pyrimidinecarboxylate, acetolactone, propiolactone, butyrolactone, and valerolactone; and aromatic esters such as methyl benzoate, ethyl benzoate, dimethyl phthalate,
  • alcohol-based solvents such as ethanol and butanol
  • aldehyde-based solvents such as formaldehyde, acetaldehyde and dimethylformamide
  • ketone-based solvents such as acetone and methyl ethyl ketone.
  • solvents having a group containing a nitrogen element such as an amino group, an amide group, a nitro group, and a nitrile group.
  • Preferred examples of solvents having an amino group include aliphatic amines such as diethylamine, triethylamine, ethylenediamine, diaminopropane, dimethylethylenediamine, diethylethylenediamine, dimethyldiaminopropane, tetramethyldiaminomethane, tetramethylethylenediamine (TMEDA), and tetramethyldiaminopropane (TMPDA); alicyclic amines such as cyclopropanediamine, cyclohexanediamine, and bisaminomethylcyclohexane; heterocyclic amines such as isophoronediamine, pyridine, methylpyridine, dimethylpyridine, methylethyl
  • nitrile solvents include acetonitrile, propionitrile, 3-chloropropionitrile, benzonitrile, 4-fluorobenzonitrile, tert-butyronitrile, isobutyronitrile, acrylonitrile, cyclohexylnitrile, capronitrile, isocapronitrile, malononitrile, and fumaronitrile.
  • Other preferred examples include solvents containing nitrogen atoms such as dimethylformamide and nitrobenzene.
  • Preferred examples of the solvent containing a halogen atom as a heteroatom include dichloromethane, chlorobenzene, trifluoromethylbenzene, chlorobenzene, chlorotoluene, and bromobenzene.
  • Preferred examples of the solvent containing a sulfur atom include dimethyl sulfoxide and carbon disulfide.
  • the amount of organic solvent used is such that the content of the total amount of the raw material ingredients relative to the total amount of the raw material ingredients and the organic solvent is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and even more preferably 8% by mass or more, with an upper limit of preferably 20% by mass or less, more preferably 17% by mass or less, even more preferably 15% by mass or less, and even more preferably 12% by mass or less.
  • the amount of organic solvent used is within the above range, the raw material ingredients are more easily maintained uniformly in the organic solvent, and the raw material ingredients are more easily selectively heated by microwave irradiation, allowing the sulfide solid electrolyte to be produced more efficiently.
  • the organic solvent used in the manufacturing method of the present embodiment is preferably one having a dielectric loss factor of 10.0 or less at 25° C.
  • the dielectric loss factor of the organic solvent is more preferably 8.0 or less, even more preferably 5.0 or less, even more preferably 1.0 or less, and particularly preferably 0.5 or less, and there is no particular lower limit, and it is usually 0.01 or more.
  • the dielectric loss factor in this specification is a dielectric loss factor at 2.45 GHz at 25° C., and is a measured value measured according to a conventional method.
  • the relative dielectric constant and the dielectric loss tangent can be measured using a dielectric constant measuring device (e.g., various devices such as an LCR meter, an impedance material analyzer, a network analyzer, a TDR measuring device, and a pulse THz spectroscopy device), and the dielectric loss factor can be calculated.
  • a dielectric constant measuring device e.g., various devices such as an LCR meter, an impedance material analyzer, a network analyzer, a TDR measuring device, and a pulse THz spectroscopy device
  • the organic solvent used in the manufacturing method of this embodiment is preferably one having a boiling point of 50°C or higher. If the boiling point is 50°C or higher, the amount of volatilization of the organic solvent when the raw material contents are selectively heated is suppressed, and the raw material contents can be more uniformly maintained in the organic solvent, making it easier to selectively heat the raw material contents and enabling a reduction in the amount of organic solvent used. From this perspective, the boiling point of the organic solvent is more preferably 65°C or higher, even more preferably 75°C or higher, even more preferably 100°C or higher, and particularly preferably 200°C or higher.
  • aromatic solvents having an aromatic ring such as aromatic hydrocarbon solvents, aromatic ether solvents, and aromatic ester solvents, as well as aliphatic hydrocarbons, alicyclic hydrocarbons, ether solvents (excluding the above aromatic ether solvents), ester solvents (excluding the above aromatic ester solvents), solvents having an amino group (amine solvents), and solvents containing halogen atoms are more preferred, and among these, aromatic solvents having an aromatic ring are particularly preferred.
  • aromatic solvents having an aromatic ring are particularly preferred.
  • aromatic solvent those selected from aromatic hydrocarbon solvents and aromatic ethers are preferred, and aromatic ethers are more preferred.
  • aromatic hydrocarbon solvent benzene, toluene, xylene, biphenyl, naphthalene, and tetrahydronaphthalene (tetralin, cyclohexylbenzene) are preferred, and as the aromatic ether, diphenyl ether (diphenyl oxide) is preferred.
  • aliphatic hydrocarbon pentane and hexane are preferred, and as the alicyclic hydrocarbon, cyclohexane is preferred.
  • ether solvent excluding the above aromatic ether solvents
  • aliphatic ethers and alicyclic ethers are preferred, of which diethyl ether and tetrahydrofuran are preferred.
  • ester solvent excluding the above aromatic ester solvents
  • aliphatic esters are preferred, of which ethyl acetate is preferred.
  • amine solvent aliphatic amines and heterocyclic amines are preferred, and among these, triethylamine and pyridine are preferred.
  • solvent containing a halogen atom dichloromethane is preferable.
  • the first step is a step of mixing the raw material contents in the organic solvent to obtain a mixture.
  • the mixture obtained in this manner is a slurry (suspension) in which the raw material contents are dispersed in the organic solvent.
  • the first step can be carried out, for example, using a mixer. It can also be carried out using a stirrer, a grinder, or the like.
  • the raw materials can be mixed using a stirrer, and the raw materials can be ground using a grinder, but they can also be mixed at the same time. In other words, it can be said that the mixture can be obtained by subjecting the raw material contents to agitation, mixing, grinding, or a combination of any of these processes in an organic solvent.
  • mixing may be performed using any of a stirrer, mixer, and grinder. From the viewpoint of efficiently obtaining a slurry (suspension) in which the raw material ingredients are dispersed in the organic solvent, it is preferable to use either a stirrer or mixer, and it is more preferable to use a mixer.
  • an agitator or mixer there is a mechanical agitation mixer that is equipped with an agitator blade inside the reaction tank and can agitate (also referred to as mixing by agitation or agitation mixing).
  • mechanical agitation mixers include high-speed agitation mixers and double-arm mixers.
  • high-speed agitation mixers include vertical axis rotary mixers and horizontal axis rotary mixers, and either type of mixer may be used.
  • the shapes of the impellers used in mechanically stirred mixers include blade type, arm type, anchor type, paddle type, full zone type, ribbon type, multi-stage blade type, double arm type, shovel type, double-shaft blade type, flat blade type, C-type blade type, etc., and from the viewpoint of promoting the reaction of the raw materials more efficiently, the shovel type, flat blade type, C-type blade type, anchor type, paddle type, full zone type, etc. are preferred, with the anchor type, paddle type, and full zone type being more preferred.
  • the rotation speed of the stirring blades can be adjusted appropriately depending on the volume of the fluid in the reaction vessel, the temperature, the shape of the stirring blades, etc., and is not particularly limited. However, it is usually sufficient to set it to about 5 rpm or more and 400 rpm or less. From the viewpoint of promoting the reaction of the raw materials more efficiently, it is preferably 10 rpm or more and 300 rpm or less, more preferably 15 rpm or more and 250 rpm or less, and even more preferably 20 rpm or more and 200 rpm or less.
  • the temperature conditions when mixing using a mixer there are no particular limitations on the temperature conditions when mixing using a mixer, and for example, it is usually -30 to 120°C, preferably -10 to 100°C, more preferably 0 to 80°C, and even more preferably 10 to 60°C.
  • the mixing time is usually 0.1 to 500 hours, and from the viewpoint of making the raw materials more uniformly dispersed and promoting the reaction, it is preferably 1 to 450 hours, more preferably 10 to 425 hours, even more preferably 20 to 400 hours, and even more preferably 40 to 375 hours.
  • a media type pulverizer using a pulverizing medium can be used.
  • Media-type pulverizers are broadly classified into container-driven pulverizers and media-agitation pulverizers. Examples of container-driven pulverizers include agitation tanks, grinding tanks, and combinations thereof such as ball mills and bead mills.
  • media-agitation pulverizers include impact pulverizers such as cutter mills, hammer mills, and pin mills; tower-type pulverizers such as tower mills; agitation tank-type pulverizers such as attritors, aquamizers, and sand grinders; flow tank-type pulverizers such as visco mills and pearl mills; flow tube-type pulverizers; annular-type pulverizers such as co-ball mills; continuous dynamic-type pulverizers; and various pulverizers such as single-shaft or multi-shaft kneaders.
  • impact pulverizers such as cutter mills, hammer mills, and pin mills
  • tower-type pulverizers such as tower mills
  • agitation tank-type pulverizers such as attritors, aquamizers, and sand grinders
  • flow tank-type pulverizers such as visco mills and pearl mills
  • the ball mills and bead mills exemplified as container-driven pulverizers are preferred, and planetary-type pulverizers are particularly preferred.
  • grinders can be selected appropriately depending on the desired scale, etc.
  • container-driven grinders such as ball mills and bead mills can be used, while for large-scale operations or mass production, other types of grinders may be used.
  • wet mill that can handle wet milling.
  • wet grinding machines include wet bead mills, wet ball mills, and wet vibration mills, among which wet bead mills using beads as grinding media are preferred because they allow the grinding conditions to be freely adjusted and are easy to handle smaller particle sizes.
  • Dry grinding machines such as dry media grinding machines such as dry bead mills, dry ball mills, and dry vibration mills, and dry non-media grinding machines such as jet mills can also be used.
  • a flow-through mill can be used, which allows for circulation operation as needed. Specifically, there is a mill that circulates the material between a mill (grinding mixer) that grinds the slurry and a temperature holding tank (reaction vessel).
  • the size of the beads or balls used in the ball mill or bead mill may be appropriately selected depending on the desired particle size, processing amount, etc.
  • the diameter of the beads is usually 0.05 mm ⁇ or more, preferably 0.1 mm ⁇ or more, more preferably 0.3 mm ⁇ or more, and the upper limit is usually 5.0 mm ⁇ or less, preferably 3.0 mm ⁇ or less, more preferably 2.0 mm ⁇ or less.
  • the diameter of the balls is usually 2.0 mm ⁇ or more, preferably 2.5 mm ⁇ or more, more preferably 3.0 mm ⁇ or more, and the upper limit is usually 20.0 mm ⁇ or less, preferably 15.0 mm ⁇ or less, more preferably 10.0 mm ⁇ or less.
  • materials include metals such as stainless steel, chrome steel, and tungsten carbide; ceramics such as zirconia and silicon nitride; and minerals such as agate.
  • the rotation speed varies depending on the scale of processing and cannot be generally specified, but is usually 10 rpm or more, preferably 20 rpm or more, and more preferably 50 rpm or more, and the upper limit is usually 1,000 rpm or less, preferably 900 rpm or less, more preferably 800 rpm or less, and even more preferably 700 rpm or less.
  • the grinding time in this case varies depending on the scale of processing and cannot be generally determined, but is usually 0.5 hours or more, preferably 1 hour or more, more preferably 5 hours or more, and even more preferably 10 hours or more, and the upper limit is usually 100 hours or less, preferably 72 hours or less, more preferably 48 hours or less, and even more preferably 36 hours or less.
  • the content of the raw material ingredients contained in the mixture obtained by mixing is preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 5 mass% or more, and even more preferably 8 mass% or more, with the upper limit being preferably 20 mass% or less, more preferably 17 mass% or less, even more preferably 15 mass% or less, and even more preferably 12 mass% or less.
  • the content of the raw material ingredients is within the above range, the raw material ingredients are more likely to be uniformly maintained in the organic solvent, and therefore the raw material ingredients are more likely to be selectively heated by microwave irradiation, allowing for more efficient production of the sulfide solid electrolyte.
  • the mixture obtained in the first step is irradiated with microwaves of 0.5 to 700 W/g and heated to 50 to 360° C.
  • microwaves 0.5 to 700 W/g and heated to 50 to 360° C.
  • microwave generator for irradiating microwaves
  • an irradiation device equipped with a high-frequency oscillator that oscillates microwaves can be used, and if the scale is small, a commercially available microwave oven can also be used.
  • the microwave frequency is preferably 0.5 GHz or more, more preferably 1.0 GHz or more, and even more preferably 1.5 GHz or more, with the upper limit being preferably 100 GHz or less, more preferably 10.0 GHz or less, and even more preferably 6.0 GHz or less.
  • the output power cannot be generalized because it can vary depending on the type of organic solvent contained in the mixture to be irradiated with microwaves, the amount of the mixture, etc., but in order to heat the raw material contents more efficiently, it must be 0.5 to 700 W/g, preferably 60 W/g or more, more preferably 100 W/g or more, and even more preferably 130 W/g or more, and the upper limit must be 700 W/g or less, more preferably 300 W/g or less, and even more preferably 280 W/g or less.
  • the microwave irradiation time in the second step may be a time sufficient to raise the temperature of the mixture to 50-360°C, and cannot be generalized as it may vary depending on the type of organic solvent contained in the mixture to be irradiated with microwaves, the amount of the mixture, etc., but is preferably 1 minute or more, more preferably 2 minutes or more, and even more preferably 3 minutes or more, with the upper limit being preferably 360 minutes or less, more preferably 300 minutes or less, and even more preferably 240 minutes or less.
  • the heating temperature by microwave irradiation can vary depending on the composition of the sulfide solid electrolyte to be obtained, and whether an amorphous or crystalline sulfide solid electrolyte is to be obtained, so it cannot be generalized, but the temperature of the mixture is 50 to 360°C, preferably 150°C or higher, more preferably 200°C or higher, and even more preferably 230°C or higher, with the upper limit being preferably 350°C or lower, more preferably 310°C or lower, and even more preferably 275°C or lower.
  • the heating temperature by microwave irradiation can vary depending on the composition of the sulfide solid electrolyte to be obtained, whether it is amorphous or crystalline, as mentioned above. In other words, depending on the heating temperature by microwave irradiation, it is possible to control whether an amorphous or crystalline sulfide solid electrolyte is obtained.
  • the temperature required for crystallization of the resulting raw sulfide solid electrolyte i.e., the amorphous sulfide solid electrolyte
  • DTA differential thermal analysis
  • DTA device a differential thermal analyzer
  • the temperature of the raw material content is preferably in the range of 5° C. or more, more preferably 10° C. or more, and even more preferably 20° C. or more relative to the crystallization temperature. There is no particular upper limit, but it may be about 40° C. or less.
  • the temperature of the raw material contents is preferably in the range of 5° C.
  • the lower limit is set to about ⁇ 40° C. or more, which is the temperature of the peak top of the exothermic peak observed at the lowest temperature side.
  • the raw material contents are selectively heated, so the temperature of the raw material contents themselves is considered to be higher than the temperature of the organic solvent (which is considered to be the same as the temperature of the mixture). Therefore, in the manufacturing method of this embodiment, the temperature of the mixture obtained by the above mixing can be known, but the temperature of the raw material contents in the mixture is known indirectly from the temperature of the mixture.
  • a sulfide solid electrolyte having an argyrodite crystal structure is obtained by setting the temperature of the mixture at 250°C.
  • a sulfide solid electrolyte having an argyrodite crystal structure requires firing at a high temperature of about 400°C according to conventional methods, the temperature of the raw material contents itself can be considered to be about the mixture temperature + 150°C. Strictly speaking, this can vary depending on the type of organic solvent in the mixture and its content, but it is advisable to use the mixture temperature + 150°C as a guideline for the temperature of the raw material contents themselves, and determine whether the crystallization temperature has been reached and set the heating temperature.
  • the manufacturing method of this embodiment may further include a heat-retaining step after the second step, and then the third step may be performed.
  • the mixture is irradiated with microwaves to maintain a temperature of 80 to 360° C. for 1 to 300 minutes, but the specific temperature setting and the like are similar to those in the above-mentioned step 2.
  • the temperature of the mixture may be varied within the above-mentioned range of 80 to 360° C., but it is preferable to maintain it within a range of ⁇ 20° C., and more preferably within a range of ⁇ 10° C., of the temperature targeted in step 2.
  • the microwave irradiation time in the incubation step is 1 minute or more, preferably 2 minutes or more, and more preferably 3 minutes or more, and the upper limit is 300 minutes or less, preferably 240 minutes or less, more preferably 210 minutes or less, even more preferably 190 minutes or less, and even more preferably 180 minutes or less.
  • the microwave power irradiated during the warming step is preferably about 0 to 133 W/g, more preferably about 0 to 100 W/g, and may be irradiated intermittently.
  • the mixture is cooled to 20 to 70° C.
  • the mixture may be cooled by keeping it at room temperature, or may be actively cooled by bringing a container for holding the mixture into contact with a heat transfer medium such as water, or may be cooled by blowing air directly onto the reaction container.
  • the second step, the heat-retaining step that is provided as necessary, and the third step need to be repeated 2 to 50 times, preferably these steps are repeated 2 to 20 times, more preferably these steps are repeated 3 to 10 times.
  • the number of times the second and third steps are repeated includes the first time.
  • the manufacturing method of this embodiment may further include drying the fluid obtained by repeating the second step, the heat-retaining step (if necessary), and the fourth step.
  • the obtained fluid contains the sulfide solid electrolyte generated by microwave irradiation, the remaining organic solvent, etc., and is usually in the form of a slurry (suspension). Therefore, by drying the fluid, a powder of the sulfide solid electrolyte is obtained.
  • Drying can be performed by irradiating the mixture with microwaves, and then drying the resulting fluid at a temperature appropriate for the type of solvent.
  • the solvent can be evaporated by drying under reduced pressure (vacuum drying) using a vacuum pump or the like at usually 5 to 200° C., preferably 10 to 180° C., more preferably 15 to 160° C.
  • Drying can be performed by filtering the fluid using a glass filter, separating the liquid from the solid by decantation, or separating the liquid from the solid by using a centrifuge.
  • the drying may be performed by any of the above-mentioned reduced pressure drying (vacuum drying), filtration, and solid-liquid separation.
  • reduced pressure drying vacuum drying
  • filtration filtration
  • solid-liquid separation may be performed after filtration and solid-liquid separation.
  • a sulfide solid electrolyte such as a sulfide solid electrolyte (lithium thiophosphate) having a molecular structure of Li 3 PS 4 can be preferably used.
  • a method for producing the sulfide solid electrolyte (raw sulfide solid electrolyte) used in the raw material inclusion will be described, mainly focusing on a sulfide solid electrolyte (lithium thiophosphate) having a molecular structure of Li 3 PS 4 .
  • the raw sulfide solid electrolyte can be produced by a conventional production method such as a mechanical milling method, a slurry method, or a melt quenching method, as described above.
  • a raw material mixture is obtained by mixing and grinding a raw material content containing at least two types of compounds in a solvent; calcining the raw material mixture to obtain a calcined product;
  • the production can be carried out by a production method including the steps of:
  • raw material content A As the raw material content containing at least two kinds of compounds (hereinafter, in order to distinguish it from the raw material content used in the above-mentioned first step, the raw material content used in the first step will be referred to as “raw material content A", and the raw material content used in "production of raw materials contained in the raw material content” will be referred to as “raw material content B”).
  • Raw material content B containing lithium sulfide and phosphorus sulfide, which are raw material compounds, is preferably used, and diphosphorus pentasulfide is preferable as the phosphorus sulfide.
  • the amount of lithium sulfide and phosphorus sulfide used may be appropriately determined depending on the sulfide solid electrolyte to be obtained, and when a sulfide solid electrolyte having a Li3PS4 structure is to be obtained using lithium sulfide and diphosphorus pentasulfide, they may be used in a molar ratio of 3:1.
  • a molar ratio corresponding to the sulfide solid electrolyte when another sulfide solid electrolyte is to be obtained, it is sufficient to use a molar ratio corresponding to the sulfide solid electrolyte, and when a sulfide solid electrolyte containing a halogen atom is to be obtained, it is sufficient to use a raw material compound containing a halogen atom corresponding to the sulfide solid electrolyte.
  • the molar ratio corresponding to the sulfide solid electrolyte, the raw material compound to be used, etc. are the same as those explained for the raw material content A described above.
  • the compounds contained in the raw material content B may be crushed before use.
  • the crushing may be performed using a crusher as described above as a crusher that can be used to obtain the above mixture.
  • a pin mill particularly a pin mill with a constant volume feeder, is preferably used.
  • the method for producing a raw sulfide solid electrolyte includes mixing and pulverizing a raw material content B containing at least two compounds in a solvent to obtain a raw material mixture.
  • phosphorus sulfide and diphosphorus pentasulfide that may be contained in the raw material content B are pre-pulverized as necessary, weighed out in an amount corresponding to the desired raw material sulfide solid electrolyte, roughly mixed to obtain raw material content B, which is then mixed and pulverized in a solvent to obtain a raw material mixture.
  • the raw material mixture contains the raw material compounds contained in raw material inclusion B, and it is believed that these compounds mainly form fine crystals. This is because the compound in raw material inclusion B becomes finer as the raw material compounds are mixed and crushed. It is also believed that some of the raw material compounds react to form raw material sulfide solid electrolyte.
  • the raw material content B may be mixed and pulverized using any of the pulverizers described above that may be used to obtain the mixture, and media-type pulverizers such as ball mills and bead mills are preferred.
  • a kneader such as a single-shaft or multi-shaft kneader may also be used.
  • the solvent used in the mixing and grinding is preferably an organic solvent, which may be appropriately selected from the organic solvents used in obtaining the mixture.
  • organic solvents preferred are hydrocarbon solvents such as aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents and aromatic hydrocarbon solvents, more preferred are aromatic hydrocarbon solvents, and particularly preferred are toluene and xylene.
  • solvents containing a hetero atom it is also preferable to use the above-mentioned solvents containing a hetero atom, and it is more preferable to use them in combination with the above-mentioned hydrocarbon solvents.
  • solvents containing heteroatoms solvents containing oxygen atoms and solvents containing nitrogen atoms are preferred, and as the solvents containing oxygen atoms, ether solvents are preferred, and as the solvents containing nitrogen atoms, solvents containing nitrile groups (nitrile solvents) are preferred, and solvents containing nitrile groups (nitrile solvents) are more preferred.
  • ether solvents tetrahydrofuran, diethyl ether, etc. are preferred, and as the nitrile solvents, propionitrile, isocapronitrile, and isobutyronitrile are preferred.
  • the solvent used in the above mixing and grinding it is preferable to use a combination of the above hydrocarbon solvent and the above solvent containing a heteroatom.
  • the content of the solvent containing a heteroatom relative to the total amount of the solvent is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and even more preferably 0.3 mass% or more, with the upper limit being preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 1 mass% or less.
  • the raw material content B and the solvent to be mixed and pulverized usually form a slurry (suspension).
  • the content of raw material content B in the slurry to be mixed and pulverized may be appropriately selected from the range of the content of raw material content A in the mixture to obtain the above mixture.
  • the method for producing a raw sulfide solid electrolyte includes calcining a raw mixture obtained by mixing and pulverizing the raw material content B to obtain a calcined product.
  • the calcination promotes the reaction of the raw material compounds contained in the raw material mixture to produce a raw sulfide solid electrolyte, and the solvent is removed to obtain a powdered raw sulfide solid electrolyte. That is, the calcined product obtained by calcination becomes the raw sulfide solid electrolyte.
  • the method of calcination is not particularly limited, but examples include methods using a hot plate, autoclave, vacuum heating device, argon gas atmosphere furnace, calcination furnace, etc.
  • methods using shear-type dryers such as FM mixers and Nauta mixers, stationary furnaces such as hearth kilns, rotary furnaces such as rotary kilns, and moreover, for industrial use, horizontal dryers having a heating means and a feed mechanism, horizontal vibration fluidized dryers, etc. can also be used.
  • the method of calcination can be selected according to the processing volume to be calcined.
  • the heating temperature and time in the calcination process can vary depending on the composition of the calcined product and whether an amorphous or crystalline calcined product is to be obtained, so it is not possible to make a general statement.
  • the heating temperature is preferably 150°C or higher, more preferably 160°C or higher, and even more preferably 170°C or higher, with the upper limit being preferably 300°C or lower, more preferably 280°C or lower, and even more preferably 250°C or lower.
  • the raw sulfide solid electrolyte may be either amorphous or crystalline.
  • it is preferably amorphous.
  • the heating temperature in the calcination is preferably a temperature at which an amorphous raw sulfide solid electrolyte can be obtained, and may be determined by the method starting from the crystallization temperature as explained above for the heating temperature by microwave irradiation.
  • the heating time is preferably 0.1 hours or more, more preferably 0.2 hours or more, and even more preferably 0.25 hours or more, with the upper limit being preferably 8 hours or less, more preferably 6 hours or less, and even more preferably 4 hours or less.
  • the calcination is preferably carried out in an inert gas atmosphere (e.g., nitrogen atmosphere, argon atmosphere) or reduced pressure atmosphere (particularly in a vacuum).
  • an inert gas atmosphere containing hydrogen gas may also be used. This is because deterioration (e.g., oxidation) of the raw material sulfide solid electrolyte can be prevented.
  • drying may be carried out before calcination.
  • the solvent contained in the raw material mixture can be removed in advance.
  • the drying method may be the same as that for the fluid obtained by irradiating microwaves as described above.
  • the raw sulfide solid electrolyte obtained by the above manufacturing method is assumed to be a sulfide solid electrolyte ( lithium thiophosphate) having a Li3PS4 structure as a molecular structure.
  • a sulfide solid electrolyte lithium thiophosphate
  • Li3PS4 structure Li3PS4 structure
  • the calcined product is merely an intermediate, and its state may change depending on the conditions of microwave irradiation, etc., and the details of the state are unknown; however, the calcined product is considered to be a precursor that will produce a sulfide solid electrolyte having an argyrodite-type crystal structure when irradiated with microwaves.
  • the sulfide solid electrolyte obtained by the manufacturing method of this embodiment is either an amorphous sulfide solid electrolyte (glass component) or a crystalline sulfide solid electrolyte. Whether it is amorphous or crystalline can be adjusted by the heating temperature by the microwave irradiation.
  • the amorphous sulfide solid electrolyte obtained by the manufacturing method of this embodiment contains lithium atoms, sulfur atoms, phosphorus atoms, and halogen atoms.
  • Representative examples include sulfide solid electrolytes composed of lithium sulfide, phosphorus sulfide, and lithium halide, such as Li 2 S-P 2 S 5 -LiI, Li 2 S-P 2 S 5 -LiCl, Li 2 S-P 2 S 5 -LiBr, and Li 2 S-P 2 S 5 -LiI-LiBr; and sulfide solid electrolytes containing other atoms such as oxygen atoms and silicon atoms, such as Li 2 S-P 2 S 5 -Li 2 O-LiI and Li 2 S-SiS 2 -P 2 S 5 -LiI, are preferred.
  • the solid electrolyte include those composed of lithium sulfide, phosphorus sulfide , and lithium halide, such as Li 2 S-P 2 S 5 -LiI, Li 2 S-P 2 S 5 -LiCl, Li 2 S-P 2 S 5 -LiBr, and Li 2 S-P 2 S 5 -LiI-LiBr.
  • the types of elements constituting the amorphous sulfide solid electrolyte can be confirmed, for example, by an ICP emission spectrometer.
  • the shape of the amorphous sulfide solid electrolyte is not particularly limited, but may be, for example, particulate.
  • the average particle size (D 50 ) of the particulate amorphous sulfide solid electrolyte may be, for example, within a range of 0.01 ⁇ m to 500 ⁇ m, or 0.1 to 200 ⁇ m.
  • the following argyrodite type crystal structure and thiolicon region II type crystal structure are preferably used as the crystalline sulfide solid electrolyte obtained by the manufacturing method of this embodiment.
  • the crystal structure represented by the composition formula Li 7 -x P 1-y Si y S 6 and Li 7+x P 1-y Si y S 6 (x is ⁇ 0.6 to 0.6, y is 0.1 to 0.6), which has the structural skeleton of Li 7 PS 6 and in which a portion of P is replaced by Si, is a cubic or orthorhombic crystal, preferably a cubic crystal, and has peaks that appear mainly at 2 ⁇ 15.5°, 18.0°, 25.0°, 30.0°, 31.4°, 45.3°, 47.0°, and 52.0° in X-ray diffraction measurement using CuK ⁇ radiation.
  • These crystal structures basically having the structural skeleton of Li7PS6 are also called argyrodite-type crystal structures. The positions of these peaks may vary within a range of ⁇ 0.5°.
  • Li4 - xGe1- xPxS4 - based thio-LISICON Region II type crystal structure see Kanno et al., Journal of the Electrochemical Society, 148(7)A742-746(2001)
  • Li4 - xGe1- xPxS4 - based thio-LISICON Region II type similar crystal structure see Solid State Ionics, 177(2006), 2721-2725)
  • thio-lisicon region II type crystal structure refers to either a Li 4-x Ge 1-x P x S 4 -based thio-lisicon region II (thio-LISICON Region II) type crystal structure or a crystal structure similar to the Li 4-x Ge 1-x P x S 4 -based thio-lisicon region II (thio-LISICON Region II) type.
  • the crystalline sulfide solid electrolyte obtained by the manufacturing method of this embodiment may have the above-mentioned thio-lisicon region II type crystal structure or may have it as the main crystal, but from the viewpoint of obtaining higher ionic conductivity, it is preferable that it has it as the main crystal.
  • the crystalline sulfide solid electrolyte obtained by the manufacturing method of the present embodiment preferably does not contain crystalline Li 3 PS 4 ( ⁇ -Li 3 PS 4 ).
  • the diffraction peaks of the Li 4-x Ge 1-x P x S The diffraction peaks of the Li4 - xGe1-xPxS4-type thio
  • the thiolicon region II type crystal structure when the thiolicon region II type crystal structure is obtained in this embodiment, it is preferable that it does not contain crystalline Li 3 PS 4 ( ⁇ -Li 3 PS 4 ).
  • the shape of the crystalline sulfide solid electrolyte is not particularly limited, but may be, for example, particulate.
  • the average particle size (D 50 ) of the particulate crystalline sulfide solid electrolyte may be, for example, within a range of 0.01 ⁇ m to 500 ⁇ m, or 0.1 to 200 ⁇ m.
  • the sulfide solid electrolyte obtained by the manufacturing method of this embodiment has high ionic conductivity and excellent battery performance, and is therefore suitable for use in batteries.
  • the sulfide solid electrolyte obtained by the manufacturing method of this embodiment may be used in any of the positive electrode layer, the negative electrode layer, and the electrolyte layer. Each layer may be manufactured by a known method.
  • the battery uses a current collector in addition to the positive electrode layer, electrolyte layer, and negative electrode layer, and a known current collector can be used.
  • a layer of a material that reacts with the solid electrolyte such as Au, Pt, Al, Ti, or Cu, coated with Au or the like can be used.
  • Lithium sulfide Li 2 S was pulverized in a nitrogen atmosphere using a pin mill equipped with a constant volume feeder (model "100UPZ", manufactured by Hosokawa Micron Corporation) (feeding rate: 80 g/min, disk rotation speed: 18,000 rpm). Furthermore, phosphorus pentasulfide (P 2 S 5 , manufactured by Italmatch Japan), lithium bromide (LiBr, manufactured by Honjo Chemical Co., Ltd.), and lithium chloride (LiCl, manufactured by Honjo Chemical Co., Ltd.) were also pulverized using the above pin mill.
  • the injection rate of phosphorus pentasulfide was 140 g/min
  • the injection rate of lithium bromide (LiBr) was 230 g/min
  • the injection rate of lithium chloride (LiCl) was 250 g/min
  • the rotation speed of the disk was 18,000 rpm for each.
  • 110 g of the crudely mixed raw material was dispersed in a mixed solvent of 720 mL of dehydrated toluene (manufactured by Wako Pure Chemical Industries, Ltd.) and 2.9 mL of dehydrated isobutyronitrile (manufactured by Kishida Chemical Co., Ltd.) (2 wt% relative to the raw material) under a nitrogen atmosphere to obtain a slurry of about 10% by mass.
  • the slurry was mixed and pulverized using a bead mill (LMZ015, manufactured by Ashizawa Finetech Co., Ltd.) while maintaining the slurry in a nitrogen atmosphere.
  • Example 1 The raw sulfide solid electrolyte obtained in Preparation Example 1 was used as the raw material inclusion. 1.5 g of the raw material sulfide solid electrolyte obtained in Preparation Example 1 was mixed in 13.5 g of a solvent containing biphenyl and diphenyl oxide, which is an organic solvent ("DAWTHERM A heat medium (product name)", manufactured by Dow Chemical Japan, Ltd., biphenyl content: 27% by mass), to obtain a mixture (slurry concentration: 10% by mass).
  • a solvent containing biphenyl and diphenyl oxide which is an organic solvent
  • the resulting mixture was placed in a microwave irradiation device ("Initiator+ (model number)" manufactured by Biotage), and microwave irradiation (output: 300 W, frequency: 2.45 GHz) was started, and the temperature of the mixture was allowed to reach 250°C (second step).
  • the microwave output was changed as needed between 0 and 200 W (the device automatically changes the output (W) to maintain the temperature) to maintain the temperature of the mixture at 250° C. for 30 minutes (warming step).
  • the microwave irradiation was stopped, and the resulting mixture was cooled to 50° C. by air purging (blowing air) (third step).
  • the ionic conductivity was measured by the following method and was found to be 0.7 mS/cm.
  • the average particle size was measured by the following method and found to be 2.23 ⁇ m (D 50 ), which was almost the same as the average particle size of Li 3 PS 4 used as the raw material, 2.53 ⁇ m (D 50 ).
  • the ionic conductivity was measured as follows. A circular pellet with a diameter of 10 mm (cross-sectional area S: 0.785 cm 2 ) and a height (L) of 0.1 to 0.3 cm was molded from the sulfide solid electrolyte to prepare a sample. Electrode terminals were attached to the top and bottom of the sample, and measurements were made at 25°C by an AC impedance method (frequency range: 1 MHz to 100 Hz, amplitude: 10 mV) to obtain a Cole-Cole plot.
  • AC impedance method frequency range: 1 MHz to 100 Hz, amplitude: 10 mV
  • powder X-ray diffraction (XRD) measurement Powder X-ray diffraction (XRD) measurements were carried out as follows. The powders obtained in the examples and comparative examples were filled into a groove having a diameter of 20 mm and a depth of 0.2 mm, and the groove was leveled with glass to prepare a sample. The sample was sealed with a Kapton film for XRD and measured under the following conditions without exposing it to air.
  • Measuring device M03xhf (model number, manufactured by Mac Science Co., Ltd.) Tube voltage: 40 kV Tube current: 40mA X-ray wavelength: Cu-K ⁇ radiation (1.5418 ⁇ )
  • the average particle size was measured as follows.
  • the particle size (D 50 ) at a cumulative volume percentage of 50% was measured using a laser diffraction particle size distribution analyzer (LA- 950 (product name), manufactured by Horiba, Ltd.), and this was taken as the average particle size.
  • Example 2 A sulfide solid electrolyte was obtained in the same manner as in Example 1, except that the series of steps from microwave irradiation to cooling was performed a total of three times (the number of times the second step, the heat-retaining step, and the third step were repeated: three times).
  • the ionic conductivity of the obtained sulfide solid electrolyte was measured by the above-mentioned method and was found to be 1.4 mS/cm. Furthermore, when the average particle size of the obtained sulfide solid electrolyte was measured by the above-mentioned method, the average particle size was 2.35 ⁇ m (D 50 ).
  • the obtained sulfide solid electrolyte powder was subjected to powder X-ray diffraction (XRD) measurement by the above-mentioned method.
  • XRD powder X-ray diffraction
  • Example 3 A sulfide solid electrolyte was obtained in the same manner as in Example 1, except that the series of steps from microwave irradiation to cooling were performed a total of four times (the number of times the second step, the heat-retaining step, and the third step were repeated: four times).
  • the ionic conductivity of the resulting sulfide solid electrolyte was measured by the above-mentioned method and was found to be 2.1 mS/cm. Furthermore, when the average particle size of the obtained sulfide solid electrolyte was measured by the above-mentioned method, the average particle size was 2.34 ⁇ m (D 50 ).
  • the obtained sulfide solid electrolyte powder was subjected to powder X-ray diffraction (XRD) measurement by the above-mentioned method.
  • XRD powder X-ray diffraction
  • Example 4 A sulfide solid electrolyte was obtained in the same manner as in Example 1, except that the microwave irradiation step in Example 1 was carried out as follows. The obtained mixture was placed in a microwave irradiation device, and microwave irradiation (output: 300 W, frequency: 2.45 GHz) was started. After the temperature of the mixture reached 300°C, the output was changed between 0 and 200 W (the device automatically changes the output (W) to maintain the temperature) as needed to maintain the temperature of the mixture at 300°C for 30 minutes. After that, the microwave irradiation was stopped, and the obtained mixture was cooled to 50°C by air purging (blowing air).
  • microwave irradiation output: 300 W, frequency: 2.45 GHz
  • the series of steps from the microwave irradiation to the cooling were repeated twice more (number of times the second step, the warming step, and the third step were repeated: 3 times), the solvent was replaced with toluene under vacuum, and then the mixture was dried at room temperature until the solvent disappeared, and then dried at 180°C for 4 hours to obtain a sulfide solid electrolyte powder.
  • the ionic conductivity of the obtained sulfide solid electrolyte was measured by the above-mentioned method and was found to be 2.6 mS/cm. Furthermore, when the average particle size of the obtained sulfide solid electrolyte was measured by the above-mentioned method, the average particle size was 2.18 ⁇ m (D 50 ).
  • the obtained sulfide solid electrolyte powder was subjected to powder X-ray diffraction (XRD) measurement by the above-mentioned method.
  • XRD powder X-ray diffraction
  • Example 1 A sulfide solid electrolyte was obtained in the same manner as in Example 1, except that the series of steps from microwave irradiation to cooling was performed only once (number of repetitions of the second step, the warming step, and the third step: once).
  • the ionic conductivity of the obtained sulfide solid electrolyte was measured by the above-mentioned method and was found to be 0.4 mS/cm. Furthermore, when the average particle size of the obtained sulfide solid electrolyte was measured by the above-mentioned method, the average particle size was 2.28 ⁇ m (D 50 ).
  • the obtained sulfide solid electrolyte powder was subjected to powder X-ray diffraction (XRD) measurement by the above-mentioned method.
  • XRD powder X-ray diffraction
  • the manufacturing method of this embodiment employs a liquid phase method, reduces the heating temperature, and suppresses granulation due to heating, making it possible to efficiently manufacture a sulfide solid electrolyte that maintains particle size.
  • the sulfide solid electrolyte obtained by the manufacturing method of this embodiment is suitable for use in batteries, particularly batteries used in information-related devices and communication devices such as personal computers, video cameras, and mobile phones.

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Publication number Priority date Publication date Assignee Title
WO2025244481A1 (ko) * 2024-05-24 2025-11-27 주식회사 솔리비스 황화물계 고체전해질의 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013016423A (ja) 2011-07-06 2013-01-24 Toyota Motor Corp 硫化物固体電解質材料、リチウム固体電池、および、硫化物固体電解質材料の製造方法
JP2015146299A (ja) * 2014-02-04 2015-08-13 東京電力株式会社 固体電解質の製造方法
JP2020015661A (ja) * 2018-07-24 2020-01-30 トヨタ モーター エンジニアリング アンド マニュファクチャリング ノース アメリカ，インコーポレイティド チオリン酸リチウム複合体材料のマイクロ波合成
JP2020095953A (ja) * 2018-12-05 2020-06-18 出光興産株式会社 アルジロダイト型結晶構造を有する固体電解質の製造方法
JP2021158120A (ja) * 2019-12-23 2021-10-07 出光興産株式会社 固体電解質の製造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6095218B2 (ja) 2013-03-26 2017-03-15 公立大学法人大阪府立大学 固体電解質で被覆された活物質の製造方法、全固体リチウム二次電池の固体電解質を含む層の形成用溶液、全固体リチウム二次電池及びその製造方法
WO2014192309A1 (ja) 2013-05-31 2014-12-04 出光興産株式会社 固体電解質の製造方法
EP3432320B1 (en) 2016-03-14 2023-05-31 Idemitsu Kosan Co.,Ltd. Solid electrolyte and method for producing solid electrolyte
WO2018054709A1 (en) 2016-09-20 2018-03-29 Basf Se Solid lithium electrolytes and process of production

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013016423A (ja) 2011-07-06 2013-01-24 Toyota Motor Corp 硫化物固体電解質材料、リチウム固体電池、および、硫化物固体電解質材料の製造方法
JP2015146299A (ja) * 2014-02-04 2015-08-13 東京電力株式会社 固体電解質の製造方法
JP2020015661A (ja) * 2018-07-24 2020-01-30 トヨタ モーター エンジニアリング アンド マニュファクチャリング ノース アメリカ，インコーポレイティド チオリン酸リチウム複合体材料のマイクロ波合成
JP2020095953A (ja) * 2018-12-05 2020-06-18 出光興産株式会社 アルジロダイト型結晶構造を有する固体電解質の製造方法
JP2021158120A (ja) * 2019-12-23 2021-10-07 出光興産株式会社 固体電解質の製造方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMISTRY OF MATERIALS, no. 29, 2017, pages 1830 - 1835
JOURNAL OF MATERIALS CHEMISTRY A, no. 9, 2018, pages 21261 - 21265
KANNO ET AL., JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 148, no. 7, 2001, pages 742 - 746
SOLID STATE IONICS, vol. 177, 2006, pages 2721 - 2725

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025244481A1 (ko) * 2024-05-24 2025-11-27 주식회사 솔리비스 황화물계 고체전해질의 제조방법

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