WO2023167237A1 - 結晶性硫化物固体電解質及びその製造方法 - Google Patents

結晶性硫化物固体電解質及びその製造方法 Download PDF

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WO2023167237A1
WO2023167237A1 PCT/JP2023/007580 JP2023007580W WO2023167237A1 WO 2023167237 A1 WO2023167237 A1 WO 2023167237A1 JP 2023007580 W JP2023007580 W JP 2023007580W WO 2023167237 A1 WO2023167237 A1 WO 2023167237A1
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solid electrolyte
sulfide solid
complexing agent
atom
lithium
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French (fr)
Japanese (ja)
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勇介 井関
拓明 山田
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Priority to CN202380025093.0A priority Critical patent/CN118805227A/zh
Priority to JP2024504723A priority patent/JPWO2023167237A1/ja
Priority to KR1020247029329A priority patent/KR20240162046A/ko
Priority to US18/842,985 priority patent/US20250183359A1/en
Publication of WO2023167237A1 publication Critical patent/WO2023167237A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/22—Alkali metal sulfides or polysulfides
    • 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
    • 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
    • H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a crystalline sulfide solid electrolyte and a method for producing the same.
  • Methods for producing the solid electrolyte used in the solid electrolyte layer are broadly divided into a solid-phase method and a liquid-phase method.
  • a heterogeneous method in which the material is not completely dissolved and passes through a solid-liquid coexistent suspension.
  • a method of dissolving a solid electrolyte in a solvent and reprecipitating it is known as a homogeneous method (see, for example, Patent Document 1), and a heterogeneous method is a polar aprotic solvent.
  • Patent Document 4 A method using two types of complexing agents is also known (Patent Document 4).
  • a drying method a method of drying a slurry containing a solid electrolyte or its precursor and a polar solvent by fluidized drying is also known (see, for example, Patent Document 5).
  • the present invention has been made in view of such circumstances, and an object thereof is to provide a crystalline sulfide solid electrolyte with improved ionic conductivity while adopting a liquid phase method.
  • the method for producing a crystalline sulfide solid electrolyte according to the present invention comprises: A first mixing of a raw material containing material containing a lithium atom, a phosphorus atom, a sulfur atom, and at least one halogen atom of a bromine atom and an iodine atom, and a complexing agent 1 of (1) below, Then, a second mixing of mixing with a complexing agent 2 of (2) below, and an instant drying step of contacting with a medium and drying, A method for producing a crystalline sulfide solid electrolyte.
  • Complexing agent 1 capable of forming a complex containing Li 3 PS 4 and the halogen atom (2) a complexing agent 2 other than the complexing agent 1 capable of forming a complex containing Li 3 PS 4
  • FIG. 1 is a flow diagram explaining an example of a dryer (medium fluidized dryer) used in the production method of the present embodiment. It is a flowchart explaining an example of the dryer (spray dryer) used in the manufacturing method of this embodiment.
  • 1 is an X-ray diffraction spectrum of a crystalline sulfide solid electrolyte obtained in an example and a powder obtained in a comparative example.
  • 1 is an X-ray diffraction spectrum of a crystalline sulfide solid electrolyte obtained in an example and a powder obtained in a comparative example.
  • this embodiment An embodiment of the present invention (hereinafter sometimes referred to as “this embodiment") will be described below.
  • the upper and lower limits of the numerical ranges of "more than”, “less than”, and “to” are numerical values that can be arbitrarily combined, and the numerical values in the examples are used as the upper and lower numerical values.
  • the rules that are considered preferable can be arbitrarily adopted. That is, one preferred rule may be employed in combination with one or more other preferred rules. It can be said that a combination of preferable ones is more preferable.
  • the liquid-phase method is attracting attention toward the practical use of all-solid-state batteries in recent years. This is because the liquid phase method has the advantage of being easy to synthesize in large quantities in addition to its versatility and applicability.
  • the solid electrolyte is dissolved, there is a problem that it is difficult to achieve high ionic conductivity compared to the solid-phase method because some of the solid electrolyte components are decomposed and lost during deposition.
  • the homogenous method since the raw material and the solid electrolyte are once completely dissolved, each component such as the raw material and the solid electrolyte can be uniformly dispersed in the liquid.
  • Complexing agents 1 and 2 below.
  • Complexing agent 1 capable of forming a complex containing Li 3 PS 4 and the halogen atom (2)
  • a complex containing a halogen atom is formed while forming Li 3 PS 4 as the basic skeleton of the solid electrolyte by the reaction of the raw material containing the solid electrolyte raw material. to form
  • the solid electrolyte raw material, as well as the complex containing Li 3 PS 4 and the halogen atom are uniformly dispersed in the complexing agent, and the solid electrolyte raw material, further Li 3 PS 4 and the halogen atom A fluid in which the complex containing is uniformly dispersed is obtained.
  • the precursor of the solid electrolyte (hereinafter, “precursor of solid electrolyte”, “electrolyte precursor”) is obtained while each component is uniformly dispersed. ) is formed, and as a result, a crystalline sulfide solid electrolyte with high ionic conductivity can be obtained.
  • the present inventors have further investigated fluids containing Li 3 PS 4 obtained by mixing solid electrolyte raw materials with complexing agents 1 and 2, and complexes such as complexes containing halogen atoms and complexes containing Li 3 PS 4 Therefore, attention was also paid to the drying method when removing the complexing agents 1 and 2. While the advantages obtained by using a complexing agent are great, the solid electrolyte raw material, the Li 3 PS 4 obtained by the reaction of the solid electrolyte raw material, the complex containing a halogen atom, the complex containing Li 3 PS 4 , etc. It has been found that components that are easily eluted by the complexing agent are eluted.
  • a crystalline sulfide solid electrolyte having an aldirodite-type crystal structure is known to be a sulfide solid electrolyte having high ionic conductivity, similar to a crystalline sulfide solid electrolyte having a thiolysicone region II-type crystal structure. there is therefore, it is considered that the crystalline sulfide solid electrolyte of the present embodiment has high ionic conductivity.
  • the crystalline sulfide solid electrolyte according to the present embodiment has a thiolysicone region II type crystal structure as a basic structure and has an aldirodite type crystal structure as a part thereof is not clear, it is as follows. Conceivable.
  • each raw material may exist locally depending on the state of mixing of these solid electrolyte raw materials.
  • the remaining lithium halide and Li3PS4 generated by the reaction of lithium sulfide and phosphorus pentasulfide are converted into the following reaction formula (1).
  • a sulfide solid electrolyte according to a second aspect of the present embodiment is the sulfide solid electrolyte of the first aspect, containing no chlorine atoms, That's what it means.
  • the sulfide solid electrolyte of the present embodiment has a thiolysicone region II type crystal structure as a basic structure, and at least one of a bromine atom and an iodine atom as a halogen atom. It has an aldirodite type crystal structure.
  • a sulfide solid electrolyte according to a third aspect of the present embodiment is the sulfide solid electrolyte of the first or second aspect, wherein the halogen atom comprises an iodine atom;
  • the sulfide solid electrolyte according to the fourth aspect is, in any one of the first to third aspects, wherein the halogen atoms include bromine atoms and iodine atoms; That's what it means.
  • the sulfide solid electrolyte of the present embodiment has a thiolysicone region II type crystal structure as a basic structure, contains an iodine atom as a halogen atom, and further contains a bromine atom and an iodine atom. , a crystalline sulfide solid electrolyte with improved ionic conductivity can be obtained.
  • a sulfide solid electrolyte according to a fifth aspect of the present embodiment is the sulfide solid electrolyte of any one of the above first to fourth aspects,
  • the sulfide solid electrolyte of the present embodiment has a thiolysicone region II type crystal structure as a basic structure, it has a diffraction peak derived from the thiolysicone region II type crystal structure.
  • a method for producing a crystalline sulfide solid electrolyte according to the sixth aspect of the present embodiment includes: A first mixing of a raw material containing material containing a lithium atom, a phosphorus atom, a sulfur atom, and at least one halogen atom of a bromine atom and an iodine atom, and a complexing agent 1 of (1) below, Then, a second mixing of mixing with a complexing agent 2 of (2) below, and an instant drying step of contacting with a medium and drying, A method for producing a crystalline sulfide solid electrolyte.
  • the fluid obtained through the first mixing and the second mixing is a fluid in which complexes such as Li 3 PS 4 , a halogen atom-containing complex, and a Li 3 PS 4 -containing complex are uniformly dispersed.
  • the solid electrolyte precursor obtained by removing the complexing agent also becomes homogeneous.
  • a method for producing a crystalline sulfide solid electrolyte according to the seventh aspect of the present embodiment is the above sixth aspect, Drying by contact with the medium is performed by at least one drying selected from fluidized drying using media particles as a medium, drying by a spray dryer, and airflow drying. That's what it means. Instant drying can be achieved more easily by performing drying by contact with a medium.
  • the complexing agent 1 is a solvent containing nitrogen atoms
  • the method for producing a crystalline sulfide solid electrolyte according to the ninth aspect is, in any one of the sixth to eighth aspects,
  • the complexing agent 2 is a solvent containing oxygen atoms, That's what it means.
  • the production method of the present embodiment employs two types of complexing agents 1 and 2, so that not only does the formation reaction of Li 3 PS 4 proceed without stagnation, but also , the raw material for the solid electrolyte, Li 3 PS 4 and the halogen atom-containing complexes are uniformly dispersed. Therefore, the fluid obtained through the first mixing and the second mixing is a fluid in which complexes such as Li 3 PS 4 , a halogen atom-containing complex, and a Li 3 PS 4 -containing complex are uniformly dispersed.
  • the solid electrolyte precursor obtained by removing the complexing agent also becomes homogeneous. As a result, a crystalline sulfide solid electrolyte having high ionic conductivity is obtained.
  • the solvent containing a nitrogen atom tends to exhibit the property of being capable of forming a complex containing Li 3 PS 4 and the halogen atom, which the complexing agent 1 has, and the complex capable of forming a complex containing Li 3 PS 4 It is suitable as the complexing agent 1 because it becomes easy to distinguish from the properties of the complexing agent 2 other than the agent 1.
  • the solvent containing an oxygen atom tends to exhibit the properties of the complexing agent 2 other than the complexing agent 1 capable of forming a complex containing Li 3 PS 4 . It is also suitable as the complexing agent 2 in that it is difficult to form a complex containing
  • a method for producing a crystalline sulfide solid electrolyte according to a tenth aspect of the present embodiment is the method according to any one of the sixth to ninth aspects,
  • the number of moles of the amount of the complexing agent 1 used with respect to the total number of moles of lithium atoms contained in the raw material content is 0.1 or more and 2.0 or less.
  • the method for producing a crystalline sulfide solid electrolyte according to the eleventh aspect is, in any one of the sixth to tenth aspects,
  • the number of moles of the amount of the complexing agent 2 used with respect to the total number of moles of Li 3 PS 4 generated from the raw material inclusion is 0.1 or more and 5.0 or less. That's what it means.
  • the above-mentioned tenth and eleventh forms are preferable for the complexing agents 1 and 2 in any one of the sixth to ninth forms and any one of the sixth to tenth forms, respectively. It stipulates the amount to be used. When the amount of the complexing agent used is within the above range, the effect of using these complexing agents can be obtained more efficiently.
  • a method for producing a crystalline sulfide solid electrolyte according to the twelfth aspect of the present embodiment is the method for producing a crystalline sulfide solid electrolyte according to any one of the sixth to eleventh aspects,
  • the raw material inclusions contain lithium sulfide and phosphorus pentasulfide
  • the method for producing a crystalline sulfide solid electrolyte according to the thirteenth aspect of the present embodiment is the method for producing a crystalline sulfide solid electrolyte according to any one of the sixth to twelfth aspects,
  • the material containing material contains at least one selected from bromine, iodine, lithium bromide and lithium iodide, That's what it means.
  • the above twelfth and thirteenth modes define preferred raw materials as solid electrolyte raw materials contained in raw material inclusions.
  • lithium sulfide and diphosphorus pentasulfide are used as the raw materials for the solid electrolyte, the formation reaction of Li 3 PS 4 by using the complexing agents 1 and 2 tends to proceed just enough.
  • bromine, iodine, lithium bromide, and lithium iodide are suitable as solid electrolyte raw materials because they easily supply bromine atoms and iodine atoms as halogen atoms.
  • a method for producing a crystalline sulfide solid electrolyte according to a fourteenth aspect of the present embodiment is the method according to any one of the sixth to thirteenth aspects,
  • the crystalline sulfide solid electrolyte of the present embodiment described above means that it is easy to obtain by the method for producing a crystalline sulfide solid electrolyte of the present embodiment.
  • solid electrolyte means an electrolyte that remains solid at 25°C under a nitrogen atmosphere.
  • the sulfide solid electrolyte in the present embodiment contains a lithium atom, a phosphorus atom, a sulfur atom, and at least one halogen atom of a bromine atom and an iodine atom, has a lithium atom as a conductive species, and has ionic conductivity attributed to the lithium atom. It is a solid electrolyte.
  • the "sulfide solid electrolyte” includes both the crystalline sulfide solid electrolyte having the crystal structure according to the present embodiment and the amorphous sulfide solid electrolyte.
  • the crystalline sulfide solid electrolyte is a sulfide solid electrolyte in which a peak derived from the sulfide solid electrolyte is observed in the X-ray diffraction pattern in X-ray diffraction measurement, and the sulfide solid in these It does not matter whether there is a peak derived from the raw material of the electrolyte.
  • the crystalline sulfide solid electrolyte includes a crystal structure derived from the sulfide solid electrolyte, and even if part of the crystal structure is derived from the sulfide solid electrolyte, the entirety of the sulfide solid electrolyte It may be a crystal structure derived from.
  • the crystalline sulfide solid electrolyte may partially contain an amorphous sulfide solid electrolyte as long as it has the above X-ray diffraction pattern. Therefore, crystalline sulfide solid electrolytes include so-called glass-ceramics obtained by heating amorphous sulfide solid electrolytes to a crystallization temperature or higher.
  • the amorphous sulfide solid electrolyte refers to a halo pattern in which no peaks other than those derived from the material are substantially observed in the X-ray diffraction pattern in X-ray diffraction measurement, It does not matter whether or not there is a peak derived from the raw material of the sulfide solid electrolyte.
  • the crystalline sulfide solid electrolyte of the present embodiment has a thiolysicone region II type crystal structure as a basic structure.
  • the “basic structure” means the main crystal structure, and more specifically means that the ratio of the thiolysicone region II type crystal structure to the total crystal is 80.0% or more.
  • the proportion of the thiolysicone region II type crystal structure in the total crystals of the crystalline sulfide solid electrolyte of the present embodiment is preferably 90.0% or more, more preferably 95.0% or more, and still more preferably 96.0%. That's it.
  • the proportion of the thiolysicone region II type crystal structure in the total crystal is determined by NMR (solid 31 P NMR) spectrum obtained by solid-state 31 P-NMR measurement. 89-91 ppm) is the ratio of the total area of each peak.
  • NMR solid 31 P NMR
  • 89-91 ppm is the ratio of the total area of each peak.
  • a conventional method may be used. For example, measurement may be performed using a nuclear magnetic resonance apparatus under the following conditions.
  • Li 4-x Ge 1-x P x S 4 system thio-LISICON Region II type crystal structure As the thiolysicone region II type crystal structure, Li 4-x Ge 1-x P x S 4 system thio-LISICON Region II type crystal structure (Kanno et al., Journal of The Electrochemical Society, 148 (7 ) A742-746 (2001)), a crystal structure similar to the Li 4-x Ge 1-x P x S 4 system thio-LISICON Region II type (Solid State Ionics, 177 (2006), 2721-2725) and the like are typical examples.
  • the crystalline sulfide solid electrolyte of the present embodiment preferably does not contain crystalline Li 3 PS 4 ( ⁇ -Li 3 PS 4 ) . It is preferred not to have diffraction peaks at 17.5° and 26.1°. This is because the ionic conductivity decreases when crystalline Li 3 PS 4 ( ⁇ -Li 3 PS 4 ) is included.
  • the constituent atoms may include the above lithium atom, phosphorus atom, sulfur atom, and at least one halogen atom selected from bromine and iodine atoms.
  • the halogen atom preferably contains both a bromine atom and an iodine atom.
  • the halogen atom does not contain a chlorine atom. Since the crystalline sulfide solid electrolyte of the present embodiment has an aldirodite-type crystal structure having at least one atom of a bromine atom and an iodine atom as a halogen atom, as described above, high ionic conductivity can be obtained. is.
  • the ratio of lithium atoms, phosphorus atoms, sulfur atoms, and halogen atoms of at least one of bromine atoms and iodine atoms contained in the crystalline sulfide solid electrolyte of the present embodiment is
  • the compounding ratio (molar ratio) is preferably 1.0 to 1.8:0.1 to 0.8:1.0 to 2.0:0.01 to 0.8, and 1.1 to 1.7: 0.2-0.6: 1.2-1.9: more preferably 0.05-0.7, 1.2-1.6: 0.25-0.5: 1.3-1.8 : 0.08 to 0.6 is more preferable.
  • the compounding ratio (molar ratio) of lithium atom:phosphorus atom:sulfur atom:bromine atom:iodine atom is 1.0 to 1.8:0.1.
  • ⁇ 0.8: 1.0 ⁇ 2.0: 0.01 ⁇ 0.4: 0.01 ⁇ 0.4 is preferred, 1.1 ⁇ 1.7: 0.2 ⁇ 0.6: 1.2 ⁇ 1.9: 0.02 ⁇ 0.35: 0.02 ⁇ 0.35 is more preferable, 1.2 ⁇ 1.6: 0.25 ⁇ 0.5: 1.3 ⁇ 1.8: 0.
  • 03-0.3: 0.03-0.3 is more preferable, 1.3-1.55: 0.3-0.5: 1.4-1.8: 0.05-0.2: 0 0.05 to 0.2 is even more preferred.
  • a crystalline sulfide solid electrolyte having a thiolysicone region II type crystal structure and higher ionic conductivity can be obtained. easier to obtain.
  • the aldirodite-type crystal structure basically has a structural framework of Li 7 PS 6 , and is a crystal structure in which part of P is substituted with Si.
  • the composition formula of the aldirodite type crystal structure is, for example, Li 7-x P 1-y Si y S 6 , Li 7+x P 1-y Si y S 6 (x is ⁇ 0.6 to 0.6, y is 0.6). 1 to 0.6).
  • a composition formula of the aldirodite-type crystal structure includes Li 7-x-2y PS 6-x-y Cl x (0.8 ⁇ x ⁇ 1.7, 0 ⁇ y ⁇ 0.25x+0.5).
  • the composition formula of the aldirodite-type crystal structure also includes Li 7-x PS 6-x Ha x (Ha is Cl or Br, and x is preferably 0.2 to 1.8).
  • the half-value width ⁇ 2 ⁇ 25.0 is larger than the half-value width ⁇ 2 ⁇ 23.5 , high ionic conductivity is likely to be obtained due to the effect of the aldirodite-type crystal structure in the crystalline sulfide solid electrolyte of the present embodiment.
  • the ratio of ⁇ 2 ⁇ 25.0 to ⁇ 2 ⁇ 23.5 ( ⁇ 2 ⁇ 25.0 / ⁇ 2 ⁇ 23.5 ) is preferably 1.1 or more, more preferably 1.4 or more, and still more preferably 1.7 or more. , more preferably 1.85 or more, and the upper limit is preferably 2.5 or less, more preferably 2.4 or less, still more preferably 2.2 or less, and even more preferably 2.05 or less.
  • the half width is a numerical value obtained as follows.
  • a maximum peak of interest (diffraction peak) ⁇ 2° range is used.
  • H G ⁇ B ⁇ A/(1+(D ⁇ C) 2 /E 2 )+(1 ⁇ A) ⁇ exp( ⁇ 1 ⁇ (D ⁇ C) 2 /E 2 ) ⁇ +F ⁇ H is summed up within the range of the above calculated peak C ⁇ 2°, and the total value is minimized by GRG non-linearity with the solver function of the spreadsheet software Excel (Microsoft) to obtain the half-value width.
  • the peak intensity of the diffraction peak is within the above range, it becomes easier to obtain high ionic conductivity due to the effect of the aldirodite type crystal structure.
  • the proportion of the aldirodite-type crystal structure in the total crystals of the crystalline sulfide solid electrolyte of the present embodiment is preferably 5.0% or less, and the lower limit is preferably 0.01% or more.
  • the ratio of the aldirodite crystal structure is within the above range, high ionic conductivity can be easily obtained due to the effect of the aldirodite crystal structure.
  • the shape of the crystalline sulfide solid electrolyte of the present embodiment is not particularly limited, but may be, for example, particulate.
  • the average particle diameter (D 50 ) of the particulate sulfide solid electrolyte can be, for example, within the range of 0.01 ⁇ m to 500 ⁇ m and 0.1 to 200 ⁇ m.
  • the average particle size (D 50 ) is the particle size that reaches 50% of the whole when the particle size distribution integrated curve is drawn, and the particle size is accumulated sequentially from the smallest particle size, and the volume distribution is , for example, the average particle size that can be measured using a laser diffraction/scattering particle size distribution analyzer.
  • the method for producing a crystalline sulfide solid electrolyte of the present embodiment includes: A first mixing of a raw material containing material containing a lithium atom, a phosphorus atom, a sulfur atom, and at least one halogen atom of a bromine atom and an iodine atom, and a complexing agent 1 of (1) below, Then, a second mixing of mixing with a complexing agent 2 of (2) below, and an instant drying step of contacting with a medium and drying, That's what it means.
  • the raw material inclusion used in the present embodiment contains a lithium atom, a phosphorus atom, a sulfur atom, and at least one halogen atom of a bromine atom and an iodine atom, and preferably at least one or more atoms selected from these atoms. It contains two or more solid electrolyte raw materials (compounds) containing
  • Solid electrolyte raw materials (compounds) contained in raw material inclusions include, for example, lithium sulfide; lithium halides such as lithium fluoride, lithium chloride, lithium bromide and lithium iodide; diphosphorus trisulfide (P 2 S 3 ) , phosphorus pentasulfide ( P2S5 ); various phosphorus fluorides ( PF3 , PF5 ), various phosphorus chlorides ( PCl3 , PCl5 , P2Cl4 ), various phosphorus bromides (PBr 3 , PBr 5 ), phosphorus halides such as various phosphorus iodides (PI 3 , P 2 I 4 ); thiophosphoryl fluoride (PSF 3 ), thiophosphoryl chloride (PSCl 3 ), thiophosphoryl bromide (PSBr 3 ) , thiophosphoryl iodide (PSI 3 ), thiophosphoryl fluoride dichloride (PS
  • Materials that can be used as raw materials other than the above include, for example, raw materials containing at least one atom selected from the above four or five types of atoms and containing atoms other than the four or five types of atoms, more specifically , lithium oxide, lithium hydroxide, lithium compounds such as lithium carbonate; alkali metal sulfides such as sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide; silicon sulfide, germanium sulfide, boron sulfide, gallium sulfide, tin sulfide (SnS, SnS 2 ), metal sulfides such as aluminum sulfide and zinc sulfide; phosphoric acid compounds such as sodium phosphate and lithium phosphate; sodium iodide, sodium fluoride, sodium chloride, sodium bromide and other sodium halides other than lithium Halides of alkali metals; metal halides such as aluminum
  • lithium sulfide phosphorus sulfides such as diphosphorus trisulfide ( P2S3 ) and phosphorus pentasulfide ( P2S5 ); fluorine ( F2 ), chlorine ( Cl2 ) , bromine ( Br2 ) , and iodine (I 2 ); and lithium halides such as lithium fluoride, lithium chloride, lithium bromide and lithium iodide.
  • phosphoric acid compounds such as lithium oxide, lithium hydroxide and lithium phosphate are preferred.
  • Examples of the combination of raw materials include a combination of lithium sulfide, diphosphorus pentasulfide and a lithium halide, and a combination of lithium sulfide, diphosphorus pentasulfide and a halogen element.
  • Lithium is preferred, and bromine and iodine are preferred as elemental halogens.
  • a halogen simple substance may be used as a raw material, the halogen simple substance and lithium sulfide may be reacted to obtain lithium halide, and then lithium sulfide and diphosphorus pentasulfide may be reacted.
  • Li 3 PS 4 containing a PS 4 structure can also be used as part of the raw material. Specifically, Li 3 PS 4 is first manufactured and prepared, and this is used as a raw material. The content of Li 3 PS 4 is preferably 60-100 mol %, more preferably 65-90 mol %, still more preferably 70-80 mol %, relative to the total amount of raw materials.
  • the content of the halogen element relative to Li 3 PS 4 is preferably 1 to 50 mol %, more preferably 10 to 40 mol %, still more preferably 20 to 30 mol %. ⁇ 28 mol% is even more preferred.
  • the lithium sulfide used in this embodiment is preferably particles.
  • the average particle diameter (D 50 ) of the lithium sulfide particles is preferably 0.1 ⁇ m or more and 1000 ⁇ m or less, more preferably 0.5 ⁇ m or more and 100 ⁇ m or less, and even more preferably 1 ⁇ m or more and 20 ⁇ m or less.
  • D 50 The average particle diameter of the lithium sulfide particles.
  • those having an average particle size approximately equal to that of the lithium sulfide particles are preferable, that is, those having an average particle size within the same range as the lithium sulfide particles. preferable.
  • the ratio of lithium sulfide to the total of lithium sulfide and diphosphorus pentasulfide is adjusted from the viewpoint of obtaining higher chemical stability and higher ionic conductivity. , preferably 70 to 80 mol %, more preferably 72 to 78 mol %, and even more preferably 74 to 78 mol %.
  • the content of lithium sulfide and diphosphorus pentasulfide with respect to the total of these is preferably 60 to 95 mol%, and 65 to 90 mol % is more preferred, and 70 to 85 mol % is even more preferred.
  • the ratio of lithium bromide to the total of lithium bromide and lithium iodide is 1 to 99 mol from the viewpoint of improving ion conductivity. %, more preferably 20 to 90 mol %, still more preferably 40 to 80 mol %, even more preferably 45 to 70 mol %.
  • the total number of moles of lithium sulfide and phosphorus pentasulfide excluding the same number of moles of lithium sulfide as the number of moles of the halogen simple substance is preferably in the range of 60 to 90%, more preferably in the range of 65 to 85%.
  • the content of elemental halogen with respect to the total amount of lithium sulfide, phosphorus pentasulfide, and elemental halogen is 1 to 50 mol%. is preferred, 2 to 40 mol% is more preferred, 3 to 25 mol% is still more preferred, and 3 to 15 mol% is even more preferred.
  • the content of elemental halogen ( ⁇ mol%) and the content of lithium halide ( ⁇ mol%) relative to the total amount are as follows: It preferably satisfies the formula (2), more preferably satisfies the following formula (3), further preferably satisfies the following formula (4), and even more preferably satisfies the following formula (5). 2 ⁇ 2 ⁇ + ⁇ 100 (2) 4 ⁇ 2 ⁇ + ⁇ 80 (3) 6 ⁇ 2 ⁇ + ⁇ 50 (4) 6 ⁇ 2 ⁇ + ⁇ 30 (5)
  • the ratio of B1:B2 is preferably 1 to 99:99 to 1, where B1 is the number of moles of bromine and B2 is the number of moles of iodine, 15:85 to 90:10 is more preferred, 20:80 to 80:20 is even more preferred, 30:70 to 75:25 is even more preferred, and 35:65 to 75:25 is particularly preferred.
  • the complexing agent 1 used in the production method of the present embodiment is a complexing agent that satisfies the above (1), that is, Li 2 S and P 2 S 5 that are preferably used as solid electrolyte raw materials, and other solid electrolyte raw materials containing halogen atoms. is a complexing agent capable of forming a complex containing Li 3 PS 4 obtained from and a halogen atom.
  • the complexing agent 1 can be used without any particular limitation as long as it has the above performance, and includes atoms that have particularly high affinity with lithium atoms, such as nitrogen atoms, oxygen atoms, and heteroatoms such as chlorine atoms. Compounds are preferred, and compounds having groups containing these heteroatoms are more preferred. This is because these heteroatoms and the group containing the heteroatom can coordinate (bond) with the lithium atom.
  • the heteroatom present in the molecule of the complexing agent 1 has a high affinity with lithium atoms, and is the main skeleton of the thiolysicone region II type crystal structure, which is the basic structure of the crystalline sulfide solid electrolyte produced according to the present embodiment.
  • Li 3 PS 4 having a PS 4 structure and solid electrolyte raw materials containing lithium atoms such as lithium halides and halogen atoms are considered to have the ability to easily form complexes.
  • the solid electrolyte raw material and the complexing agent 1 are mixed to form a complex containing Li 3 PS 4 and a halogen atom.
  • an electrolyte precursor in which the halogen atoms are more uniformly dispersed and fixed can be obtained, resulting in an increase in ionic conductivity. It is considered that a high solid electrolyte can be obtained.
  • the ability of the complexing agent 1 to form a complex containing Li 3 PS 4 and a halogen atom can be directly confirmed by, for example, an infrared absorption spectrum measured by FT-IR analysis (diffuse reflection method).
  • FT-IR analysis infrared absorption spectrum measured by FT-IR analysis
  • the powder obtained by stirring the complexing agent 1 tetramethylethylenediamine, hereinafter simply referred to as "TMEDA” and lithium iodide (LiI)
  • FT-IR analysis diffuse reflectance method
  • the powder obtained by stirring the complexing agent 1 and lithium iodide showed the spectrum of TMEDA itself and, in particular, C- It can be confirmed that the peaks derived from N stretching vibration are different.
  • LiI-TMEDA complex is formed by stirring and mixing TMEDA and lithium iodide (for example, Aust. J. Chem., 1988, 41, 1925-34, especially Fig. 34). 2 etc.), it is considered that a LiI-TMEDA complex is formed.
  • the property (1) satisfied by the complexing agent 1, that is, the property capable of forming a complex containing Li 3 PS 4 and a halogen atom can be specifically confirmed by, for example, FT-IR analysis (diffuse reflection method). It is a property that can be
  • the complexing agent 1 preferably has at least two coordinable (bondable) heteroatoms in the molecule, and more preferably has a group containing at least two heteroatoms in the molecule.
  • a solid electrolyte raw material containing a lithium atom and a halogen atom such as Li3PS4 and lithium halide is bound via at least two heteroatoms in the molecule.
  • a nitrogen atom is preferable, and an amino group is preferable as a group containing a nitrogen atom. That is, an amine compound is preferable as a complexing agent.
  • the amine compound is not particularly limited as long as it has an amino group in the molecule, since it can promote the formation of a complex, but compounds having at least two amino groups in the molecule are preferred.
  • Li 3 PS 4 and a solid electrolyte raw material containing lithium atoms such as lithium halide and halogen atoms can be bound via at least two nitrogen atoms in the molecule.
  • amine compounds examples include amine compounds such as aliphatic amines, alicyclic amines, heterocyclic amines, and aromatic amines, which can be used singly or in combination.
  • aliphatic primary diamines such as ethylenediamine, diaminopropane, and diaminobutane; N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N'-dimethyldiaminopropane.
  • diaminobutane such as diaminobutane, N,N,N
  • the number of carbon atoms in the aliphatic amine is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and the upper limit is preferably 10 or less, more preferably 8 or less, and still more preferably 7 or less.
  • the number of carbon atoms in the aliphatic hydrocarbon group in the aliphatic amine is preferably 2 or more, and the upper limit is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.
  • Alicyclic amines include primary alicyclic diamines such as cyclopropanediamine and cyclohexanediamine; secondary alicyclic diamines such as bisaminomethylcyclohexane; N,N,N',N'-tetramethyl-cyclohexanediamine, Alicyclic tertiary diamines such as bis(ethylmethylamino)cyclohexane; , heterocyclic secondary diamines such as dipiperidylpropane; heterocyclic tertiary diamines such as N,N-dimethylpiperazine and bismethylpiperidylpropane; and the like.
  • the number of carbon atoms in the alicyclic amine or heterocyclic amine is preferably 3 or more, more preferably 4 or more, and the upper limit is preferably 16 or less, more preferably 14 or less.
  • aromatic amines include aromatic primary diamines such as phenyldiamine, tolylenediamine and naphthalenediamine; N-methylphenylenediamine, N,N'-dimethylphenylenediamine, N,N'-bismethylphenylphenylenediamine, Aromatic secondary diamines such as N,N'-dimethylnaphthalenediamine and N-naphthylethylenediamine; N,N-dimethylphenylenediamine, N,N,N',N'-tetramethylphenylenediamine, N,N,N' , N'-tetramethyldiaminodiphenylmethane, N,N,N',N'-tetramethylnaphthalenediamine, and other aromatic tertiary diamines;
  • the number of carbon atoms in the aromatic amine is preferably 6 or more, more preferably 7 or more, still more preferably 8 or more, and the upper limit is preferably 16
  • the amine compound used in this embodiment may be substituted with a substituent such as an alkyl group, an alkenyl group, an alkoxyl group, a hydroxyl group, a cyano group, or a halogen atom.
  • a substituent such as an alkyl group, an alkenyl group, an alkoxyl group, a hydroxyl group, a cyano group, or a halogen atom.
  • diamine was exemplified as a specific example, amine compounds that can be used in the present embodiment are not limited to diamines.
  • various diamines such as trimethylamine, triethylamine, ethyldimethylamine, and the above aliphatic diamines
  • piperidine compounds such as piperidine, methylpiperidine and tetramethylpiperidine
  • pyridine compounds such as pyridine and picoline
  • morpholine compounds such as morpholine, methylmorpholine and thiomorpholine
  • imidazole compounds such as imidazole and methylimidazole
  • monoamines such as alicyclic monoamines such as monoamines corresponding to the above alicyclic diamines, heterocyclic monoamines corresponding to the above heterocyclic diamines, and aromatic monoamines corresponding to the above aromatic diamines, diethylenetriamine, N , N′,N′′-trimethyldiethylenetriamine, N,N,N′,N′′,N′′-pentamethyldiethylenetriamine, triethylenetetramine, N,N′-bis[(dimethylamin
  • a tertiary amine having a tertiary amino group as an amino group more preferably a tertiary diamine having two tertiary amino groups.
  • Preferred are tertiary diamines having two tertiary amino groups at both ends, and more preferred are aliphatic tertiary diamines having tertiary amino groups at both ends.
  • the aliphatic tertiary diamines having tertiary amino groups at both ends are preferably tetramethylethylenediamine, tetraethylethylenediamine, tetramethyldiaminopropane, and tetraethyldiaminopropane. Tetramethylethylenediamine and tetramethyldiaminopropane are preferred.
  • a compound having a group other than an amino group such as a nitro group, an amide group, etc., which contains a nitrogen atom as a heteroatom, also has the same effect as the amine compound.
  • the amount of the complexing agent 1 added is preferably such that the molar ratio of the amount of the complexing agent 1 added to the total molar amount of Li atoms contained in the raw material for the solid electrolyte is 0.5. It is 1 or more and 2.0 or less, more preferably 0.5 or more and 1.5 or less, still more preferably 0.8 or more and 1.2 or less, and most preferably 1.0.
  • the complexing agent 2 used in the production method of the present embodiment is a complexing agent that satisfies the above (2), that is, Li 3 PS 4 obtained from Li 2 S and P 2 S 5 or the like preferably used as a solid electrolyte raw material. It is a complexing agent other than the complexing agent 1 capable of forming a complex containing In particular, it is preferable that the rate of forming Li 3 PS 4 is faster than that of the complexing agent 1 .
  • Complexing agent 1 has an excellent balance of ability to form Li 3 PS 4 and ability to form a complex containing Li 3 PS 4 and a halogen atom . Therefore, the formation reaction of Li 3 PS 4 proceeds, and when the concentration of Li 2 S or the like present in the system decreases, the rate of the formation reaction of Li 3 PS 4 slows down and gradually stagnate.
  • the complexing agent 1 by further mixing the complexing agent 2, which has a higher ability to form Li 3 PS 4 than the complexing agent 1, Li 2 S and the like existing in the reaction field Even if the concentration is low, it becomes possible to accelerate the Li 3 PS 4 formation reaction again.
  • the presence of the complexing agent 1, which is superior to the complexing agent 2 in the ability to form a complex containing Li PS 4 and a halogen atom, allows the properties of both the complexing agent 1 and the complexing agent 2 to be enhanced. Since it can be effectively utilized, the Li 3 PS 4 formation reaction proceeds, and a complex containing the formed Li 3 PS 4 and halogen atoms is formed without stagnation.
  • the complexing agent 2 is a complex containing Li 3 PS 4 of dimethoxyethane (DME), which will be described later.
  • DME dimethoxyethane
  • THF tetrahydrofuran
  • the complexing agent 2 can be used without any particular limitation as long as it has the above performance, and includes atoms that have particularly high affinity with lithium atoms, such as nitrogen atoms, oxygen atoms, and heteroatoms such as chlorine atoms. Compounds are preferred, and compounds having groups containing these heteroatoms are more preferred. This is because these heteroatoms and the group containing the heteroatom can coordinate (bond) with the lithium atom.
  • the heteroatom present in the molecule of the complexing agent 2 has a high affinity with lithium atoms, and is the main skeleton of the thiolysicone region II type crystal structure, which is the basic structure of the crystalline sulfide solid electrolyte produced according to the present embodiment.
  • an oxygen atom is preferable, and the group containing an oxygen atom preferably has one or more functional groups selected from ether groups and ester groups, and among these, it is particularly preferable to have an ether group. That is, as the complexing agent 2, an ether compound is particularly preferable.
  • the complexing agent 2 preferably does not contain a nitrogen atom as a heteroatom. Therefore, in the present embodiment, the complexing agent 1 that contains a nitrogen atom as a heteroatom is employed, and the complexing agent 2 that does not contain a nitrogen atom but contains an oxygen atom as a heteroatom is employed. is preferred. As a result, the functions of the complexing agent 1 and the complexing agent 2 can be effectively utilized, and the ionic conductivity of the obtained crystalline sulfide solid electrolyte can be improved.
  • ether compounds include ether compounds such as aliphatic ethers, alicyclic ethers, heterocyclic ethers, and aromatic ethers, which can be used singly or in combination.
  • aliphatic ethers include monoethers such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether and tert-butyl methyl ether; diethers such as dimethoxymethane, dimethoxyethane, diethoxymethane and diethoxyethane; Polyethers having three or more ether groups such as diethylene glycol dimethyl ether (diglyme) and triethylene oxide glycol dimethyl ether (triglyme); and ethers containing hydroxyl groups such as diethylene glycol and triethylene glycol.
  • monoethers such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether and tert-butyl methyl ether
  • diethers such as dimethoxymethane, dimethoxyethane, diethoxymethane and diethoxyethane
  • Polyethers having three or more ether groups such as diethylene glycol dimethyl
  • the number of carbon atoms in the aliphatic ether is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and the upper limit is preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less.
  • the number of carbon atoms in the aliphatic hydrocarbon group in the aliphatic ether is preferably 1 or more, and the upper limit is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
  • Alicyclic ethers include ethylene oxide, propylene oxide, tetrahydrofuran, tetrahydropyran, dimethoxytetrahydrofuran, cyclopentyl methyl ether, dioxane, dioxolane, etc.
  • Heterocyclic ethers include furan, benzofuran, benzopyran, dioxene, dioxin. , morpholine, methoxyindole, hydroxymethyldimethoxypyridine and the like.
  • the number of carbon atoms in the alicyclic ether and heterocyclic ether is preferably 3 or more, more preferably 4 or more, and the upper limit is preferably 16 or less, more preferably 14 or less.
  • Aromatic ethers include methylphenyl ether (anisole), ethylphenyl ether, dibenzyl ether, diphenyl ether, benzylphenyl ether, naphthyl ether and the like.
  • the number of carbon atoms in the aromatic ether is preferably 7 or more, more preferably 8 or more, and the upper limit is preferably 16 or less, more preferably 14 or less, and still more preferably 12 or less.
  • the ether compound used in this embodiment may be substituted with a substituent such as an alkyl group, an alkenyl group, an alkoxyl group, a hydroxyl group, a cyano group, or a halogen atom.
  • the ether compound used in the present embodiment is preferably an aliphatic ether, more preferably dimethoxyethane or tetrahydrofuran.
  • ester compounds include ester compounds such as aliphatic esters, alicyclic esters, heterocyclic esters, and aromatic esters, which can be used singly or in combination.
  • aliphatic esters include formic acid esters such as methyl formate, ethyl formate, and triethyl formate; acetate esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate; , ethyl propionate, propyl propionate, butyl propionate and other propionate esters; dimethyl oxalate, diethyl oxalate and other oxalic acid esters; dimethyl malonate, diethyl malonate and other malonic acid esters; dimethyl succinate, succinic acid Succinic acid esters such as diethyl can be mentioned.
  • formic acid esters such as methyl formate, ethyl formate, and triethyl formate
  • acetate esters such as methyl acetate, ethyl acetate, propyl
  • the number of carbon atoms in the aliphatic ester is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and the upper limit is preferably 10 or less, more preferably 8 or less, and still more preferably 7 or less.
  • the number of carbon atoms in the aliphatic hydrocarbon group in the aliphatic ester is preferably 1 or more, more preferably 2 or more, and the upper limit is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. .
  • Examples of alicyclic esters include methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, dimethyl cyclohexanedicarboxylate, dibutyl cyclohexanedicarboxylate, and dibutyl cyclohexenedicarboxylate.
  • Examples of heterocyclic esters include methyl pyridinecarboxylate, pyridine Examples include ethyl carboxylate, propyl pyridinecarboxylate, methyl pyrimidine carboxylate, ethyl pyrimidine carboxylate, and lactones such as acetolactone, propiolactone, butyrolactone and valerolactone.
  • the number of carbon atoms in the alicyclic ester or heterocyclic ester is preferably 3 or more, more preferably 4 or more, and the upper limit is preferably 16 or less, more preferably 14 or less.
  • aromatic esters examples include benzoic acid esters such as methyl benzoate, ethyl benzoate, propyl benzoate, and butyl benzoate; trimellitate such as melitate, triethyl trimellitate, tripropyl trimellitate, tributyl trimellitate and trioctyl trimellitate;
  • the number of carbon atoms in the aromatic ester is preferably 8 or more, more preferably 9 or more, and the upper limit is preferably 16 or less, more preferably 14 or less, and still more preferably 12 or less.
  • the ester compound used in this embodiment may be substituted with a substituent such as an alkyl group, an alkenyl group, an alkoxyl group, a hydroxyl group, a cyano group, or a halogen atom.
  • a substituent such as an alkyl group, an alkenyl group, an alkoxyl group, a hydroxyl group, a cyano group, or a halogen atom.
  • the ester compound used in the present embodiment is preferably an aliphatic ester, more preferably an acetate ester, and particularly preferably ethyl acetate.
  • the method for measuring the appropriate timing for adding the complexing agent 2 is not particularly limited. A higher effect can be exhibited by adding the complexing agent 2 at the timing when it is lowered.
  • the residual amount of lithium sulfide is preferably 35 mol% or less, more preferably 30 mol% or less, still more preferably 25 mol% or less, relative to the input amount, and then the complexing agent 2 is added. , the complex formation reaction can be further accelerated.
  • the amount of lithium sulfide remaining in the system can be measured by the method described in Examples.
  • the amount of the complexing agent 2 added is preferably 0, with respect to the total number of moles of Li 3 PS 4 generated from the raw material content. .1 or more and 5.0 or less, more preferably 0.2 or more and 4.0 or less, and still more preferably 0.5 or more and 3.5 or less.
  • the number of moles of the amount of the complexing agent 2 used with respect to the total mole amount of Li atoms contained in the solid raw material is preferably 0.01 or more and 5.0 or less, and more preferably. is 0.05 or more and 3.0 or less, more preferably 0.1 or more and 2.0 or less.
  • a solvent can be added when mixing the solid electrolyte raw material and the complexing agent.
  • a solid complex is formed in a liquid complexing agent, separation of the components may occur if the complex is readily soluble in the complexing agent. Therefore, by using a solvent in which the complex does not dissolve, elution of the components in the electrolyte precursor can be suppressed.
  • a solvent in which the complex does not dissolve elution of the components in the electrolyte precursor can be suppressed.
  • complex formation is promoted, each main component can be more uniformly present, and an electrolyte precursor in which halogen atoms are more dispersed and fixed can be obtained. As a result, the effect of obtaining high ionic conductivity is likely to be exhibited.
  • the method for producing a crystalline sulfide solid electrolyte of the present embodiment is a so-called heterogeneous method, and the complex is preferably precipitated without being completely dissolved in the liquid complexing agent.
  • the solubility of the complex can be adjusted by adding solvent.
  • Halogen atoms in particular tend to be eluted from the complex, and the desired complex can be obtained by adding a solvent to suppress the elution of the halogen atoms.
  • a crystalline sulfide solid electrolyte having high ionic conductivity can be obtained through an electrolyte precursor in which components such as halogen atoms are dispersed.
  • a solvent having a solubility parameter of 10 or less is preferable.
  • the solubility parameter is described in various documents such as "Kagaku Binran” (published in 2004, revised 5th edition, Maruzen Co., Ltd.), etc., and the value ⁇ calculated by the following formula (1): ((cal/cm 3 ) 1/2 ), also called Hildebrand parameter, SP value.
  • halogen atoms By using a solvent with a solubility parameter of 10 or less, halogen atoms, raw materials containing halogen atoms such as lithium halides, and halogen atoms constituting co-crystals contained in the complex are relatively reduced compared to the above complexing agents. (for example, an aggregate in which a lithium halide and a complexing agent are combined) can be made into a state in which it is difficult to dissolve, and the halogen atoms can be easily fixed in the complex.
  • the solvent used in the present embodiment has the property of not dissolving the complex.
  • the solubility parameter of the solvent is preferably 9.5 or less, more preferably 9.0 or less, and even more preferably 8.5 or less.
  • solvents that have been widely used in the production of solid electrolytes
  • aliphatic hydrocarbon solvents for example, aliphatic hydrocarbon solvents, alicyclic hydrocarbon Solvents, hydrocarbon solvents such as aromatic hydrocarbon solvents; alcohol solvents, ester solvents, aldehyde solvents, ketone solvents, ether solvents with 4 or more carbon atoms on one side, solvents containing carbon atoms and heteroatoms, etc. and the like, and from among these, preferably those having the solubility parameter in the above range may be appropriately selected and used.
  • aliphatics such as hexane (7.3), pentane (7.0), 2-ethylhexane, heptane (7.4), octane (7.5), decane, undecane, dodecane, tridecane, etc.
  • Hydrocarbon solvent Alicyclic hydrocarbon solvent such as cyclohexane (8.2) and methylcyclohexane; benzene, toluene (8.8), xylene (8.8), mesitylene, ethylbenzene (8.8), tert-butyl Aromatic hydrocarbon solvents such as benzene, trifluoromethylbenzene, nitrobenzene, chlorobenzene (9.5), chlorotoluene (8.8), bromobenzene; alcohols such as ethanol (12.7) and butanol (11.4) system solvent; aldehyde solvents such as formaldehyde, acetaldehyde (10.3) and dimethylformamide (12.1), acetone (9.9), ketone solvents such as methyl ethyl ketone; dibutyl ether, cyclopentyl methyl ether (8.4) , tert-butyl methyl ether, and anisole; and solvents containing carbon
  • aliphatic hydrocarbon solvents aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, and ether solvents are preferable.
  • Ethylbenzene, diethyl ether, diisopropyl ether, dibutyl ether, dimethoxyethane, cyclopentyl methyl ether, tert-butyl methyl ether, and anisole are more preferred, diethyl ether, diisopropyl ether, and dibutyl ether are still more preferred, and diisopropyl ether and dibutyl ether are even more preferred.
  • especially cyclohexane is preferred.
  • the solvent used in the present embodiment is preferably the organic solvent exemplified above, and is an organic solvent different from the above complexing agent. In this embodiment, these solvents may be used alone or in combination.
  • the first mixing of mixing the raw material content and the complexing agent 1, and then the second mixing of mixing with the complexing agent 2 are included.
  • the form in which the raw material containing substance and the complexing agent are mixed may be either solid or liquid. is in a liquid state, it is usually mixed in the form of a liquid complexing agent in which a solid raw material is present.
  • a solvent may be further mixed as necessary.
  • the complexing agent includes the solvent added as necessary, unless otherwise specified.
  • the method of mixing the raw material inclusion and the complexing agent 1 and the complexing agent 2 and the solid electrolyte raw material and the complexing agent contained in the raw material inclusion are mixed.
  • a solid electrolyte raw material and a complexing agent may be put into a mixing device and mixed. For example, if the complexing agent is supplied into the tank and the stirring blades are operated, then the solid electrolyte raw material is gradually added. preferred because it improves
  • the solid electrolyte raw material may not be solid. Specifically, fluorine and chlorine are gaseous, and bromine is liquid at normal temperature and normal pressure.
  • the solid electrolyte raw material is liquid, it may be supplied into the tank together with the agent separately from other solid solid electrolyte raw materials, and if the solid electrolyte raw material is gaseous, the complexing agent It can be supplied by blowing into the mixture of the solid raw material and the raw material.
  • the production method of the present embodiment is characterized by mixing the raw material content and the complexing agent. It can also be produced by a method that does not use equipment used for the purpose of pulverizing the electrolyte raw material. That is, the solid electrolyte raw material and the complexing agent contained in the raw material-containing material are mixed simply by performing the first mixing and the second mixing of the raw material-containing material and the complexing agent, and Li 3 PS 4 is obtained. Furthermore, complexes such as a complex containing a halogen atom and a complex containing Li 3 PS 4 can be formed.
  • the mixture of the raw material content and the complexing agent may be pulverized with a pulverizer, but from the viewpoint of improving productivity, It is preferred not to use a grinder in at least the first mixing, i.e. it is preferred that no grinding mixing takes place in the first mixing.
  • any general mixer can be used without any particular limitation.
  • mechanical stirring mixers include high-speed stirring mixers, double-arm mixers, etc., from the viewpoint of improving the uniformity of the raw material in the mixture of the raw material content and the complexing agent and obtaining higher ionic conductivity. Therefore, a high-speed stirring mixer is preferably used.
  • the high-speed stirring mixer includes a vertical shaft rotary mixer, a horizontal shaft rotary mixer, and the like, and either type of mixer may be used.
  • the shape of the stirring impeller used in the mechanical stirring mixer includes anchor type, blade type, arm type, ribbon type, multistage blade type, double arm type, shovel type, twin blade type, flat blade type, and C type.
  • a shovel type, a flat blade type, a C-type blade type, and the like are preferable from the viewpoint of improving the uniformity of the raw material in the raw material and obtaining a higher ion conductivity.
  • the installation location of the circulation line is not particularly limited, but it is preferable to install it in a location where the water is discharged from the bottom of the mixer and returned to the top of the mixer. By doing so, it becomes easier to evenly agitate the raw material, which tends to settle, by putting it on convection caused by circulation. Furthermore, it is preferable that the return port is positioned below the surface of the liquid to be stirred. By doing so, it is possible to suppress the object to be stirred from splashing and adhering to the wall surface inside the mixer.
  • the temperature conditions for mixing the raw material content and the complexing agent are not particularly limited. ⁇ 5°C).
  • the mixing time varies depending on the type of stirrer used, etc., so it cannot be generalized, but it is usually about 0.1 to 150 hours, from the viewpoint of more uniform mixing and higher ionic conductivity. It is preferably 1 to 120 hours, more preferably 4 to 100 hours, still more preferably 8 to 80 hours.
  • the complex obtained by mixing the raw material content and the complexing agent includes those composed of the complexing agent, a lithium atom, a phosphorus atom, a sulfur atom, and a halogen atom. .
  • the complex obtained in the present embodiment is not completely dissolved in the liquid complexing agent, and is usually solid.
  • a suspension in which the complex is suspended in a solvent that is added as necessary results. Therefore, it can be said that the manufacturing method of the present embodiment corresponds to a heterogeneous system in the so-called liquid phase method.
  • Co-crystals are composed of complexing agents, lithium atoms, phosphorus atoms, sulfur atoms and halogen atoms, typically lithium atoms and other atoms through and/or through the complexing agent. It is presumed that they form a complex structure in which they are directly bonded without Here, it can be confirmed by, for example, gas chromatography analysis that the complexing agent constitutes a cocrystal. Specifically, the complexing agent contained in the co-crystal can be quantified by dissolving the powder of the complex in methanol and subjecting the resulting methanol solution to gas chromatography analysis. Although the content of the complexing agent in the complex varies depending on the molecular weight of the complexing agent, it is generally about 10% by mass or more and 70% by mass or less, preferably 15% by mass or more and 65% by mass or less.
  • a co-crystal containing halogen atoms is preferable from the viewpoint of improving the ion conductivity.
  • the complexing agent 1 solid electrolyte raw materials containing Li3PS4 and lithium atoms such as lithium halides and halogen atoms are bonded (coordinated) via the complexing agent 1, and the halogen atoms are more dispersed. It becomes easy to obtain a co-crystal that has been fixed as a result, and the ionic conductivity is improved.
  • halogen atoms in the complex form a co-crystal can be confirmed by confirming that the complex contains a predetermined amount of halogen atoms even when the fluid obtained through the second mixing is subjected to solid-liquid separation. .
  • the halogen atoms that do not form the co-crystal are more easily eluted than the halogen atoms that form the co-crystal and are discharged into the liquid during solid-liquid separation.
  • composition analysis by ICP analysis (inductively coupled plasma emission spectroscopy) of the complex or solid electrolyte shows that the ratio of halogen atoms in the complex or solid electrolyte is significantly lower than the ratio of halogen atoms supplied from the raw material.
  • the amount of halogen atoms remaining in the complex is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more, relative to the charged composition.
  • the upper limit of the amount of halogen atoms remaining in the complex is 100% by mass.
  • the residual amount of Li 2 S at the end of the first mixing is preferably 1.0% or more, more preferably 3.0% or more, and still more preferably 5.0% or more.
  • the upper limit is preferably 35.0% or less, more preferably 30.0% or less, and still more preferably 25.0% or less.
  • the term "remaining amount of Li 2 S" refers to the amount of unreacted Li 2 S in the reaction field when Li 2 S is used as a raw material, which is obtained by the method described in the Examples. It is a numerical value that serves as an index for understanding the progress of the reaction.
  • the Li 2 S remaining amount at the time when the second mixing is completed is preferably as small as possible. It is 0% or less, more preferably 5.0% or less, and particularly preferably 2.5% or less. According to the production method of the present embodiment, by sequentially using two different complexing agents 1 and 2, the remaining amount of Li 2 S can be suppressed to an extremely small amount as described above. It becomes possible to obtain a crystalline sulfide solid electrolyte having ionic conductivity.
  • the method for producing a crystalline sulfide solid electrolyte of the present embodiment has an instant drying step of contacting with a medium and drying after the second mixing. In this step, from the fluid containing Li 3 PS 4 , a complex such as a complex containing a halogen atom and a complex containing Li 3 PS 4 , and a complexing agent obtained through the second mixing, the complexing agent is is removed to obtain an electrolyte precursor powder and a sulfide solid electrolyte powder.
  • the complexing agent can be instantaneously removed from the fluid by bringing the fluid into contact with the medium and drying it, the complex and Li 3 PS 4 containing Li 3 PS 4 as well as the halogen atom can be removed from the fluid instantaneously. It is possible to suppress the elution of components that are likely to be eluted by the complexing agent from the complexes, etc., contained therein, and as a result, a crystalline sulfide solid electrolyte having high ionic conductivity can be obtained.
  • the "instantaneous drying process” means a process that can be dried instantaneously, and it cannot be said unconditionally because it can change depending on the method adopted, but the “instantaneous” is the above-mentioned second.
  • the time required for the fluid obtained through the first mixing and the second mixing (usually slurry) to become powder such as an electrolyte precursor is 1 minute or less. It is preferably 45 seconds or less, more preferably 30 seconds or less, still more preferably 15 seconds or less.
  • Instant drying which is drying by contact with a medium
  • the fluid is dried by contact with the medium, i.e., the complexing agent can be removed from the fluid.
  • Preferable methods include fluidized drying using media particles, drying using a spray dryer, airflow drying, and the like.
  • the spray dryer uses gas as a medium as described later, it is a method of drying by contacting the medium. Flash drying is similar.
  • Fluidized drying using a medium increases the heat transfer area of the fluid (slurry) obtained through the second mixing, which is the object to be dried, and conducts heat quickly and uniformly. is promoted, it becomes possible to dry instantaneously. Therefore, it is possible to suppress the elution of components that are easily eluted by the complexing agent, such as halogen atoms, as much as possible, and it is possible to suppress quality deterioration such as a decrease in ionic conductivity.
  • the fluid since the fluid is made to flow using a medium, it is possible to dry uniformly without being affected by the viscosity of the fluid, so it is possible to handle fluids with a wide range of viscosities.
  • fluidized drying In fluidized drying using media particles as a medium, when fluidized drying is performed while media particles are fluidized in a dryer, the medium is already heated in the dryer and has a heat quantity.
  • the fluid to be dried has an increased heat transfer area by flowing with the fluidized catalytic cracking catalyst of the media particles, and in addition, it is heated by the heat of the medium, so the complexing agent is removed. It is possible to shorten the drying time.
  • the conventional drying By performing such drying, while suppressing the decrease in ionic conductivity due to the elution of components that are easily eluted into the complexing agent such as halogen atoms, which is the merit of the above-mentioned instant drying, the conventional drying, For example, it is possible to suppress aggregation caused by a dry state with low uniformity due to batch-type drying such as vacuum drying, and to suppress quality deterioration. Furthermore, since fluidized drying using a medium can employ a flow system, excellent productivity can also be obtained.
  • a dryer capable of performing fluidized drying using a medium (also referred to as a "medium fluidized dryer"), it is particularly possible to dry while the fluid to be dried is fluidized by media particles as a medium. It is also possible to use a dryer commercially available as a fluidized bed dryer, which can be used without limitation and has a format in which media particles are contained as a medium in the dryer and the media particles are dried while flowing. .
  • the drying apparatus shown in FIG. 1 includes a medium fluidized dryer that can perform fluidized drying by fluidizing the medium using media particles as a medium, and solids (powder) and halogen atoms contained in the fluid discharged by the dryer. and a complex containing Li 3 PS 4 from which the complexing agent has been removed.
  • the medium-fluidized dryer shown in FIG. 1 is of a type that uses media particles as a medium. It is a device that removes the complexing agent from the fluid and dries it. When the fluid is supplied into the fluidized bed of the media particles, the fluid flows and the heat transfer area increases, enabling drying in a shorter time. Inside the dryer there is a partition, preferably with a plurality of vents, for supplying the gas. By having the partition plate, the media particles as the medium do not stay at the bottom, and the gas supplied into the dryer through the air vent causes convection in the dryer to form a fluidized bed.
  • a discharge port is provided for discharging the gas supplied from below and the fluid containing the powder contained in the fluid obtained by the second mixing, that is, the powder such as the electrolyte precursor. and the fluid discharged from the outlet is supplied to the bag filter.
  • the bag filter is equipped with multiple stages of filters, and the filter collects the powder in the fluid and recovers it as an electrolyte precursor, etc., and the gas in the fluid is discharged from the upper outlet of the bag filter. exhausted.
  • media particles are used as the medium, and as shown in Fig. 1, it is effective to use a form in which the media particles are maintained in a fluidized state by gas.
  • gas it is preferable to use an inert gas such as nitrogen or argon from the viewpoint of suppressing deterioration of the electrolyte precursor or the like due to oxidation, and nitrogen is more preferable in consideration of cost.
  • the particle size of the media particles varies depending on the size of the fluidized bed dryer, etc., and cannot be categorically defined. , it is preferably 1.0 mm or more and 3.0 mm or less. In addition, when the particle size of the media particles is within the above range, it is possible to suppress exhaust to the outside of the dryer along with the fluid containing the gas used for the fluidized drying and the electrolyte precursor and the like contained in the dried fluid. It is possible to reduce the collection amount in the bag filter.
  • gas is used to move the medium
  • the gas is preferably heated.
  • a heated gas is used because the gas also serves as a heat source for drying the fluid.
  • the media particles are also heated.
  • Heating is performed by the media particles, making it possible to dry in an extremely short time.
  • the drying temperature in the main drying can be a temperature according to the type of solvent other than the complexing agent contained in the fluid and the solvent other than the complexing agent used as necessary.
  • the reaction can be carried out at a temperature equal to or higher than the boiling point of the complexing agent and, if necessary, the solvent other than the complexing agent.
  • the drying temperature varies depending on the boiling point of the complexing agent to be used, etc., and cannot be unconditionally specified. is 60-100°C, more preferably 65-80°C.
  • the gas supply temperature is usually about 60 to 200° C., preferably 70 to 180° C., from the viewpoint of drying in a shorter time. It is more preferably 80 to 160° C., still more preferably 90 to 150° C., and the supply rate of the gas is usually about 0.5 to 10.0 m/s based on the supply temperature. From the viewpoint of maintaining good fluidity, it is preferably 1.0 to 8.0 m/s, more preferably 1.5 to 5.0 m/s, and even more preferably 2.0 to 3.5 m/s.
  • the amount of gas supplied is the area of the cross-section of the fluidized bed of media particles, which is the medium, in the direction perpendicular to the direction of gas flow It can be said that it is the area of the cross section perpendicular to ).
  • the temperature of the fluid at the outlet of the fluidized bed dryer is usually about 50 to 120 ° C. From the point of view, it is preferably 55 to 100°C, more preferably 60 to 90°C, still more preferably 65 to 80°C. Within the above range, the drying temperature in the fluidized bed dryer is likely to fall within the above preferred drying temperature range.
  • the temperature of the fluid can be adjusted by adjusting the supply amount and temperature of the gas, the supply amount of the fluid to be dried, and the like, and can be easily adjusted by adjusting the supply amount of the fluid.
  • a bag filter is preferably used as shown in FIG. 1 from the viewpoint of efficiently collecting the powder obtained by drying, that is, the electrolyte precursor and the like.
  • the filter used for the bag filter can be used without any particular limitation, including polypropylene, nylon, acrylic, polyester, cotton, wool, heat-resistant nylon, polyamide/polyimide, PPS (polyphenylene sulfide), glass fiber, PTFE (poly tetrafluoroethylene), etc., and a functional filter such as an electrostatic filter can also be used.
  • a filter composed of heat-resistant nylon, polyamide/polyimide, PPS (polyphenylene sulfide), glass fiber, and PTFE (polytetrafluoroethylene) is preferable, and composed of heat-resistant nylon, PPS (polyphenylene sulfide), and PTFE (polytetrafluoroethylene).
  • a filter composed of PTFE (polytetrafluoroethylene) is particularly preferable.
  • the bag filter may have a blowing-off means, for example, a pulsating back pressure system or a pulse jet system is preferable, and a pulse jet system is particularly preferable.
  • a blowing-off means for example, a pulsating back pressure system or a pulse jet system is preferable, and a pulse jet system is particularly preferable.
  • An induced draft fan may be installed in the line from the exhaust port of the bag filter to forcibly exhaust the gas discharged from the exhaust port.
  • spray dryer As a spray dryer that can be used in the instant drying step, the fluid obtained through the second mixing is sprayed from a spray nozzle together with a heated gas (unheated gas may be used), and if necessary, separately A form of drying by contacting with a heated gas (non-heated gas may be used) may be mentioned.
  • a device having a preferred configuration as a spray dryer is shown in FIG.
  • the spray dryer shown in FIG. 2 sprays slurry using gas from a spray nozzle and dries it by contacting it with heated gas supplied from another line.
  • the spray dryer may have a plurality of input lines, and the type of the input line is not particularly limited, and may be of a type capable of injecting a plurality of fluids from one nozzle.
  • a preferred example includes a nozzle called a 4-fluid nozzle, which includes two nozzles for ejecting slurry and two nozzles for ejecting gas.
  • the conditions of use when using a spray dryer may be appropriately determined according to the type of complexing agent contained in the fluid to be dried, that is, the boiling point of the complexing agent and solvent used as necessary Although it cannot be defined unconditionally because it changes depending on the 80 to 190°C, more preferably 90 to 175°C, still more preferably 100 to 160°C.
  • the gas supply rate may be usually about 0.001 to 1.0 m / s, preferably 0.005 to 0.0 m / s, based on the supply temperature and the cross section of the spray dryer. .5 m/s, more preferably 0.01 to 0.1 m/s, still more preferably 0.015 to 0.05 m/s.
  • the amount of gas supplied can vary greatly depending on the supply temperature and the cross section of the spray dryer. should be determined according to the feed temperature and the diameter of the spray dryer.
  • the amount of gas supplied to the nozzle is not particularly limited as long as the fluid can be sprayed from the nozzle, but it is usually about 5 to 100 NL / min. From the viewpoint of drying in a shorter time, it is preferably 10 to 80 NL/min, more preferably 20 to 70 NL/min, still more preferably 30 to 60 NL/min, and even more preferably 35 to 45 NL/min.
  • the amount of the fluid obtained through the second mixing to be supplied to the nozzle cannot be set indiscriminately because it varies depending on the scale of the spray dryer, and may be determined as appropriate according to the scale. It may be about 1 to 50 g/min, preferably 3 to 40 g/min, more preferably 5 to 30 g/min, and still more preferably 10 to 20 g/min from the viewpoint of drying in a shorter time.
  • the gas supplied as a heating medium or the like and the fluid containing powder such as an electrolyte precursor contained in the fluid to be dried are supplied to the bag filter in the same manner as in the fluidized drying, and the electrolyte precursor is dried. It is sufficient to collect the powder of the body or the like.
  • the bag filter the bag filter described as being usable in the fluidized drying may be employed.
  • Airflow drying Flash drying can also be employed in the flash drying process.
  • Airflow drying may be performed by using a device commercially available as a airflow drying device.
  • a heated gas is supplied to a drying tube (a cylindrical tank may be used), and the above-mentioned fluid to be dried is supplied to the drying tube.
  • Apparatus in the form of supply may be mentioned.
  • a flash drying apparatus having a cylindrical tank does not have a fluidized bed (no fluidization by media particles) in the fluidized drying described above, so a fluidized drying apparatus such as that shown in FIG. 1 should be used.
  • a fluidized drying apparatus such as that shown in FIG. 1 should be used.
  • the drying temperature and the conditions of the airflow (gas) supplied for drying may be appropriately determined according to the type of complexing agent contained in the fluid to be dried. , that is, it depends on the boiling point of the complexing agent and the solvent used as necessary, so it cannot be defined unconditionally, but it is determined from the conditions of the drying temperature, gas supply temperature, and supply amount in the fluidized drying do it.
  • the gas supplied as a heat medium or the like and the fluid containing powder such as an electrolyte precursor contained in the fluid to be dried are supplied to the bag filter in the same manner as in the fluidized drying, A powder such as an electrolyte precursor may be recovered.
  • the bag filter the bag filter described as being usable in the fluidized drying may be employed.
  • filtration using a glass filter or the like solid-liquid separation by decantation, or drying by solid-liquid separation using a centrifugal separator or the like may be performed.
  • energy consumption can be reduced by removing part of the complexing agent by solid-liquid separation or the like in advance and then performing drying by the above-described instant drying.
  • solid-liquid separation specifically, the fluid (slurry) obtained through the second mixing is transferred to a container, and after the solid precipitates, a complexing agent that becomes the supernatant and, if necessary, are added Decantation to remove the solvent and filtration using a glass filter with a pore size of about 10 to 200 ⁇ m, preferably 20 to 150 ⁇ m, are easy.
  • the method for producing a crystalline sulfide solid electrolyte of the present embodiment may further include heating.
  • the powder obtained by the instant drying step contains the crystalline sulfide solid electrolyte as described above, but may also contain an electrolyte precursor, an amorphous sulfide solid electrolyte, and the like. Therefore, by including heating, the electrolyte precursor, the amorphous sulfide solid electrolyte, etc., contained in addition to the crystallized sulfide-based solid electrolyte are crystallized, and the purity of the crystalline sulfide solid electrolyte is increased. can be improved.
  • the crystalline sulfide solid electrolyte contains Li 3 PS 4 , a complex containing a halogen atom, and Li 3 PS 4 obtained through the second mixing in the flash drying step. It is obtained by removing a complex such as a complex and a fluid containing a complexing agent to obtain an electrolyte precursor or the like, which is then crystallized by heating if necessary. It is preferable that the amount of the complexing agent in the crystalline sulfide solid electrolyte is as small as possible, but the complexing agent may be contained to an extent that does not impair the performance of the crystalline sulfide solid electrolyte.
  • the content of the complexing agent in the crystalline sulfide solid electrolyte is usually 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. is.
  • an amorphous solid electrolyte has been prepared by mechanical pulverization such as mechanical milling, or other melting and quenching treatments. It was necessary to obtain the amorphous solid electrolyte by heating it later.
  • a crystalline solid electrolyte having a thiolysicone region II type crystal structure can be obtained even by a method that does not involve mechanical pulverization or other melt quenching treatment, which is different from the conventional mechanical milling treatment. It can be said that it is superior to the manufacturing method by
  • the fluid obtained by the instant drying step includes solids (powder) such as electrolyte precursors, amorphous sulfide solid electrolytes, and crystalline sulfide solid electrolytes. can be included.
  • the heating temperature in heating is preferably within the following temperature range regardless of the solid (powder) contained in the fluid.
  • the heating temperature is the temperature at which the crystalline sulfide solid electrolyte to be obtained crystallizes (for example, the electrolyte precursor contained in the fluid is heated at a rate of 10 ° C./min using a differential thermal analysis device (DTA device).
  • DTA device differential thermal analysis device
  • DTA differential thermal analysis
  • the heating temperature for obtaining the crystalline sulfide solid electrolyte depends on the structure of the crystalline solid electrolyte to be obtained, and as described above, depends on the crystallization temperature. Although it cannot be defined unconditionally, for example, when obtaining the crystalline solid electrolyte of the present embodiment, the crystalline sulfide solid electrolyte of the present embodiment has a thiolysicone region II type crystal structure as a basic structure. Therefore, it can be set in consideration of the crystallization temperature of the thiolysicone region II type crystal structure.
  • the heating temperature in this case is usually preferably 130° C. or higher, more preferably 135° C. or higher, and still more preferably 140° C. or higher. , and more preferably 250° C. or less.
  • a crystalline sulfide solid electrolyte may be obtained by heating the obtained amorphous sulfide solid electrolyte. .
  • a crystalline sulfide solid electrolyte of better quality can be obtained.
  • the heating temperature for obtaining the amorphous solid electrolyte is preferably 5° C. or lower, more preferably 10° C. or lower, and still more preferably 10° C. or lower, starting from the temperature at which the crystalline sulfide solid electrolyte to be obtained crystallizes. The temperature may be in the range of 20° C.
  • the lower limit is not particularly limited, but it may be about ⁇ 40° C. or more at the peak top of the exothermic peak observed on the lowest temperature side.
  • the heating temperature for obtaining the amorphous solid electrolyte varies depending on the structure of the crystalline solid electrolyte to be obtained, and cannot be categorically defined. is generally preferably 135° C. or lower, more preferably 130° C. or lower, and still more preferably 125° C. or lower, and the lower limit is not particularly limited, but is preferably 50° C. or higher, more preferably 70° C. or higher, and still more preferably 80° C. °C or higher, more preferably 100°C or higher, and particularly preferably 110°C or higher.
  • the heating time is not particularly limited as long as the desired crystalline sulfide solid electrolyte or amorphous sulfide solid electrolyte can be obtained. For example, it is preferably 1 minute or longer, more preferably 10 minutes or longer. It is preferably 30 minutes or more, more preferably 1 hour or more.
  • the upper limit of the heating time is not particularly limited, but is preferably 24 hours or less, more preferably 10 hours or less, still more preferably 5 hours or less, and even more preferably 3 hours or less.
  • the heating is preferably performed in an inert gas atmosphere (eg, nitrogen atmosphere, argon atmosphere) or a reduced pressure atmosphere (especially in a vacuum). This is because deterioration (for example, oxidation) of the crystalline solid electrolyte can be prevented.
  • the heating method is not particularly limited, and examples thereof include a method using a hot plate, a vacuum heating device, an argon gas atmosphere furnace, and a firing furnace.
  • a horizontal dryer having a heating means and a feeding mechanism, a horizontal vibrating fluidized dryer, or the like may be used, and the drying may be selected according to the amount to be heated.
  • the amorphous sulfide solid electrolyte obtained as an intermediate contains lithium atoms, phosphorus atoms, sulfur atoms and halogen atoms .
  • Solids composed of lithium sulfide, phosphorus sulfide and lithium halide such as SP 2 S 5 -LiI, Li 2 SP 2 S 5 -LiBr, Li 2 SP 2 S 5 -LiI-LiBr Electrolytes: Solid electrolytes further containing other atoms such as oxygen atoms, silicon atoms, etc., such as Li 2 SP 2 S 5 —Li 2 O—LiI, Li 2 S—SiS 2 —P 2 S 5 —LiI. is preferably mentioned.
  • lithium sulfide such as Li 2 SP 2 S 5 -LiI, Li 2 SP 2 S 5 -LiBr, Li 2 SP 2 S 5 -LiI-LiBr and the like
  • Solid electrolytes composed of phosphorus sulfide and lithium halide are preferred.
  • the type of atoms forming the amorphous solid electrolyte can be confirmed by, for example, an ICP emission spectrometer.
  • Crystal sulfide solid electrolyte examples include the crystalline sulfide solid electrolyte having the thiolysicone region II type crystal structure of the present embodiment as a basic structure. That is, the crystalline sulfide solid electrolyte of the present embodiment can be suitably obtained by the production method of the present embodiment. Further, the crystalline solid electrolyte obtained by the production method of the present embodiment may be a so-called glass-ceramics obtained by heating an amorphous solid electrolyte to a crystallization temperature or higher.
  • 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 solid electrolyte is, for example, within the range of 0.01 ⁇ m to 500 ⁇ m, further 0.1 to 200 ⁇ m.
  • Powder X-ray diffraction (XRD) measurements were carried out as follows.
  • the powder of the solid electrolyte in each example was ground into a groove with a diameter of 25 mm and a depth of 1 mm to form a sample. This sample was measured under the following conditions without exposure to air using an airtight sample holder.
  • Measuring device D2 PHASER, manufactured by Bruker Co., Ltd.
  • Tube voltage 30 kV
  • Tube current 10mA
  • X-ray wavelength Cu-K ⁇ ray (1.5418 ⁇ )
  • Optical system Concentration method Slit configuration: Solar slit 4°, divergence slit 1 mm, K ⁇ filter (Ni plate) used
  • Peak intensity and half width were calculated by the following methods.
  • a maximum peak ⁇ 0.5° range is used.
  • a (0 ⁇ A ⁇ 1) is the ratio of the Lorentz function
  • B is the peak intensity corrected for the background
  • C is the 2 ⁇ maximum peak
  • D is the peak position in the range used for calculation (C ⁇ 0.5 °)
  • E the value width parameter
  • F the background
  • G the value width parameter
  • H G ⁇ B ⁇ A/(1+(D ⁇ C) 2 /E 2 )+(1 ⁇ A) ⁇ exp( ⁇ 1 ⁇ (D ⁇ C) 2 /E 2 ) ⁇ +F ⁇ H was summed within the above calculated peak C ⁇ 0.5° range, and the total value was minimized by GRG non-linearity using the solver function of the spreadsheet software Excel (Microsoft) to obtain the peak intensity.
  • the half width was calculated as a Gaussian function.
  • the ionic conductivity was measured as follows. Circular pellets 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 were molded from the crystalline solid electrolytes obtained in Examples and Comparative Examples to prepare samples. . Electrode terminals were taken from the top and bottom of the sample, and measurement was performed at 25° C. by the AC impedance method (frequency range: 5 MHz to 0.5 Hz, amplitude: 10 mV) to obtain a Cole-Cole plot.
  • This slurry was allowed to stand to settle the solid content, and after removing 2000 mL of the supernatant, 2000 mL of cyclohexane was added. This decantation was performed three times to obtain a cyclohexane slurry containing lithium sulfide, lithium iodide and lithium bromide.
  • Li 2 S Lithium sulfide
  • P 2 S 5 diphosphorus pentasulfide
  • a total of 10 g was weighed and cooled with an acetone-liquid nitrogen mixture. After cooling for 30 minutes, 100 mL of tetrahydrofuran (THF) was added while stirring with a stirrer while inert gas was flowing, and the mixture was further stirred for 3 days.
  • THF tetrahydrofuran
  • the resulting slurry was filtered, the resulting solid was washed with THF five times, and the solvent was vacuum-dried to obtain a Li 3 PS 4 -3THF complex.
  • the complex was vacuum-dried at 90° C. for 5 hours to obtain amorphous g-Li 3 PS 4 .
  • 5 g of the g-Li 3 PS 4 was weighed in a Schlenk bottle containing a stirrer in a glove box under an inert gas atmosphere, and N,N,N,N-tetramethylethane- 20 mL of 1,2-diamine (tetramethylethylenediamine, TMEDA) was added and stirred. After reacting for 3 days, the solvent was vacuum-dried (at room temperature) to obtain a Li 3 PS 4 -TMEDA complex.
  • LiI was prepared in the same manner as in Production Example 2 above, except that 5 g of LiI was weighed instead of g-Li 3 PS 4 and the solvent was vacuum-dried (room temperature) and then dried at 100°C. -TMEDA complexes were made.
  • Example 1 To the slurry containing lithium sulfide, lithium iodide and lithium bromide obtained in Production Example 1, 661.4 g of diphosphorus pentasulfide (P 2 S 5 ) and 24 L of cyclohexane were added, and a circulation line equipped with rotary blades was added. Transferred to a 35 L reactor. To this, 3.1 L of tetramethylethylenediamine (complexing agent 1) was added, and mixing (first mixing) by circulation stirring was started at room temperature at a rotor speed of 80 rpm and a pump flow rate of 3 L/min.
  • complexing agent 1 tetramethylethylenediamine
  • Ceramic particles having a particle size of 2 mm were used as the media particles of the medium, and the filling rate of the ceramic particles was set to 30% by volume with respect to the volume of the fluidized medium dryer. Nitrogen was used as the gas for fluidizing the media particles serving as the medium. After the operation of the fluidized medium dryer entered a steady state, drying was continued for 48 hours, and the powder (electrolyte precursor) collected by the bag filter was recovered. The recovered powder was heated under vacuum at a heating temperature of 110° C. for 2 hours to obtain an amorphous sulfide solid electrolyte. Further, the amorphous sulfide solid electrolyte was heated under vacuum at 180° C. for 2 hours to obtain a crystalline sulfide solid electrolyte.
  • Example 1 In Example 1, after performing the first mixing, the fluid (slurry) bead mill obtained by the first mixing ("LME4 (model number)", Ashizawa Finetech Co., Ltd., 0.5 mm diameter zirconia beads (filled with 8.7 kg), and pulverization and mixing by a bead mill was performed for 4 hours under the conditions of a pump flow rate of 2 L/min and a bead mill peripheral speed of 12 m/sec to obtain a fluid (slurry). Next, powder was obtained in the same manner as in Example 1 using a medium fluidized bed dryer having the configuration shown in FIG. 1 and a fluidized bed dryer equipped with a bag filter. The obtained powder was subjected to XRD measurement. The results are shown in FIG. FIG.
  • the crystalline sulfide solid electrolyte of this embodiment has high ionic conductivity. Therefore, it is suitable for use in batteries, particularly in batteries used in information-related devices such as personal computers, video cameras, and mobile phones, and communication devices.

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