Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0562—Solid materials
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • 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
• • 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
  • 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
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/12—Surface area
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/14—Pore volume
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2220/00—Batteries for particular applications
  • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2220/00—Batteries for particular applications
  • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0065—Solid electrolytes
  • H01M2300/0068—Solid electrolytes inorganic
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a method for producing a sulfide-based solid electrolyte.
• Patent Documents 1 and 2 describe that a solid electrolyte is produced by reacting raw materials in N-methyl-2-pyrrolidone or hydrocarbon.
• Non-Patent Document 1 describes that a solid electrolyte is produced by reacting lithium sulfide and diphosphorus pentasulfide in tetrahydrofuran.
• the solid electrolyte obtained by the method for producing a solid electrolyte disclosed in Patent Document 1, specifically, the method for producing a solid electrolyte in which a raw material is reacted in N-methyl-2-pyrrolidone may have low ionic conductivity.
• the solid electrolyte production method of Patent Document 2 specifically, the solid electrolyte production method in which a raw material is reacted in a hydrocarbon, when there is no mixing and grinding apparatus such as a mill, the raw material, Li 2 S, or the like remains. was there.
• the solid electrolyte obtained by the said nonpatent literature 1 had low ionic conductivity.
• the present invention has been made in view of the above problems, and a method for producing a solid electrolyte in which Li 2 S as a raw material does not remain and ionic conductivity is sufficient without using an apparatus such as a mill. The purpose is to provide.
• the following method for producing a solid electrolyte can be provided.
• An alkali metal sulfide, one or more sulfur compounds selected from phosphorus sulfide, germanium sulfide, silicon sulfide and boron sulfide, and a halogen compound are contacted in a solvent having a solubility parameter of 9.0 or more.
• the manufacturing method of a solid electrolyte including a process. 2.
• the method for producing a solid electrolyte according to 1 or 2 wherein the solvent is a cyclic ether. 4).
• the alkali metal sulfide is lithium sulfide (Li 2 S)
• the sulfur compound is diphosphorus pentasulfide (P 2 S 5 )
• the mixing ratio of Li 2 S and P 2 S 5 Li 2 S: P
• a solid electrolyte can be produced without using a special device such as a mill.
• the method for producing a solid electrolyte of the present invention includes a step of bringing the following raw materials (A) to (C) into contact in a solvent having a solubility parameter of 9.0 or more.
• Alkali metal sulfide examples include Li 2 S (lithium sulfide) and Na 2 S (sodium sulfide). Of these, lithium sulfide is preferable. Lithium sulfide can be used without particular limitation, but high purity is preferred. Lithium sulfide can be produced, for example, by the methods described in JP-A-7-330312, JP-A-9-283156, JP-A 2010-163356, JP-A 2011-084438, and JP-A 2011-136899.
• lithium hydroxide and hydrogen sulfide are reacted at 70 ° C. to 300 ° C. in a hydrocarbon-based organic solvent to produce lithium hydrosulfide, and then the reaction solution is dehydrosulfurized to form lithium sulfide.
• Can be synthesized Japanese Patent Laid-Open No. 2010-163356.
• lithium hydroxide and hydrogen sulfide are reacted at 10 ° C. to 100 ° C. in an aqueous solvent to produce lithium hydrosulfide, and then this reaction solution is dehydrosulfurized to synthesize lithium sulfide (special feature). Open 2011-084438).
• Lithium sulfide preferably has a total lithium oxide lithium salt content of 0.15% by mass or less, more preferably 0.1% by mass or less, and a content of lithium N-methylaminobutyrate.
• the content is preferably 0.15% by mass or less, more preferably 0.1% by mass or less.
• the total content of the lithium salt of sulfur oxide is 0.15% by mass or less, the solid electrolyte obtained by the melt quenching method or the mechanical milling method becomes a glassy electrolyte (fully amorphous).
• the total content of the lithium salt of sulfur oxide exceeds 0.15% by mass, the obtained electrolyte may become a crystallized product from the beginning.
• lithium N-methylaminobutyrate when the content of lithium N-methylaminobutyrate is 0.15% by mass or less, the deteriorated product of lithium N-methylaminobutyrate does not deteriorate the cycle performance of the lithium ion battery.
• lithium sulfide with reduced impurities when lithium sulfide with reduced impurities is used, a high ion conductive electrolyte can be obtained.
• lithium sulfide When lithium sulfide is produced based on the above-mentioned JP-A-7-330312 and JP-A-9-283156, it is preferable to purify lithium sulfide because it contains a lithium salt of sulfur oxide.
• lithium sulfide produced by the method for producing lithium sulfide described in JP-A-2010-163356 may be used without purification because it contains a very small amount of lithium oxide lithium salt and the like.
• a purification method for example, a purification method described in International Publication No. WO2005 / 40039 and the like can be mentioned. Specifically, the lithium sulfide obtained as described above is washed at a temperature of 100 ° C. or higher using an organic solvent.
• lithium sulfide described in JP2011-136899A it is preferable to use lithium sulfide described in JP2011-136899A.
• lithium sulfide having a large specific surface area can be prepared.
• the present invention allows the reaction to proceed easily without the above modification by reacting in a specific solvent. Therefore, from the viewpoint of reducing the production process, the above modification is performed. It is preferable not to do so. This is particularly useful when there is a greater merit in manufacturing cost when the manufacturing process is reduced than when the reaction rate is further increased.
• the particle size of the alkali metal sulfide particles used as a raw material is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, and even more preferably 50 ⁇ m or less. .
• the particle size of the alkali metal sulfide particles used as a raw material may be more than 100 ⁇ m. This is useful when the reduction in the step of reducing the particle size of the alkali metal sulfide particles has a large merit in production cost.
• the particle size of the alkali metal sulfide particles is measured by a LASER diffraction method using a Mastersizer 2000 of MALVERN, and calculated from the volume-based average particle size. The measurement is desirably performed directly in the slurry state without passing through the dry state. This is because once drying is performed, particles are aggregated at the time of drying, and the apparent particle size may be increased.
• the alkali metal sulfide particles preferably have a pore volume of 0.01 ml / g or more.
• the pore volume is 0.01 ml / g or more, it becomes easy to react with raw materials other than the alkali metal sulfide particles, and the alkali metal sulfide particles are easily pulverized and more easily reacted.
• (B) Sulfur compound As the raw material (B), phosphorus sulfide such as P 2 S 3 (phosphorus trisulfide) and P 2 S 5 (phosphorus pentasulfide), SiS 2 (silicon sulfide), Al 2 S 3 ( Aluminum sulfide), GeS 2 (germanium sulfide), B 2 S 3 (diarsenic trisulfide), or the like can be used. Phosphorus sulfide is preferable, and P 2 S 5 is particularly preferable. In addition, you may use a raw material (B) in mixture of 2 or more types. P 2 S 5 can be used without particular limitation as long as it is industrially manufactured and sold.
• P 2 S 5 can be used without particular limitation as long as it is industrially manufactured and sold.
• (C) Halogen compound As the halogen compound, LiF, LiCl, LiBr, LiI, BCl 3 , BBr 3 , BI 3 , AlF 3 , AlBr 3 , AlI 3 , AlCl 3 , SiF 4 , SiCl 4 , SiCl 3 , Si 2 Cl 6, SiBr 4, SiBrCl 3 , SiBr 2 Cl 2, SiI 4, PF 3, PF 5, PCl 3, PCl 5, PBr 3, PI 3, P 2 Cl 4, P 2 I 4, SF 2, SF 4 , SF 6 , S 2 F 10 , SCl 2 , S 2 Cl 2 , S 2 Br 2 , GeF 4 , GeCl 4 , GeBr 4 , GeI 4 , GeF 2 , GeCl 2 , GeBr 2 , GeI 2 , AsF 3 , AsCl 3, AsBr 3, AsI 3, AsF 5, SeF 4, SeF 6, SeCl 2, SeCl 4, Se Br 2, SeBr 4,
• a lithium or phosphorus compound is preferred.
• a bromine compound is preferable.
• LiCl, LiBr, LiI is PCl 5, PCl 3, PBr 5 and PBr 3, more preferably LiCl, LiBr, LiI and PBr 3, particularly preferably LiBr, and PBr 3.
• vitrification accelerator for reducing the glass transition temperature
• examples of vitrification promoters include Li 3 PO 4 , Li 4 SiO 4 , Li 4 GeO 4 , Li 3 BO 3 , Li 3 AlO 3 , Li 3 CaO 3 , Li 3 InO 3, Na 3 PO 4 , Na
• examples include inorganic compounds such as 4 SiO 4 , Na 4 GeO 4 , Na 3 BO 3 , Na 3 AlO 3 , Na 3 CaO 3 , and Na 3 InO 3 .
• simple phosphorus (P), simple sulfur (S), silicon (Si), LiBO 2 (lithium metaborate), LiAlO 3 (lithium aluminate), NaBO 2 (Sodium metaborate), NaAlO 3 (sodium aluminate), POCl 3 , POBr 3 and the like can also be used.
• component (A) is lithium sulfide and component (B) diphosphorus pentasulfide.
• the ratio [(A) + (B) :( C)] of the molar amount of the raw material (C) to the total molar amount of the raw materials (A) and (B) is preferably 50:50 to 99: 1 (molar ratio). More preferably 80:20 to 98: 2 (molar ratio), still more preferably 85:15 to 98: 2 (molar ratio), and particularly preferably 90:10 to 98: 2. .
• the blending amount of the raw material (D) is preferably 1 to 10 mol%, particularly 1 to 5 mol% with respect to the total of the raw materials (A), (B) and (C). It is preferable that The solid electrolyte glass obtained in the present invention may consist essentially of the above raw materials (A) to (C) and optionally the raw material (D), or may consist only of these components. Good. “Substantially” means that the composition mainly comprises the raw materials (A) to (C) and optionally the raw material (D). For example, the raw materials (A) to (D) are the raw materials. It means 95% by weight or more or 98% by weight or more based on the whole.
• a solvent having a solubility parameter of 9.0 or more the raw material is easily dissolved, and a solid electrolyte can be efficiently produced without using a mill or the like.
• the solubility parameter of the solvent is preferably 9-20, and particularly preferably 9-15.
• the solubility parameter (SP value) is a value referring to, for example, Chemical Handbook Application (Revised 3rd edition) Maruzen, Adhesion Handbook (4th edition) Nikkan Kogyo Shimbun, Polymer Data Handbook (Polymer Society). . Solvents having a solubility parameter of 9.0 or more include hydroxyl group, carboxy group, nitrile group, amino group, amide bond, nitro group, —C ( ⁇ S) —bond, ether (—O—) bond, —Si—O—.
• methanol (14.5) As a polar solvent containing one kind of polar group, methanol (14.5) (the values in parentheses indicate solubility parameters; the same applies hereinafter), ethanol (12.7), n-propanol, isopropanol (11 .5), n-butanol, isobutanol, n-pentanol, ethylene glycol (14.2), formic acid (13.5), acetic acid (12.6), acetonitrile (11.9), propionitrile, malononitrile , Succinonitrile, fumaronitrile, trimethylsilylcyanide, N-methylpyrrolidone, triethylamine, pyridine, dimethylformamide (12.0), dimethylacetamide, nitromethane, carbon disulfide, diethyl ether, diisopropyl ether, t-butyl methyl ether, phenyl Methyl ether, dimethoxy Tan, diethoxyethane
• polar solvents containing two types of polar groups include 2,2,2-trifluoroethanol, hexafluoroisopropanol, 2-aminoethanol, chloroacetic acid, trifluoroacetic acid, methoxypropionitrile, 3-ethoxypropionitrile, Examples include methyl cyanoacetate and difluoroacetonitrile.
• the solvent is preferably a solvent having an ether (—O—) bond, more preferably a cyclic ether, and more preferably THF.
• Examples of the solvent having an ether (—O—) bond include a solvent having one ether (—O—) bond, for example, a solvent represented by the following formula (E).
• R 1 —O—R 2 (E) R 1 and R 2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 1 and R 2 may combine to form a ring.
• R 1 and R 2 are preferably an alkylene group.
• the hydrocarbon group may be branched or unbranched.
• the hydrocarbon group preferably has 2 to 5 carbon atoms.
• R 1 and R 2 are preferably bonded to form a ring.
• the solvent whose solubility parameter is less than 9.0 may be mixed in the solvent at the time of manufacture.
• the solvent having a solubility parameter of less than 9.0 include hexane (7.3), heptane, octane, decane, cyclohexane, ethylcyclohexane, methylcyclohexane, toluene (8.8), xylene (8.8), and ethylbenzene.
• Ipsol 100 (manufactured by Idemitsu Kosan Co., Ltd.), Ipsol 150 (manufactured by Idemitsu Kosan Co., Ltd.), IP solvent (manufactured by Idemitsu Kosan Co., Ltd.), liquid paraffin, petroleum ether, cyclopentyl methyl ether and the like.
• the ratio of the solvent having a solubility parameter of 9.0 or more and the solvent having a solubility parameter of less than 9.0 is not particularly limited.
• the latter is 1 wt% or more and 40 wt% or less with respect to the total of the former and the latter.
• the solvent having the above solubility parameter of 9.0 or more and the solvent having the solubility parameter of less than 9.0 do not need to be dehydrated.
• the amount of moisture affects the amount of alkali metal hydroxide in the atomized product. Since there exists a possibility of giving, Preferably water content is 50 ppm or less, More preferably, it is 30 ppm or less.
• the boiling point of the solvent is preferably 65 to 200 ° C. If the boiling point is low, the vapor pressure at the reaction temperature is high and a pressure vessel may be necessary. If the boiling point is high, the load for evaporating the solvent from the produced solid electrolyte may increase.
• Solvents having a boiling point of 65 to 200 ° C. include ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, ethylene glycol, formic acid, acetic acid, acetonitrile, propionitrile, malononitrile, fumaronitrile.
• Trimethylsilylcyanide triethylamine, pyridine, dimethylformamide, dimethylacetamide, nitromethane, diisopropyl ether, phenylmethyl ether, diethoxyethane, THF, dioxane, dimethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyl ethyl ketone, ethyl acetate , Acetic anhydride, dimethyl sulfoxide, dichloroethane, dichlorobenzene, hexafluorobenzene, trifluoromethylbenzene, trifluoroethane Nord, aminoethanol, chloroacetic acid, trifluoroacetic acid, methoxy propionitrile, ethoxy propionitrile, methyl cyanoacetate, difluoroacetonitrile, glyme, dimethyl carbonate, methyl ethyl carbonate, cycl
• the temperature is preferably 20 to 200 ° C, particularly preferably 50 to 150 ° C.
• the time is preferably 1 to 40 hours, more preferably 1 to 20 hours, and particularly preferably 2 to 15 hours.
• the amount of the solvent may be such that the raw material becomes a solution or slurry by the addition of the solvent.
• the amount of the raw material (total amount) added to 1 liter of solvent is about 0.001 to 1 kg, preferably 0.005 to 0.5 kg, and particularly preferably 0.01 to 0.3 kg. .
• the contact method is not particularly limited, and known devices such as a reaction vessel with a stirrer and various mills can be used.
• a solid electrolyte can be produced efficiently without using a special mixing and grinding device such as a bead mill, but the above device may be used as necessary.
• This azeotropic gas was dehydrated by condensing with a condenser outside the system. During this time, the same amount of toluene as the distilled toluene was continuously supplied to keep the reaction liquid level constant. The amount of water in the condensate gradually decreased, and no distillation of water was observed 6 hours after the introduction of hydrogen sulfide (the total amount of water was 22 ml). During the reaction, the solid was dispersed and stirred in toluene, and there was no moisture separated from toluene. Thereafter, the hydrogen sulfide was switched to nitrogen and circulated at 300 ml / min for 1 hour. The solid content was filtered and dried to obtain white powder of lithium sulfide.
• the purity of lithium sulfide was 99.0%. Further, X-ray diffraction measurement confirmed that no peaks other than the crystal pattern of lithium sulfide were detected.
• the average particle size was 450 ⁇ m (slurry solution).
• the particle diameter of lithium sulfide was measured using Mastersizer 2000 of MALVERN by the LASER diffraction method, and calculated from the volume standard average particle diameter. It was 14.8 m ⁇ 2 > / g when the specific surface area of the obtained lithium sulfide was measured using AUTOSORB6 (made by Sysmex Corporation) with the BET method by nitrogen gas. The pore volume was measured with the same device as the specific surface area, and it was 0.15 ml / g when determined by interpolating to 0.99 from a measurement point of relative pressure (P / P 0 ) of 0.99 or more. .
• Production Example 2 [Atomization treatment] 26 g of lithium sulfide obtained in Production Example 1 was weighed into a Schlenk bottle in a glove box. Under a nitrogen atmosphere, 500 ml of dehydrated toluene (manufactured by Wako Pure Chemical Industries) and 250 ml of dehydrated ethanol (manufactured by Wako Pure Chemical Industries) were added in this order, and the mixture was stirred with a stirrer at room temperature for 24 hours. After the reforming treatment, the bath temperature was raised to 120 ° C., and hydrogen sulfide gas was circulated at 200 ml / min for 90 minutes to carry out the treatment.
• dehydrated toluene manufactured by Wako Pure Chemical Industries
• dehydrated ethanol manufactured by Wako Pure Chemical Industries
• the atomized lithium sulfide was evaluated in the same manner as in Production Example 1.
• the lithium sulfide had a purity of 97.2%, an amount of lithium hydroxide of 0.3%, an average particle size of 9.1 ⁇ m (undried slurry solution), a specific surface area of 43.2 m 2 / g, and a pore volume of 0.68 ml / g. It was. Purity and lithium hydroxide content were each determined by titration. The total analysis value does not reach 100% because it contains lithium carbonate, other ionic salts, and residual solvent.
• Example 1 The inside of the flask equipped with a stirrer was replaced with nitrogen, and 3.37 g of lithium sulfide of Production Example 2 (in consideration of purity, 3.27 g of this corresponds to lithium sulfide), diphosphorus pentasulfide (Aldrich) 5 .32 g, LiBr (Aldrich) 1.41 g was charged with 125 ml of tetrahydrofuran (THF: Wako Pure Chemical Industries, Ltd.) having a water content of 10 ppm, and contacted at 140 ° C. for 24 hours. The solubility parameter of THF is 9.1. The solid component was separated by filtration and vacuum dried at 120 ° C. for 40 minutes to produce a solid electrolyte.
• THF tetrahydrofuran
• the ion conductivity was measured by the following method. The solid electrolyte was filled in a tablet molding machine, and a compact was obtained by applying a pressure of 10 MPa.
• a mixture obtained by mixing carbon and a solid electrolyte at a weight ratio of 1: 1 as an electrode is placed on both sides of the molded body, and pressure is applied again with a tablet molding machine, thereby forming a molded body for conductivity measurement (diameter of about 10 mm). , About 1 mm thick).
• the molded body was subjected to ionic conductivity measurement by AC impedance measurement.
• the conductivity value was a value at 25 ° C.
• Example 2 The inside of the flask equipped with a stirrer was replaced with nitrogen, and 1.0 g of lithium sulfide of Production Example 2 (0.97 g corresponding to lithium sulfide in consideration of purity), diphosphorus pentasulfide (Aldrich) 1 .65 g, LiBr (Aldrich) 0.44 g was charged with 30 ml of tetrahydrofuran (THF: Wako Pure Chemical Industries, Ltd.) having a water content of 10 ppm, and reacted at room temperature for 20 hours. After completion of the reaction, THF was removed by drying under reduced pressure at room temperature, and further dried at 80 ° C. for 1 hour.
• THF tetrahydrofuran
• the ionic conductivity of the obtained solid electrolyte was 0.17 ⁇ 10 ⁇ 4 S / cm.
• the obtained solid electrolyte glass was further subjected to vacuum heat treatment at 140 ° C. for 2 hours to produce a solid electrolyte.
• the ionic conductivity of the obtained solid electrolyte was 7.9 ⁇ 10 ⁇ 4 S / cm.
• Example 3 The inside of the flask equipped with a stirrer was replaced with nitrogen, and 1.0 g of lithium sulfide of Production Example 2 (0.97 g corresponding to lithium sulfide in consideration of purity), diphosphorus pentasulfide (Aldrich) 1 .65 g, LiBr (Aldrich) 0.63 g was charged with 30 ml of tetrahydrofuran (THF: Wako Pure Chemical Industries, Ltd.) having a water content of 10 ppm, and reacted at room temperature for 20 hours. After completion of the reaction, THF was removed by drying under reduced pressure at room temperature, and further dried at 80 ° C. for 1 hour.
• THF tetrahydrofuran
• the ionic conductivity of the obtained solid electrolyte was 0.07 ⁇ 10 ⁇ 4 S / cm.
• the obtained solid electrolyte glass was further subjected to vacuum heat treatment at 140 ° C. for 2 hours to produce a solid electrolyte.
• the ionic conductivity of the obtained solid electrolyte was 3.9 ⁇ 10 ⁇ 4 S / cm.
• the ionic conductivity was measured in the same manner as in Example 1.
• Example 4 The inside of the flask equipped with a stirrer was replaced with nitrogen, and 1.0 g of lithium sulfide of Production Example 2 (0.97 g corresponding to lithium sulfide in consideration of purity), diphosphorus pentasulfide (Aldrich) 1 .65 g, LiBr (Aldrich) 0.51 g was charged with 30 ml of tetrahydrofuran (THF: Wako Pure Chemical Industries, Ltd.) having a water content of 10 ppm, and reacted at room temperature for 20 hours. After completion of the reaction, THF was removed by drying under reduced pressure at room temperature, and further dried at 80 ° C. for 1 hour.
• THF tetrahydrofuran
• the resulting solid electrolyte had an ionic conductivity of 0.08 ⁇ 10 ⁇ 4 S / cm.
• no peak was observed other than the halo pattern derived from amorphous, and it was confirmed that the glass was solid electrolyte glass.
• the obtained solid electrolyte glass was further subjected to vacuum heat treatment at 140 ° C. for 2 hours to produce a solid electrolyte.
• the ionic conductivity of the solid electrolyte obtained by the vacuum heat treatment was 4 ⁇ 10 ⁇ 4 S / cm.
• the ionic conductivity was measured in the same manner as in Example 1.
• Example 5 In Example 2, a solid electrolyte was produced in the same manner as in Example 2 except that the vacuum heat treatment temperature of the solid electrolyte glass was changed from 140 ° C to 120 ° C.
• the ionic conductivity of the solid electrolyte obtained by the vacuum heat treatment was 3.6 ⁇ 10 ⁇ 4 S / cm.
• Example 6 a solid electrolyte was produced in the same manner as in Example 2 except that the vacuum heat treatment temperature of the solid electrolyte glass was changed from 140 ° C to 160 ° C.
• the ionic conductivity of the solid electrolyte obtained by the vacuum heat treatment was 9.4 ⁇ 10 ⁇ 4 S / cm.
• Comparative Example 1 The inside of the flask equipped with a stirrer was replaced with nitrogen, and 1.2 g of lithium sulfide of Production Example 2 (1.17 g corresponding to lithium sulfide in consideration of purity), diphosphorus pentasulfide (Aldrich) 1 .88 g, 30 ml of tetrahydrofuran (THF: Wako Pure Chemical Industries, Ltd.) having a water content of 10 ppm was charged and reacted at room temperature for 20 hours. After completion of the reaction, the solid component was separated by filtration. After that, THF was further added and stirred for 10 minutes, and then the solid component was filtered. This operation was repeated a total of 3 times. Then, THF was removed by drying under reduced pressure at room temperature, and further dried at 80 ° C. for 1 hour.
• diphosphorus pentasulfide Aldrich
• THF tetrahydrofuran
• the obtained solid electrolyte glass was further subjected to vacuum heat treatment at 140 ° C. for 2 hours to produce a solid electrolyte.
• the resulting solid electrolyte had an ionic conductivity of 1.2 ⁇ 10 ⁇ 4 S / cm.
• a peak derived from a Thio-LISICON region III crystal could be observed.
• the ionic conductivity was measured in the same manner as in Example 1.
• Example 2 the conductivity of Examples 2 to 4 is lower than that of Example 1 because the addition of LiBr in addition to lithium sulfide and diphosphorus pentasulfide makes it easier for THF to remain. The reason is that more THF remains because the subsequent drying temperature is low (the former is 120 ° C. and the latter is 80 ° C.).
• the production method of the present invention is suitable as a method for producing a sulfide-based solid electrolyte.

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• 2014
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  • 2014-04-21 WO PCT/JP2014/002238 patent/WO2014174829A1/ja not_active Ceased

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