WO2023090283A1 - 硫化リチウムの製造方法 - Google Patents

硫化リチウムの製造方法 Download PDF

Info

Publication number
WO2023090283A1
WO2023090283A1 PCT/JP2022/042189 JP2022042189W WO2023090283A1 WO 2023090283 A1 WO2023090283 A1 WO 2023090283A1 JP 2022042189 W JP2022042189 W JP 2022042189W WO 2023090283 A1 WO2023090283 A1 WO 2023090283A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
lithium
composition
hydrogen gas
sulfide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/042189
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
建 河村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Kinzoku Co Ltd
Original Assignee
Mitsui Mining and Smelting Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Mining and Smelting Co Ltd filed Critical Mitsui Mining and Smelting Co Ltd
Priority to KR1020247014773A priority Critical patent/KR20240109988A/ko
Priority to US18/706,623 priority patent/US20240417253A1/en
Priority to CN202280074063.4A priority patent/CN118302381A/zh
Priority to JP2023561579A priority patent/JPWO2023090283A1/ja
Priority to EP22895565.4A priority patent/EP4438555A4/en
Publication of WO2023090283A1 publication Critical patent/WO2023090283A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C01B17/24—Preparation by reduction
    • C01B17/28—Preparation by reduction with reducing gases
    • 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
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/22—Alkali metal sulfides or polysulfides
    • C01B17/36—Purification
    • 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
    • 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 lithium sulfide.
  • Lithium sulfide was generally synthesized by reacting hydrogen sulfide on a lithium source compound.
  • Patent Document 1 describes a method for producing lithium sulfide by bringing lithium carbonate, which is a lithium source, into contact with hydrogen sulfide at a temperature of 450° C. or higher under a state of fluidization and reacting the two.
  • Patent Document 2 describes a method for producing lithium sulfide by reacting lithium hydroxide and hydrogen sulfide, in which a reaction gas containing hydrogen sulfide gas and hydrogen gas is generated by reacting hydrogen gas and sulfur vapor. describes a method for producing particulate lithium sulfide by bringing the generated reaction gas into contact with particulate lithium hydroxide to react the two.
  • Lithium sulfide produced by the above-described conventional method contains lithium sulfate, lithium thiosulfate, and lithium oxide as by-products, or lithium carbonate, which is the starting material, remains. There is a need for a process capable of producing pure lithium sulfide. Accordingly, an object of the present invention is to provide a method capable of producing high-purity lithium sulfide.
  • a diffraction peak B When having a diffraction peak B at a position of ⁇ 1.0°, the intensity of the diffraction peak A is Ia , and the intensity of the diffraction peak B is Ib , the value of the Ib with respect to the Ia is A preparation step of preparing a composition that is 0.04 or more; A method for producing lithium sulfide, comprising a reaction step of reacting the composition with hydrogen gas.
  • FIG. 1 is a diagram showing X-ray diffraction measurement results for lithium sulfide obtained in Examples and Reference Examples.
  • lithium sulfide (Li 2 S) of the present invention high-purity lithium sulfide is produced by reacting lithium sulfide containing impurities with hydrogen gas (H 2 ) to reduce the amount of the impurities. It has one of the characteristics in the point obtained.
  • Lithium sulfide containing impurities, which is to be treated by the method of the present invention can also be said to be a composition containing lithium sulfide and impurities. In this sense, lithium sulfide containing impurities, which is an object to be treated by the method of the present invention, is also referred to as a "composition" in the following description.
  • a step of preparing a composition which is an object to be treated in this production method, is performed.
  • the composition prepared by this step can be obtained by a conventionally known method for producing lithium sulfide.
  • Conventionally known methods for producing lithium sulfide include, for example, (1) a method for producing lithium sulfide by bringing lithium carbonate into dry contact with a sulfur-containing gas and heating the lithium carbonate (for example, Japanese Patent Laid-Open No. 2012-221819), (2) A method of producing lithium sulfide by contacting lithium carbonate in a fluid state with a gaseous sulfur compound at a temperature of 450 ° C.
  • Lithium sulfide produced by these methods may contain, as an impurity, lithium sulfate, which is a by-product of the reaction of the starting raw material, lithium carbonate, with sulfur.
  • the composition that is the object to be treated in this production method can be a composition containing lithium sulfide and lithium sulfate.
  • the content of lithium sulfate, that is, impurities in the composition can be determined by X-ray diffraction (hereinafter also referred to as "XRD") of the composition. ) can be expressed quantitatively by measuring.
  • XRD X-ray diffraction
  • the value of I b /I a may be 0.19 or less, or may be 0.070 or less.
  • Peak A is a diffraction peak derived from the (200) plane of lithium sulfide
  • peak B is a diffraction peak derived from the (11-1) plane of lithium sulfate.
  • a heating step of reacting the composition and hydrogen gas in an atmosphere containing hydrogen gas while the powder of the composition, which is the object to be processed, is left stationary or is fluidized. can be attached.
  • the heating step can be performed in an open system. Performing the heating step in an open system means that the reaction system in which the heating step is performed does not exist in a closed space.
  • the step of heating the composition in the present production method can be performed while an atmosphere containing hydrogen gas is circulated through the powder of the composition. Specifically, the composition is heated by heating the heating furnace in which the powder of the composition is placed, while circulating 100% hydrogen gas or a hydrogen-containing gas containing hydrogen gas. can be done.
  • lithium sulfate which is an impurity contained in the composition, reacts with hydrogen gas to reduce lithium sulfate and produce lithium sulfide. As a result, the purity of lithium sulfide is increased.
  • the purity of lithium sulfide obtained by the present production method is not particularly limited, but for example, it is preferably 95% by mass or more, more preferably 97% by mass or more, and even more preferably 99% by mass or more. preferable.
  • the hydrogen-containing gas may be hydrogen gas and other gases such as various inert gases such as nitrogen gas and rare gases such as argon. and so on. It is preferable to use the hydrogen gas diluted with an inert gas from the viewpoint of carrying out the present production method safely and from the viewpoint of efficiently carrying out the reaction.
  • the ratio of hydrogen gas to the total of both is preferably, for example, 1.0% by volume or more, more preferably 1.5% by volume or more. 0 vol % or more is more preferable.
  • the ratio is, for example, preferably 4.0% by volume or less, more preferably 3.5% by volume or less, and even more preferably 3.0% by volume or less. This is because good safety and reaction efficiency can be obtained.
  • the atmosphere used when heating the composition is preferably 100% hydrogen gas, or hydrogen gas diluted to a predetermined concentration with an inert gas, and other gases are contained in the atmosphere. from the viewpoint of obtaining high-purity lithium sulfide. In the following description, for the sake of convenience, both 100% hydrogen gas and hydrogen-containing gas are collectively referred to simply as "hydrogen gas" depending on the context.
  • the heating temperature is, for example, preferably 800° C. or higher, more preferably 859° C. or higher.
  • the heating temperature is, for example, preferably 1377° C. or lower, more preferably 1000° C. or lower, and even more preferably 900° C. or lower. This is because the lithium sulfate contained in the unrefined lithium sulfide can be sufficiently reduced and removed with hydrogen gas.
  • the heating temperature is the heating temperature of the heating furnace.
  • the composition When the composition is heated and reacted with hydrogen gas, the composition may be heated, for example, to the predetermined temperature described above, and then the hydrogen gas may be circulated. Gas may be circulated.
  • the time for which the composition is allowed to react with hydrogen gas in a heated state can be appropriately adjusted according to other conditions such as the heating temperature.
  • the reaction time is preferably set so that the lithium sulfate contained in the crude lithium sulfide is sufficiently removed.
  • the reaction time in the present invention is preferably 1 hour or longer, more preferably 2 hours or longer, and still more preferably 3 hours or longer.
  • the flow rate of the hydrogen gas to be supplied for reacting with the composition can be appropriately adjusted according to the reaction temperature and reaction time.
  • the flow rate is preferably such that the number of moles of hydrogen gas with respect to the number of moles of lithium sulfate is, for example, 0.019 mol/min or more and 0.038 mol/min or less. This is because the lithium sulfate contained in the unrefined lithium sulfide can be sufficiently removed.
  • the flow of hydrogen gas is stopped and the heating of the reaction system is stopped to react. is preferably stopped. This is because the intended lithium sulfide can be obtained with high purity.
  • the obtained lithium sulfide can be subjected to a pulverization step and a sieving step as a post-treatment to obtain a powder having an appropriate particle size distribution.
  • Lithium sulfide obtained by this production method is useful as a raw material for, for example, a sulfide-based solid electrolyte for lithium ion batteries, taking advantage of its high purity.
  • lithium sulfide and diphosphorus pentasulfide ( P2S5 ) or other sulfides can be mechanically milled to synthesize solid electrolytes such as Li7P3S11 and LiPS4 .
  • P2S5 diphosphorus pentasulfide
  • LiPS4 Li7P3S11 and LiPS4
  • LiCl lithium chloride
  • LiBr lithium bromide
  • a crystalline solid electrolyte for example, a solid electrolyte having a crystal phase with an aldirodite-type crystal structure can be synthesized.
  • the substance to be reacted with lithium sulfide to synthesize the solid electrolyte is not particularly limited.
  • silicon sulfide (SiS 2 ), germanium sulfide (GeS 2 ), and the like can be used in addition to the above diphosphorus pentasulfide.
  • lithium carbonate Li 2 CO 3
  • lithium carbonate has extremely low hygroscopicity, and its particle size can be easily adjusted. It has comparatively advantageous features.
  • the preparation step powdery lithium carbonate is used, and the composition can be produced by reacting sulfur (S) vapor and hydrogen gas with solid-phase lithium carbonate.
  • sulfur (S) vapor and hydrogen gas with solid-phase lithium carbonate.
  • lithium sulfide can be obtained by gas-solid reaction (in other words, dry reaction) without using a solvent such as water.
  • the reaction apparatus used for production may be a continuous apparatus or a batch-type apparatus.
  • the lithium carbonate powder preferably has an average particle size of, for example, 1 ⁇ m or more, more preferably 3 ⁇ m or more, and particularly preferably 6 ⁇ m or more.
  • the average particle size is, for example, preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, and particularly preferably 55 ⁇ m or less.
  • the average particle size of lithium carbonate referred to in this specification is the volume cumulative particle size D50 at a cumulative volume of 50% by volume measured by a laser diffraction scattering particle size distribution measurement method.
  • the lithium carbonate powder can be subjected to the firing step in an atmosphere containing sulfur gas and hydrogen gas while the lithium carbonate powder is left stationary or fluidized.
  • the firing process can be performed in an open system. Conducting the firing process in an open system means that the reaction system in which the firing process is performed does not exist in a closed space.
  • the lithium carbonate firing step in the preparation step can be performed while an atmosphere containing sulfur gas and hydrogen gas is circulated through the lithium carbonate powder. Specifically, lithium carbonate can be fired while a mixed gas containing sulfur gas and hydrogen gas is circulated in a heating furnace in which lithium carbonate powder is placed. By adopting such a firing method, lithium carbonate can be industrially produced efficiently.
  • the mixed gas used for firing may contain, for example, only sulfur gas and hydrogen gas, or may contain other gases in addition to sulfur gas and hydrogen gas.
  • gases include various inert gases such as nitrogen gas and rare gases such as argon.
  • the mixed gas does not contain gases other than sulfur gas, hydrogen gas, and an inert gas that is used as necessary, in order to successfully produce the target lithium sulfide.
  • the reaction for producing lithium sulfide from lithium carbonate in the preparation step is represented by the following formula (1).
  • the mixed gas used for firing lithium carbonate contains only sulfur gas and hydrogen gas.
  • an inert gas such as nitrogen gas is used as a diluent gas, the diluent gas and hydrogen gas are mixed, and sulfur gas is mixed therein to prepare a mixed gas to be supplied to lithium carbonate.
  • the ratio of hydrogen gas to the total of both is preferably, for example, 1.0% by volume or more, more preferably 1.5% by volume or more. 0 vol % or more is more preferable.
  • the ratio is, for example, preferably 4.0% by volume or less, more preferably 3.5% by volume or less, and even more preferably 3.0% by volume or less. This is because good safety and reaction efficiency can be obtained.
  • the sulfur gas to be mixed with the hydrogen gas can be obtained by liquefying solid sulfur by heating and then vaporizing it. At this time, it is preferable from the viewpoint of efficiency to heat solid sulfur to, for example, 200° C. or higher and 380° C. or lower under atmospheric pressure.
  • the amount of mixed gas containing hydrogen gas and sulfur gas supplied to lithium carbonate is appropriately determined in relation to the amount of lithium carbonate. Specifically, it is as follows.
  • the supply amount is determined in relation to the number of moles of lithium carbonate, which is the object to be fired. That is, sulfur gas is preferably contained in the firing atmosphere so that the number of moles of sulfur element relative to the number of moles of lithium carbonate is within a predetermined range. Specifically, the number of moles of sulfur element relative to 1 mole of lithium carbonate is, for example, preferably 6.0 mol or more, more preferably 7.8 mol or more, and 7.9 mol or more. is more preferred. On the other hand, the number of moles of the sulfur element is, for example, preferably 19.0 moles or less, more preferably 17.9 moles or less, and even more preferably 14.9 moles or less. By-production of impurities is suppressed, and high-purity lithium sulfide is obtained. Lithium sulfate (Li 2 SO 4 ) is a typical substance that is a by-product of the firing of lithium carbonate.
  • the amount of elemental sulfur supplied to lithium carbonate can be calculated from the amount of decrease in solid sulfur, for example, when sulfur gas is generated by heating solid sulfur.
  • the supply amount is determined in relation to the number of moles of lithium carbonate, which is the object to be fired. That is, it is preferable that the value of the number of moles of hydrogen gas with respect to the number of moles of lithium carbonate is contained in the firing atmosphere so as to be within a predetermined range. Specifically, it is preferable that hydrogen gas is included in the firing atmosphere such that the molar number of hydrogen gas with respect to the molar number of lithium carbonate is 8.5 or more and 12.0 or less. That is, the number of moles of hydrogen gas per 1 mole of lithium carbonate is, for example, preferably 8.5 moles or more, more preferably 9.0 moles or more, and even more preferably 9.5 moles or more. .
  • the number of moles of the hydrogen gas is, for example, preferably 12.0 moles or less, more preferably 11.0 moles or less, and even more preferably 10.0 moles or less.
  • the amount of hydrogen gas supplied to lithium carbonate can be measured, for example, by a flow meter installed between the hydrogen gas source (eg hydrogen gas cylinder) and the reaction system (eg heating furnace).
  • the hydrogen gas source eg hydrogen gas cylinder
  • the reaction system eg heating furnace
  • the firing temperature is preferably, for example, 650°C or higher, more preferably 700°C or higher, and even more preferably 723°C or higher, which is the melting point of lithium carbonate.
  • the firing temperature is, for example, preferably 1,310° C. or lower, more preferably 1,000° C. or lower, and 800° C. or lower, from the viewpoint of good reaction efficiency of lithium carbonate and prevention of decomposition of lithium carbonate. is more preferable.
  • the mixed gas containing sulfur gas and hydrogen gas When the mixed gas containing sulfur gas and hydrogen gas is supplied to lithium carbonate to bake the lithium carbonate, the mixed gas may be supplied to lithium carbonate after the temperature of the reaction system reaches 650 ° C. or higher. This is preferable from the viewpoint of reliably producing lithium sulfide. For example, when lithium carbonate is placed in a heating furnace and fired, it is preferable to circulate the mixed gas in the heating furnace after the temperature in the heating furnace reaches 650° C. or higher.
  • the mixed gas is not supplied into the reaction system, and only the inert gas is supplied into the reaction system, from the viewpoint of suppressing the generation of impurities such as lithium sulfate.
  • an inert gas such as nitrogen gas is circulated in the heating furnace until the temperature in the heating furnace reaches 650 ° C., and the mixed gas is It is preferable not to circulate.
  • the firing time is set so that lithium sulfide is reliably generated after setting the supply amounts of elemental sulfur and hydrogen gas to the values described above.
  • the diffraction peak at the position of is peak A
  • the value of Ib relative to Ia that is, the value of Ib / Ia is preferably 0.19 or less, more preferably
  • the value of Ic relative to Ia is preferably 0.024 or less, more preferably 0.011 or less, and still more preferably 0.001 or less.
  • part of the mixed gas supplied for firing lithium carbonate may be discharged from the reaction system in an unreacted state, or a by-product of the reaction may be discharged from the reaction system.
  • a by-product of the reaction may be discharged from the reaction system.
  • sulfur gas when sulfur gas is discharged from the reaction system in an unreacted state, the sulfur gas can be solidified and removed, for example, by cooling the discharged gas.
  • hydrogen sulfide gas is discharged from the reaction system as a by-product of the reaction, for example, by bubbling the discharged gas into an aqueous solution of hypochlorous acid or its salt, hydrogen sulfide is oxidized and removed. can do.
  • This composition contains lithium sulfate as an impurity in such an amount that the value of the above-described XRD peak intensity ratio I b /I a is 0.04 or more.
  • This composition is subjected to a reaction step with hydrogen gas to remove lithium sulfate contained in the composition and increase the purity of lithium sulfide.
  • Example 1 Preparation of mixed gas Hydrogen gas (concentration 3.5 vol%) diluted with nitrogen gas was prepared. Separately, solid sulfur was prepared and placed in a flask, and the flask was heated to 200° C. to 380° C. with a mantle heater to vaporize the solid sulfur and generate sulfur gas. Then, sulfur gas and hydrogen gas diluted with nitrogen gas were mixed to obtain a mixed gas. The ratio of sulfur gas and hydrogen gas in this mixed gas can be adjusted by adjusting the heating temperature of solid sulfur, the flow rate of hydrogen gas diluted with nitrogen gas, etc., so that the amount of hydrogen gas relative to sulfur is 0.00. It was set to be 88 or more and 1.15 or less.
  • Lithium carbonate powder having a D50 of 5.9 ⁇ m was prepared. An amount of lithium carbonate powder shown in Table 1 below was placed in a tubular furnace.
  • Examples 2 and 3 and Reference Example In Examples 2 and 3, lithium sulfide was produced in the same manner as in Example 1, except that the conditions shown in Tables 1 and 2 were used. In Reference Example, no heating was performed in the reaction process. Lithium sulfide was produced in the same manner as in Example 1 except that the conditions shown in Tables 1 and 2 were used.
  • lithium sulfide having an Ib / Ia of 0.001 or less was obtained from a composition having an Ib / Ia of 0.04 or more.
  • lithium sulfide having an I b /I a of 0.0425 was obtained from a composition having an I b /I a of 0.04 or more. From the above, it was found that higher purity lithium sulfide can be obtained in the example than in the reference example.
  • high-purity lithium sulfide can be produced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
PCT/JP2022/042189 2021-11-22 2022-11-14 硫化リチウムの製造方法 Ceased WO2023090283A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
KR1020247014773A KR20240109988A (ko) 2021-11-22 2022-11-14 황화리튬의 제조 방법
US18/706,623 US20240417253A1 (en) 2021-11-22 2022-11-14 Method for producing lithium sulfide
CN202280074063.4A CN118302381A (zh) 2021-11-22 2022-11-14 硫化锂的制造方法
JP2023561579A JPWO2023090283A1 (https=) 2021-11-22 2022-11-14
EP22895565.4A EP4438555A4 (en) 2021-11-22 2022-11-14 PROCESS FOR PRODUCING LITHIUM SULFIDE

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-189603 2021-11-22
JP2021189603 2021-11-22

Publications (1)

Publication Number Publication Date
WO2023090283A1 true WO2023090283A1 (ja) 2023-05-25

Family

ID=86396964

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/042189 Ceased WO2023090283A1 (ja) 2021-11-22 2022-11-14 硫化リチウムの製造方法

Country Status (6)

Country Link
US (1) US20240417253A1 (https=)
EP (1) EP4438555A4 (https=)
JP (1) JPWO2023090283A1 (https=)
KR (1) KR20240109988A (https=)
CN (1) CN118302381A (https=)
WO (1) WO2023090283A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026023118A1 (ja) * 2024-07-26 2026-01-29 三菱マテリアル株式会社 硫化リチウム、および、硫化物系固体電解質の製造方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0580021A (ja) * 1990-08-09 1993-03-30 Yazaki Corp 炭酸ガス検知センサ
JP2012221819A (ja) 2011-04-12 2012-11-12 Mitsui Mining & Smelting Co Ltd リチウムイオン電池固体電解質材料用硫化リチウムの製造方法
JP2013075816A (ja) 2011-09-13 2013-04-25 Nippon Chem Ind Co Ltd 硫化リチウム、その製造方法及び無機固体電解質の製造方法
JP2013227180A (ja) * 2012-04-26 2013-11-07 Furukawa Co Ltd 硫化リチウムの製造方法
JP2014169196A (ja) * 2013-03-01 2014-09-18 Nippon Chem Ind Co Ltd 硫化リチウムの製造方法及び無機固体電解質の製造方法
JP2014193799A (ja) 2013-02-27 2014-10-09 Toray Fine Chemicals Co Ltd 金属硫化物の製造方法
JP2015003843A (ja) * 2013-06-21 2015-01-08 東レ・ファインケミカル株式会社 金属硫化物の製造方法
JP2016150860A (ja) 2015-02-16 2016-08-22 古河機械金属株式会社 硫化リチウムの製造方法
CN110642273A (zh) * 2018-06-27 2020-01-03 比亚迪股份有限公司 碳酸锂颗粒及由含锂卤水制备碳酸锂颗粒的方法
CN111908431A (zh) * 2020-07-08 2020-11-10 天津理工大学 一种制备和提纯硫化锂的方法
WO2022009810A1 (ja) * 2020-07-09 2022-01-13 三井金属鉱業株式会社 硫化リチウムの製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2464455B (en) * 2008-10-14 2010-09-15 Iti Scotland Ltd Lithium-containing transition metal sulfide compounds

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0580021A (ja) * 1990-08-09 1993-03-30 Yazaki Corp 炭酸ガス検知センサ
JP2012221819A (ja) 2011-04-12 2012-11-12 Mitsui Mining & Smelting Co Ltd リチウムイオン電池固体電解質材料用硫化リチウムの製造方法
JP2013075816A (ja) 2011-09-13 2013-04-25 Nippon Chem Ind Co Ltd 硫化リチウム、その製造方法及び無機固体電解質の製造方法
JP2013227180A (ja) * 2012-04-26 2013-11-07 Furukawa Co Ltd 硫化リチウムの製造方法
JP2014193799A (ja) 2013-02-27 2014-10-09 Toray Fine Chemicals Co Ltd 金属硫化物の製造方法
JP2014169196A (ja) * 2013-03-01 2014-09-18 Nippon Chem Ind Co Ltd 硫化リチウムの製造方法及び無機固体電解質の製造方法
JP2015003843A (ja) * 2013-06-21 2015-01-08 東レ・ファインケミカル株式会社 金属硫化物の製造方法
JP2016150860A (ja) 2015-02-16 2016-08-22 古河機械金属株式会社 硫化リチウムの製造方法
CN110642273A (zh) * 2018-06-27 2020-01-03 比亚迪股份有限公司 碳酸锂颗粒及由含锂卤水制备碳酸锂颗粒的方法
CN111908431A (zh) * 2020-07-08 2020-11-10 天津理工大学 一种制备和提纯硫化锂的方法
WO2022009810A1 (ja) * 2020-07-09 2022-01-13 三井金属鉱業株式会社 硫化リチウムの製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HOSHINO TSUYOSHI: "Innovative lithium recovery technique from seawater by using world-first dialysis with a lithium ionic superconductor", DESALINATION., ELSEVIER, AMSTERDAM., NL, vol. 359, 29 December 2014 (2014-12-29), NL , pages 59 - 63, XP029189773, ISSN: 0011-9164, DOI: 10.1016/j.desal.2014.12.018 *
See also references of EP4438555A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026023118A1 (ja) * 2024-07-26 2026-01-29 三菱マテリアル株式会社 硫化リチウム、および、硫化物系固体電解質の製造方法

Also Published As

Publication number Publication date
EP4438555A1 (en) 2024-10-02
KR20240109988A (ko) 2024-07-12
US20240417253A1 (en) 2024-12-19
CN118302381A (zh) 2024-07-05
EP4438555A4 (en) 2025-06-18
JPWO2023090283A1 (https=) 2023-05-25

Similar Documents

Publication Publication Date Title
WO2023090271A1 (ja) 硫化リチウムの製造方法
JP7071899B2 (ja) 固体電解質の製造方法
JP6761024B2 (ja) 固体電解質及び固体電解質の製造方法
US10879559B2 (en) Method for producing solid electrolyte
JP6145091B2 (ja) イオン伝導性物質の製造方法、イオン伝導性物質、結晶化イオン伝導性物質及び電池
US20220332578A1 (en) Plasma-assisted synthesis for solid-state electrolyte materials
JP6055770B2 (ja) ガラス粒子
JP2013075816A (ja) 硫化リチウム、その製造方法及び無機固体電解質の製造方法
JP2014169196A (ja) 硫化リチウムの製造方法及び無機固体電解質の製造方法
JP6923173B2 (ja) 硫黄含有複合体、その製造方法、及び固体電解質の製造方法
WO2014192309A1 (ja) 固体電解質の製造方法
WO2016204253A1 (ja) 固体電解質の製造方法
WO2017159666A1 (ja) 固体電解質の製造方法
WO2018110647A1 (ja) 硫化物固体電解質の製造方法
US9991554B2 (en) Sulfide glass, and method for producing sulfide glass ceramic
WO2013084396A1 (ja) リチウムシリケート系化合物及びその製造方法、二次電池用の正極活物質及び正極、並びに二次電池
WO2023090283A1 (ja) 硫化リチウムの製造方法
WO2020017500A1 (ja) 固体電解質の製造方法
JP6162981B2 (ja) 硫化リチウムの製造方法及び無機固体電解質の製造方法
JP2016204219A (ja) 硫化リチウム、及び硫化物固体電解質の製造方法
Yamada et al. Growth of idiomorphic LiMnPO 4 crystals in molten NaCl–KCl and LiF–NaCl–KCl fluxes
WO2023090282A1 (ja) 硫化リチウム及びその製造方法並びに硫化物固体電解質の製造方法
US20230271155A1 (en) Plasma system for producing solid-state electrolyte material
WO2024181099A1 (ja) 水酸化リチウムの製造方法、リチウムを含む硫化物固体電解質原料の製造方法、及び硫化物固体電解質の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22895565

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023561579

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 18706623

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 202280074063.4

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2022895565

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2022895565

Country of ref document: EP

Effective date: 20240624