WO2024142410A1 - ガーネット型酸化物固体電解質の製造方法 - Google Patents

ガーネット型酸化物固体電解質の製造方法 Download PDF

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Publication number
WO2024142410A1
WO2024142410A1 PCT/JP2022/048704 JP2022048704W WO2024142410A1 WO 2024142410 A1 WO2024142410 A1 WO 2024142410A1 JP 2022048704 W JP2022048704 W JP 2022048704W WO 2024142410 A1 WO2024142410 A1 WO 2024142410A1
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WIPO (PCT)
Prior art keywords
garnet
type oxide
solid electrolyte
oxide solid
heating
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PCT/JP2022/048704
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English (en)
French (fr)
Japanese (ja)
Inventor
雅裕 鈴木
一 松本
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.)
National Institute of Advanced Industrial Science and Technology AIST
JTEKT Corp
Original Assignee
National Institute of Advanced Industrial Science and Technology AIST
JTEKT Corp
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Publication date
Application filed by National Institute of Advanced Industrial Science and Technology AIST, JTEKT Corp filed Critical National Institute of Advanced Industrial Science and Technology AIST
Priority to DE112022008137.6T priority Critical patent/DE112022008137T5/de
Priority to KR1020257014925A priority patent/KR20250085801A/ko
Priority to JP2024567174A priority patent/JP7774269B2/ja
Priority to PCT/JP2022/048704 priority patent/WO2024142410A1/ja
Priority to CN202280102827.6A priority patent/CN120418890A/zh
Publication of WO2024142410A1 publication Critical patent/WO2024142410A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • 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

  • Patent Document 1 is a method of removing lithium carbonate formed on the surface of a garnet-type oxide solid electrolyte by polishing, thereby increasing the ionic conductivity of the garnet-type oxide solid electrolyte.
  • the method for producing a garnet-type oxide solid electrolyte of the present disclosure includes: compressing and molding Li 7 La 3 Zr 2 O 12 (LLZO) powder having a median diameter (D50) of 0.02 to 0.2 ⁇ m to obtain an intermediate; The intermediate product is heated at 950 to 1050° C. for 2 to 7 hours, and then cooled to room temperature over 4 hours or more to obtain a first garnet-type oxide solid electrolyte.
  • LLZO Li 7 La 3 Zr 2 O 12
  • the manufacturing method described in (1) above can produce garnet-type oxide solid electrolytes of various shapes with high ionic conductivity.
  • the first garnet-type oxide solid electrolyte is contacted with at least one selected from an organic plastic ionic crystal and an ionic liquid to obtain a second garnet-type oxide solid electrolyte.
  • the manufacturing method described in (2) above can produce a second garnet-type oxide solid electrolyte with higher ionic conductivity.
  • the LLZO powder is pressurized under conditions of 72 MPa or more to obtain the intermediate.
  • the manufacturing method described in (3) above ensures sufficient hardness of the intermediate, so the shape of the intermediate can be maintained.
  • the method for producing a garnet-type oxide solid electrolyte includes the steps of: 1) A pressing step of pressing Li 7 La 3 Zr 2 O 12 (LLZO) powder having a median diameter (D50) of 0.02 to 0.2 ⁇ m to obtain an intermediate; 2) a heating and cooling step of heating the intermediate at 950 to 1050° C. for 2 to 7 hours and then cooling to room temperature over 4 hours or more to obtain a first garnet-type oxide solid electrolyte; including.
  • LLZO Li 7 La 3 Zr 2 O 12
  • the LLZO powder having the above-mentioned predetermined median diameter can be obtained, for example, by removing isopropanol with an evaporator from an isopropanol suspension obtained by grinding a commercially available LLZO powder having a median diameter (D50) of more than 0.2 ⁇ m in isopropanol using a bead mill.
  • D50 median diameter
  • the upper limit of the pressure when obtaining the LLZO powder intermediate is limited by the upper limit of the pressure that can be applied by the pressurizing device used in the hydraulic press, and is, for example, 650 MPa or less, but may be higher. As a result, the shape of the intermediate is maintained through the subsequent heating and cooling process and the contact process described later.
  • Step 1) Obtaining Intermediate 1 Intermediate 1 was obtained by putting 60 mg of LLZO powder with a median diameter (D50) of 0.1 ⁇ m into a powder molding machine with an inner diameter of 10 mm in a dry chamber with a dew point of -50°C or less, and then uniaxially press-molding the LLZO powder with a median diameter (D50) of 0.1 ⁇ m at 433 MPa using a hydraulic press.
  • the diameter of intermediate 1 is 10 mm.
  • Intermediate 2 was produced using LLZO powder with a median diameter (D50) of 1 ⁇ m. Intermediate 2 was obtained by treating in the same manner as for obtaining intermediate 1 described above, except that LLZO powder with a median diameter (D50) of 1 ⁇ m was used instead of LLZO powder with a median diameter (D50) of 0.1 ⁇ m. The diameter of intermediate 2 is 10 mm.
  • the first garnet-type oxide solid electrolyte 2 was produced using the above-mentioned intermediate 2.
  • the first garnet-type oxide solid electrolyte 2 was obtained by treating in the same manner as in the above-mentioned "Obtaining garnet-type oxide solid electrolyte 1", except that the above-mentioned intermediate 2 was used and heating was performed under the conditions of "Effect of heating time on ionic conductivity” and "Effect of heating temperature on ionic conductivity” described below.
  • the diameter of the first garnet-type oxide solid electrolyte 2 was 8 mm to 9.5 mm, which was slightly smaller than before firing.
  • the Li symmetric cell 2 was manufactured in the same manner as the Li symmetric cell 1, except that the first garnet-type oxide solid electrolyte 2 was used instead of the first garnet-type oxide solid electrolyte 1.
  • the Li symmetric cell 3 was manufactured in the same manner as the Li symmetric cell 1, except that the first garnet-type oxide solid electrolyte 3 was used instead of the first garnet-type oxide solid electrolyte 1.
  • the ionic conductivity of the first garnet-type oxide solid electrolyte 2 and the first garnet-type oxide solid electrolyte 3 was measured by the same measurement method as that of the first garnet-type oxide solid electrolyte 1, except that the Li symmetric cell 2 and the Li symmetric cell 3 were used instead of the Li symmetric cell 1.
  • the first garnet-type oxide solid electrolyte 2 (0.5h) was obtained by a heating and cooling process in which the intermediate 2 was heated to 1000°C using a firing furnace under the above-mentioned dry chamber conditions, the heating time was 30 minutes, and then cooled to room temperature in the firing furnace over 2 to 4 hours.
  • the first garnet-type oxide solid electrolyte 2 (1h) was obtained by a heating and cooling process in which the intermediate 2 was heated to 1000°C using a firing furnace under the above-mentioned dry chamber conditions, the heating time was 1 hour, and then cooled to room temperature in the firing furnace over 2 to 4 hours.
  • the first garnet-type oxide solid electrolyte 2 (6h) was obtained by a heating and cooling process in which the intermediate 2 was heated to 1000°C using a sintering furnace under the above-mentioned dry chamber conditions, for a heating time of 6 hours, and then cooled to room temperature in the sintering furnace over 2 to 4 hours.
  • the first garnet-type oxide solid electrolyte 2 (8h) was obtained by a heating and cooling process in which the intermediate 2 was heated to 1000°C using a sintering furnace under the above-mentioned dry chamber conditions, for a heating time of 8 hours, and then cooled to room temperature in the sintering furnace over 2 to 4 hours.
  • FIG. 1 shows the measurement results of the ion conductivity of the first garnet-type oxide solid electrolyte 2 with different heating times. According to FIG. 1, it can be seen that the first garnet-type oxide solid electrolyte 2 (2h), the first garnet-type oxide solid electrolyte 2 (4h), and the first garnet-type oxide solid electrolyte 2 (6h) have an ion conductivity of 4.0 ⁇ 10 ⁇ 5 S/cm or more.
  • the first garnet-type oxide solid electrolyte 1 (800°C) was obtained by a heating and cooling process in which the intermediate 1 was heated to 800°C using a firing furnace under the above-mentioned dry chamber conditions, for a heating time of 2 hours, and then cooled to room temperature in the firing furnace over 2 to 4 hours.
  • the first garnet-type oxide solid electrolyte 1 is a first garnet-type oxide solid electrolyte manufactured using LLZO powder having a median diameter (D50) of 0.1 ⁇ m.
  • the first garnet-type oxide solid electrolytes 2 and 3 are first garnet-type oxide solid electrolytes manufactured using LLZO powder having a median diameter (D50) of 1 ⁇ m and 10 ⁇ m, respectively. That is, according to FIG.
  • the first garnet-type oxide solid electrolyte manufactured using LLZO powder having a median diameter (D50) of 0.02 to 0.2 ⁇ m has a significantly higher ion conductivity than the first garnet-type oxide solid electrolyte manufactured using LLZO powder having a median diameter (D50) of 1 ⁇ m or more.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Conductive Materials (AREA)
PCT/JP2022/048704 2022-12-29 2022-12-29 ガーネット型酸化物固体電解質の製造方法 Ceased WO2024142410A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE112022008137.6T DE112022008137T5 (de) 2022-12-29 2022-12-29 Verfahren zur herstellung eines granat-typ-oxid-festelektrolyts
KR1020257014925A KR20250085801A (ko) 2022-12-29 2022-12-29 가닛형 산화물 고체 전해질의 제조 방법
JP2024567174A JP7774269B2 (ja) 2022-12-29 2022-12-29 ガーネット型酸化物固体電解質の製造方法
PCT/JP2022/048704 WO2024142410A1 (ja) 2022-12-29 2022-12-29 ガーネット型酸化物固体電解質の製造方法
CN202280102827.6A CN120418890A (zh) 2022-12-29 2022-12-29 石榴石型氧化物固体电解质的制造方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2022/048704 WO2024142410A1 (ja) 2022-12-29 2022-12-29 ガーネット型酸化物固体電解質の製造方法

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WO2024142410A1 true WO2024142410A1 (ja) 2024-07-04

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JP (1) JP7774269B2 (https=)
KR (1) KR20250085801A (https=)
CN (1) CN120418890A (https=)
DE (1) DE112022008137T5 (https=)
WO (1) WO2024142410A1 (https=)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010143785A (ja) * 2008-12-18 2010-07-01 National Institute Of Advanced Industrial Science & Technology リチウムイオン伝導性酸化物およびその製造方法、並びに該酸化物により構成された固体電解質
WO2020183806A1 (ja) * 2019-03-14 2020-09-17 セイコーエプソン株式会社 ガーネット型固体電解質の前駆体溶液、ガーネット型固体電解質の前駆体溶液の製造方法およびガーネット型固体電解質

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102745545B1 (ko) 2014-10-28 2024-12-26 유니버시티 오브 메릴랜드, 컬리지 파크 고체상 배터리용 계면층 및 그 제조방법

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010143785A (ja) * 2008-12-18 2010-07-01 National Institute Of Advanced Industrial Science & Technology リチウムイオン伝導性酸化物およびその製造方法、並びに該酸化物により構成された固体電解質
WO2020183806A1 (ja) * 2019-03-14 2020-09-17 セイコーエプソン株式会社 ガーネット型固体電解質の前駆体溶液、ガーネット型固体電解質の前駆体溶液の製造方法およびガーネット型固体電解質

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KR20250085801A (ko) 2025-06-12
JPWO2024142410A1 (https=) 2024-07-04
JP7774269B2 (ja) 2025-11-21
CN120418890A (zh) 2025-08-01
DE112022008137T5 (de) 2025-10-09

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