WO2022260056A1 - 全固体電気化学素子及び硫黄－炭素複合体 - Google Patents

全固体電気化学素子及び硫黄－炭素複合体 Download PDF

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Publication number
WO2022260056A1
WO2022260056A1 PCT/JP2022/023033 JP2022023033W WO2022260056A1 WO 2022260056 A1 WO2022260056 A1 WO 2022260056A1 JP 2022023033 W JP2022023033 W JP 2022023033W WO 2022260056 A1 WO2022260056 A1 WO 2022260056A1
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Prior art keywords
positive electrode
active material
electrode active
sulfur
negative electrode
Prior art date
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Ceased
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PCT/JP2022/023033
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English (en)
French (fr)
Japanese (ja)
Inventor
諒 原田
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GS Yuasa International Ltd
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GS Yuasa International Ltd
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Priority to CN202280040839.0A priority Critical patent/CN117461163A/zh
Priority to EP22820235.4A priority patent/EP4329008A4/en
Priority to US18/566,915 priority patent/US20240274793A1/en
Priority to JP2023527882A priority patent/JPWO2022260056A1/ja
Publication of WO2022260056A1 publication Critical patent/WO2022260056A1/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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

Definitions

  • An all-solid-state electrochemical device includes a positive electrode active material layer, a separation layer, and a negative electrode active material layer, wherein the positive electrode active material layer contains a sulfur-carbon composite, and the sulfur-carbon The composite contains sulfur and porous carbon, and the carbon has an average pore size of 0.5 nm or more and 3.0 nm or less and an average particle size of 0.1 ⁇ m or more and 30.0 ⁇ m or less.
  • the positive electrode base material 4 has conductivity. Whether or not a material has "conductivity" is determined using a volume resistivity of 10 7 ⁇ cm as a threshold measured according to JIS-H-0505 (1975).
  • the material for the positive electrode substrate metals such as aluminum, titanium, tantalum and stainless steel, or alloys thereof are used. Among these, aluminum or an aluminum alloy is preferable from the viewpoint of potential resistance, high conductivity, and cost.
  • Examples of the positive electrode substrate include foil, deposited film, mesh, porous material, and the like, and foil is preferable from the viewpoint of cost. Therefore, aluminum foil or aluminum alloy foil is preferable as the positive electrode substrate. Examples of aluminum or aluminum alloy include A1085, A3003, A1N30, etc. defined in JIS-H-4000 (2014) or JIS-H-4160 (2006).
  • the average particle size of carbon in the sulfur-carbon composite is 0.1 ⁇ m or more and 30.0 ⁇ m or less, preferably 1.0 ⁇ m or more and 25.0 ⁇ m or less, more preferably 3.0 ⁇ m or more and 20.0 ⁇ m or less. It is more preferably 0 ⁇ m or more and 17.0 ⁇ m or less, and even more preferably 4.5 ⁇ m or more and 15.4 ⁇ m or less.
  • the average particle size of the carbon is equal to or less than the upper limit, the voids in the positive electrode active material layer can be reduced, and ion and electron conduction paths in the positive electrode active material layer can be easily constructed.
  • the negative electrode active material layer 6 may be a nonporous layer (solid layer) containing lithium element.
  • the negative electrode active material layer 6 may be a porous layer having particles containing lithium element.
  • the negative electrode active material layer 6 may be a layer consisting only of a negative electrode active material substantially containing lithium element.
  • the negative electrode active material layer 6 may be a pure metal lithium foil or a lithium alloy foil.
  • the average thickness of the negative electrode active material layer 6 is preferably 5 ⁇ m or more and 1,000 ⁇ m or less, more preferably 10 ⁇ m or more and 500 ⁇ m or less, and 30 ⁇ m or more and 300 ⁇ m or less. More preferred.
  • the “average thickness” of the negative electrode active material layer refers to the average value of thicknesses measured at arbitrary five points in the negative electrode active material layer.
  • the isolation layer 3 may contain optional components such as binders, thickeners and fillers.
  • Optional components such as binders, thickeners, and fillers can be selected from the materials exemplified for the positive electrode 1 .
  • the average thickness of the isolation layer 3 is preferably 1 ⁇ m or more and 50 ⁇ m or less, more preferably 3 ⁇ m or more and 20 ⁇ m or less.
  • the energy density of the all-solid-state battery 10 can be increased by setting the average thickness of the isolation layer 3 to the upper limit or less.
  • the following steps are performed as an example of the heat treatment in which the first heating step and the second heating step are performed.
  • the first heating step and the second heating step sulfur particles are supported not only on the surface of the porous carbon but also in the pores in a highly dispersed manner, so that the utilization rate of sulfur can be increased.
  • (1-1) First Heating Step In the first heating step, heating is performed at a temperature at which sulfur melts. Specifically, the temperature of the mixture is raised from room temperature to the range of 112° C. or more and 159° C. or less, and then the temperature is maintained within that range. The retention time is preferably 5 hours or more. Through this process, the surface of the porous carbon is uniformly coated with sulfur.
  • (1-2) Second Heating Step heating is performed at a temperature at which sulfur vaporizes.
  • the temperature is preferably raised to 250° C. or higher and maintained.
  • the sulfur uniformly supported on the surface of the porous carbon in the first heating step can be vaporized in the vicinity of the pores of the porous carbon.
  • the positive electrode active material layer contains a sulfur-carbon composite, the average pore diameter of the carbon is 3.0 nm or less, and the average particle diameter is 30.0 ⁇ m or less.
  • the cell voltage in the charging curve is lower than in Comparative Examples 1 to 4 in which the carbon has an average pore size of more than 3.0 nm or an average particle size of more than 30.0 ⁇ m.
  • the positive electrode active material layer of the all-solid-state battery has an average carbon pore diameter of 3.0 nm or less and contains a sulfur-carbon composite with an average particle diameter of 30.0 ⁇ m or less. Polarization is reduced.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
PCT/JP2022/023033 2021-06-09 2022-06-08 全固体電気化学素子及び硫黄－炭素複合体 Ceased WO2022260056A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202280040839.0A CN117461163A (zh) 2021-06-09 2022-06-08 全固体电化学元件和硫－碳复合物
EP22820235.4A EP4329008A4 (en) 2021-06-09 2022-06-08 ELECTROCHEMICAL SOLID-STATE ELEMENT AND SULFUR-CARBON COMPLEX
US18/566,915 US20240274793A1 (en) 2021-06-09 2022-06-08 All-solid-state electrochemical device and sulfur-carbon composite
JP2023527882A JPWO2022260056A1 (https=) 2021-06-09 2022-06-08

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-096961 2021-06-09
JP2021096961 2021-06-09

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WO2022260056A1 true WO2022260056A1 (ja) 2022-12-15

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US (1) US20240274793A1 (https=)
EP (1) EP4329008A4 (https=)
JP (1) JPWO2022260056A1 (https=)
CN (1) CN117461163A (https=)
WO (1) WO2022260056A1 (https=)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025110163A1 (ja) * 2023-11-22 2025-05-30 株式会社Ｇｓユアサ 非水電解質蓄電素子用正極及び非水電解質蓄電素子
KR20250158752A (ko) 2023-03-10 2025-11-06 이데미쓰 고산 가부시키가이샤 정극 합재, 정극 합재의 제조 방법 및 리튬 이온 전지
WO2026033763A1 (ja) * 2024-08-08 2026-02-12 日産自動車株式会社 正極材料ならびにこれを用いた正極合剤およびリチウム二次電池

Citations (4)

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Publication number Priority date Publication date Assignee Title
WO2016009936A1 (ja) * 2014-07-15 2016-01-21 東レ株式会社 電極材料、リチウム硫黄電池電極、リチウム硫黄電池および電極材料の製造方法
JP2016075916A (ja) 2001-10-30 2016-05-12 株式会社半導体エネルギー研究所 半導体装置
JP2018521465A (ja) * 2015-06-05 2018-08-02 ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングＲｏｂｅｒｔ Ｂｏｓｃｈ Ｇｍｂｈ リチウム−硫黄電池用の微多孔性カーボンナノシートを含む硫黄−炭素複合体およびそれを調製するためのプロセス
JP2020031027A (ja) * 2018-08-24 2020-02-27 時空化学株式会社 Ｌｉ２Ｓ−Ｐ２Ｓ５−ＳｅＳ２系ガラスセラミックからなる全固体リチウム硫黄電池用固体電解質、前記固体電解質に適した正極材料及びこれらの製造方法、並びにこれらを含む全固体リチウム硫黄電池

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JP6243103B2 (ja) * 2012-06-29 2017-12-06 出光興産株式会社 正極合材
US10109847B2 (en) * 2012-12-05 2018-10-23 Robert Bosch Gmbh Sulfur-carbon composite material, its application in lithium-sulfur battery and method for preparing said composite material
JP6385486B2 (ja) * 2016-03-11 2018-09-05 東京電力ホールディングス株式会社 固体電池用正極材およびその製造方法、ならびに、固体電池用正極材を用いた全固体リチウム硫黄電池およびその製造方法

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2016075916A (ja) 2001-10-30 2016-05-12 株式会社半導体エネルギー研究所 半導体装置
WO2016009936A1 (ja) * 2014-07-15 2016-01-21 東レ株式会社 電極材料、リチウム硫黄電池電極、リチウム硫黄電池および電極材料の製造方法
JP2018521465A (ja) * 2015-06-05 2018-08-02 ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングＲｏｂｅｒｔ Ｂｏｓｃｈ Ｇｍｂｈ リチウム−硫黄電池用の微多孔性カーボンナノシートを含む硫黄−炭素複合体およびそれを調製するためのプロセス
JP2020031027A (ja) * 2018-08-24 2020-02-27 時空化学株式会社 Ｌｉ２Ｓ−Ｐ２Ｓ５−ＳｅＳ２系ガラスセラミックからなる全固体リチウム硫黄電池用固体電解質、前記固体電解質に適した正極材料及びこれらの製造方法、並びにこれらを含む全固体リチウム硫黄電池

Non-Patent Citations (1)

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Title
See also references of EP4329008A4

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20250158752A (ko) 2023-03-10 2025-11-06 이데미쓰 고산 가부시키가이샤 정극 합재, 정극 합재의 제조 방법 및 리튬 이온 전지
WO2025110163A1 (ja) * 2023-11-22 2025-05-30 株式会社Ｇｓユアサ 非水電解質蓄電素子用正極及び非水電解質蓄電素子
WO2026033763A1 (ja) * 2024-08-08 2026-02-12 日産自動車株式会社 正極材料ならびにこれを用いた正極合剤およびリチウム二次電池

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US20240274793A1 (en) 2024-08-15
CN117461163A (zh) 2024-01-26
EP4329008A4 (en) 2025-05-14
JPWO2022260056A1 (https=) 2022-12-15
EP4329008A1 (en) 2024-02-28

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