JP7299620B2 - リチウム固体電解質界面処理法 - Google Patents
リチウム固体電解質界面処理法 Download PDFInfo
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- JP7299620B2 JP7299620B2 JP2019523729A JP2019523729A JP7299620B2 JP 7299620 B2 JP7299620 B2 JP 7299620B2 JP 2019523729 A JP2019523729 A JP 2019523729A JP 2019523729 A JP2019523729 A JP 2019523729A JP 7299620 B2 JP7299620 B2 JP 7299620B2
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- solid electrolyte
- coating layer
- lithium
- metal
- garnet
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- 239000007784 solid electrolyte Substances 0.000 title claims description 154
- 229910052744 lithium Inorganic materials 0.000 title claims description 102
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 80
- 238000000034 method Methods 0.000 title claims description 55
- 239000000463 material Substances 0.000 claims description 80
- 239000011247 coating layer Substances 0.000 claims description 76
- 239000002223 garnet Substances 0.000 claims description 53
- 239000010410 layer Substances 0.000 claims description 30
- 238000000231 atomic layer deposition Methods 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 21
- 239000006182 cathode active material Substances 0.000 claims description 15
- 239000006183 anode active material Substances 0.000 claims description 13
- 229910052787 antimony Inorganic materials 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052758 niobium Inorganic materials 0.000 claims description 11
- 238000007747 plating Methods 0.000 claims description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims description 10
- 229910052712 strontium Inorganic materials 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 238000005240 physical vapour deposition Methods 0.000 claims description 8
- 229910052701 rubidium Inorganic materials 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 238000000407 epitaxy Methods 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 238000004518 low pressure chemical vapour deposition Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 description 48
- 239000002184 metal Substances 0.000 description 48
- 239000011701 zinc Substances 0.000 description 23
- 239000011734 sodium Substances 0.000 description 19
- 239000008188 pellet Substances 0.000 description 18
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 14
- 229910052718 tin Inorganic materials 0.000 description 14
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- 239000010936 titanium Substances 0.000 description 13
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- 210000004027 cell Anatomy 0.000 description 12
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- 229910052749 magnesium Inorganic materials 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
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- 239000010949 copper Substances 0.000 description 10
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
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- 239000000203 mixture Substances 0.000 description 6
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 5
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
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- 150000003839 salts Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910005533 GaO Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 description 3
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
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- 239000012467 final product Substances 0.000 description 3
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 3
- PVADDRMAFCOOPC-UHFFFAOYSA-N germanium monoxide Inorganic materials [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 3
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
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- 229910052715 tantalum Inorganic materials 0.000 description 3
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 3
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- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
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- 229910000417 bismuth pentoxide Inorganic materials 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
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- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
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- 101100317222 Borrelia hermsii vsp3 gene Proteins 0.000 description 1
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- H01M10/05—Accumulators with non-aqueous electrolyte
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| EP3635804A4 (en) * | 2017-06-06 | 2021-03-10 | The Regents of The University of Michigan | Method for suppressing metal propagation in solid electrolytes |
| US10553874B2 (en) | 2017-08-04 | 2020-02-04 | Uchicago Argonne, Llc | Protective coatings for lithium anodes |
| US11959166B2 (en) | 2018-08-14 | 2024-04-16 | Massachusetts Institute Of Technology | Methods of fabricating thin films comprising lithium-containing materials |
| DE102018219925A1 (de) * | 2018-11-21 | 2020-05-28 | Robert Bosch Gmbh | Kompositelektrode mit homogenem Abscheidungsverhalten |
| DE102018221164A1 (de) | 2018-12-06 | 2020-06-10 | Volkswagen Aktiengesellschaft | Schutzschicht für eine Lithium-Metall-Anode einer Festkörperbatterie |
| TW202044646A (zh) * | 2019-04-04 | 2020-12-01 | 美商希爾格得有限公司 | 用於高能量可充電鋰電池之聚醯胺—醯亞胺塗覆分隔件 |
| CN110085910B (zh) * | 2019-05-14 | 2021-02-02 | 中南大学 | 全固态锂电池、石榴石固态电解质及其制备方法 |
| CN110504482A (zh) * | 2019-08-08 | 2019-11-26 | 南开大学 | 固态锂电池石榴石型固态电解质材料的制备及表面处理方法与应用 |
| WO2021059939A1 (ja) * | 2019-09-27 | 2021-04-01 | 株式会社カネカ | 酸化物、固体電解質、および全固体リチウムイオン二次電池 |
| US11404698B2 (en) * | 2019-10-30 | 2022-08-02 | GM Global Technology Operations LLC | Liquid metal interfacial layers for solid electrolytes and methods thereof |
| JP7540151B2 (ja) * | 2019-12-19 | 2024-08-27 | 日本電気硝子株式会社 | 蓄電デバイス用部材及び蓄電デバイス |
| CN111087238B (zh) * | 2019-12-30 | 2021-12-31 | 潍坊歌尔微电子有限公司 | 钛酸铋钠基无铅压电陶瓷及其制备方法 |
| US12347830B2 (en) * | 2020-02-07 | 2025-07-01 | Uchicago Argonne, Llc | Interface design for high current density cycling of solid state battery |
| US11978847B2 (en) | 2020-04-14 | 2024-05-07 | Saint-Gobain Ceramics & Plastics, Inc. | Ion conductive material, electrolyte including ion conductive material, and methods of forming |
| US12266752B2 (en) | 2020-04-22 | 2025-04-01 | Uchicago Argonne, Llc | Modification of lithium ion electrode materials via atomic layer deposition techniques |
| KR102839601B1 (ko) | 2020-04-23 | 2025-07-30 | 세인트-고바인 세라믹스 앤드 플라스틱스, 인크. | 이온 전도층 및 형성 방법 |
| KR102538169B1 (ko) | 2020-04-23 | 2023-05-31 | 세인트-고바인 세라믹스 앤드 플라스틱스, 인크. | 이온 전도층 및 형성 방법 |
| CN111710915B (zh) * | 2020-06-28 | 2022-12-16 | 宜春清陶能源科技有限公司 | 一种固态锂离子电池 |
| CN114256504A (zh) * | 2020-09-23 | 2022-03-29 | 中国科学院上海硅酸盐研究所 | 一种固体电解质的表面修饰方法 |
| CN112768753A (zh) * | 2020-12-30 | 2021-05-07 | 广东微电新能源有限公司 | 固态电解质的制备方法、固态电池 |
| US12270101B2 (en) | 2021-03-19 | 2025-04-08 | Uchicago Argonne, Llc | Formation of lithium-metal-oxygen layer and removal of lithium carbonate on solid state electrolytes |
| US11414749B1 (en) | 2021-03-19 | 2022-08-16 | Uchicago Argonne, Llc | Formation of lithium-metal-carbon protecting layer and removal of lithium carbonate on lithium metal |
| CN115732750A (zh) * | 2021-08-31 | 2023-03-03 | 中国科学院化学研究所 | 一种表面修饰金属氧化物的固态电解质及其制备方法和应用 |
| KR20240162036A (ko) * | 2022-01-21 | 2024-11-14 | 에스케이온 주식회사 | Lgps계 고체 전해질 |
| US20230361338A1 (en) * | 2022-05-03 | 2023-11-09 | Samsung Electronics Co., Ltd. | Solid-state battery and method of manufacturing solid-state battery utilizing spray pyrolysis |
| JP2025522747A (ja) * | 2022-07-12 | 2025-07-17 | ハイドロ-ケベック | 表面改質固体電解質、それらを調製するためのプロセス、および電気化学セルにおけるそれらの使用 |
| KR102835018B1 (ko) * | 2022-10-14 | 2025-07-15 | 삼성에스디아이 주식회사 | 고체 전해질 및 그 제조 방법 |
| KR102885283B1 (ko) * | 2023-07-11 | 2025-11-11 | 삼성에스디아이 주식회사 | 고체 전해질과 그 제조 방법 및 이를 포함하는 고체 전해질 막과 전고체 이차 전지 |
| US20250062391A1 (en) * | 2023-08-16 | 2025-02-20 | GM Global Technology Operations LLC | Lithium ion cells including coated solid-state electrolytes and methods of forming the same |
| CN119495806A (zh) * | 2025-01-19 | 2025-02-21 | 吉林大学 | 一种具有界面修饰层的石榴石型固态电解质、制备方法及其在锂金属对称电池中的应用 |
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| US20130323603A1 (en) | 2012-06-04 | 2013-12-05 | Hyundai Motor Company | Solid high-ionic conductor for battery and lithium-sulfur battery using the same |
| JP2015041573A (ja) | 2013-08-23 | 2015-03-02 | 株式会社豊田中央研究所 | ガーネット型イオン伝導性酸化物、複合体、リチウム二次電池、ガーネット型イオン伝導性酸化物の製造方法及び複合体の製造方法 |
| WO2016069749A1 (en) | 2014-10-28 | 2016-05-06 | University Of Maryland, College Park | Interfacial layers for solid-state batteries methods of making same |
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| US6955866B2 (en) * | 1998-09-03 | 2005-10-18 | Polyplus Battery Company | Coated lithium electrodes |
| KR100659816B1 (ko) * | 2002-04-26 | 2006-12-19 | 미츠이 마이닝 & 스멜팅 콤파니 리미티드 | 비수 전해액 이차전지용 음극 및 그 제조방법 그리고 비수전해액 이차전지 |
| KR100477751B1 (ko) * | 2002-11-16 | 2005-03-21 | 삼성에스디아이 주식회사 | 비수계 전해액 및 이를 채용한 리튬 전지 |
| US20130216910A1 (en) * | 2010-11-09 | 2013-08-22 | 3M Innovative Properties Company | High capacity alloy anodes and lithium-ion electrochemical cells containing same |
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| US8940446B1 (en) * | 2013-08-06 | 2015-01-27 | Quantumscape Corporation | Solid state lithium-air based battery cell |
| JP6165546B2 (ja) * | 2013-08-09 | 2017-07-19 | 株式会社日立製作所 | 固体電解質および全固体リチウムイオン二次電池 |
| WO2017190135A1 (en) * | 2016-04-29 | 2017-11-02 | University Of Maryland, College Park | Metal alloy layers on substrates, methods of making same, and uses thereof |
| KR20190055842A (ko) * | 2016-10-07 | 2019-05-23 | 더 리젠츠 오브 더 유니버시티 오브 미시건 | 고체 상태 배터리용 안정화 코팅 |
| KR20190130155A (ko) * | 2017-03-31 | 2019-11-21 | 더 리젠츠 오브 더 유니버시티 오브 미시건 | 고체 전해질의 표면을 처리하기 위한 시스템 및 방법 |
| CN110710037B (zh) * | 2017-03-31 | 2024-03-08 | 密执安州立大学董事会 | 与固态电解质形成简易锂金属阳极界面的系统和方法 |
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| US20130323603A1 (en) | 2012-06-04 | 2013-12-05 | Hyundai Motor Company | Solid high-ionic conductor for battery and lithium-sulfur battery using the same |
| JP2015041573A (ja) | 2013-08-23 | 2015-03-02 | 株式会社豊田中央研究所 | ガーネット型イオン伝導性酸化物、複合体、リチウム二次電池、ガーネット型イオン伝導性酸化物の製造方法及び複合体の製造方法 |
| WO2016069749A1 (en) | 2014-10-28 | 2016-05-06 | University Of Maryland, College Park | Interfacial layers for solid-state batteries methods of making same |
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| EP3535796A1 (en) | 2019-09-11 |
| US20240222691A1 (en) | 2024-07-04 |
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| EP3535796B1 (en) | 2022-06-15 |
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| KR20190088477A (ko) | 2019-07-26 |
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