CN113614971A - 高空气稳定性无机硫化物固体电解质及其制备方法与应用 - Google Patents
高空气稳定性无机硫化物固体电解质及其制备方法与应用 Download PDFInfo
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- CN113614971A CN113614971A CN201980093980.5A CN201980093980A CN113614971A CN 113614971 A CN113614971 A CN 113614971A CN 201980093980 A CN201980093980 A CN 201980093980A CN 113614971 A CN113614971 A CN 113614971A
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- inorganic sulfide
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- 229910052945 inorganic sulfide Inorganic materials 0.000 title claims abstract description 37
- 239000002203 sulfidic glass Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000002001 electrolyte material Substances 0.000 claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 110
- 238000000227 grinding Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 abstract description 44
- 239000003792 electrolyte Substances 0.000 abstract description 29
- 239000007784 solid electrolyte Substances 0.000 description 39
- 238000002441 X-ray diffraction Methods 0.000 description 19
- 229910001416 lithium ion Inorganic materials 0.000 description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 15
- 238000000498 ball milling Methods 0.000 description 15
- 239000006104 solid solution Substances 0.000 description 15
- 239000012071 phase Substances 0.000 description 14
- 238000010586 diagram Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 238000001354 calcination Methods 0.000 description 10
- 230000008859 change Effects 0.000 description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Inorganic materials [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 229910001216 Li2S Inorganic materials 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001453 impedance spectrum Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 229910005842 GeS2 Inorganic materials 0.000 description 3
- 229910012820 LiCoO Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 229910003480 inorganic solid Inorganic materials 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 238000012552 review Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- -1 sulfur ions Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910018130 Li 2 S-P 2 S 5 Inorganic materials 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002227 LISICON Substances 0.000 description 1
- 229910012923 LiCoO2In Inorganic materials 0.000 description 1
- 241000612182 Rexea solandri Species 0.000 description 1
- 229910020343 SiS2 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000002226 superionic conductor Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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Abstract
一种高空气稳定性无机硫化物固体电解质及其制备方法与应用。采用Sb元素取代硫化物电解质中部分或者全部的P元素,从而获得具有更高的空气稳定性以及更高离子迁移率的电解质,可以应用于全固态锂二次电池中。所获得的该类型无机硫化物电解质材料有Li10M(P1‑aSba)2S12、Li6(P1‑aSba)S5X和Li3(P1‑aSba)S4,其中M为Ge、Si、Sn中的一种或者多种;X为F、C1、Br、I中的一种或者多种;0.01≤a≤1。
Description
PCT国内申请,说明书已公开。
Claims (11)
- PCT国内申请,权利要求书已公开。
Applications Claiming Priority (3)
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CN201910358953.8A CN110085908B (zh) | 2019-04-30 | 2019-04-30 | 高空气稳定性无机硫化物固体电解质及其制备方法与应用 |
CN2019103589538 | 2019-04-30 | ||
PCT/CN2019/123481 WO2020220676A1 (zh) | 2019-04-30 | 2019-12-06 | 高空气稳定性无机硫化物固体电解质及其制备方法与应用 |
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CN201980093980.5A Pending CN113614971A (zh) | 2019-04-30 | 2019-12-06 | 高空气稳定性无机硫化物固体电解质及其制备方法与应用 |
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US (1) | US20220131182A1 (zh) |
EP (1) | EP3893308B1 (zh) |
JP (1) | JP7129075B2 (zh) |
KR (1) | KR20210148306A (zh) |
CN (2) | CN110085908B (zh) |
ES (1) | ES2943111T3 (zh) |
WO (1) | WO2020220676A1 (zh) |
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CN110085908B (zh) * | 2019-04-30 | 2021-09-17 | 国联汽车动力电池研究院有限责任公司 | 高空气稳定性无机硫化物固体电解质及其制备方法与应用 |
JP2022547101A (ja) * | 2019-09-06 | 2022-11-10 | ローディア オペレーションズ | Li-p-s製品の新規な製造方法及び対応する製品 |
CN111710902B (zh) * | 2020-06-01 | 2021-11-09 | 国联汽车动力电池研究院有限责任公司 | 玻璃-陶瓷型硫化物电解质及其制备方法和应用 |
JP2023543227A (ja) * | 2020-09-23 | 2023-10-13 | ソリッド パワー オペレーティング, インコーポレイティド | 固体電解質材料及びそれを使用して製造される固体電池 |
CN112777632B (zh) * | 2021-01-25 | 2022-05-03 | 武汉船用电力推进装置研究所(中国船舶重工集团公司第七一二研究所) | 一种硫化物锂离子固态电解质及其制备方法和应用 |
CN113097560A (zh) * | 2021-04-09 | 2021-07-09 | 浙江大学山东工业技术研究院 | 一种高空气稳定性纳米晶硫化物固体电解质和固态电池及其制备方法 |
CN113363569B (zh) * | 2021-06-30 | 2023-05-05 | 国联汽车动力电池研究院有限责任公司 | 一种高稳定性无机硫化物固体电解质及其制备方法 |
CN113471521B (zh) * | 2021-06-30 | 2022-08-19 | 国联汽车动力电池研究院有限责任公司 | 一种无机硫化物固体电解质及其制备方法 |
CN114933331B (zh) * | 2022-05-13 | 2023-02-17 | 上海屹锂新能源科技有限公司 | 一种硫化物固态电解质及其制备方法 |
CN116706212B (zh) * | 2023-05-09 | 2024-02-02 | 高能时代(珠海)新能源科技有限公司 | 一种固态电解质的制备方法及制备装置 |
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CN110085908B (zh) | 2021-09-17 |
WO2020220676A1 (zh) | 2020-11-05 |
EP3893308A1 (en) | 2021-10-13 |
KR20210148306A (ko) | 2021-12-07 |
ES2943111T3 (es) | 2023-06-09 |
CN110085908A (zh) | 2019-08-02 |
JP7129075B2 (ja) | 2022-09-01 |
EP3893308A4 (en) | 2022-03-16 |
EP3893308B1 (en) | 2023-02-08 |
JP2022502341A (ja) | 2022-01-11 |
US20220131182A1 (en) | 2022-04-28 |
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