Gradient-morph LiCoO2 single crystals with stabilized energy density above 3400 W h L−1
The cycling stability of LiCoO[subscript 2] under high voltages (>4.5 V) was plagued by hybrid anion- and cation-redox (HACR) induced oxygen escape and uncontrolled phase collapse. With DEMS and in situ XANES mapping at the NSLS-II, we demonstrate that oxygen escape triggers irreversible transfor...
| Main Authors: | , , , , , , , , , , , , |
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| Format: | Article |
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Royal Society of Chemistry (RSC)
2021
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| Online Access: | https://hdl.handle.net/1721.1/132623 |
| _version_ | 1826209469787275264 |
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| author | Zhu, Zhi Yu, Daiwei Shi, Zhe Gao, Rui Xiao, Xianghui Waluyo, Iradwikanari Ge, Mingyuan Dong, Yanhao Xue, Weijiang Xu, Guiyin Lee, Wah-Keat Hunt, Adrian Li, Ju |
| author2 | Massachusetts Institute of Technology. Department of Nuclear Science and Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Nuclear Science and Engineering Zhu, Zhi Yu, Daiwei Shi, Zhe Gao, Rui Xiao, Xianghui Waluyo, Iradwikanari Ge, Mingyuan Dong, Yanhao Xue, Weijiang Xu, Guiyin Lee, Wah-Keat Hunt, Adrian Li, Ju |
| author_sort | Zhu, Zhi |
| collection | MIT |
| description | The cycling stability of LiCoO[subscript 2] under high voltages (>4.5 V) was plagued by hybrid anion- and cation-redox (HACR) induced oxygen escape and uncontrolled phase collapse. With DEMS and in situ XANES mapping at the NSLS-II, we demonstrate that oxygen escape triggers irreversible transformations into “bad” surface phases that rapidly propagate inward. Enabling HACR but stopping global oxygen migration is key to a stable high-energy cathode. Therefore, we developed ∼10 μm single crystals with LiCoO[subscript 2] in the bulk smoothly transitioning to Co-free LiMn[subscript 0.75]Ni[subscript0.25]O[subscript 2] at the surface. By means of initial electrochemical formation, a semi-coherent LiMn[subscript 1.5]Ni[subscript 0.5]O[subscript 4] spinel-like shell was established in operando with little oxygen loss to integrally wrap the LiCoO[subscript 2] bulk. Then we obtained gradient-morph LiCoO[[subscript 2] single crystals to prevent the percolating migration of oxygen out of the particle and achieved enhanced HACR reversibility at high voltages. The gradient-morph HACR cathode undergoes substantially stabilized cycling when charged to above 4.6 V, and hence a stable cyclic volumetric energy density of >3400 W h L−1 has been achieved in a pouch full-cell coupled with a commercial graphite anode and lean electrolyte (2 g A h−1), exhibiting up to 2906 W h L−1 even after 300 cycles. |
| first_indexed | 2024-09-23T14:23:01Z |
| format | Article |
| id | mit-1721.1/132623 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T14:23:01Z |
| publishDate | 2021 |
| publisher | Royal Society of Chemistry (RSC) |
| record_format | dspace |
| spelling | mit-1721.1/1326232022-10-01T20:59:12Z Gradient-morph LiCoO2 single crystals with stabilized energy density above 3400 W h L−1 Zhu, Zhi Yu, Daiwei Shi, Zhe Gao, Rui Xiao, Xianghui Waluyo, Iradwikanari Ge, Mingyuan Dong, Yanhao Xue, Weijiang Xu, Guiyin Lee, Wah-Keat Hunt, Adrian Li, Ju Massachusetts Institute of Technology. Department of Nuclear Science and Engineering Massachusetts Institute of Technology. Department of Materials Science and Engineering Massachusetts Institute of Technology. Department of Electrical Engineering and Computer Science The cycling stability of LiCoO[subscript 2] under high voltages (>4.5 V) was plagued by hybrid anion- and cation-redox (HACR) induced oxygen escape and uncontrolled phase collapse. With DEMS and in situ XANES mapping at the NSLS-II, we demonstrate that oxygen escape triggers irreversible transformations into “bad” surface phases that rapidly propagate inward. Enabling HACR but stopping global oxygen migration is key to a stable high-energy cathode. Therefore, we developed ∼10 μm single crystals with LiCoO[subscript 2] in the bulk smoothly transitioning to Co-free LiMn[subscript 0.75]Ni[subscript0.25]O[subscript 2] at the surface. By means of initial electrochemical formation, a semi-coherent LiMn[subscript 1.5]Ni[subscript 0.5]O[subscript 4] spinel-like shell was established in operando with little oxygen loss to integrally wrap the LiCoO[subscript 2] bulk. Then we obtained gradient-morph LiCoO[[subscript 2] single crystals to prevent the percolating migration of oxygen out of the particle and achieved enhanced HACR reversibility at high voltages. The gradient-morph HACR cathode undergoes substantially stabilized cycling when charged to above 4.6 V, and hence a stable cyclic volumetric energy density of >3400 W h L−1 has been achieved in a pouch full-cell coupled with a commercial graphite anode and lean electrolyte (2 g A h−1), exhibiting up to 2906 W h L−1 even after 300 cycles. 2021-09-22T14:21:19Z 2021-09-22T14:21:19Z 2020-05 2020-01 Article http://purl.org/eprint/type/JournalArticle 1754-5692 1754-5706 https://hdl.handle.net/1721.1/132623 Zhu, Zhi et al. "Gradient-morph LiCoO2 single crystals with stabilized energy density above 3400 W h L−1." Energy & Environmental Science 13, 6 (May 2020): 1865-1878. © 2020 The Royal Society of Chemistry https://doi.org/10.1039/D0EE00231C Energy & Environmental Science Creative Commons Attribution 3.0 unported license https://creativecommons.org/licenses/by/3.0/ application/pdf Royal Society of Chemistry (RSC) Royal Society of Chemistry (RSC) |
| spellingShingle | Zhu, Zhi Yu, Daiwei Shi, Zhe Gao, Rui Xiao, Xianghui Waluyo, Iradwikanari Ge, Mingyuan Dong, Yanhao Xue, Weijiang Xu, Guiyin Lee, Wah-Keat Hunt, Adrian Li, Ju Gradient-morph LiCoO2 single crystals with stabilized energy density above 3400 W h L−1 |
| title | Gradient-morph LiCoO2 single crystals with stabilized energy density above 3400 W h L−1 |
| title_full | Gradient-morph LiCoO2 single crystals with stabilized energy density above 3400 W h L−1 |
| title_fullStr | Gradient-morph LiCoO2 single crystals with stabilized energy density above 3400 W h L−1 |
| title_full_unstemmed | Gradient-morph LiCoO2 single crystals with stabilized energy density above 3400 W h L−1 |
| title_short | Gradient-morph LiCoO2 single crystals with stabilized energy density above 3400 W h L−1 |
| title_sort | gradient morph licoo2 single crystals with stabilized energy density above 3400 w h l 1 |
| url | https://hdl.handle.net/1721.1/132623 |
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