Twinning mediated intralayer frustration governs structural degradation in layered Li-rich oxide cathode
Abstract Layered Li-rich Mn-based (LRM) oxides are promising cathode materials for next-generation high-energy batteries. However, their commercialization is hindered by intrinsic structural issues and subsequent degradation processes. In order to address the degradation mechanisms, we use operando...
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Nature Portfolio
2025-07-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-61386-w |
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| author | Tingting Yang Maolin Yang Zhongyuan Huang Rui Wang Wenhai Ji Peng-Han Lu Tao Zeng Zenan Li Jun Wang Rafal E. Dunin-Borkowski Lei Jin Yinguo Xiao |
| author_facet | Tingting Yang Maolin Yang Zhongyuan Huang Rui Wang Wenhai Ji Peng-Han Lu Tao Zeng Zenan Li Jun Wang Rafal E. Dunin-Borkowski Lei Jin Yinguo Xiao |
| author_sort | Tingting Yang |
| collection | DOAJ |
| description | Abstract Layered Li-rich Mn-based (LRM) oxides are promising cathode materials for next-generation high-energy batteries. However, their commercialization is hindered by intrinsic structural issues and subsequent degradation processes. In order to address the degradation mechanisms, we use operando neutron diffraction and scanning transmission electron microscopy to follow the microstructural degeneration of the LRM oxides in a prepared full cell with a graphite anode. The methods enable both real-time phase analysis and structural evolution mapping across a wide field of view. The LRM oxide is observed to initially have a partially ordered Li2MnO3-like structure with multiple planar defects. It transitions from an ordered monoclinic phase to a disordered rhombohedral phase as a result of irreversible Li+ migration and transition metal rearrangement during cycling. Especially after the first full charge, the interlayer (001) twining-like structures and local intralayer frustrations formed. Over cycling, the intralayer frustrations further develop into pore-like microstructures along the {012} twinning boundary in the bulk of the particles, which contributes significantly to performance reduction. The results clarify the link between microstructure degradation and performance loss and provide valuable insights into the optimization of high-performance cathodes. |
| format | Article |
| id | doaj-art-e588a8d557f94b0c8872b2d09aa73c28 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Nature Portfolio |
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| series | Nature Communications |
| spelling | doaj-art-e588a8d557f94b0c8872b2d09aa73c282025-08-20T03:46:28ZengNature PortfolioNature Communications2041-17232025-07-011611910.1038/s41467-025-61386-wTwinning mediated intralayer frustration governs structural degradation in layered Li-rich oxide cathodeTingting Yang0Maolin Yang1Zhongyuan Huang2Rui Wang3Wenhai Ji4Peng-Han Lu5Tao Zeng6Zenan Li7Jun Wang8Rafal E. Dunin-Borkowski9Lei Jin10Yinguo Xiao11School of Advanced Materials, Peking University, Shenzhen Graduate SchoolSchool of Advanced Materials, Peking University, Shenzhen Graduate SchoolSchool of Advanced Materials, Peking University, Shenzhen Graduate SchoolDepartment of Engineering, University of CambridgeSpallation Neutron Source Science CenterErnst Ruska-Centre for Microscopy and Spectroscopy with Electrons, Forschungszentrum Jülich GmbHSchool of Advanced Materials, Peking University, Shenzhen Graduate SchoolSchool of Innovation and Entrepreneurship, Southern University of Science and TechnologySchool of Innovation and Entrepreneurship, Southern University of Science and TechnologyErnst Ruska-Centre for Microscopy and Spectroscopy with Electrons, Forschungszentrum Jülich GmbHErnst Ruska-Centre for Microscopy and Spectroscopy with Electrons, Forschungszentrum Jülich GmbHSchool of Advanced Materials, Peking University, Shenzhen Graduate SchoolAbstract Layered Li-rich Mn-based (LRM) oxides are promising cathode materials for next-generation high-energy batteries. However, their commercialization is hindered by intrinsic structural issues and subsequent degradation processes. In order to address the degradation mechanisms, we use operando neutron diffraction and scanning transmission electron microscopy to follow the microstructural degeneration of the LRM oxides in a prepared full cell with a graphite anode. The methods enable both real-time phase analysis and structural evolution mapping across a wide field of view. The LRM oxide is observed to initially have a partially ordered Li2MnO3-like structure with multiple planar defects. It transitions from an ordered monoclinic phase to a disordered rhombohedral phase as a result of irreversible Li+ migration and transition metal rearrangement during cycling. Especially after the first full charge, the interlayer (001) twining-like structures and local intralayer frustrations formed. Over cycling, the intralayer frustrations further develop into pore-like microstructures along the {012} twinning boundary in the bulk of the particles, which contributes significantly to performance reduction. The results clarify the link between microstructure degradation and performance loss and provide valuable insights into the optimization of high-performance cathodes.https://doi.org/10.1038/s41467-025-61386-w |
| spellingShingle | Tingting Yang Maolin Yang Zhongyuan Huang Rui Wang Wenhai Ji Peng-Han Lu Tao Zeng Zenan Li Jun Wang Rafal E. Dunin-Borkowski Lei Jin Yinguo Xiao Twinning mediated intralayer frustration governs structural degradation in layered Li-rich oxide cathode Nature Communications |
| title | Twinning mediated intralayer frustration governs structural degradation in layered Li-rich oxide cathode |
| title_full | Twinning mediated intralayer frustration governs structural degradation in layered Li-rich oxide cathode |
| title_fullStr | Twinning mediated intralayer frustration governs structural degradation in layered Li-rich oxide cathode |
| title_full_unstemmed | Twinning mediated intralayer frustration governs structural degradation in layered Li-rich oxide cathode |
| title_short | Twinning mediated intralayer frustration governs structural degradation in layered Li-rich oxide cathode |
| title_sort | twinning mediated intralayer frustration governs structural degradation in layered li rich oxide cathode |
| url | https://doi.org/10.1038/s41467-025-61386-w |
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