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| Format: | Preprint |
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2025
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| Online-Zugang: | https://arxiv.org/abs/2509.20622 |
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| author | Lomeli, Eder G. Li, Qinghao Hsu, Kuan H. Lee, Gi-Hyeok Zhuo, Zengqing Polzin, Bryant-J. Gim, Jihyeon Shi, Boyu Lee, Eungje Wang, Yujia Li, Haobo Yu, Pu Wu, Jinpeng Shen, Zhi-Xun Yan, Shishen Illa, Lauren Kas, Josh J. Rehr, John J. Vinson, John Moritz, Brian Liu, Yi-Sheng Guo, Jinghua Chuang, Yi-de Yang, Wanli Devereaux, Thomas P. |
| author_facet | Lomeli, Eder G. Li, Qinghao Hsu, Kuan H. Lee, Gi-Hyeok Zhuo, Zengqing Polzin, Bryant-J. Gim, Jihyeon Shi, Boyu Lee, Eungje Wang, Yujia Li, Haobo Yu, Pu Wu, Jinpeng Shen, Zhi-Xun Yan, Shishen Illa, Lauren Kas, Josh J. Rehr, John J. Vinson, John Moritz, Brian Liu, Yi-Sheng Guo, Jinghua Chuang, Yi-de Yang, Wanli Devereaux, Thomas P. |
| contents | Modern energy applications, especially electric vehicles, demand high energy batteries. However, despite decades of intensive efforts, the highest energy density and commercially viable batteries are still based on LiCoO2, the very first generation of cathode materials. The technical bottleneck is the stability of oxide-based cathodes at high operating voltages. The fundamental puzzle is that we actually never understood the redox mechanism of LiCoO2. Conventional wisdom generally defines redox to be centered on cations at low voltages, and on anions, i.e. oxygen, at high voltages by forming oxidized chemical states like O2 or peroxo-species. Here, through in-situ and ex-situ spectroscopy coupled with theoretical calculations, we show that high-energy layered cathodes, represented by LiCoO2 and LiNiO2, operate through enhancement of negative charge transfer (NCT) ground states upon charging throughout the whole voltage range - i.e., NCT evolution itself is the intrinsic redox mechanism regardless of voltage ranges. NCT inherently engages high covalency and oxygen holes, leading to optimized performance without conventional redox centers in LiCoO2. The level of NCT, i.e., number of ligand holes, naturally explains many seemingly controversial results. The redefinition of redox mechanism reveals the pathway toward viable high energy battery electrodes. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2509_20622 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Negative Charge Transfer: Ground State Precursor towards High Energy Batteries Lomeli, Eder G. Li, Qinghao Hsu, Kuan H. Lee, Gi-Hyeok Zhuo, Zengqing Polzin, Bryant-J. Gim, Jihyeon Shi, Boyu Lee, Eungje Wang, Yujia Li, Haobo Yu, Pu Wu, Jinpeng Shen, Zhi-Xun Yan, Shishen Illa, Lauren Kas, Josh J. Rehr, John J. Vinson, John Moritz, Brian Liu, Yi-Sheng Guo, Jinghua Chuang, Yi-de Yang, Wanli Devereaux, Thomas P. Materials Science Strongly Correlated Electrons Modern energy applications, especially electric vehicles, demand high energy batteries. However, despite decades of intensive efforts, the highest energy density and commercially viable batteries are still based on LiCoO2, the very first generation of cathode materials. The technical bottleneck is the stability of oxide-based cathodes at high operating voltages. The fundamental puzzle is that we actually never understood the redox mechanism of LiCoO2. Conventional wisdom generally defines redox to be centered on cations at low voltages, and on anions, i.e. oxygen, at high voltages by forming oxidized chemical states like O2 or peroxo-species. Here, through in-situ and ex-situ spectroscopy coupled with theoretical calculations, we show that high-energy layered cathodes, represented by LiCoO2 and LiNiO2, operate through enhancement of negative charge transfer (NCT) ground states upon charging throughout the whole voltage range - i.e., NCT evolution itself is the intrinsic redox mechanism regardless of voltage ranges. NCT inherently engages high covalency and oxygen holes, leading to optimized performance without conventional redox centers in LiCoO2. The level of NCT, i.e., number of ligand holes, naturally explains many seemingly controversial results. The redefinition of redox mechanism reveals the pathway toward viable high energy battery electrodes. |
| title | Negative Charge Transfer: Ground State Precursor towards High Energy Batteries |
| topic | Materials Science Strongly Correlated Electrons |
| url | https://arxiv.org/abs/2509.20622 |