Co-free gradient lithium-rich cathode for high-energy batteries with optimized cyclability
Lithium-rich layered oxides (LLOs) hold the promise for high-energy battery cathodes. However, its application has been hindered by voltage decay associated with irreversible reactions at high voltages despite decades of intensive efforts. Here, we first theoretically studied the molecular orbitals of Mn-based Li-rich configurations. We found that the <i>π</i>-bond ring formed within the LiMn<sub>6</sub> structure could participate in stable redox reactions as one unit, but Co could disrupt its symmetry. We thus designed and synthesized Co-free concentration-gradient LLOs (CF-CG-LLOs) materials. The combination of concentration gradient and Co removal leads to exceptional capacity retention without any fading over 100 cycles of the pouch cell. More importantly, it exhibits an extraordinarily low voltage decay of 0.15 mV/cycle, accompanied by a high Coulombic efficiency of 99.86%. This concept and demonstration of CF-CG-LLO cathodes reveal a viable avenue toward low-cost, high-energy-density battery cathodes.
Authors
- Zengqing Zhuo (ORCID: https://orcid.org/0000-0001-6602-760X)
- Shu Zhao (ORCID: https://orcid.org/0000-0003-4377-1086)
- Haozhe Du
- Wanli Yang (ORCID: https://orcid.org/0000-0003-0666-8063)
- Haijun Yu (ORCID: https://orcid.org/0000-0003-0204-9943)
- Ligang Xu (ORCID: https://orcid.org/0000-0002-9414-0674)
- Lingqiao Wu
- Mingxue Tang (ORCID: https://orcid.org/0000-0001-5819-5048)
- Shiqi Liu (ORCID: https://orcid.org/0000-0003-3230-9099)
- Jie Liu (ORCID: https://orcid.org/0000-0002-5402-1881)
- Tianhao Wu (ORCID: https://orcid.org/0000-0001-9795-1782)
- Yuqiang Li (ORCID: https://orcid.org/0000-0001-7715-1155)
- Haotian Yang (ORCID: https://orcid.org/0009-0000-0830-7603)
- Lihang Wang (ORCID: https://orcid.org/0009-0006-2653-9671)
Institutions
- Lawrence Berkeley National Laboratory (US)
- Beijing University of Technology (CN)
- Division of Materials Science and Engineering (AU)
- Center for High Pressure Science and Technology Advanced Research (CN)
- University of Science and Technology Beijing (CN)
Publication Details
- Journal
- Proceedings of the National Academy of Sciences
- Published
- 2024-12-04
- DOI
- https://doi.org/10.1073/pnas.2412460121
- Citations
- 24
- Primary Topic
- Advancements in Battery Materials
- Type
- article
- Field-Weighted Citation Impact
- 5.01
Funders
- U.S. Department of Energy
- National Natural Science Foundation of China
- Samsung Science and Technology Foundation
- Samsung
- Office of Science
- National Key Research and Development Program of China