@article{35894,
  author = {Liliang Huang and Peichen Zhong and Yang Ha and Zijian Cai and Young‐Woon Byeon and Tzu‐Yang Huang and Yingzhi Sun and Fengyu Xie and Han‐Ming Hau and Haegyeom Kim and Mahalingam Balasubramanian and Bryan D McCloskey and Wanli Yang and Gerbrand Ceder},
  title = {Optimizing Li‐Excess Cation‐Disordered Rocksalt Cathode Design Through Partial Li Deficiency},
  abstract = {<p><span>Li-excess disordered rocksalts (DRXs) are emerging as promising cathode materials for Li-ion batteries due to their ability to use earth-abundant transition metals. In this work, a new strategy based on partial Li deficiency engineering is introduced to optimize the overall electrochemical performance of DRX cathodes. Specifically, by using Mn-based DRX as a proof-of-concept, it is demonstrated that the introduction of cation vacancies during synthesis (e.g., Li</span><sub><span>1.3-</span><em><span>x</span></em></sub><span>Mn</span><sup><span>2+</span></sup><sub><span>0.4-</span><em><span>x</span></em></sub><span>Mn</span><sup><span>3+</span></sup><sub><em><span>x</span></em></sub><span>Nb</span><sub><span>0.3</span></sub><span>O</span><sub><span>1.6</span></sub><span>F</span><span>0.4</span><span>,&nbsp;</span><em>x</em><span>&nbsp;= 0, 0.2, and 0.4) improves both the discharge capacity and rate performance due to the more favored short-range order in the presence of Mn</span><span>3+</span><span>. Density functional theory calculations and Monte Carlo simulations, in combination with spectroscopic tools, reveal that introducing 10% vacancies (Li</span><sub><span>1.1</span></sub><span>Mn</span><sup><span>2+</span></sup><sub><span>0.2</span></sub><span>Mn</span><sup><span>3+</span></sup><sub><span>0.2</span></sub><span>Nb</span><sub><span>0.3</span></sub><span>O</span><sub><span>1.6</span></sub><span>F</span><sub><span>0.4</span></sub><span>) enables both Mn</span><sup><span>2+</span></sup><span>/Mn</span><sup><span>3+</span></sup><span>&nbsp;redox and excellent Li percolation. However, a more aggressive vacancy doping (e.g., 20% vacancies in Li</span><sub><span>0.9</span></sub><span>Mn</span><sup><span>3+</span></sup><sub><span>0.4</span></sub><span>Nb</span><sub><span>0.3</span></sub><span>O</span><span><sub>1.6</sub></span><span>F</span><sub><span>0.4</span></sub><span>) impairs performance because it induces phase separation between an Mn-rich and a Li-rich phase.</span></p>},
  year = {2023},
  journal = {Advanced Energy Materials},
  volume = {13},
  pages = {2202345},
  month = {01/2023},
  issn = {1614-6832},
  url = {https://onlinelibrary.wiley.com/toc/16146840/13/4},
  doi = {10.1002/aenm.202202345},
  language = {eng},
}