@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},
  booktitle = {Advanced Energy Materials},
  journal = {Advanced Energy Materials},
  series = {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},
}