Mei Yu, Li Yujin, Wang Haoji, Gao Jinqiang, Ni Lianshan, Silvester Debbie S, Banks Craig E, Deng Wentao, Chen Baishan, Zou Guoqiang, Hou Hongshuai, Liu Tongchao, Ji Xiaobo, Liang Chaoping, Amine Khalil
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China.
Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States.
J Am Chem Soc. 2025 Feb 5;147(5):4438-4449. doi: 10.1021/jacs.4c15631. Epub 2025 Jan 22.
Li-rich cation-disordered rocksalt (DRX) materials introduce new paradigms in the design of high-capacity Li-ion battery cathode materials. However, DRX materials show strikingly sluggish kinetics due to random Li percolation with poor rate performance. Here, we demonstrate that Li stuffing into the tetrahedral sites of the Mn-based rocksalt skeleton injects a novel tetrahedron-octahedron-tetrahedron diffusion path, which acts as a low-energy-barrier hub to facilitate high-speed Li transport. Moreover, the enhanced stability of lattice oxygen and the suppression of transition metal migration preserve the efficacy of the Li percolation network during cycling. Overall, the tetrahedral Li stuffing DRX material exhibits high energy density (311 mAh g, 923 Wh kg) and high power density (251 mAh g, 697 Wh kg at 1000 mA g). Our results highlight the potential to develop high-performance and earth-abundant cathode materials within the extensive range of rocksalt compounds.
富锂阳离子无序岩盐（DRX）材料为高容量锂离子电池正极材料的设计引入了新范式。然而，由于随机锂渗透导致倍率性能较差，DRX材料表现出显著迟缓的动力学。在此，我们证明将锂填充到锰基岩盐骨架的四面体位置会引入一种新颖的四面体-八面体-四面体扩散路径，该路径作为低能垒枢纽促进高速锂传输。此外，晶格氧稳定性的增强和过渡金属迁移的抑制在循环过程中保持了锂渗透网络的有效性。总体而言，四面体锂填充DRX材料展现出高能量密度（311 mAh g，923 Wh kg）和高功率密度（在1000 mA g下为25 mAh g，697 Wh kg）。我们的结果突出了在广泛的岩盐化合物范围内开发高性能且储量丰富的正极材料的潜力。
