Zeng Tao, Jiao Ziqin, Gao Xiaoyu, Yang Maolin, Wang Xiaohu, Zhao Wenguang, Tang Wei, Chu Mihai, He Ze, Li Jinqi, Huang Zhongyuan, Chen Guojie, Chen Ziwei, Wang Rui, Wang Liming, Zhang Junrong, He Lunhua, Pu Yuguang, Xiao Yinguo
School of Advanced Materials, Peking University, Shenzhen Graduate School, Shenzhen, 518055, China.
School of Chemistry, Sun Yat-sen University, Guangzhou, 510275, China.
Angew Chem Int Ed Engl. 2025 Jul 7;64(28):e202501777. doi: 10.1002/anie.202501777. Epub 2025 May 20.
Li-rich manganese-based oxides (LRMO) are promising cathode materials for next-generation lithium-ion batteries due to their high-capacity and low-cost merits. However, the low initial coulombic efficiency (ICE) and irreversible oxygen release of LRMO severely hinder their commercialization processes. Here, we employ glyoxal treatment to modulate the hybridization between transition metal (TM) 3d and oxygen (O) 2p orbitals in LRMO. This approach is found to reduce the Co/Mn t-O 2p hybridization in LRMO while simultaneously activating the Co/Co redox below the Fermi level. Our findings demonstrate that tuning TM 3d-O 2p orbital hybridization can be a viable approach to improve the ICE of LMRO. Specifically, the ICE of LRMO can be elevated from 85.3% to 102.5%, and a high specific capacity of 291.2 mAh g can be achieved at 0.1 C. Moreover, the treated LRMO cathodes exhibit significantly enhanced capacity retention.
富锂锰基氧化物（LRMO）因其高容量和低成本的优点，是下一代锂离子电池很有前景的正极材料。然而，LRMO较低的初始库仑效率（ICE）和不可逆的氧释放严重阻碍了它们的商业化进程。在此，我们采用乙二醛处理来调节LRMO中过渡金属（TM）3d和氧（O）2p轨道之间的杂化。结果发现，这种方法可以减少LRMO中Co/Mn t-O 2p杂化，同时激活费米能级以下的Co/Co氧化还原。我们的研究结果表明，调节TM 3d-O 2p轨道杂化可能是提高LMRO的ICE的一种可行方法。具体而言，LRMO的ICE可以从85.3%提高到102.5%，在0.1 C下可以实现291.2 mAh g的高比容量。此外，经过处理的LRMO正极表现出显著增强的容量保持率。
