Dual lanthanides synergistically boost stability and kinetics for spinel LiMn2O4 cathodes.
Zhushun Zhang, Jun Du, Tenghao Li, Hengchao Sun, Shuai Bing Li, Huakun Peng, Peng Liu, Dapeng Du, Tianyi Wang, Chengyin Wang, Likun Pan, Jiabao Li
Abstract
Open AccessMn-site doping in spinel LiMn2O4 (LMO) mitigates Mn3+-induced Jahn-Teller distortion. However, this strategy faces inherent trade-offs. Specifically, low-valent doping weakens oxygen bonding, while high-valent doping increases Mn3+ content. To overcome these limitations, this work proposes dual-lanthanide (La3+/Ce3+) co-doping. Through sol-gel synthesis, LiLa0.1Ce0.1Mn1.8O4 (LLCMO) achieves synergistic performance enhancements. Particularly, La reduces Mn3+ content to 43.13%, suppressing lattice distortion and widening Li+ diffusion pathways via its large ionic radius. Concurrently, Ce (in a mixed Ce3+/Ce4+ state) enhances charge delocalization, lowering electron transfer barriers and boosting conductivity. Critically, La-Ce cooperation mitigates Mn dissolution while stabilizing the spinel framework. Consequently, LLCMO exhibits a 3.2-fold higher Li+ diffusion coefficient than pristine LMO. Furthermore, it delivers 111.2 mAh g-1 at 0.5 C with 90.9% retention after 100 cycles, and remarkably retains 76.0 mAh g-1 after 1000 cycles even at 10 C. Thus, this dual-doping strategy establishes a generalizable design principle for enhancing stability/kinetics in diverse cathodes via a synergistic division-of-labor mechanism.