<p>Mn-site doping in spinel LiMn<sub>2</sub>O<sub>4</sub> (LMO) mitigates Mn<sup>3+</sup>-induced Jahn-Teller distortion. However, this strategy faces inherent trade-offs. Specifically, low-valent doping weakens oxygen bonding, while high-valent doping increases Mn<sup>3+</sup> content. To overcome these limitations, this work proposes dual-lanthanide (La<sup>3+</sup>/Ce<sup>3+</sup>) co-doping. Through sol-gel synthesis, LiLa<sub>0.1</sub>Ce<sub>0.1</sub>Mn<sub>1.8</sub>O<sub>4</sub> (LLCMO) achieves synergistic performance enhancements. Particularly, La reduces Mn<sup>3+</sup> content to 43.13%, suppressing lattice distortion and widening Li+ diffusion pathways via its large ionic radius. Concurrently, Ce (in a mixed Ce<sup>3+</sup>/Ce<sup>4+</sup> 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<sup>−1</sup> at 0.5 C with 90.9% retention after 100 cycles, and remarkably retains 76.0 mAh g<sup>−1</sup> 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.</p><p></p>

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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

摘要

Mn-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.