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Volume 106
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Yang, N., You, Y., Ou, S., Wang, L., Li, Z., Xu, J., . . . Yuan, M. (2025). Nb5+ doping modulates crystal morphology and electronic structure of spinel LiMn2O4 for high-rate long-cycle cathode materials. Particuology, 106, 236-247. https://doi.org/10.1016/j.partic.2025.08.023
Nb5+ doping modulates crystal morphology and electronic structure of spinel LiMn2O4 for high-rate long-cycle cathode materials
Ningfei Yang, Yang You, Shengwen Ou, Lianghua Wang, Zhen Li, Jingyue Xu, Haoran Luo, Mingliang Yuan *
School of Mineral Processing and Bioengineering, Central South University, Changsha, 410083, China
10.1016/j.partic.2025.08.023
Volume 106, November 2025, Pages 236-247
School of Mineral Processing and Bioengineering, Central South University, Changsha, 410083, China
E-mail: mlydoc@126.com
Highlights

• Crystal morphology of LiMn2O4 is precisely regulated by Nb5+ doping.

• This study elucidates underlying mechanism by which Nb5+ doping modulates local electronic structure of LiMn2O4.

• Cathode delivers superior rate capability and impressive cycling stability.


Abstract

Manganese dissolution and the Jahn-Teller distortion represent the primary factors limiting the cycle life of spinel LiMn2O4. In this study, Nb5+-doped Li1.05Mn2-xNbxO4 (0 ≤ x ≤ 0.03) with truncated octahedral morphology was successfully synthesized via a simple high-temperature solid-state method. Nb5+ doping not only enhanced the structural stability of LiMn2O4 but also increased the Li + diffusion rate. SEM analysis revealed that Nb5+ doping effectively suppressed (110) plane growth, thereby mitigating Mn dissolution. Simultaneously, TEM results indicated that a thinner cathode electrolyte interphase film was formed upon doping, which contributed to enhanced cycling stability. Further DFT calculations confirmed that Nb5+ doping improved the structural stability of LiMn2O4 through a dual mechanism: reducing the occupancy of the Mn eg orbitals and strengthening the Mn-O bonding energy. On the other hand, Nb5+ doping expands the lattice, with CV and EIS tests showing increased Li+ diffusion rates. PDOS calculations revealed a narrowed band gap, which improved the electronic conductivity, thereby endowing LiMn2O4 with high-rate performance. Hence, Li1.05Mn2-xNbxO4 exhibits superior rate capability and extended cycle life. Specifically, Li1.05Mn1.99Nb0.01O4 delivered an initial discharge capacity of 124.61 mAh/g with 88.43 % capacity retention after 500 cycles at 1 C, and maintained 74.61 mAh/g even at 10 C.

Graphical abstract
Keywords
Nb-doping; Spinel LiMn2O4; Crystal surface control; Lithium-ion battery
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