Understanding the Role of Nb Doping in Modulating Ionic Diffusion Kinetics and Particle Size in Spinel LiMn2O4

Junda Li , Xiaoxia Yang , Jiayong Chen , Guanjie Yan , Bo Wang , Ruimin Qin , Chunliu Li , Yaqiong Su , Zhongzhu Liu , Luanna Silveira Parreira , Robson S. Monteiro , Laijun Liu , Leidang Zhou , Weibo Hua

Battery Energy ›› 2026, Vol. 5 ›› Issue (1) : e70074

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Battery Energy ›› 2026, Vol. 5 ›› Issue (1) :e70074 DOI: 10.1002/bte2.70074
RESEARCH ARTICLE
Understanding the Role of Nb Doping in Modulating Ionic Diffusion Kinetics and Particle Size in Spinel LiMn2O4
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Abstract

The increased primary particle size generally leads to reduced electrochemical performance of electrode materials in Li-ion batteries. Herein, we report the simultaneous achievement of enhanced rate performance and increased particle size in spinel LiMn2O4 (LMO) through niobium (Nb) incorporation. After Nb incorporation, the surface energies of the (100), (110), and (111) crystal planes are significantly reduced, resulting in the formation of larger particles. Moreover, Nb doping increases the lattice parameter of the spinel structure, thereby facilitating Li+ transport and reducing polarization. Electrochemical tests demonstrate that the LMO cathode with 0.4 wt.% Nb delivers an initial discharge capacity of 130 mAh g−1 and retains 93.9% of its capacity after 100 cycles at 1 C and 45°C.

Keywords

kinetics / lithium-ion batteries / niobium (Nb) doping / spinel LiMn2O4 (LMO) / surface energy

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Junda Li, Xiaoxia Yang, Jiayong Chen, Guanjie Yan, Bo Wang, Ruimin Qin, Chunliu Li, Yaqiong Su, Zhongzhu Liu, Luanna Silveira Parreira, Robson S. Monteiro, Laijun Liu, Leidang Zhou, Weibo Hua. Understanding the Role of Nb Doping in Modulating Ionic Diffusion Kinetics and Particle Size in Spinel LiMn2O4. Battery Energy, 2026, 5(1): e70074 DOI:10.1002/bte2.70074

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References

[1]

D. Xia, J. Yao, C. Shi, et al., “Toward Stable, High-Energy, Partially Disordered Mn-Rich Spinel Cathodes by Revealing and Mitigating Surface Degradation,” Advanced Materials37, no. 34 (2025): 2501352, https://doi.org/10.1002/adma.202501352.

[2]

M. M. Thackeray, “Exploiting the Spinel Structure for Li-Ion Battery Applications: A Tribute to John B. Goodenough,” Advanced Energy Materials11, no. 2 (2021): 2001117, https://doi.org/10.1002/aenm.202001117.

[3]

S. Lei, J. Li, W. Sun, P. Ge, and Y. Yang, “Upcycling of Low-Value Cathode Materials From Spent Lithium-Ion Battery to High-Voltage Cathode With Ultrahigh Rate Capability and Reversibility,” Advanced Energy Materials15, no. 16 (2025): 202406064, https://doi.org/10.1002/aenm.202406064.

[4]

W. Ou, S. D. Marks, R. F. de Menezes, et al., “Unveiling the Mechanism of Mn Dissolution Through a Dynamic Cathode–Electrolyte Interphase on LiMn2O4,” Advanced Energy Materials15, no. 22 (2025): 2404652, https://doi.org/10.1002/aenm.202404652.

[5]

C. Zhang, B. Chen, Q. Chen, et al., “Regulation of Molecular Microheterogeneity in Electrolytes Enables Ampere-Hour-Level Aqueous LiMn2O4‖Li4Ti5O12 Pouch Cells,” Advanced Materials36, no. 29 (2024): 2405913, https://doi.org/10.1002/adma.202405913.

[6]

X. Ye, X. Fei, M. Liu, et al., “Laser-Induced Regeneration of Spent LiMn2O4 Cathode Into High-Performance Ni-Doped LiMn2O4 Cathode,” Advanced Materials37, no. 3 (2025): 2416537, https://doi.org/10.1002/adma.202416537.

[7]

G. Tan, S. Wan, J. J. Chen, H. Q. Yu, and Y. Yu, “Reduced Lattice Constant in Al-Doped LiMn2O4 Nanoparticles for Boosted Electrochemical Lithium Extraction,” Advanced Materials36, no. 9 (2024): 2310657, https://doi.org/10.1002/adma.202310657.

[8]

S. Yang, P. Yan, W. Bao, et al., “Surface Magnesium Substitution at Spinel Lithium Manganate 8a Tetrahedral Sites for Suppressed Manganese Dissolution and Enhanced Cycle Stability,” ACS Energy Letters8, no. 9 (2023): 4278-4286, https://doi.org/10.1021/acsenergylett.3c01560.

[9]

Y. Niu, J. Wang, P. Wang, H. Xing, K. Zhang, and Y. Xu, “Multi-Doping Induces Truncated Octahedral Structure Formation in Lithium Manganate Cathode Material,” Applied Surface Science681 (2025): 161552, https://doi.org/10.1016/j.apsusc.2024.161552.

[10]

Y. K. Lee, J. Park, and W. Lu, “Electronic and Bonding Properties of LiMn2O4 Spinel With Different Surface Orientations and Doping Elements and Their Effects on Manganese Dissolution,” Journal of the Electrochemical Society163, no. 7 (2016): A1359-A1368, https://doi.org/10.1149/2.0991607jes.

[11]

S. Sun, X. Zhang, J. Cui, and S. Liang, “Identification of the Miller Indices of a Crystallographic Plane: A Tutorial and a Comprehensive Review on Fundamental Theory, Universal Methods Based on Different Case Studies and Matters Needing Attention,” Nanoscale12, no. 32 (2020): 16657-16677, https://doi.org/10.1039/d0nr03637d.

[12]

Y. Xiao, X. D. Zhang, Y. F. Zhu, et al., “Suppressing Manganese Dissolution via Exposing Stable {111} Facets for High-Performance Lithium-Ion Oxide Cathode,” Advanced science (Weinheim, Baden-Wurttemberg, Germany)6, no. 4 (2019): 1801908, https://doi.org/10.1002/advs.201801908.

[13]

Y. Guo, Y. Yu, P. Ning, and J. Chen, “Enhanced High-Rate and Long-Cycle Performance of Mg2+–Al3+ Co-Doped Spinel LiMn2O4 Cathode Materials for Li-Ion Batteries,” Journal of Alloys and Compounds1005 (2024): 176000, https://doi.org/10.1016/j.jallcom.2024.176000.

[14]

J. Lu, C. Zhan, T. Wu, et al., “Effectively Suppressing Dissolution of Manganese From Spinel Lithium Manganate via a Nanoscale Surface-Doping Approach,” Nature Communications5 (2014): 5693, https://doi.org/10.1038/ncomms6693.

[15]

X. Hou, X. Liu, H. Wang, X. Zhang, J. Zhou, and M. Wang, “Specific Countermeasures to Intrinsic Capacity Decline Issues and Future Direction of LiMn2O4 Cathode,” Energy Storage Materials57 (2023): 577-606, https://doi.org/10.1016/j.ensm.2023.02.015.

[16]

B. Zhang, Y. Zhang, J. Duan, et al., “Suppressing the Mn Dissolution in LiMn2O4 Positive Materials Toward Long-Life Lithium-Ion Battery Through Gd2O3 Surface Modification,” Ionics29, no. 1 (2023): 43-50, https://doi.org/10.1007/s11581-022-04745-7.

[17]

A. J. Lovett, V. Daramalla, D. Nayak, et al., “3D Nanocomposite Thin Film Cathodes for Micro-Batteries With Enhanced High-Rate Electrochemical Performance Over Planar Films,” Advanced Energy Materials13 (2023): 2302053, https://doi.org/10.1002/aenm.202302053.

[18]

T. Ohzuku, M. Kitagawa, and T. Hirai, “Electrochemistry of Manganese Dioxide in Lithium Nonaqueous Cell: III. X-Ray Diffractional Study on the Reduction of Spinel-Related Manganese Dioxide,” Journal of the Electrochemical Society137, no. 3 (1990): 769-775, https://doi.org/10.1149/1.2086552.

[19]

X. Yang, T. Zhao, X. Zhai, J. Zhang, S. Wang, and W. Hua, “Suppressing Voltage Decay in O2-Type Li-Rich Layered Cathode Materials Through Microstrain Alleviation,” Industrial & Engineering Chemistry Research63 (2024): 4197-4204, https://doi.org/10.1021/acs.iecr.3c04501.

[20]

Z. Guo, H. Jiang, X. Sun, et al., “Ultrafast Non-Equilibrium Phase Transition Induced Twin Boundaries of Spinel Lithium Manganate,” Advanced Energy Materials14, no. 5 (2024): 2302484, https://doi.org/10.1002/aenm.202302484.

[21]

R. Wang, X. Chen, Z. Huang, et al., “Twin Boundary Defect Engineering Improves Lithium-Ion Diffusion for Fast-Charging Spinel Cathode Materials,” Nature Communications12, no. 1 (2021): 3085, https://doi.org/10.1038/s41467-021-23375-7.

[22]

Y. Yang, C. Gao, T. Luo, et al., “Unlocking the Potential of Li-Rich Mn-Based Oxides for High-Rate Rechargeable Lithium-Ion Batteries,” Advanced Materials35, no. 52 (2023): e2307138, https://doi.org/10.1002/adma.202307138.

[23]

P. Yang, D. Gao, Y. Yang, et al., “Enhancing d–p Orbital Coupling by Hf Doping to Construct a Stable LiMn2O4 Cathode for Lithium-Ion Batteries,” Nano Energy125 (2024): 109570, https://doi.org/10.1016/j.nanoen.2024.109570.

[24]

C. Tomon, S. Sarawutanukul, N. Phattharasupakun, et al., “Core-Shell Structure of LiMn2O4 Cathode Material Reduces Phase Transition and Mn Dissolution in Li-ion Batteries,” Chemical Communications5, no. 54 (2022), https://doi.org/10.1038/s42004-022-00670-y.

[25]

J. Lin, X. Chen, E. Fan, et al., “A Green Repair Pathway for Spent Spinel Cathode Material: Coupled Mechanochemistry and Solid-Phase Reactions,” eScience3, no. 3 (2023): 100110, https://doi.org/10.1016/j.esci.2023.100110.

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2026 The Author(s). Battery Energy published by Xijing University and John Wiley & Sons Australia, Ltd.

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