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Vol. 16 (2024)

Mitigating Lattice Distortion of High-Voltage LiCoO2 via Core-Shell Structure Induced by Cationic Heterogeneous Co-Doping for Lithium-Ion Batteries

https://doi.org/10.1007/s40820-023-01269-1
Zezhou Lin
Department of Applied Physics and Research Institute for Smart Energy, The Hong Kong Polytechnic University, Hong Kong, People’s Republic of China
Ke Fan
Department of Applied Physics and Research Institute for Smart Energy, The Hong Kong Polytechnic University, Hong Kong, People’s Republic of China
Tiancheng Liu
Department of Applied Physics and Research Institute for Smart Energy, The Hong Kong Polytechnic University, Hong Kong, People’s Republic of China
Zhihang Xu
Department of Applied Physics, The Hong Kong Polytechnic University, Hong Kong, People’s Republic of China
Gao Chen
Department of Applied Physics and Research Institute for Smart Energy, The Hong Kong Polytechnic University, Hong Kong, People’s Republic of China
Honglei Zhang
Department of Applied Physics and Research Institute for Smart Energy, The Hong Kong Polytechnic University, Hong Kong, People’s Republic of China
Hao Li
Department of Applied Physics and Research Institute for Smart Energy, The Hong Kong Polytechnic University, Hong Kong, People’s Republic of China
Xuyun Guo
Department of Applied Physics, The Hong Kong Polytechnic University, Hong Kong, People’s Republic of China
Xi Zhang
Institute of Nanosurface Science and Engineering, Guangdong Provincial Key Laboratory of Micro/Nano Optomechatronics Engineering, Shenzhen University, Shenzhen, People’s Republic of China
Ye Zhu
Department of Applied Physics, The Hong Kong Polytechnic University, Hong Kong, People’s Republic of China
Peiyu Hou
School of Physics and Technology, University of Jinan, Jinan, Shandong, People’s Republic of China
Haitao Huang
Department of Applied Physics and Research Institute for Smart Energy, The Hong Kong Polytechnic University, Hong Kong, People’s Republic of China

Corresponding Author: Haitao Huang

aphhuang@polyu.edu.hk

Nano-Micro Letters, Vol. 16 (2024), Article Number: 48

Abstract

Inactive elemental doping is commonly used to improve the structural stability of high-voltage layered transition-metal oxide cathodes. However, the one-step co-doping strategy usually results in small grain size since the low diffusivity ions such as Ti4+ will be concentrated on grain boundaries, which hinders the grain growth. In order to synthesize large single-crystal layered oxide cathodes, considering the different diffusivities of different dopant ions, we propose a simple two-step multi-element co-doping strategy to fabricate core–shell structured LiCoO2 (CS-LCO). In the current work, the high-diffusivity Al3+/Mg2+ ions occupy the core of single-crystal grain while the low diffusivity Ti4+ ions enrich the shell layer. The Ti4+-enriched shell layer (~ 12 nm) with Co/Ti substitution and stronger Ti–O bond gives rise to less oxygen ligand holes. In-situ XRD demonstrates the constrained contraction of c-axis lattice parameter and mitigated structural distortion. Under a high upper cut-off voltage of 4.6 V, the single-crystal CS-LCO maintains a reversible capacity of 159.8 mAh g−1 with a good retention of ~ 89% after 300 cycles, and reaches a high specific capacity of 163.8 mAh g−1 at 5C. The proposed strategy can be extended to other pairs of low- (Zr4+, Ta5+, and W6+, etc.) and high-diffusivity cations (Zn2+, Ni2+, and Fe3+, etc.) for rational design of advanced layered oxide core–shell structured cathodes for lithium-ion batteries.


Highlights:
1 A simple two-step multi-element co-doping strategy is proposed to fabricate core-shell structured LiCoO2 based on the different diffusivities of dopant ions.
2 The high diffusivity Al3+/Mg2+ ions occupy the core of single-crystal grain while the low diffusivity Ti4+ ions enrich the shell layer.
3 In-situ XRD demonstrates the mitigated structural distortion under a high cut-off voltage of 4.6 V, resulting in a significantly improved cycling stability.

Keywords

Lithium-ion battery LiCoO2 Heterogeneous co-doping Core–shell structure High-voltage stability
Lin, Zezhou, Ke Fan, Tiancheng Liu, Zhihang Xu, Gao Chen, Honglei Zhang, Hao Li, Xuyun Guo, Xi Zhang, Ye Zhu, Peiyu Hou, and Haitao Huang. 2023. “Mitigating Lattice Distortion of High-Voltage LiCoO2 via Core-Shell Structure Induced by Cationic Heterogeneous Co-Doping for Lithium-Ion Batteries”. Nano-Micro Letters 16 (December):48. https://doi.org/10.1007/s40820-023-01269-1.
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