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Title: | Mitigating lattice distortion of high-voltage LiCoO<sub>2</sub> via core-shell structure induced by cationic heterogeneous co-doping for lithium-ion batteries | Authors: | Lin, ZZ Fan, K Liu, TC Xu, ZH Chen, G Zhang, HL Li, H Guo, XY Zhang, X Zhu, Y Hou, PY Huang, HT |
Issue Date: | Dec-2024 | Source: | Nano-micro letters, Dec. 2024, v. 16, no. 1, 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 (similar to 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 similar to 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. | Keywords: | Lithium-ion battery LiCoO2 Heterogeneous co-doping Core-shell structure High-voltage stability |
Publisher: | Springer | Journal: | Nano-micro letters | ISSN: | 2311-6706 | EISSN: | 2150-5551 | DOI: | 10.1007/s40820-023-01269-1 | Rights: | © The Author(s) 2023 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/. The following publication Lin, Z., Fan, K., Liu, T. et al. Mitigating Lattice Distortion of High-Voltage LiCoO2 via Core-Shell Structure Induced by Cationic Heterogeneous Co-Doping for Lithium-Ion Batteries. Nano-Micro Lett. 16, 48 (2024) is available at https://dx.doi.org/10.1007/s40820-023-01269-1. |
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