Manipulating local chemistry and coherent structures for high-rate and long-life sodium-ion battery cathodes

Wang, Haoji, Chen, Hongyi ORCID: https://orcid.org/0000-0001-5529-2942, Mei, Yu, Gao, Jinqiang, Ni, Lianshan, Hong, Ningyun, Zhang, Baichao, Zhu, Fangjun, Huang, Jiangnan, Wang, Kai, Deng, Wentao, Silvester, Debbie S ORCID: https://orcid.org/0000-0002-7678-7482, Banks, Craig E ORCID: https://orcid.org/0000-0002-0756-9764, Yasar, Sedat, Song, Bai, Zou, Guoqiang ORCID: https://orcid.org/0000-0001-7115-6190, Hou, Hongshuai ORCID: https://orcid.org/0000-0001-8201-4614 and Ji, Xiaobo ORCID: https://orcid.org/0000-0002-5405-7913 (2024) Manipulating local chemistry and coherent structures for high-rate and long-life sodium-ion battery cathodes. ACS Nano. ISSN 1936-0851

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Abstract

Layered sodium transition-metal (TM) oxides generally suffer from severe capacity decay and poor rate performance during cycling, especially at a high state of charge (SoC). Herein, an insight into failure mechanisms within high-voltage layered cathodes is unveiled, while a two-in-one tactic of charge localization and coherent structures is devised to improve structural integrity and Na+ transport kinetics, elucidated by density functional theory calculations. Elevated Jahn–Teller [Mn3+O6] concentration on the particle surface during sodiation, coupled with intense interlayer repulsion and adverse oxygen instability, leads to irreversible damage to the near-surface structure, as demonstrated by X-ray absorption spectroscopy and in situ characterization techniques. It is further validated that the structural skeleton is substantially strengthened through the electronic structure modulation surrounding oxygen. Furthermore, optimized Na+ diffusion is effectively attainable via regulating intergrown structures, successfully achieved by the Zn2+ inducer. Greatly, good redox reversibility with an initial Coulombic efficiency of 92.6%, impressive rate capability (86.5 mAh g–1 with 70.4% retention at 10C), and enhanced cycling stability (71.6% retention after 300 cycles at 5C) are exhibited in the P2/O3 biphasic cathode. It is believed that a profound comprehension of layered oxides will herald fresh perspectives to develop high-voltage cathode materials for sodium-ion batteries.