Structure design enables stable anionic and cationic redox chemistry in a T2-type Li-excess layered oxide cathode

Xin Cao; Haifeng Li; Yu Qiao; Min Jia; Hirokazu Kitaura; Jianan Zhang; Ping He; Jordi Cabana; Haoshen Zhou

doi:10.1016/j.scib.2021.11.014

Structure design enables stable anionic and cationic redox chemistry in a T2-type Li-excess layered oxide cathode

Sci Bull (Beijing). 2022 Feb 26;67(4):381-388. doi: 10.1016/j.scib.2021.11.014. Epub 2021 Nov 19.

Authors

Xin Cao¹, Haifeng Li², Yu Qiao³, Min Jia⁴, Hirokazu Kitaura⁴, Jianan Zhang⁵, Ping He⁶, Jordi Cabana², Haoshen Zhou⁷

Affiliations

¹ Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 305-8568, Japan; Graduate School of System and Information Engineering, University of Tsukuba, Tsukuba 305-8573, Japan.
² Department of Chemistry, University of Illinois at Chicago, Chicago, IL 60607, USA.
³ Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 305-8568, Japan. Electronic address: yuqiao@xmu.edu.cn.
⁴ Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 305-8568, Japan.
⁵ College of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, China.
⁶ Center of Energy Storage Materials & Technology, College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, and Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, China.
⁷ Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 305-8568, Japan; Center of Energy Storage Materials & Technology, College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, and Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, China. Electronic address: hszhou@nju.edu.cn.

PMID: 36546090
DOI: 10.1016/j.scib.2021.11.014

Abstract

Coupled with anionic and cationic redox chemistry, Li-rich/excess cathode materials are prospective high-energy-density candidates for the next-generation Li-ion batteries. However, irreversible lattice oxygen loss would exacerbate irreversible transition metal migration, resulting in a drastic voltage decay and capacity degeneration. Herein, a metastable layered Li-excess cathode material, T2-type Li_0.72[Li_0.12Ni_0.36Mn_0.52]O₂, was developed, in which both oxygen stacking arrangement and Li coordination environment fundamentally differ from that in conventional O3-type layered structures. By means of the reversible Li migration processes and structural evolutions, not only can voltage decay be effectively restrained, but also excellent capacity retention can be achieved upon long-term cycling. Moreover, irreversible/reversible anionic/cationic redox activities have been well assigned and quantified by various in/ex-situ spectroscopic techniques, further clarifying the charge compensation mechanism associated with (de)lithiation. These findings of the novel T2 structure with the enhanced anionic redox stability will provide a new scope for the development of high-energy-density Li-rich cathode materials.

Keywords: Cathode materials; Lattice oxygen release; Layered oxides; Structural stability; Voltage decay.