Identifying the intrinsic anti-site defect in manganese-rich NASICON-type cathodes

Yuan Liu, Xiaohui Rong, Rui Bai, Ruijuan Xiao, Chunliu Xu, Chu Zhang, Juping Xu, Wen Yin, Qinghua Zhang, Xinmiao Liang, Yaxiang Lu, Junmei Zhao (), Liquan Chen and Yong-Sheng Hu ()
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Yuan Liu: Chinese Academy of Sciences
Xiaohui Rong: Chinese Academy of Sciences
Rui Bai: Chinese Academy of Sciences
Ruijuan Xiao: Chinese Academy of Sciences
Chunliu Xu: Chinese Academy of Sciences
Chu Zhang: Chinese Academy of Sciences
Juping Xu: Spallation Neutron Source Science Center
Wen Yin: Spallation Neutron Source Science Center
Qinghua Zhang: Chinese Academy of Sciences
Xinmiao Liang: Chinese Academy of Sciences
Yaxiang Lu: Chinese Academy of Sciences
Junmei Zhao: Chinese Academy of Sciences
Liquan Chen: Chinese Academy of Sciences
Yong-Sheng Hu: Chinese Academy of Sciences

Nature Energy, 2023, vol. 8, issue 10, 1088-1096

Abstract: Abstract Manganese-rich NASICON-type materials have triggered widespread attention for developing advanced polyanionic cathodes, primarily driven by their abundant reserves and promising cycling performance with high operating voltages (~3.8 V for Mn2+/3+/4+, versus Na+/Na). However, the charge/discharge profiles exhibit significant voltage hysteresis, which leads to a limited reversible capacity, thereby preventing their application. Here, we demonstrate that the voltage hysteresis in manganese-rich NASICON-type cathodes (Na3MnTi(PO4)3) is closely related to the intrinsic anti-site defect (IASD), which forms during synthesis and is captured in our characterizations. Combining electrochemical analysis and spectroscopic techniques, we draw a comprehensive picture of sluggish Na+ diffusion behaviours in the IASD-affected structure during cycling, and rationalize the relationship of voltage hysteresis, phase separation and delayed charge compensation. Furthermore, a Mo-doping strategy is developed to decrease the defect concentration, which enhances the initial Coulombic efficiency from 76.2% to 85.9%. Overall, this work sheds light on the voltage hysteresis in NASICON-type cathodes and provides guidelines for designing high-performance polyanionic electrodes.

Date: 2023
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DOI: 10.1038/s41560-023-01301-z

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