Fluorination effect for stabilizing cationic and anionic redox activities in cation-disordered cathode materials
Abstract
We see that cation-disordered Li-excess cathodes with oxygen redox reactions are promising candidates for high-energy-density Li ion batteries. Nevertheless, the oxygen redox process that is required for the high capacity often comes with the oxygen loss, which leads to severe capacity degradation and voltage decay. In this work, we have successfully synthesized a series of Li-excess cation-disordered cathodes (Li1.2Mn0.4+xTi0.4-xO2-xFx) (0 ≤ x ≤ 0.2) with different fluorine (F) contents. The electrochemical performance results show that the Li1.2Mn0.55Ti0.25O1.85F0.15 (LMTOF0.15) exhibits the highest reversible capacity (275 mAh g-1, under 30 mA g-1), cyclability, and voltage retentions. The mapping of resonant inelastic X-ray scattering (mRIXS) and differential electrochemical mass spectroscopy (DEMS) results reveal that the fluorination enhances the reversible lattice oxygen redox reaction while suppressing irreversible gas release and surface reactions. The X-ray Absorption Spectroscopy (XAS) during the initial two cycles shows that F-substitution alleviates the reduction of the Mn valence state during the whole (dis)charge processes in the bulk and at the surface of the material, results in higher average discharge voltage. In addition, the introduction of F improves the structural stability and suppresses local lattice distortion of the material. Therefore, LMTOF0.15 is able to cycle with smaller polarization, less interfacial sidemore »
- Authors:
-
- Xiamen Univ. (China)
- Pennsylvania State Univ., University Park, PA (United States)
- Xiamen Univ. (China); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of California, San Diego, CA (United States)
- Ecole Polytechnique Federale Lausanne (Switzerland)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Dongguan Neutron Science Center, Dongguan (China)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National key Research and Development Program of China; National Natural Science Foundation of China (NSFC)
- OSTI Identifier:
- 1843951
- Grant/Contract Number:
- AC02-05CH11231; 2018YFB0905400; 29135009; 21761132030
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Energy Storage Materials
- Additional Journal Information:
- Journal Volume: 32; Journal ID: ISSN 2405-8297
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; cation-disordered Li-Excess cathodes; fluorine substitution; anionic redox; cyclability; voltage decay
Citation Formats
Zhou, Ke, Zheng, Shiyao, Ren, Fucheng, Wu, Jue, Liu, Haodong, Luo, Mingzeng, Liu, Xiangsi, Xiang, Yuxuan, Zhang, Chunyang, Yang, Wanli, He, Lunhua, and Yang, Yong. Fluorination effect for stabilizing cationic and anionic redox activities in cation-disordered cathode materials. United States: N. p., 2020.
Web. doi:10.1016/j.ensm.2020.07.012.
Zhou, Ke, Zheng, Shiyao, Ren, Fucheng, Wu, Jue, Liu, Haodong, Luo, Mingzeng, Liu, Xiangsi, Xiang, Yuxuan, Zhang, Chunyang, Yang, Wanli, He, Lunhua, & Yang, Yong. Fluorination effect for stabilizing cationic and anionic redox activities in cation-disordered cathode materials. United States. https://doi.org/10.1016/j.ensm.2020.07.012
Zhou, Ke, Zheng, Shiyao, Ren, Fucheng, Wu, Jue, Liu, Haodong, Luo, Mingzeng, Liu, Xiangsi, Xiang, Yuxuan, Zhang, Chunyang, Yang, Wanli, He, Lunhua, and Yang, Yong. Sun .
"Fluorination effect for stabilizing cationic and anionic redox activities in cation-disordered cathode materials". United States. https://doi.org/10.1016/j.ensm.2020.07.012. https://www.osti.gov/servlets/purl/1843951.
@article{osti_1843951,
title = {Fluorination effect for stabilizing cationic and anionic redox activities in cation-disordered cathode materials},
author = {Zhou, Ke and Zheng, Shiyao and Ren, Fucheng and Wu, Jue and Liu, Haodong and Luo, Mingzeng and Liu, Xiangsi and Xiang, Yuxuan and Zhang, Chunyang and Yang, Wanli and He, Lunhua and Yang, Yong},
abstractNote = {We see that cation-disordered Li-excess cathodes with oxygen redox reactions are promising candidates for high-energy-density Li ion batteries. Nevertheless, the oxygen redox process that is required for the high capacity often comes with the oxygen loss, which leads to severe capacity degradation and voltage decay. In this work, we have successfully synthesized a series of Li-excess cation-disordered cathodes (Li1.2Mn0.4+xTi0.4-xO2-xFx) (0 ≤ x ≤ 0.2) with different fluorine (F) contents. The electrochemical performance results show that the Li1.2Mn0.55Ti0.25O1.85F0.15 (LMTOF0.15) exhibits the highest reversible capacity (275 mAh g-1, under 30 mA g-1), cyclability, and voltage retentions. The mapping of resonant inelastic X-ray scattering (mRIXS) and differential electrochemical mass spectroscopy (DEMS) results reveal that the fluorination enhances the reversible lattice oxygen redox reaction while suppressing irreversible gas release and surface reactions. The X-ray Absorption Spectroscopy (XAS) during the initial two cycles shows that F-substitution alleviates the reduction of the Mn valence state during the whole (dis)charge processes in the bulk and at the surface of the material, results in higher average discharge voltage. In addition, the introduction of F improves the structural stability and suppresses local lattice distortion of the material. Therefore, LMTOF0.15 is able to cycle with smaller polarization, less interfacial side reaction and Mn dissolution, and therefore results in enhanced cyclability. This work provides a comprehensive understanding of the fluorination effect on the cationic and anionic redox activities in cation-disordered Li-excess cathodes.},
doi = {10.1016/j.ensm.2020.07.012},
journal = {Energy Storage Materials},
number = ,
volume = 32,
place = {United States},
year = {Sun Jul 19 00:00:00 EDT 2020},
month = {Sun Jul 19 00:00:00 EDT 2020}
}
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