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Title: Both cationic and anionic redox chemistry in a P2-type sodium layered oxide

Abstract

We report the demand for high energy Na-ion batteries has promoted intensive research on high energy oxygen redox chemistry in layered transition metal oxide cathodes. However, most layered cathodes with oxygen redox might suffer from irreversible electrochemical reaction, fast capacity decay and underlying O2 release. Herein, we report that copper element with a strong electronegativaty can stablize Na-deficient P2-Na2/3Mn0.72Cu0.22Mg0.06O2 phase to achieve both cationic and anionic redox chemistry. Hard and soft X-ray absorption spectra demonstrate that all Mn3+/Mn4+, Cu2+/Cu3+ and O2-/(O2)n- participate in the redox reaction upon Na+ ions extraction and insertion. Density functional theory (DFT) calculations confirm that the strong covalency between copper and oxygen ensures the cationic and anionic redox activity in P2-Na2/3Mn0.72Cu0.22Mg0.06O2 phase. The P2-Na2/3Mn0.72Cu0.22Mg0.06O2 cathode could deliver stable cycling life with 87.9% capacity retention at 1C during 100 cycles, as well as high rate performance (70.3 mA h g-1 cycled at 10C). In conclusion, our findings not only provide a promising guidelines to enhance the electrochemical performance of layered oxides based on anionic redox activity, but also explore the potential science behind oxygen redox process.

Authors:
 [1];  [2]; ORCiD logo [1];  [3];  [1];  [1];  [2];  [1];  [1];  [1];  [1];  [2]; ORCiD logo [3];  [1]
  1. Univ. of Maryland, College Park, MD (United States)
  2. Chinese Academy of Sciences (CAS), Beijing (China). CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, CAS Research/Education Center for Excellence in Molecular Sciences, Beijing National Laboratory for Molecular Sciences (BNLMS), Inst. of Chemistry
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC)
OSTI Identifier:
1593270
Alternate Identifier(s):
OSTI ID: 1592180
Report Number(s):
BNL-213544-2020-JAAM
Journal ID: ISSN 2211-2855
Grant/Contract Number:  
SC0012704; EE0008202
Resource Type:
Accepted Manuscript
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 69; Journal Issue: C; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Sodium-ion batteries; Cathode; Anionic redox; P2-type; Electrochemistry

Citation Formats

Wang, Peng-Fei, Xiao, Yao, Piao, Nan, Wang, Qin-Chao, Ji, Xiao, Jin, Ting, Guo, Yu-Jie, Liu, Sufu, Deng, Tao, Cui, Chunyu, Chen, Long, Guo, Yu-Guo, Yang, Xiao-Qing, and Wang, Chunsheng. Both cationic and anionic redox chemistry in a P2-type sodium layered oxide. United States: N. p., 2020. Web. https://doi.org/10.1016/j.nanoen.2020.104474.
Wang, Peng-Fei, Xiao, Yao, Piao, Nan, Wang, Qin-Chao, Ji, Xiao, Jin, Ting, Guo, Yu-Jie, Liu, Sufu, Deng, Tao, Cui, Chunyu, Chen, Long, Guo, Yu-Guo, Yang, Xiao-Qing, & Wang, Chunsheng. Both cationic and anionic redox chemistry in a P2-type sodium layered oxide. United States. https://doi.org/10.1016/j.nanoen.2020.104474
Wang, Peng-Fei, Xiao, Yao, Piao, Nan, Wang, Qin-Chao, Ji, Xiao, Jin, Ting, Guo, Yu-Jie, Liu, Sufu, Deng, Tao, Cui, Chunyu, Chen, Long, Guo, Yu-Guo, Yang, Xiao-Qing, and Wang, Chunsheng. Fri . "Both cationic and anionic redox chemistry in a P2-type sodium layered oxide". United States. https://doi.org/10.1016/j.nanoen.2020.104474. https://www.osti.gov/servlets/purl/1593270.
@article{osti_1593270,
title = {Both cationic and anionic redox chemistry in a P2-type sodium layered oxide},
author = {Wang, Peng-Fei and Xiao, Yao and Piao, Nan and Wang, Qin-Chao and Ji, Xiao and Jin, Ting and Guo, Yu-Jie and Liu, Sufu and Deng, Tao and Cui, Chunyu and Chen, Long and Guo, Yu-Guo and Yang, Xiao-Qing and Wang, Chunsheng},
abstractNote = {We report the demand for high energy Na-ion batteries has promoted intensive research on high energy oxygen redox chemistry in layered transition metal oxide cathodes. However, most layered cathodes with oxygen redox might suffer from irreversible electrochemical reaction, fast capacity decay and underlying O2 release. Herein, we report that copper element with a strong electronegativaty can stablize Na-deficient P2-Na2/3Mn0.72Cu0.22Mg0.06O2 phase to achieve both cationic and anionic redox chemistry. Hard and soft X-ray absorption spectra demonstrate that all Mn3+/Mn4+, Cu2+/Cu3+ and O2-/(O2)n- participate in the redox reaction upon Na+ ions extraction and insertion. Density functional theory (DFT) calculations confirm that the strong covalency between copper and oxygen ensures the cationic and anionic redox activity in P2-Na2/3Mn0.72Cu0.22Mg0.06O2 phase. The P2-Na2/3Mn0.72Cu0.22Mg0.06O2 cathode could deliver stable cycling life with 87.9% capacity retention at 1C during 100 cycles, as well as high rate performance (70.3 mA h g-1 cycled at 10C). In conclusion, our findings not only provide a promising guidelines to enhance the electrochemical performance of layered oxides based on anionic redox activity, but also explore the potential science behind oxygen redox process.},
doi = {10.1016/j.nanoen.2020.104474},
journal = {Nano Energy},
number = C,
volume = 69,
place = {United States},
year = {2020},
month = {1}
}

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