Highly reversible oxygen redox in layered compounds enabled by surface polyanions
Abstract
Oxygen-anion redox in lithium-rich layered oxides can boost the capacity of lithium-ion battery cathodes. However, the over-oxidation of oxygen at highly charged states aggravates irreversible structure changes and deteriorates cycle performance. Here, we investigate the mechanism of surface degradation caused by oxygen oxidation and the kinetics of surface reconstruction. Considering Li2MnO3, we show through density functional theory calculations that a high energy orbital (lO2p’) at under-coordinated surface oxygen prefers over-oxidation over bulk oxygen, and that surface oxygen release is then kinetically favored during charging. We use a simple strategy of turning under-coordinated surface oxygen into polyanionic (SO4)2-, and show that these groups stabilize the surface of Li2MnO3 by depressing gas release and side reactions with the electrolyte. Experimental validation on Li1.2Ni0.2Mn0.6O2 shows that sulfur deposition enhances stability of the cathode with 99.0% capacity remaining (194 mA h g-1) after 100 cycles at 1 C. Our work reveals a promising surface treatment to address the instability of highly charged layered cathode materials.
- Authors:
-
[4];
[2];
[2];
[5];
[6]
- Harbin Inst. of Technology (China); Univ. of Texas, Austin, TX (United States)
- Harbin Inst. of Technology (China)
- Chongqing Univ. (China)
- Harbin Inst. of Technology, Weihai (China)
- Univ. of Texas, Austin, TX (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Univ. of Texas, Austin, TX (United States)
- Publication Date:
- Research Org.:
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1734597
- Report Number(s):
- LLNL-JRNL-795628
Journal ID: ISSN 2041-1723; 995477
- Grant/Contract Number:
- AC52-07NA27344
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; batteries; electronic materials; energy
Citation Formats
Chen, Qing, Pei, Yi, Chen, Houwen, Song, Yan, Zhen, Liang, Xu, Cheng-Yan, Xiao, Penghao, and Henkelman, Graeme. Highly reversible oxygen redox in layered compounds enabled by surface polyanions. United States: N. p., 2020.
Web. doi:10.1038/s41467-020-17126-3.
Chen, Qing, Pei, Yi, Chen, Houwen, Song, Yan, Zhen, Liang, Xu, Cheng-Yan, Xiao, Penghao, & Henkelman, Graeme. Highly reversible oxygen redox in layered compounds enabled by surface polyanions. United States. https://doi.org/10.1038/s41467-020-17126-3
Chen, Qing, Pei, Yi, Chen, Houwen, Song, Yan, Zhen, Liang, Xu, Cheng-Yan, Xiao, Penghao, and Henkelman, Graeme. Wed .
"Highly reversible oxygen redox in layered compounds enabled by surface polyanions". United States. https://doi.org/10.1038/s41467-020-17126-3. https://www.osti.gov/servlets/purl/1734597.
@article{osti_1734597,
title = {Highly reversible oxygen redox in layered compounds enabled by surface polyanions},
author = {Chen, Qing and Pei, Yi and Chen, Houwen and Song, Yan and Zhen, Liang and Xu, Cheng-Yan and Xiao, Penghao and Henkelman, Graeme},
abstractNote = {Oxygen-anion redox in lithium-rich layered oxides can boost the capacity of lithium-ion battery cathodes. However, the over-oxidation of oxygen at highly charged states aggravates irreversible structure changes and deteriorates cycle performance. Here, we investigate the mechanism of surface degradation caused by oxygen oxidation and the kinetics of surface reconstruction. Considering Li2MnO3, we show through density functional theory calculations that a high energy orbital (lO2p’) at under-coordinated surface oxygen prefers over-oxidation over bulk oxygen, and that surface oxygen release is then kinetically favored during charging. We use a simple strategy of turning under-coordinated surface oxygen into polyanionic (SO4)2-, and show that these groups stabilize the surface of Li2MnO3 by depressing gas release and side reactions with the electrolyte. Experimental validation on Li1.2Ni0.2Mn0.6O2 shows that sulfur deposition enhances stability of the cathode with 99.0% capacity remaining (194 mA h g-1) after 100 cycles at 1 C. Our work reveals a promising surface treatment to address the instability of highly charged layered cathode materials.},
doi = {10.1038/s41467-020-17126-3},
journal = {Nature Communications},
number = 1,
volume = 11,
place = {United States},
year = {Wed Jul 08 00:00:00 EDT 2020},
month = {Wed Jul 08 00:00:00 EDT 2020}
}
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