Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide
Abstract
Sodium-ion batteries are attractive for large-scale energy storage due to the abundance of sodium, but the deficient capacity achieved by cathode materials prevents their further applications. Chemical substitution of Na in transition metal layers is a promising solution to utilize both the cationic and anionic redox activities for boosting energy storage. Unfortunately, different from the classic Li-rich Li2MnO3, a pure prototype with anionic redox activity has not been found among the typical Na-rich cathodes. In this paper, we originally design a Na-rich layered oxide prototype, namely Na3RuO4 (Ru5+), which delivers a partial reversible capacity solely via the participation of oxygen anions. More importantly, the anionic redox activity is validated by the in situ Raman observation of reversible peroxo-based O–O (de)bonding upon cycling. Finally, our findings not only highlight the multiple electron-transfer strategy for capacity extension, but also broaden the horizon in designing Na-rich electrode materials for high-energy sodium-ion batteries.
- Authors:
-
[1];
[2];
[3];
[4];
[4];
[6]
- National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan). Energy Technology Research Inst.; Univ. of Tsukuba (Japan). Graduate School of System and Information Engineering
- Nanjing Univ. (China). Center of Energy Storage Materials & Technology. College of Engineering and Applied Sciences. National Lab. of Solid State Microstructures. Collaborative Innovation Center of Advanced Microstructures
- National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan). Energy Technology Research Inst.
- Shanghai Jiao Tong Univ. (China). State Key Lab. of Metal Matrix Composites. School of Material Science and Engineering
- Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
- Nanjing Univ. (China). Center of Energy Storage Materials & Technology. College of Engineering and Applied Sciences. National Lab. of Solid State Microstructures. Collaborative Innovation Center of Advanced Microstructures; National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan). Energy Technology Research Inst.; Univ. of Tsukuba (Japan). Graduate School of System and Information Engineering
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States); National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan); Nanjing Univ. (China); Shanghai Jiao Tong Univ. (China)
- Sponsoring Org.:
- USDOE Office of Science (SC); Japan Science and Technology Agency (JST); National Basic Research Program of China; National Natural Science Foundation of China (NSFC); Natural Science Foundation of Jiangsu Province (China); China Scholarship Council (CSC)
- OSTI Identifier:
- 1471523
- Grant/Contract Number:
- AC02-06CH11357; 2014CB932300; 21373111; 21633003; 51602144; BK20170630
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Energy & Environmental Science
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 2; Journal ID: ISSN 1754-5692
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Qiao, Yu, Guo, Shaohua, Zhu, Kai, Liu, Pan, Li, Xiang, Jiang, Kezhu, Sun, Cheng-Jun, Chen, Mingwei, and Zhou, Haoshen. Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide. United States: N. p., 2018.
Web. doi:10.1039/C7EE03554C.
Qiao, Yu, Guo, Shaohua, Zhu, Kai, Liu, Pan, Li, Xiang, Jiang, Kezhu, Sun, Cheng-Jun, Chen, Mingwei, & Zhou, Haoshen. Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide. United States. https://doi.org/10.1039/C7EE03554C
Qiao, Yu, Guo, Shaohua, Zhu, Kai, Liu, Pan, Li, Xiang, Jiang, Kezhu, Sun, Cheng-Jun, Chen, Mingwei, and Zhou, Haoshen. Fri .
"Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide". United States. https://doi.org/10.1039/C7EE03554C. https://www.osti.gov/servlets/purl/1471523.
@article{osti_1471523,
title = {Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide},
author = {Qiao, Yu and Guo, Shaohua and Zhu, Kai and Liu, Pan and Li, Xiang and Jiang, Kezhu and Sun, Cheng-Jun and Chen, Mingwei and Zhou, Haoshen},
abstractNote = {Sodium-ion batteries are attractive for large-scale energy storage due to the abundance of sodium, but the deficient capacity achieved by cathode materials prevents their further applications. Chemical substitution of Na in transition metal layers is a promising solution to utilize both the cationic and anionic redox activities for boosting energy storage. Unfortunately, different from the classic Li-rich Li2MnO3, a pure prototype with anionic redox activity has not been found among the typical Na-rich cathodes. In this paper, we originally design a Na-rich layered oxide prototype, namely Na3RuO4 (Ru5+), which delivers a partial reversible capacity solely via the participation of oxygen anions. More importantly, the anionic redox activity is validated by the in situ Raman observation of reversible peroxo-based O–O (de)bonding upon cycling. Finally, our findings not only highlight the multiple electron-transfer strategy for capacity extension, but also broaden the horizon in designing Na-rich electrode materials for high-energy sodium-ion batteries.},
doi = {10.1039/C7EE03554C},
journal = {Energy & Environmental Science},
number = 2,
volume = 11,
place = {United States},
year = {2018},
month = {1}
}
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Figures / Tables:
Figure 1: Structure of as-prepared Na3RuO4 layered Na-rich oxide: (a) XRD patterns with SEM image inset; (b) Schematic of crystal structure; (c) Scanning area electron diffraction (SAED) patterns; (d) High-angle annular dark field (HAADF) STEM images. The corresponding crystal structure is inset for clarity.
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