Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide

Qiao, Yu; Guo, Shaohua; Zhu, Kai; Liu, Pan; Li, Xiang; Jiang, Kezhu; Sun, Cheng-Jun; Chen, Mingwei; Zhou, Haoshen

doi:10.1039/C7EE03554C

Title: Reversible anionic redox activity in Na₃RuO₄ cathodes: a prototype Na-rich layered oxide

Journal Article · 26 January 2018 · Energy & Environmental Science

DOI: https://doi.org/10.1039/C7EE03554C · OSTI ID:1471523

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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

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.

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Research Organization:: Argonne National Laboratory (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 Organization:: 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)

Grant/Contract Number:: AC02-06CH11357; 2014CB932300; 21373111; 21633003; 51602144; BK20170630

OSTI ID:: 1471523

Journal Information:: Energy & Environmental Science, Vol. 11, Issue 2; ISSN 1754-5692

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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