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Title: Suppressing the chromium disproportionation reaction in O3-type layered cathode materials for high capacity sodium-ion batteries

Abstract

Chromium-based layered cathode materials suffer from the irreversible disproportionation reaction of Cr4+ to Cr3+ and Cr6+, which hinders the reversible multi-electron redox of Cr ions in layered cathodes, and limits their capacity and reversibility. To address this problem, a novel O3-type layer-structured transition metal oxide of NaCr1/3Fe1/3Mn1/3O2 (NCFM) was designed and studied as a cathode material. A high reversible capacity of 186 mA h g-1 was achieved at a current rate of 0.05C in a voltage range of 1.5 to 4.2 V. X-ray diffraction revealed an O3 → (O3 + P3) → (P3 + O3'') → O3'' phase-transition pathway for NCFM during charge. X-ray absorption, X-ray photoelectron and electron energy-loss spectroscopy measurements revealed the electronic structure changes of NCFM during Na+ deintercalation/intercalation processes. It is confirmed that the disproportionation reaction of Cr4+ to Cr3+ and Cr6+ can be effectively suppressed by Fe3+ and Mn4+ substitution. These results demonstrated that the reversible multi-electron oxidation/reduction of Cr ions can be achieved in NCFM during charge and discharge accompanied by CrO6 octahedral distortion and recovery.

Authors:
; ; ; ; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE
OSTI Identifier:
1347025
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Materials Chemistry. A; Journal Volume: 5; Journal Issue: 11
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE

Citation Formats

Cao, Ming-Hui, Wang, Yong, Shadike, Zulipiya, Yue, Ji-Li, Hu, Enyuan, Bak, Seong-Min, Zhou, Yong-Ning, Yang, Xiao-Qing, and Fu, Zheng-Wen. Suppressing the chromium disproportionation reaction in O3-type layered cathode materials for high capacity sodium-ion batteries. United States: N. p., 2017. Web. doi:10.1039/C6TA10818K.
Cao, Ming-Hui, Wang, Yong, Shadike, Zulipiya, Yue, Ji-Li, Hu, Enyuan, Bak, Seong-Min, Zhou, Yong-Ning, Yang, Xiao-Qing, & Fu, Zheng-Wen. Suppressing the chromium disproportionation reaction in O3-type layered cathode materials for high capacity sodium-ion batteries. United States. doi:10.1039/C6TA10818K.
Cao, Ming-Hui, Wang, Yong, Shadike, Zulipiya, Yue, Ji-Li, Hu, Enyuan, Bak, Seong-Min, Zhou, Yong-Ning, Yang, Xiao-Qing, and Fu, Zheng-Wen. Sun . "Suppressing the chromium disproportionation reaction in O3-type layered cathode materials for high capacity sodium-ion batteries". United States. doi:10.1039/C6TA10818K.
@article{osti_1347025,
title = {Suppressing the chromium disproportionation reaction in O3-type layered cathode materials for high capacity sodium-ion batteries},
author = {Cao, Ming-Hui and Wang, Yong and Shadike, Zulipiya and Yue, Ji-Li and Hu, Enyuan and Bak, Seong-Min and Zhou, Yong-Ning and Yang, Xiao-Qing and Fu, Zheng-Wen},
abstractNote = {Chromium-based layered cathode materials suffer from the irreversible disproportionation reaction of Cr4+ to Cr3+ and Cr6+, which hinders the reversible multi-electron redox of Cr ions in layered cathodes, and limits their capacity and reversibility. To address this problem, a novel O3-type layer-structured transition metal oxide of NaCr1/3Fe1/3Mn1/3O2 (NCFM) was designed and studied as a cathode material. A high reversible capacity of 186 mA h g-1 was achieved at a current rate of 0.05C in a voltage range of 1.5 to 4.2 V. X-ray diffraction revealed an O3 → (O3 + P3) → (P3 + O3'') → O3'' phase-transition pathway for NCFM during charge. X-ray absorption, X-ray photoelectron and electron energy-loss spectroscopy measurements revealed the electronic structure changes of NCFM during Na+ deintercalation/intercalation processes. It is confirmed that the disproportionation reaction of Cr4+ to Cr3+ and Cr6+ can be effectively suppressed by Fe3+ and Mn4+ substitution. These results demonstrated that the reversible multi-electron oxidation/reduction of Cr ions can be achieved in NCFM during charge and discharge accompanied by CrO6 octahedral distortion and recovery.},
doi = {10.1039/C6TA10818K},
journal = {Journal of Materials Chemistry. A},
number = 11,
volume = 5,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2017},
month = {Sun Jan 01 00:00:00 EST 2017}
}