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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 Cr 4+ to Cr 3+ and Cr 6+, 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 NaCr 1/3Fe 1/3Mn 1/3O 2 (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 Cr 4+ to Cr 3+ and Cr 6+ can be effectively suppressed by Fe 3+ and Mn 4+ substitution. Lastly, these results demonstrated that the reversible multi-electron oxidation/reduction of Cr ions can be achieved in NCFM during charge and discharge accompanied by CrO 6 octahedral distortion and recovery.

Authors:
 [1];  [2];  [1];  [1];  [3];  [3];  [1];  [3]; ORCiD logo [1]
  1. Fudan Univ., Shanghai (People's Republic of China)
  2. Shanghai Institute of Space Power-Sources, Shanghai (People's Republic of China)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1346753
Report Number(s):
BNL-113648-2017-JA
Journal ID: ISSN 2050-7488; JMCAET; R&D Project: MA453MAEA; VT0301010
Grant/Contract Number:
SC00112704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 11; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

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. Tue . "Suppressing the chromium disproportionation reaction in O3-type layered cathode materials for high capacity sodium-ion batteries". United States. doi:10.1039/C6TA10818K. https://www.osti.gov/servlets/purl/1346753.
@article{osti_1346753,
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. Lastly, 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 = {Tue Feb 14 00:00:00 EST 2017},
month = {Tue Feb 14 00:00:00 EST 2017}
}

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  • 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 formore » 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.« less
  • High rate capability and long cycle life are challenging goals for the development of room temperature sodium-ion batteries. Here we report a new single phase quaternary O3-type layer-structured transition metal oxide Na(NiCoFeTi) 1/4O 2 synthesized by a simple solid-state reaction as a new cathode material for sodium-ion batteries. It can deliver a reversible capacity of 90.6 mA h g –1 at a rate as high as 20C. At 5C, 75.0% of the initial specific capacity can be retained after 400 cycles with a capacity-decay rate of 0.07% per cycle, demonstrating a superior long-term cyclability at high current density. X-ray diffractionmore » and absorption characterization revealed reversible phase transformations and electronic structural changes during the Na + deintercalation/intercalation process. Ni, Co and Fe ions contribute to charge compensation during charge and discharge. Although Ti ions do not contribute to the charge transfer, they play a very important role in stabilizing the structure during charge and discharge by suppressing the Fe migration. Additionally, Ti substitution can also smooth the charge–discharge plateaus effectively, which provides a potential advantage for the commercialization of this material for room temperature sodium-ion batteries.« less
  • We report a new layered Na(Mn₀.₂₅Fe₀.₂₅Co₀.₂₅Ni₀.₂₅)O₂ compound with O3 oxygen stacking. It delivers 180 mAh/g initial discharge capacity and 578 Wh/kg specific energy density with good cycling capability at high cutoff voltage. In situ X-ray diffraction (XRD) shows a reversible structure evolution of O3-P3-O3'-O3'' upon Na de-intercalation. The excellent capacity and cycling performance at high cutoff voltage make it an important model system for studying the general issue of capacity fading in layered Na cathode compounds.