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

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.
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  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:
Report Number(s):
Journal ID: ISSN 2050-7488; JMCAET; R&D Project: MA453MAEA; VT0301010
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 11; Journal ID: ISSN 2050-7488
Royal Society of Chemistry
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Country of Publication:
United States
OSTI Identifier: