Journal
CHEMISTRY OF MATERIALS
Volume 26, Issue 2, Pages 1219-1225Publisher
AMER CHEMICAL SOC
DOI: 10.1021/cm403597h
Keywords
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Funding
- Agence Nationale de la Recherche (Blanc Inter II, SIMI 8) [2011-IS08-001-01]
- Ministry of Economic Affairs of Taiwan [101-EC-17-A-08-S1-183]
- French National Research Agency [ANR-NSC-101-2923-E-011-001-MY3]
- National Science Council of Taiwan [ANR-NSC-101-2923-E-011-001-MY3]
- Region Aquitaine
- CNRS
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Sodium intercalation in P2-Na2/3Co2/3Mn1/3O2 (obtained by a coprecipitation method) was investigated by ex situ and in situ X-ray absorption spectroscopy. The electronic transitions at the O K-edge and the charge compensation mechanism, during the sodium intercalation process, were elucidated by combining Density Function Theory (DFT) calculations and X-ray absorption spectroscopy (XAS) data. The pre-edge of the oxygen K-edge moves to higher energy while the integrated intensity dramatically decreases, indicating that the population of holes in O 2p states is reduced with increasing numbers of sodium ions. From the K-edge and L-edge observations, the oxidation states of pristine Co and Mn were determined to be +III and +IV, respectively. The absorption energy shifts to lower positions during the discharging process for both the Co and the Mn edges, suggesting that the redox pairs, that is, Co3+/Co2+ and Mn4+/Mn3+, are both involved in the reaction.
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