期刊
JOURNAL OF MATERIALS CHEMISTRY A
卷 2, 期 24, 页码 9099-9110出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4ta01161a
关键词
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资金
- Europaischer Fonds fur regionale Entwicklung (EFRE) under project BATMAT [200720132/35]
- Hans-L. Merkle Stiftung of the Robert Bosch GmbH
- project KaLiPat
Structural changes in a 0.5Li(2)MnO(3)center dot 0.5LiCoO(2) cathode material were investigated by X-ray absorption spectroscopy. It is observed that both Li2MnO3 and LiCoO2 components of the material exist as separate domains, however, with some exchange of transition metal (TM) ions in their slab layers. A large irreversible capacity observed during activation of the material in the 1st cycle can be attributed to an irreversible oxygen release from Li2MnO3 domains during lithium extraction. The average valence state of manganese ions remains unchanged at 4+ during charge and discharge. In the absence of conventional redox processes, lithium extraction/reinsertion from/into Li2MnO3 domains occurs with the participation of oxygen anions in redox reactions and most likely involves the ion-exchange process. In contrast, lithium deintercalation/intercalation from/into LiCoO2 domains occurs topotactically, involving a conventional Co3+/Co4+ redox reaction. The presence of Li2MnO3 domains and their unusual participation in electrochemical processes enable LiCoO2 domains of the material to sustain a higher cut-off voltage without undergoing irreversible structural changes.
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