期刊
ADVANCED ENERGY MATERIALS
卷 4, 期 15, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/aenm.201400498
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- Office of Vehicle Technologies of the U.S. Department of Energy [DE-AC02-05CH11231]
Li2MnO3 is a critical component in the family of Li-excess materials, which are attracting attention as advanced cathode materials for Li-ion batteries. Here, first-principle calculations are presented to investigate the electrochemical activity and structural stability of stoichiometric LixMnO3 (0 <= x <= 2) as a function of Li content. The Li2MnO3 structure is electrochemically activated above 4.5 V on delithiation and charge neutrality in the bulk of the material is mainly maintained by the oxidization of a portion of the oxygen ions from O2- to O1-. While oxygen vacancy formation is found to be thermodynamically favorable for x < 1, the activation barriers for O2- and O1- migration remain high throughout the Li composition range, impeding oxygen release from the bulk of the compound. Defect layered structures become thermodynamically favorable at lower Li content (x < 1), indicating a tendency towards the spinel-like structure transformation. A critical phase transformation path for forming nuclei of spinel-like domains within the matrix of the original layered structure is proposed. Formation of defect layered structures during the first charge is shown to manifest in a depression of the voltage profile on the first discharge, providing one possible explanation for the observed voltage fade of the Li-excess materials.
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