Structural and Chemical Evolution of the Layered Li-Excess LixMnO3 as a Function of Li Content from First-Principles Calculations

Lee, Eunseok; Persson, Kristin A.

doi:10.1002/aenm.201400498

Title: Structural and Chemical Evolution of the Layered Li-Excess Li_xMnO₃ as a Function of Li Content from First-Principles Calculations

Journal Article · Thu Jun 26 00:00:00 EDT 2014 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.201400498· OSTI ID:1511383

Lee, Eunseok ^[1]; Persson, Kristin A. ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

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 Li_xMnO₃ (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 O^2- to O^1-. While oxygen vacancy formation is found to be thermodynamically favorable for x < 1, the activation barriers for O^2- and O^1- 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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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Vehicle Technologies Office (VTO)

DOE Contract Number:: AC02-05CH11231

OSTI ID:: 1511383

Journal Information:: Advanced Energy Materials, Vol. 4, Issue 15; ISSN 1614-6832

Publisher:: Wiley

Country of Publication:: United States

Language:: English

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Title: Structural and Chemical Evolution of the Layered Li-Excess LixMnO3 as a Function of Li Content from First-Principles Calculations

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Title: Structural and Chemical Evolution of the Layered Li-Excess Li_xMnO₃ as a Function of Li Content from First-Principles Calculations