Understanding the electronic and ionic conduction and lithium over-stoichiometry in LiMn${}_2$O${}_4$ spinel

Abstract

We report a first-principles study of defect thermodynamics and transport in spinel-type lithium manganese oxide LiMn${}_2$O${}_4$, an important lithium-ion battery electrode material, using density-functional theory and the Heyd-Scuseria-Ernzerhof screened hybrid functional. We find that intrinsic point defects in LiMn${}_2$O${}_4$ have low formation energies and hence can occur with high concentrations. The electronic conduction proceeds via hopping of small polarons and the ionic conduction occurs via lithium vacancy and/or interstitialcy migration mechanisms. The total conductivity is dominated by the electronic contribution. LiMn${}_2$O${}_4$ is found to be prone to lithium over-stoichiometry, i.e., lithium excess at the manganese sites, and Mn${}^{3+}$/Mn${}^{4+}$ disorder. Other defects such as manganese antisites and vacancies and lithium interstitials may also occur in LiMn${}_2$O${}_4$ samples. In light of our results, we discuss possible implications of the defects on the electrochemical properties and provide explanations for the experimental observations and guidelines for defect-controlled synthesis and defect characterization.

11 pages, 6 figures

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Cited by in corpus (5)

• Defect physics, delithiation mechanism, and electronic and ionic conduction in layered lithium manganese oxide cathode materials
• Defect physics in complex energy materials
• $Ab-initio$ investigation of the thermodynamics of cation distribution and the electronic and magnetic structures in the LiMn${}_2$O${}_4$ spinel
• Unraveling the effects of inter-site Hubbard interactions in spinel Li-ion cathode materials
• Local electronic transport across probe/ionic conductor interface in scanning probe microscopy