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Title: Shell Model for Atomistic Simulation of Lithium Diffusion in Mixed Mn/Ti Oxides

Mixed Mn/Ti oxides present attractive physicochemical properties such as their ability to accommodate Li for application in Li-ion batteries. In this work, atomic parameters for Mn were developed to extend an existing shell model of the Li-Ti-O system and allow simulations of pure and lithiated Mn and mixed Mn/Ti oxide polymorphs. The shell model yielded good agreement with experimentally-derived structures (i.e. lattice parameters and inter-atomic distances) and represented an improvement over existing potential models. The shell model was employed in molecular dynamics (MD) simulations of Li diffusion in the 1×1 c direction channels of LixMn1 yTiyO2 with the rutile structure, where 0 ≤ x ≤ 0.25 and 0 ≤ y ≤ 1. In the infinite dilution limit, the arrangement of Mn and Ti ions in the lattice was found to have a significant effect on the activation energy for Li diffusion in the c channels due to the destabilization of half of the interstitial octahedral sites. Anomalous diffusion was demonstrated for Li concentrations as low as x = 0.125, with a single Li ion positioned in every other c channel. Further increase in Li concentration showed not only the substantial effect of Li-Li repulsive interactions on Li mobility but alsomore » their influence on the time dependence of Li diffusion. The results of the MD simulations can inform intrinsic structure-property relationships for the rational design of improved electrode materials for Li-ion batteries.« less
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Journal Article
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Journal Name: Journal of Physical Chemistry C, 118(42):24231-24239
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
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Country of Publication:
United States
Environmental Molecular Sciences Laboratory