Molecular Modeling of Materials for Li-ion batteries

Project investigator: Pussana Hirunsit, NANOTEC and Suwit Suthirakun, Suranaree University of Technology


Employing the first-principles plane-wave approach, we explored the behavior of electron transport in the V2O5 cathode. Polaron migrations along different crystallographic directions in the presence and absence of Li+ ions were systematically examined using linear interpolation (LE) and nudged elastic band (NEB) methods. We find that the NEB calculations, based on structural optimizations of TS structures, generally exhibit lower hopping barriers than those obtained from the LE calculations. Both methods consistently predict that the [010] hopping, in the presence and absence of a nearby Li+ ion, is kinetically least favorable since the migration involves displacements of rigid 3-coordinated O atoms. Computations based on the LE method reveal anisotropic polaron mobilities where the estimated hopping frequencies within the layer are approximately one order of magnitude higher than the normal. The prediction based on the LE calculations is consistent with the experimental results. Lithiation dramatically affects the behavior of polaron movement. It significantly increases the reaction energies and hopping barriers due to the strong polaron-ion interaction. In addition, it is predicted that polaron hopping in the V2O5 cathode is non-adiabatic where lithiation has negligible effects on the adiabaticity.

Overview of the electron transport in the V2O5 cathode from P. Watthaisong, S. Jungthawan, P. Hirunsit, S. Suthirakun, Transport properties of electron small polarons in a V2O5 cathode of Li-ion batteries: A computational study, RSC Adv. 9 (2019) 19483–19494. Published by The Royal Society of Chemistry.