An extensive molecular dynamics (MD) simulation study of several carbonate based electrolytes near electrode surfaces has been conducted using polarizable force field in order to understand the influence of electrode potential on the structure and composition of interfacial layers. Our simulations demonstrated that the composition of electrolyte near charged electrodes significantly differs from electrolyte bulk composition and therefore can strongly influence which compounds are more susceptible to redox reactions and the mechanisms of formation of solid electrolyte interphase (SEI) and passivation layer on electrode surfaces. Specifically, our simulations addressed the following issues: a) the influence of the electrode surface topography (basal plane or prismatic graphite) on the composition of interfacial layer in EC/DMC/LiPF6 electrolyte as a function of electrode potential, b) the role of addition of LiDFOB salt and the ability of DFOB anion to screen out the surface of positively charged electrode from interaction with PF6 anions; c) the comparison of interfacial layer structures for EC/DMC/LiPF6 and EC/PC/LiPF6 electrolytes,   The obtained MD simulations results are discussed in light of reported in the literature experimental data and observations.

Molecular dynamics simulations of carbonates based electrolytes at charged surfaces

248th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.