Impact of Charged Surfaces on the Structure and Dynamics of Polymer Electrolytes: Insights from Atomistic Simulations

Abstract

Polymer electrolytes are intensely investigated for use as solid electrolytes in next generation lithium-ion and lithium-metal batteries. However, little is known about the structural and dynamical properties of polymer electrolytes close to electrode surfaces. Here, a PEO-LiTFSI polymer electrolyte, confined between two oppositely charged graphite-like electrodes, is studied via molecular dynamics simulations. Three different surface charges of $\sigma_S = 0$, $\pm 0.5$ and $\pm 1$ $e$/nm$^2$ are considered. Upon charging, a very strong and component-specific layering is observed. Only for the highest surface charge, lithium ions get desolvated and come into direct contact with the negative electrode. The layer structure goes along with the emergence of free energy barriers, which lead to a reduction of the lithium-ion dynamics, as quantified by spatially resolved mean square displacements, corrected for a drift component. Interchain transfers that are known to be very important for long-range lithium-ion transport in polymer electrolytes play no significant role for transitions of lithium ions between different layers.