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

TL;DR

This study uses atomistic simulations to explore how charged surfaces influence the structure and ion dynamics of polymer electrolytes near electrodes, revealing layer formation, ion desolvation, and reduced mobility at high surface charges.

Contribution

It provides new insights into the effects of electrode surface charge on polymer electrolyte structure and lithium-ion transport mechanisms near electrodes.

Findings

Strong, component-specific layering occurs with surface charging.

High surface charge causes lithium desolvation and direct contact with electrodes.

Lithium-ion mobility decreases due to energy barriers at charged surfaces.

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.