  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.
