Overscreening and Underscreening in Solid-Electrolyte Grain Boundary Space-Charge Layers

Polycrystalline solids can exhibit material properties that differ significantly from those of equivalent single-crystal samples, in part, because of a spontaneous redistribution of mobile point defects into so-called space-charge regions adjacent to grain boundaries. The general analytical form of these space-charge regions is known only in the dilute limit, where defect-defect correlations can be neglected. Using kinetic Monte Carlo simulations of a three-dimensional Coulomb lattice gas, we show that grain boundary space-charge regions in nondilute solid electrolytes exhibit overscreening-damped oscillatory space-charge profiles-and underscreening-decay lengths that are longer than the corresponding Debye length and that increase with increasing defect-defect interaction strength. Overscreening and underscreening are known phenomena in concentrated liquid electrolytes, and the observation of functionally analogous behavior in solid electrolyte space-charge regions suggests that the same underlying physics drives behavior in both classes of systems. We therefore expect theoretical approaches developed to study nondilute liquid electrolytes to be equally applicable to future studies of solid electrolytes.

Automated summary

Polycrystalline solids can exhibit unique material properties due to the redistribution of mobile defects at grain boundaries. Simulation studies show that non-dilute solid electrolytes have distinct overscreening and underscreening characteristics in their grain boundary space-charge regions, similar to concentrated liquid electrolytes, indicating a common underlying physics driving behavior in both systems. This suggests that theoretical approaches developed for non-dilute liquid electrolytes can be applied to solid electrolytes in future studies.