Structure and diffusion of molten alkali carbonate salts at the liquid-vacuum interface

Abstract

The liquid-vacuum interface of molten alkali carbonate salts is studied with molecular dynamics simulations. Three salts comprised of LixNayKzCO3 near their respective eutectic concentrations are considered to understand the distribution of ions relative to a liquid-vacuum interface and their diffusivity. These simulations show that each of the cations accumulate at the interface preferentially compared to carbonate. The cation ordering is found to inversely correspond to cation radius, with K being the most likely occupant at the surface, followed by Na, Li, and then the anion. Similar to other studies, the carbonate is found to diffuse more slowly than the cations, but we do observe small differences in diffusion between compositions that present opportunities to optimize ion transport. These results hold consequences for our understanding of ion behavior in molten carbonate salts and the performance of devices employ these electrolytes.