Salt-in-water and water-in-salt electrolytes: The effects of the asymmetry in cation and anion valence on their properties

Abstract

We investigated the structural, dynamic, energetic, and electrostatic properties of electrolytes based on the ion pairs LiCl and Li2SO4. Atomistic molecular dynamics simulations were used to simulate these aqueous electrolytic solutions at two different concentrations 2 M (normal) and 21 M (superconcentrated, WiSE). The effects of the valence asymmetry of the Li2SO4electrolyte were also discussed for both salt concentrations. Our results differ in the physical aspect of pure electrolytes, showing the drastic effect of high concentration, in particular on the viscosity, which is dramatically increased in WiSE. This is a consequence of their reduced ionic mobility and has a direct effect on ionic conductivity. Also, our results for graphene-based supercapacitors, as indicated by some experimental work, do not indicate any better performance of WiSEs over normal electrolytes. In fact, the differences in the total capacitance, due to the concentration of ions, presented by both electrolytes are negligible. The valence asymmetry can be clearly observed in some properties but for most of them its effects could not be quantified or isolated.