Salt Effects on Ionic Conductivity Mechanisms in Ethylene Carbonate Electrolytes: Interplay of Viscosity and Ion-ion Relaxations

Abstract

The intricate role of shear viscosity and ion-pair relaxations on ionic conductivity mechanisms and the underlying changes induced by salt concentration ($c$) in organic liquid electrolytes remain poorly understood despite their widespread technological importance. Using molecular dynamics simulations employing nonpolarizable force fields for $c$ ranging between 10$^{-3}$ to 10$^1$ M, we show that the low and high $c$ regimes of the EC-LiTFSI electrolytes are distinctly characterized by $\eta\sim\tau_c^{1/2}$ and $\eta\sim\tau_c^{1}$, where $\eta$ and $\tau_c$ are shear viscosity and cation-anion relaxation timescales, respectively. Our extensive simulations and analyses suggest a universal relationship between the ionic conductivity and $c$ as $\sigma(c)\sim c^{\alpha}e^{-c/c_{0}} (\alpha>0)$. The proposed relationship convincingly explains the ionic conductivity over a wide range of $c$, where the term $c^\alpha$ accounts for the uncorrelated motion of ions and $e^{-c/c_0}$ captures the salt-induced changes in shear viscosity. Our simulations suggest vehicular mechanism to be dominant at low $c$ regime which transitions into a structural diffusion mechanism at high $c$ regime, where structural relaxation is the dominant form of ion transport mechanism. Our findings shed light on some of the fundamental aspects of the ion conductivity mechanisms in liquid electrolytes, offering insights into optimizing the ion transport in EC-LiTFSI electrolytes.