From solvent free to dilute electrolytes: Essential components for a continuum theory

TL;DR

This paper develops a continuum model for highly concentrated electrolytes and ionic liquids, capturing complex phenomena like self-assembly and non-monotonic screening, which are not explained by existing models.

Contribution

It introduces a self-consistent spatiotemporal framework for ternary electrolyte systems that accounts for short and long-range interactions and morphology evolution.

Findings

Model describes multiple bulk and interfacial morphologies.

Captures non-monotonic electrical screening lengths observed experimentally.

Provides insights into transport mechanisms beyond classical relations.

Abstract

The increasing number of experimental observations on highly concentrated electrolytes and ionic liquids show qualitative features that are distinct from dilute or moderately concentrated electrolytes, such as self-assembly, multiple-time relaxation, and under-screening, which all impact the emergence of fluid/solid interfaces, and transport in these systems. Since these phenomena are not captured by existing mean field models of electrolytes, there is a paramount need for a continuum framework for highly concentrated electrolytes and ionic liquids. In this work, we present a self-consistent spatiotemporal framework for a ternary composition that comprises ions and solvent employing free energy that consists of short and long range interactions, together with a dissipation mechanism via Onsagers' relations. We show that the model can describe multiple bulk and interfacial morphologies at steady-state. Thus, the dynamic processes in the emergence of distinct morphologies become equally as important as the interactions that are specified in the equilibrium-free energy. The model equations not only provide insights to transport mechanisms beyond the Stokes-Einstein-Smoluchowski relations but also enables to qualitative recovery in the full range (three distinct regions) of non-monotonic electrical screening length that has been recently observed in experiments using organic solvent to dilute ionic liquids.