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

Nir Gavish, Doron Elad, Arik Yochelis

Research output: Contribution to journalArticlepeer-review

59 Scopus citations


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 underscreening, which all impact the emergence of fluid/solid interfaces, and the transport in these systems. Because 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 liquid mixtures. In this work, we present a self-consistent spatiotemporal framework for a ternary composition that comprises ions and solvent employing a free energy that consists of short- and long-range interactions, along with an energy dissipation mechanism obtained by Onsager's 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 by the free energy. The model equations not only provide insights into transport mechanisms beyond the Stokes-Einstein-Smoluchowski relations but also enable qualitative recovery of three distinct regions in the full range of the nonmonotonic electrical screening length that has been recently observed in experiments in which organic solvent is used to dilute ionic liquids.

Original languageEnglish
Pages (from-to)36-42
Number of pages7
JournalJournal of Physical Chemistry Letters
Issue number1
StatePublished - 4 Jan 2018

ASJC Scopus subject areas

  • General Materials Science
  • Physical and Theoretical Chemistry


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