Dynamics of Ion Transport in Ionic Liquids

Abstract

A gap in understanding the link between continuum theories of ion transport in ionic liquids and the underlying microscopic dynamics has hindered the development of frameworks for transport phenomena in these concentrated electrolytes. Here, we construct a continuum theory for ion transport in ionic liquids by coarse graining a simple exclusion process of interacting particles on a lattice. The resulting dynamical equations can be written as a gradient flow with a mobility matrix that vanishes at high densities. This form of the mobility matrix gives rise to a charging behaviour that is different to the one known for electrolytic solutions, but which agrees qualitatively with the phenomenology observed in experiments and simulations.

To appear in PRL

References in corpus (3)

• Theory of Chemical Kinetics and Charge Transfer based on Nonequilibrium Thermodynamics
• Are Room Temperature Ionic Liquids Dilute Electrolytes?
• Local molecular field theory for effective attractions between like charged objects in systems with strong Coulomb interactions

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• Electric-field-induced oscillations in ionic fluids: a unified formulation of modified Poisson-Nernst-Planck models and its relevance to correlation function analysis
• The Role of Energy Scales for the Structure of Ionic Liquids at Electrified Interfaces -- A Theory-Based Approach
• Controlling turbulent drag across electrolytes using electric fields
• Reversible heat production during electric double layer buildup depends sensitively on the electrolyte and its reservoir
• Frequency-Dependent Conductivity of Concentrated Electrolytes: A Stochastic Density Functional Theory
• Charging dynamics of electric double layer nanocapacitors in mean-field
• The effect of short-range interaction and correlations on the charge and electric field distribution in a model solid electrolyte