Effect of proximity to ionic liquid-solvent demixing on electrical double layers

CarolinaCruz, Svyatoslav Kondrat, Enrique Lomba, AlinaCiach

Journal of Molecular Liquids, Volume 294, 111368 (2019)

Abstract

There is a growing interest in the properties of ionic liquids (ILs) and IL-solvent mixtures at metallic interfaces, particularly due to their applications in energy storage. The main focus so far has been on electrical double layers with ILs far from phase transitions. However, systems in the vicinity of their phase transformations are known to exhibit some remarkable features, such as wetting transitions and capillary condensation. Herein, we develop a mean-field model suitable for the IL-solvent mixtures close to demixing, and combine it with the Carnahan-Starling (CS) and lattice-gas expressions for the excluded volume interactions. This model is then solved analytically, using perturbation expansion, and numerically. We demonstrate that, besides the well-known camel and bell-shaped capacitances, there is a bird-shaped capacitance, having three peaks as a function of voltage, which emerge due to the proximity to demixing. In addition, we find that the camel-shaped capacitance, which is a signature of dilute electrolytes, can appear at high IL densities for ionophobic electrodes. We also discuss the differences and implications arising from the CS and lattice-gas expressions for excluded volume interactions in the context of our model.

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This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No. 711859.