Coarse-grained simulations of an ionic liquid-based capacitor: I. Density, ion size, and valency effects

We introduce a hierarchy of generic coarse-grained models of ionic liquids of increasing complexity. We use them in molecular dynamics simulations to study the differential capacitance of a capacitor consisting of an ionic liquid between two planar electrodes. The primary goal is to explain the complex dependence of the differential capacitance Cd on the electrode potential U in simple terms, e.g. in terms of the size and valency of the ions. For this purpose we introduce the symmetric model A, which qualitatively reproduces the Cd(U) dependence predicted by the mean-field theory but also reveals strong quantitative deviations. We further introduce size asymmetry in model A by increasing the cation size. In model B we vary the cation valency, keeping the sizes of both ions constant. We show that simultaneous increases in size and valency may compensate for each other, leading to a Cd(U) very similar to that for the symmetric case. We interpret distinct features in Cd(U) on the basis of the density profiles of the ions and charge density profiles. We focus on the first two ion layers at the electrode, and demonstrate that the polarization of the ionic liquid proceeds through replacement of one ion type by the other, in contrast to the simple increase in ion concentrations typical for dilute systems. The understanding gained for the simple models serves as a reference for interpretation of complex effects of ion size, valency and shape. This is carried through in part II (a separate article) where we show how the planar shape of ions in model C brings new features to the Cd(U) curve and also to the polarization mechanism.