Ionic liquid near a charged wall: structure and capacitance of electrical double layer

We study the effects of ion size asymmetry and short-range correlations on the electrical double layer in ionic liquids: we perform molecular dynamics simulations of a model ionic liquid between two "electrodes" and calculate the differential capacitance of each as a function of the electrode potential. The capacitance curve has an asymmetric "bell-shape" character, in qualitative agreement with recent experiments and the mean-field theory (MFT) which takes into account the limitation on the maximal local density of ions. The short-range ionic correlations, not included in the MFT, lead to an overscreening effect which changes radically the structure of the double layer at small and moderate charging. With the radius of cations taken to be twice as large as anions, the position of the main capacitance maximum is shifted positively from the potential of zero charge (PZC), as predicted by MFT. An extension of the theory (EMFT), however, reproduces the simulated capacitance curve almost quantitatively. Capacitance curves for real ionic liquids will be affected by nonspherical shape of ions and sophisticated pair potentials, varying from liquid to liquid. But understanding the capacitance behavior of such model system is a basis for rationalizing those more specific features.