Density functional study of the electric double layer formed by a high density electrolyte.

We use a classical density functional theory (DFT) to study the electric double layer formed by charged hard spheres near a planar charged surface. The DFT predictions are found to be in good agreement with recent computer simulation results. We study the capacitance of the charged hard-sphere system at a range of densities and surface charges and find that the capacitance exhibits a local minimum at low ionic densities and small electrode charge. Although this charging behavior is typical for an aqueous electrolyte solution, the local minimum gradually turns into a maximum as the density of the hard spheres increases. Charged hard spheres at high density provide a reasonable first approximation for ionic liquids. In agreement with experiment, the capacitance of this model ionic liquid double layer has a maximum at small electrode charge density.