Mean-Field Theory of Electrical Double Layer In Ionic Liquids with Account of Short-Range Correlations

We develop the theory of the electrical double layer in ionic liquids as proposed earlier by Kornyshev (2007). In the free energy function we keep the so called short-range correlation terms which were omitted there. With some simplifying assumptions, we arrive at a modified expression for differential capacitance, which makes differential capacitance curves less sharply depending on electrode potential and having smaller values at extrema than in the previous theory. This brings the results closer to typical experimental observations, and makes it appealing to use this formalism for treatment of experimental data. Implications on Debye length and the extent of ion paring in ionic liquids are then briefly discussed. (C) 2016 Elsevier Ltd. All right reserved.