Negative Differential Capacitance from Composition-Dependent Stern Capacitance in a Binary Mixture

Abstract

We develop a thermodynamic theory of electric double layers in binary liquid mixtures by allowing the Stern-layer capacitance to depend on the local solvent composition. This coupling produces an additional negative contribution to the inverse differential capacitance. As a result, the surface potential can become a nonmonotonic function of the surface charge density, leading to negative differential capacitance and a voltage-induced first-order transition between two electric-double-layer states. We determine the coexistence condition using a common-tangent construction for the surface-charge-controlled grand potential and obtain phase diagrams in terms of the Stern-capacitance contrast, surface charge density, bulk composition, and surface potential. We also compare the theory with capacitance data for tetrabutylammonium chloride in water/1-propanol mixtures, finding semi-quantitative agreement in the continuous-response regime. These results suggest that solvent exchange inside the Stern layer can strongly control the capacitance and interfacial phase behavior of binary mixtures.