Generalized Helmholtz model describes capacitance profiles of ionic liquids and concentrated aqueous electrolytes.

In this work, we propose and validate a generalization of the Helmholtz model that can account for both "bell-shaped" and "camel-shaped" differential capacitance profiles of concentrated electrolytes, the latter being characteristic of ionic liquids. The generalization is based on introducing voltage dependence of both the dielectric constant "ϵ_r(V)" and thickness "L(V)" of the inner Helmholtz layer, as validated by molecular dynamics (MD) simulations. We utilize MD simulations to study the capacitance profiles of three different electrochemical interfaces: (1) graphite/[BMIm⁺][ BF 4 − ] ionic liquid interface; (2) Au(100)/[BMIm⁺][ BF 4 − ] ionic liquid interface; (3) Au(100)/1M [Na⁺][Cl⁻] aqueous interface. We compute the voltage dependence of ϵ_r(V) and L(V) and demonstrate that the generalized Helmholtz model qualitatively describes both camel-shaped and bell-shaped differential capacitance profiles of ionic liquids and concentrated aqueous electrolytes (in lieu of specific ion adsorption). In particular, the camel-shaped capacitance profile that is characteristic of ionic liquid electrolytes arises simply from combination of the voltage-dependent trends of ϵ_r(V) and L(V). Furthermore, explicit analysis of the inner layer charge density for both concentrated aqueous and ionic liquid double layers reveal similarities, with these charge distributions typically exhibiting a dipolar region closest to the electrode followed by a monopolar peak at larger distances. It is appealing that a generalized Helmholtz model can provide a unified description of the inner layer structure and capacitance profile for seemingly disparate aqueous and ionic liquid electrolytes. [ABSTRACT FROM AUTHOR]