Theory of electrolyte solutions in a slit charged pore: Effects of structural interactions and specific adsorption of ions

Journal of Chemical Physics. 2023. Vol. 159. No. 2. Article 024709.

Victoria A. Vasileva, Daria A. Mazur, Yury A. Budkov

In this paper, we present a continuation of our research on modeling electrolyte solutions within charged pores. We make use of the model developed by Blossey et al. [Phys. Rev. E 95, 060602 (2017)], which takes into account the structural interactions between ions through a bilinear form over the gradients of local ionic concentrations in the grand thermodynamic potential, as well as their steric interactions through the lattice gas model. The structural interactions may describe the effects of the molecular structure of ions at a phenomenological level. For example, these effects include steric effects due to non-spherical shapes of ions, their conformational lability, and solvent effects. In addition, we explore their specific interactions with the pore walls by incorporating external attractive potentials. Our primary focus is on observing the behavior of ionic concentration profiles and the disjoining pressure as the pore width changes. By starting with the local mechanical equilibrium condition, we derive a general expression for the disjoining pressure. Our findings indicate that considering the structural interactions of ions leads to a pronounced minimum on the disjoining pressure profiles at small pore widths. We attribute this minimum to the formation of electric double layers on the electrified surfaces of the pore. In addition, our results demonstrate that the inclusion of the attractive interactions of ions with the pore walls enhances this minimum and shifts it to smaller pore thicknesses. Our theoretical discoveries may be useful for those involved in supercapacitor electrochemical engineering, particularly when working with porous electrodes that have been infused with concentrated electrolyte solutions.

Keywords: двойной электрический слой, Electric double layer, Disjoining pressure, Расклинивающее давление, electrolytes, электролиты, Stress tensor, тензор напряжений, mean-field theory, теория среднего поля