Diffusion of ionic components in electrolytes not only eliminates the gradients of ionic concentrations but also alters the local dielectric environment, and the coupling effect between kinetic dielectric decrement and ionic concentration gradient on the diffusion dynamics is not well understood. Herein, taking the charging process in electrical double layer systems as a case study, we conduct a multiscale investigation of ion diffusions in aqueous electrolytes by combining the dynamic density functional theory and an ion-concentration-dependent dielectric constant model. By properly considering the time evolutions of local dielectric constant coupled with ion density, we report an interesting phenomenon on the suppression of surface charge density that is not captured by conventional models. In addition, we show that the usage of aqueous electrolyte with small dielectric decrement coefficients promotes the capacitance, in quantitative agreement with experimental measurements.

Using a dynamic density functional theory, we study the charging dynamics, the final equilibrium structure, and the energy storage in an electrical double layer capacitor with nanoscale cathode–anode separation in a slit geometry. We derive a simple expression for the surface charge density that naturally separates the effects of the charge polarization due to the ions from those due to the polarization of the dielectric medium and allows a more intuitive understanding of how the ion distribution within the cell affects the surface charge density. We find that charge neutrality in the half-cell does not hold during the dynamic charging process for any cathode–anode separation, and also does not hold at the final equilibrium state for small separations. Therefore, the charge accumulation in the half-cell in general does not equal the surface charge density. The relationships between the surface charge density and the charge accumulation within the half-cell are systematically investigated by tuning the electrolyte concentration, cathode–anode separation, and applied voltage. For high electrolyte concentrations, we observe charge inversion at which the charge accumulation exceeds the surface charge at special values of the separation. In addition, we find that the energy density has a maximum at intermediate electrolyte concentrations for a high applied voltage.