Dynamics and Energetics of Ion Adsorption at the Interface between a Pure Ionic Liquid and Carbon Electrodes.

Molecular dynamics simulations have been used extensively to determine equilibrium properties of the electrode-electrolyte interface in supercapacitors held at various potentials. While such studies are essential to understand and optimize the performance of such energy storage systems, investigation of the dynamics of adsorption during the charge of the supercapacitors is also necessary. Dynamical properties are especially important to get an insight into the power density of supercapacitors, one of their main assets. In this work, we propose a new method to coarse-grain simulations of all-atom systems and compute effective Lennard-Jones and Coulomb parameters, allowing subsequently to analyze the trajectories of adsorbing ions. We focus on pure 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide in contact with planar carbon electrodes. We characterize the evolution of the ion orientation and ion-electrode distance during adsorption and show that ions reorientate as they adsorb. We then determine the forces experienced by the adsorbing ions and demonstrate that Coulomb forces are dominant at a long range while van der Waals forces are dominant at a short range. We also show that there is an almost equal contribution from the two forces at an intermediate distance, explaining the peak of ion density close to the electrode surface.