Molecular Insights into the Potential and Temperature Dependences of the Differential Capacitance of a Room-Temperature Ionic Liquid at Graphite Electrodes

Molecular dynamics simulation studies of the structure and the differential capacitance (DC) for the ionic liquid (IL) N-methyl-N-propylpyrrolidinium bis(trifluoromethane)sulfonyl imide ([pyr13][TFSI]) near a graphite electrode have been performed as a function temperature and electrode potential. The IL exhibits a multilayer structure that extends 20−30 Å from the electrode surface. The composition and ion orientation in the innermost layer were found to be strongly dependent on the electrode potential. While at potentials near the potential of zero charge (PZC), both cations and anions adjacent to the surface are oriented primarily perpendicular to the surface, the counterions in first layer orient increasingly parallel to the surface with increasing electrode potential. A minimum in DC observed around −1 VRPZC (potential relative to the PZC) corresponds to the point of highest density of perpendicularly aligned TFSI near the electrode. Maxima in the DC observed around +1.5 and −2.5 VRPZC are associated with the onset of “saturation”, or crowding, of the interfacial layer. The asymmetry of DC versus electrode polarity is the result of strong interactions between the fluorine of TFSI and the surface, the relatively large footprint of TFSI compared to pyr13, and the tendency of the propyl tails of pyr13 to remain adsorbed on the surface even at high positive potentials. Finally, an observed decreased DC and the disappearance of the minimum in DC near the PZC with increasing temperature are likely due to the increasing importance of entropic/excluded volume effects (interfacial crowding) with increasing temperature.