Effects of Oxygen-Containing Functional Groups on Supercapacitor Performance

Molecular dynamics (MD) simulations of the interface between graphene and the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate (BMIM OTf) were carried out to gain molecular-level insights into the performance of graphene-based supercapacitors and, in particular, determine the effects of the presence of oxygen-containing defects at the graphene surface on their integral capacitance. The MD simulations predict that increasing the surface coverage of hydroxyl groups negatively affects the integral capacitance, whereas the effect of the presence of epoxy groups is much less significant. The calculated variations in capacitance are found to be directly correlated to the interfacial structure. Indeed, hydrogen bonding between hydroxyl groups and SO3 moieties prevents BMIM+ and OTf– ions from interacting favorably in the interfacial layer and restrains the orientation and mobility of OTf– ions, thereby reducing the interfacial permittivity of the ionic liquid. The results of the simulations can facilitate the rational design of electrode materials for supercapacitors.