Density functional theory of alkali metals at the IL/graphene electrochemical interface.

The mechanism of charge transfer between metal ions and graphene in the presence of an ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate) is investigated by means of density functional theory calculations. For that purpose, two different comparisons are established: (i) the behavior of Li+ and K+ when adsorbed onto the basal plane of graphene and (ii) the differences between Li+ approaching the carbon surface from the basal plane and being intercalated through the edge plane of trilayer graphene. In the first case, it is found that the metal ions must overcome high energy barriers due to their interaction with the ionic liquid before reaching an equilibrium position close to the interface. In addition, no significant charge transfer between any of the metals and graphene takes place until very close energetically unfavorable distances. The second configuration shows that Li+ has no equilibrium position in the proximity of the interface but instead has an equilibrium position when it is inside the electrode for which it has to cross an energy barrier. In this case, the formation of a LiC12 complex is observed since the charge transfer at the equilibrium distance is achieved to a considerable extent. Thus, the interfacial charge transfer resistance on the electrode in energy devices based on ionic liquids clearly depends not only on the binding of the ionic liquid to the metal cations and their ability to form a dense solvation shell around them but also on the surface topography and its effect on the ion packing on the surface.

Molecular dynamics simulation of the behaviour of water in nano-confined ionic liquid-water mixtures.

This work describes the behaviour of water molecules in 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid under nanoconfinement, between graphene sheets. By means of molecular dynamics simulations, the adsorption of water molecules at the graphene surface is studied. A depletion of water molecules in the vicinity of the neutral and negatively charged graphene surfaces, and their adsorption at the positively charged surface are observed in line with the preferential hydration of the ionic liquid anions. The findings are appropriately described using a two-level statistical model. The confinement effect on the structure and dynamics of the mixtures is thoroughly analyzed using the density and the potential of mean force profiles, as well as by the vibrational densities of the states of water molecules near the graphene surface. The orientation of water molecules and the water-induced structural transitions in the layer closest to the graphene surface are also discussed.