Effect of Switching the Length of Alkyl Chains on Electric Double Layer Structure and Differential Capacitance at the Electrode Interface of Quaternary Ammonium-Based Ionic Liquids Studied Using Molecular Dynamics Simulation

Electric double-layer structure at the electrode interface has been studied by using molecular dynamics simulation on four quaternary ammonium-based ionic liquids (QaILs) to investigate the effect of switching the alkyl chain length of the Qa cation. These four QaILs are composed of a common anion, bis­(trifluoromethanesulfonyl)- amide (TFSA^–) and different cations: butyltrimethylammonium (N₁₁₁₄⁺, k = 1), dibutyldimethylammonium (N₁₁₄₄⁺, k = 2), tributylmethylammonium (N₁₄₄₄⁺, k = 3), and tetrabutylammonium (N₄₄₄₄⁺, k = 4), where k represents the number of butyl chains. The difference in k affects the potential dependence for the composition of the first ionic layer and the orientation of butyl chains in the layer. For the case of k = 1, 2, 3, the butyl chains parallel to the interface increases as the potential becomes negative, but further negative potential results in the increase in perpendicular ones. In the case of k = 1, all the cations in the first ionic layer show the perpendicular orientation at the negative potentials, forming a honeycomb lattice consisting of only cations. On the other hand, in the case of k = 4, no change in orientation has been observed due to the geometrical restrictions. The difference in k also affects the differential capacitance. The potential dependence of differential capacitance shows bell shape for the smaller two (k = 1, 2) and camel shape for the larger two (k = 3, 4). The camel shape for larger IL cations agrees with the prediction from the mean-field lattice gas model and recent experimental results. The differential capacitance at negative potentials deviated to the values higher than the model prediction and the discrepancy becomes greater for smaller k. The results indicate that the potential dependence of ionic orientation significantly affects the differential capacitance. Even for k = 4, which does not show the orientational change, the discrepancy has been observed, indicating that not only the orientational change but also the densification of ions in the first ionic layer are the factors we should take into account beyond the lattice gas model.