3D structure of the electric double layer of ionic liquid–alcohol mixtures at the electrochemical interface

Abstract

Mixtures of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate with amphiphilic cosolvents, such as methanol and ethanol, nanoconfined between graphene walls are studied by means of molecular dynamics simulations and the results are compared with those of the pure ionic liquid and its mixtures with water confined in the same conditions. We investigate the adsorption of cosolvent molecules at the graphene walls as well as their distribution across the system. The results show that, due to a higher affinity of the polar groups to be close to the anions in combination with the electrostatic and excluded volume interactions, there exists a high tendency of the OH groups to lie close to the anode, inducing small changes in the first cation layer. The orientation of cosolvent molecules is found to be closely related to the alignment of the molecular dipole moment. We also investigate the lateral ionic distribution in the layers close to the electrodes, which shows a structural transition from liquid-like lamellar ordering to solid-like hexagonal patterns as the size of the cosolvent molecules increases leading to smaller position fluctuations of the ions. The dependence of the specific patterns on the nature of the electrodes is also studied. This study strongly suggests that the ionic patterns formed in the first ionic layers next to the charged interfaces are universal since their existence does not crucially depend on the atomic composition of the interfacial material, but only on the net charge density of the considered ionic layer, which significantly changes the ionic mobility in this region.