The effects of dication symmetry on ionic liquid electrolytes in supercapacitors

摘要

The effects of dication symmetry on the structure and capacitance of the electrical double layers (EDLs) of dicationic ionic liquids (DILs) near graphene electrodes were investigated by molecular dynamics (MD) simulation in this work. Symmetrical 1-hexyl-3-dimethylimidazolium di[bis(trifluoromethyl) imide]([C-6(mim)(2)](Tf2N)(2)) and asymmetrical 1-(1-trimethylammonium-yl-hexyl)-3-methylimidazolium di[bis(trifluoro-methanesulfonyl)imide] ([C-6(tma)(mim)](Tf2N)(2)) were both employed. Radial distribution function (RDF) analysis of the two DILs revealed a shorter distance between the cation-anion pairs in symmetrical [C-6(mim)(2)](Tf2N)(2)), which was attributed to the closely packed imidazolium ring-anion pairs. In contrast, the trimethylammonium head groups and anions exhibit a relatively longer distance, but a stronger correlation in asymmetrical [C-6(tma)(mim)](Tf2N)(2). In addition, it was illustrated that more symmetrical DIL ions in EDLs are distributed near graphite electrodes and exhibit closer distances to the electrode, which is most probably due to the parallel orientation of imidazolium rings, reducing the distance between the cation and the graphene. In contrast, asymmetrical DILs, with one trimethylammonium head group and one imidazolium ring in the dications, are loosely packed due to their tilting orientation near graphene surfaces. However, the capacitance-potential (C-V) curves of the two DILs are almost the same, regardless of the opposite sign of potential of zero charge (PZC), indicating the insignificant influence of dication symmetry on the capacitance of DIL-based supercapacitors.