Structure and Capacitance of Electrical Double Layers in Tricationic Ionic Liquids with Organic Solvents

Tricationic ionic liquid (TIL) electrolytes have been successfully employed in supercapacitors with graphene electrodes, but the low power density of the TILs-based supercapacitors caused by strong cations-anions associations requires enhancement by adding organic solvents to the liquid. In this paper, the role of the solvents acetonitrile (ACN) and ethylene carbonate (EC) on the ion diffusion, the conductivity of the TIL [C₆(mim)₃](Tf₂N)₃, and the structures and the capacitances of the electrical double layers (EDLs) in TIL/ACN and TIL/EC electrolytes were probed by molecular dynamics (MD) simulations. The results indicate that adding organic solvents to the liquid significantly reduces interactions between ions, thereby greatly improving the ion diffusion coefficients and the conductivity of the TIL, and the maximum conductivity is found at the 0.55 M TIL/ACN electrolyte concentration. Moreover, the reduced packing of counterions and the strong expulsion of coions near charged electrodes are observed in the organic electrolytes, especially in the TIL/EC electrolyte. Further analyses on EDLs affirm that the asymmetric camel-shaped differential capacitance-voltage (C-V) curve in the pure TIL electrolyte is weakly changed by the solvent ACN or EC. Besides, the EDL capacitance in the TIL-based hybrid electrolytes is improved slightly by the organic solvents. Comparing the integral capacitances in TIL/ACN and TIL/EC with different solvent contents, it is found that reducing the solvent polarity may be more beneficial to promote the EDL capacitance. Comprehensively, in this work, the 0.55 M TIL/ACN electrolyte is the optimal choice for the high-performance supercapacitor. Hence, solvating TIL electrolytes in supercapacitors by suitable solvents can effectively enhance the power density without compromising energy density.