Ionic Liquid Mixtures As Electrolytes for Electrochemical Capacitors

While known for a higher power density than batteries, electrochemical capacitors are limited by their energy density for some energy storage applications. Since the energy density of the device is proportional to the square of operating potential window, an effective way to increase energy density of the device is by increasing this voltage window.  Ionic liquid electrolytes are beneficial for this reason since they can theoretically operate at up to 6 V, though experimentally, the value is between 3-4 V, depending on the properties of electrode materials. Electrode materials can be made from high surface area carbons that contain a network of pores (activated carbon, carbide-derived carbon) or lower surface area carbons that consist of an outer surface where charging and discharging takes place. Though they boast a large operating potential window, ionic liquids are known to contain large and bulky ions. This can make it difficult to use an ionic liquid on a porous carbon with a range of pore sizes, some being very small, even though the specific surface area of the electrode material is higher. It has also been shown that the capacitance of porous electrodes is maximized when the ion size and pore size are equal.¹  In this case, the ion is small enough to fit inside the pores while still large enough to take advantage of the surface area within the pore walls. While the outer surface materials allow a more accessible surface for adsorbing large ions, their capacitance is limited by their specific surface area. By designing an electrolyte based on mixed ionic liquids, ² we can match the ions in the mixture to the multiple pore sizes of the electrode material. Imidazolium-based ionic liquids are chosen based on their variable alkyl chain length which alters the cation size and the TFSI is chosen as the anion for all ionic liquids.  Different porous carbons with varying pore size distributions are used to illustrate the effect of ionic liquid mixture electrolytes.

1.        Lin, R. et al. Solvent effect on the ion adsorption from ionic liquid electrolyte into sub-nanometer carbon pores. Electrochim. Acta 54, 7025–7032 (2009).

2.        Van Aken, K. L., Beidaghi, M. & Gogotsi, Y. Formulation of Ionic-Liquid Electrolyte to Expand the Voltage Window of Supercapacitors. Angew. Chemie 127, 4888–4891 (2015).