Electrochemical quartz crystal microbalance (EQCM) and cyclic voltammetry (CV) measurements were used to characterize ion adsorption in carbide-derived carbon (CDC) with two different average pore sizes (1 and 0.65 nm), from neat and solvated 1-Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMI-TFSI) electrolytes. From the electrode mass change in neat EMI-TFSI, it was shown that one net charge stored corresponds almost to one single ion at high polarization; in that case, no ion-pairing or charge screening by co-ions were observed. In 2 M EMI-TFSI in acetonitrile electrolyte, experimental solvation numbers were estimated for EMI(+) cation, showing a partial desolvation when cations were adsorbed in confined carbon pores. The extent of desolvation increased when decreasing the carbon pore size (from 1 down to 0.65 nm). The results also suggest that EMI(+) cation owns higher mobility than TFSI(-) anion in these electrolytes.

Supercapacitors store charge through the electrosorption of ions on microporous electrodes. Despite major efforts to understand this phenomenon, a molecular-level picture of the electrical double layer in working devices is still lacking as few techniques can selectively observe the ionic species at the electrode/electrolyte interface. Here, we use in situ NMR to directly quantify the populations of anionic and cationic species within a working microporous carbon supercapacitor electrode. Our results show that charge storage mechanisms are different for positively and negatively polarized electrodes for the electrolyte tetraethylphosphonium tetrafluoroborate in acetonitrile; for positive polarization charging proceeds by exchange of the cations for anions, whereas for negative polarization, cation adsorption dominates. In situ electrochemical quartz crystal microbalance measurements support the NMR results and indicate that adsorbed ions are only partially solvated. These results provide new molecular-level insight, with the methodology offering exciting possibilities for the study of pore/ion size, desolvation and other effects on charge storage in supercapacitors.