The high intercalation capacitance of MXenes is attractive, but their performance as electrodes in supercapacitors is limited by mass transport when increasing the thickness and mass loading of the electrodes. Here, we report a combined experimental and computational study, through which we reveal the diffusion of hydrated ionic species at the interlayer spaces. We find that the cyclic voltammetry (CV) curves for the delaminated Ti3C2T x exhibit distinct features in acid (H2SO4) and alkaline (KOH) electrolytes. The calculated migration profiles of K+ and H+ using density functional theory, in the presence and absence of water, suggest that the intercalated water molecules stabilize the charged ions, facilitating their diffusion from two dimension to three dimension manifested by reduced activation barriers and movement pathways. In addition, we show that the diffusion of low and high concentrations of protons is significantly different; that is, protons of high concentrations can be adsorbed at both sides of the interlayer spaces, and water drives frequent proton hopping between stable adsorption sites as shown in the ab initio molecular dynamics simulations. The calculations can thus explain the varied capacitance and distorted CV curves when the experiments are conducted in acid and alkaline electrolytes. These results can provide guidance for improving the fast transport of ions and electrons in MXenes with high mass loading.
Keywords: DFT calculations; MXene; cyclic voltammetry; diffusion mechanism.