Accelerating charging dynamics in subnanometre pores

Supercapacitors have exceptional power density and cyclability but smaller energy density than batteries. Their energy density can be increased using ionic liquids and electrodes with subnanometre pores, but this tends to reduce their power density and compromise the key advantage of supercapacitors. To help address this issue through material optimization, here we unravel the mechanisms of charging subnanometre pores with ionic liquids using molecular dynamics simulations, navigated by a phenomenological model. We show that charging of ionophilic pores is a diffusive process, often accompanied by overfilling followed by de-filling. In sharp contrast to conventional expectations, charging is fast because ion diffusion during charging can be an order of magnitude faster than in the bulk, and charging itself is accelerated by the onset of collective modes. Further acceleration can be achieved using ionophobic pores by eliminating overfilling/ de-filling and thus leading to charging behaviour qualitatively different from that in conventional, ionophilic pores.