  Having smaller energy density than batteries, supercapacitors have
exceptional power density and cyclability. Their energy density can be
increased using ionic liquids and electrodes with sub-nanometer 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 sub-nanometer pores with ionic liquids
using molecular 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 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 behavior qualitatively different from that in conventional, ionophilic
pores.
