Date of Award


Document Type


Degree Name

Doctor of Philosophy (PhD)

Legacy Department

Mechanical Engineering


Qiao, Rui

Committee Member

Saylor, John R.

Committee Member

Stuart, Steve J.

Committee Member

Xuan, Xiangchun


Electrochemical capacitors store electrical energy physically in the electrical double layers at the electrode/electrolyte interfaces. In spite of their high power density and extraordinary cyclability, the widespread deployment of electrochemical capacitors is limited by their moderate energy density. The current surge in interest in electrochemical capacitors is driven by recent breakthroughs in developing novel electrode and electrolyte materials. In particular, electrodes featuring sub-nanometer pores and room-temperature ionic liquids are promising materials for next-generation electrochemical capacitors. To realize the full potential of these materials, a basic understanding of the charge storage mechanisms in them is essential. In this Dissertation, using atomistic simulations, we investigated the charge storage in sub-nanometer pores using room-temperature ionic liquids as electrolytes. These simulations of the equilibrium charge storage in slit-shaped nanopores in contact with room-temperature ionic liquids showed that the capacitance of the nanopores exhibits a U-shaped scaling behavior in pores with width from 0.75 to 1.26 nm. The left branch of the capacitance scaling curve directly corresponds to the anomalous capacitance increase and thus confirms prior experimental observations. The right branch of the curve indirectly agrees with experimental findings that so far have received little attention. We also found that the charge storage in sub-nanometer pores follows a distinct voltage dependent behavior. At low voltages, charge storage is achieved by swapping co-ions in the pore with counter-ions in the bulk electrolytes. As voltage increases, further charge storage is due mainly to the removal of co-ions from the pore, leading to a capacitance increase. The capacitance eventually reaches a maximum when all co-ions are expelled from the pore. At even higher electrode voltages, additional charge storage is realized by counter-ion insertion into the pore, accompanied by a reduction of capacitance. The molecular origins of these phenomena were elucidated by a new theoretical framework we developed specifically for the charge storage in nanopores using solvent-free electrolytes. These simulations of the charging dynamics of sub-nanometer pores in contact with room-temperature ionic liquids showed that the charging of ionophilic pores, of width comparable to the size of ion, is a diffusive process. Such a process is often accompanied by overfilling and 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 behavior qualitatively different from that in conventional, ionophilic pores. Overall, our studies indicated that electrodes with sub-nanometer pores and room-temperature ionic liquids can potentially enable the development of electrochemical capacitors with concurrently high power and energy densities. The fundamental insights gained in our studies help guide the rational design and optimization of these materials to realize their full potentials.