The growing demands of next-generation applications for high power and energy sources necessitate advances in hierarchically porous carbon-based energy storage materials, which improve the overall kinetics of electrolytic reactions by providing efficient ion and electron transport pathways and facilitate electrolyte infiltration into the electrode during charging/discharging. Herein, we fabricate hierarchically structured porous carbon electrodes (cNPIM), prepared by solution casting of a polymer of intrinsic microporosity (PIM-1) followed by nonsolvent-induced phase separation and carbonization. The obtained material exhibits a considerable surface area (∼2100 m2 g−1), high electrical conductivity (150 S cm−1), high specific capacitances (345, 235, and 195 F g−1 in three-, two-electrode aqueous systems, and two-electrode organic systems, respectively) at 1 A g−1, and an exceptional specific energy of 43.2 W h kg−1 at a specific power of 1.25 kW kg−1, featuring a pore size gradient in the surface normal direction.
