Porous carbon nanofiber (CNF) electrodes for supercapacitors were prepared by using polyacrylonitrile (PAN) and cucurbituril (CB), which is a macrocyclic compound comprising glycoluril units containing hollow cores. Mixture of PAN and CB in dimethyl sulfoxide was electrospun, and thermally treated to produce CNF electrodes. Their thermal stability, surface morphology, carbon microstructures, and surface porosity were investigated. Electrochemical properties were measured using three-electrode with synthesized CNFs without further treatment as a working electrode and 1 M Na2SO4 as an electrolyte. CNFs derived from PAN and CB exhibited a high specific capacitance of 183.5 F g− 1 and an energy density of 25.4 Wh kg− 1 at 0.5 A g− 1 with stable cyclic stability during 1000 cycles, which is significantly higher than those for CNFs derived from PAN only. This demonstrated that the introduction of CB successfully improved the energy storage performance of CNF electrodes.

For electrodes in electrochemical double-layer capacitors, carbon nanofibers (CNFs) were prepared by thermal treatment of precursor polymer nanofibers, fabricated by electrospinning. Poly(acrylonitrile-co-vinylimidazole) (PAV) was employed as a precursor polymer of carbon nanofibers due to the effective cyclization of PAV polymer chains during thermal treatment compared to a typical precursor, polyacrylonitrile (PAN). PAV solutions with different comonomer compositions were prepared and electrospun to produce precursor nanofibers. Surface images obtained from scanning electron microscopy showed that their nanofibrous structure was well preserved after carbonization. It was also confirmed that electrospun PAV nanofibers were successfully converted to carbon nanofibers after the carbonization step by Raman spectroscopy. Carbon nanofiber electrodes derived from PAV showed higher specific capacitances and energy/power densities than those from PAN, which was tested by coin-type cells. It was also shown that PAV with an acrylonitrile/vinylimidazole composition of 83:17 is most promising for the carbon nanofiber precursor exhibiting a specific capacitance of 114 F/g. Their energy and power density are 70.1 Wh/kg at 1 A/g and 9.5 W/kg at 6 A/g, respectively. In addition, pouch cells were assembled to load the higher amount of electrode materials in the cells, and a box-like cyclic voltammetry was obtained with high capacitances.