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.
Isotactic polyacrylonitrile (PAN) with triad isotacticity of 0.53, which was determined by 13C NMR, using dialkylmagnesium as an initiator, was successfully synthesized. Isothermal treatment of iso-PAN was conducted in air at 200, 220, 250 and 280℃. Structural evolutions and chemical changes were studied with Fourier transformation infrared and wide-angle X-ray diffraction during stabilization. A new parameter CNF=I2240cm-1/ (I1595cm-1+f*I1595cm-1) was defined to evaluate residual nitrile groups. Crystallinity and crystal size were calculated with X-ray diffraction dates. The results indicated that the nitrile groups had partly converted into a ladder structure as stabilization proceeded. The rate of reaction increased with treatment temperature; crystallinity and crystal size decreased proportionally to pyrolysis temperature. The iso-conversional method coupled with the Kissinger and Flynn-Wall-Ozawa methods were used to determine kinetic parameters via differential scanning calorimetry analysis with different heating rates. The active energy of the reaction was 171.1 and 169.1 kJ/mol, calculated with the two methods respectively and implied the sensitivity of the reaction with temperature.