Hollow carbon nanofibers with hierarchical porous shells were prepared by NaOH activation of the electrospinning SiCNO fibers, followed by carbonization treatment. By adjusting the carbonization temperature, porous hollow carbon nanofibers with different Brunauer−Emmett−Teller (BET) specific surface areas and total pore volumes are obtained, both of which are explored as electrode materials for supercapacitors. It was found that the obtained products (HCF800) possess the highest BET specific surface area of 2628.10 m 2 /g and the largest pore volume of 2.32 cm 3 /g when the carbonized temperature was designed at 800 °C, thus displaying the best supercapacitor performance. The electrochemical results in a three-electrode system show that HCF800 exhibits a high specific capacitance of 330.11 F/g as the discharge current density is 1 A/g and still maintains 65.3% of its original specific capacitance when the current density reaches 20 A/g. Moreover, in a twoelectrode system, HCF800 also exhibits an excellent specific capacity of 259.86 F/g at a current density of 1 A/g, marvelous cyclic stability with the specific capacitance retention of 95.3% even after 10,000 cycles, and a large energy density of 12.99 W h/kg at 1.0 A/g. Significantly, the supercapacitor performance of these porous hollow carbon nanofibers is also superior to that of many previously reported carbon materials, which proved them to be worthy candidates for high-performance electrode materials.
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