Study on the Controlled Synthesis of Petroleum Coke-Derived Modified Porous Carbon and Its Electrochemical Performance in Supercapacitors

Traditional petroleum coke-based porous carbons suffer from low specific surface area, insufficient surface active sites, and inferior rate and cycling performance. Herein, a series of sulfur/fluorine-co-doped hierarchical porous carbon (S+F-PC) cathode materials were synthesized controllably from industrial solid-waste petroleum coke via KOH high-temperature activation and heteroatom doping strategies. Polyaniline/carbon nanotube (PANI/CNTs) core–shell composites were fabricated as anodes through in situ oxidative polymerization, and S+F-PC//PANI/CNT asymmetric aqueous supercapacitors were assembled. The structural and chemical modulation mechanisms of dual heteroatom doping, as well as the electrochemical energy storage kinetics of electrodes and devices, were systematically investigated using SEM, TEM, XRD, XPS, BET, CV, GCD, EIS, and long-cycle tests. The results verify the synergistic modification effect of sulfur and fluorine co-doping. S-induced lattice distortion creates abundant mesopores and pseudocapacitive active sites, while F atoms stabilize the carbon skeleton to avoid high-temperature structural collapse and enhance the graphitization degree. The optimized S+F-PC exhibits an interconnected micropore–mesopore–macropore hierarchical network and a specific surface area of 172.2 m2/g, delivering a high specific capacitance of 477 F/g at 1 A/g, outperforming pure PC, and single-S-doped and -F-doped counterparts. The PANI/CNTs core–shell structure effectively alleviates the volume expansion of PANI during cycling, and the one-dimensional CNTs form a continuous conductive network. The PANI/CNT anode achieves a specific capacitance of 417 F/g, with a capacity retention of 91.4%, after 10,000 cycles. The assembled asymmetric supercapacitor realizes a stable voltage window of 1.6 V. It presents a specific capacitance of 117 F/g at 1 A/g, a maximum energy density of 41 Wh/kg at a power density of 2000 W/kg, and 87.2% capacity retention after 10,000 cycles. This work provides a feasible strategy for the high-value recycling of industrial-waste petroleum coke and the design of high-performance heteroatom-doped carbon electrodes and matched asymmetric aqueous supercapacitors.