Heteroatom Polymer-Derived 3D High-Surface-Area and Mesoporous Graphene Sheet-Like Carbon for Supercapacitors

Current supercapacitors suffer from low energy density mainly due to the high degree of microporosity and insufficient hydrophilicity of their carbon electrodes. Development of a supercapacitor capable of simultaneously storing as much energy as a battery, along with providing sufficient power and long cycle stability would be valued for energy storage applications and innovations. Differing from commonly studied reduced graphene oxides, in this work we identified an inexpensive heteroatom polymer (polyaniline-PANI) as a carbon/nitrogen precursor, and applied a controlled thermal treatment at elevated temperature to convert PANI into 3D high-surface-area graphene-sheet-like carbon materials. During the carbonization process, various transition metals including Fe, Co, and Ni were added, which play critical roles in both catalyzing the graphitization and serving as pore forming agents. Factors including post-treatments, heating temperatures, and types of metal were found crucial for achieving enhanced capacitance performance on resulting carbon materials. Using FeCl₃ as precursor along with optimal heating temperature 1000 °C and mixed acid treatment (HCl+HNO₃), the highest Brunauer-Emmett-Teller (BET) surface area of 1645 m²g^-1 was achieved on the mesopore dominant graphene-sheet-like carbon materials. The unique morphologies featured with high-surface areas, dominant mesopores, proper nitrogen doping, and 3D graphene-like structures correspond to remarkably enhanced electrochemical specific capacitance up to 478 Fg^-1 in 1.0 M KOH at a scan rate of 5 mV s^-1. Furthermore, in a real two-electrode system of a symmetric supercapacitor, a specific capacitance of 235 Fg^-1 using Nafion binder is obtained under a current density of 1 Ag^-1 by galvanostatic charge-discharge tests in 6.0 M KOH. Long-term cycle stability up to 5000 cycles by using PVDF binder in electrode was systematically evaluated as a function of types of metals and current densities.