Prominent Structural Dependence of Quantum Capacitance Unraveled by Nitrogen‐Doped Graphene Mesosponge

Abstract Porous carbons are important electrode materials for supercapacitors. One of the challenges associated with supercapacitors is improving their energy density without relying on pseudocapacitance, which is based on fast redox reactions that often shorten device lifetimes. A possible solution involves achieving high total capacitance ( C tot ), which comprises Helmholtz capacitance ( C H ) and possibly quantum capacitance ( C Q ), in high‐surface carbon materials comprising minimally stacked graphene walls. In this work, a templating method is used to synthesize 3D mesoporous graphenes with largely identical pore structures (≈2100 m 2 g −1 with an average pore size of ≈7 nm) but different concentrations of oxygen‐containing functional groups (0.3–6.7 wt.%) and nitrogen dopants (0.1–4.5 wt.%). Thus, the impact of the heteroatom functionalities on C tot is systematically investigated in an organic electrolyte excluding the effect of pore structures. It is found that heteroatom functionalities determine C tot , resulting in the cyclic voltammetry curves being rectangular or butterfly‐shaped. The nitrogen functionalities are found to significantly enhance C tot owing to increased C Q .