An N‐superdoped 3D graphene network structure with an N‐doping level up to 15.8 at% for high‐performance supercapacitor is designed and synthesized, in which the graphene foam with high conductivity acts as skeleton and nested with N‐superdoped reduced graphene oxide arogels. This material shows a highly conductive interconnected 3D porous structure (3.33 S cm −1 ), large surface area (583 m 2 g −1 ), low internal resistance (0.4 Ω), good wettability, and a great number of active sites. Because of the multiple synergistic effects of these features, the supercapacitors based on this material show a remarkably excellent electrochemical behavior with a high specific capacitance (of up to 380, 332, and 245 F g −1 in alkaline, acidic, and neutral electrolytes measured in three‐electrode configuration, respectively, 297 F g −1 in alkaline electrolytes measured in two‐electrode configuration), good rate capability, excellent cycling stability (93.5% retention after 4600 cycles), and low internal resistance (0.4 Ω), resulting in high power density with proper high energy density.
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