Modular Graphene-Based 3D Covalent Networks: Functional Architectures for Energy Applications

The development of ordered graphene-based materials combining high stability, large surface areas, ability to act as absorbent of relevant chemical species, and solution processability is of significance for energy applications. A poorly explored approach relies on the controlled nanostructuration of graphene into robust and highly ordered 3D networks as a route to further leverage the exceptional properties of this unique material. Here, a simple yet effective and scalable one-step method is reported to prepare graphene-based 3D covalent networks (G3DCNs) with tunable interlayer distance via controlled polymerization of benzidines with graphene oxide at different reaction temperatures under catalyst- and template-free conditions. The reduced form of G3DCNs is used as electrodes in supercapacitors; it reveals a high specific capacitance of 156 F g⁻¹ at a current density of 1 A g⁻¹ in a two-electrode configuration and 460 F g⁻¹ at a current density of 0.5 A g⁻¹ in a three-electrode configuration, combined with an excellent cycling stability over 5000 cycles. The present study will promote the quantitative understanding of structure–property relationship, for the controlled fabrication of 3D graphene-based multifunctional materials.