▎ 摘　　要

Three-dimensional (3D) graphene-assembled monoliths (GAs), especially ones prepared by self assembly in the liquid phase, represent promising forms to realize the practical applications of graphene due to their high surface utilization and operability. However, the understanding of the assembly process and structure control of 3D GAs, as a new class of carbon materials, is quite inadequate. In this Perspective, we give a demonstration of the assembly process and discuss the key factors involved in the structure control of 3D GAs to pave the way for their future applications. It is shown that the assembly process starts with the phase separation, which is responsible for the formation of the 3D networked structure and liquid phase as the spacers avoid the parallel overlap of graphene layers and help form an interlinked pore system. Well tailored graphene sheets and selected assembly media must be a precondition for a well-controlled assembly process and microstructure of a 3D GA. The potential applications in energy storage featuring high rate and high volumetric energy density demonstrate advantages of 3D GAs in real applications.