Laser‐Induced Graphene Enabled Additive Manufacturing of Multifunctional 3D Architectures with Freeform Structures

3D printing has become an important strategy for constructing graphene smart structures with arbitrary shapes and complexities. Compared with graphene oxide ink/gel/resin based manners, laser‐induced graphene (LIG) is unique for facile and scalable assembly of 1D and 2D structures but still faces size and shape obstacles for constructing 3D macrostructures. In this work, a brand‐new LIG based additive manufacturing (LIG‐AM) protocol is developed to form bulk 3D graphene with freeform structures without introducing extra binders, templates, and catalysts. On the basis of selective laser sintering, LIG‐AM creatively irradiates polyimide (PI) powder‐bed for triggering both particle‐sintering and graphene‐converting processes layer‐by‐layer, which is unique for assembling varied types of graphene architectures including identical‐section, variable‐section, and graphene/PI hybrid structures. In addition to exploring combined graphitizing and fusing discipline, processing efficiency and assembling resolution of LIG‐AM are also balanceable through synergistic control of lasing power and powder‐feeding thickness. By further studying various process dependent properties, a LIG‐AM enabled aircraft‐wing section model is finally printed to comprehensively demonstrate its shiftable process, hybridizable structure, and multifunctional performance including force‐sensing, anti‐icing/deicing, and microwave shielding and absorption.