Macro‐Sized All‐Graphene 3D Structures via Layer‐by‐Layer Covalent Growth for Micro‐to‐Macro Inheritable Electrical Performances

Abstract Creating 3D‐engineered macroscopic architectures while inheriting the superior properties of individual building blocks remains one of the fundamental challenges in nanotechnology. Stable covalent interconnection between micro/nanoblocks is a desired but underexplored strategy to meet the challenges, rather than current dependently‐used weak physical forces or organic cross‐linking, which disrupts the continuity of chemical composition and electrical properties. Herein, a novel layer‐by‐layer covalent growth protocol is developed to construct all‐graphene macrostructures (AGM) with micro‐to‐macro inheritable electrical properties by laser‐assisted covalent linkage of polyethersulfone‐derived 3D porous graphene microblocks without introducing any catalysts, templates, and additives. Creatively, along with graphene generation and inter‐layer bonding, a quality optimization process is integrated into one‐step laser irradiation, which is unique and efficient for synthesizing high‐crystalline graphene. With the covalently nondestructive bridge and free of non‐graphene foreign phase impurities, AGM shows unprecedented electrical conductivity, especially a more than 100‐fold improvement in cross‐layer conductivity compared with non‐covalent assembly. Furthermore, the covalent growth mechanism of AGM is clarified by molecular dynamics simulations. Finally, the application efficacy of AGM with enhanced isotropic conductivity is verified by using it as a supercapacitor electrode. This methodology enables the as‐obtained AGM to possess the potential for high‐performance‐pursuing, multi‐disciplinary, or large‐scale applications.