▎ 摘　　要

Graphene-derived layer-by-layer (LbL) assemblies in the form of films or fibers have recently attracted particular interests owing to their low cost, facile fabrication, and outstanding mechanical properties, which could be further tuned by surface functionalization that cross-links graphene sheets in the assembly. However, this interfacial engineering approach has not yet been finely utilized considering the dual roles of cross-links in modifying the intrinsic properties of graphene sheets and their interlayer interactions. In this work, combining first-principles calculations and continuum-mechanics-based model analysis, we find that the functionalization weakens the intrinsic mechanical resistance of graphene, whereas it enhances interlayer load transfer through interlayer cross-linking. There are optimum cross-linking, densities or concentrations of the surface functional groups that maximize the overall tensile stiffness, tensile strength and strain to failure of graphene-derived LbL assemblies, arising from the competition between intralayer and interlayer load-bearing mechanisms, as defined by the type of functionalization and size of graphene sheets. Our work quantifies the ultimate mechanical performance of graphene-derived LbL assemblies, on the condition that their microstructures and functionalization could be adequately controlled in the fabrication process.