General, Vertical, Three-Dimensional Printing of Two-Dimensional Materials with Multiscale Alignment

Two-dimensional (2D) materials (e.g., boron nitride (BN), graphene, and MoS₂) have great potential in emerging energy, environmental, and electronics applications. Assembly of 2D materials into vertically aligned structures is highly desirable (, low tortuosity for rapid ion transport in fast charging-discharging batteries, guiding thermal transport for efficient thermal management), yet extremely challenging due to the energetically unfavorable in processing. Herein, we reported a general three-dimensional (3D) printing method to fabricate vertically aligned 2D materials in multiscale, using BN nanosheet as the proof-of-concept. The 3D-printed macroscale rods are composed of vertically aligned BN nanosheets at the nanoscale. The formation of the hierarchical aligned structure is enabled by the optimized ink that holds a significant shear-thinning behavior and an ultrahigh storage modulus, as identified at a narrow region in the printability diagram. The resulting vertically aligned multiscale structure with 2D nanosheets demonstrated an outstanding through-plane thermal conductivity, up to 5.65 W m^-1 K^-1, significantly higher than the value of conventional BN based structures where the sheets are horizontally aligned. The vertical 3D printing of 2D BN nanosheets can be expanded to other 2D materials in constructing hierarchically aligned structures for a range of emerging technologies such as batteries, membranes, and structural materials.