RESUMO
Assembling graphene sheets into macroscopic fibers with graphitic layers uniaxially aligned along the fiber axis is of both fundamental and technological importance. However, the optimal performance of graphene-based fibers has been far lower than what is expected based on the properties of individual graphene. Here we show that both mechanical properties and electrical conductivity of graphene-based fibers can be significantly improved if bridges are created between graphene edges through covalent conjugating aromatic amide bonds. The improved electrical conductivity is likely due to extended electron conjugation over the aromatic amide bridged graphene sheets. The larger sheets also result in improved π-π stacking, which, along with the robust aromatic amide linkage, provides high mechanical strength. In our experiments, graphene edges were bridged using the established wet-spinning technique in the presence of an aromatic amine linker, which selectively reacts to carboxyl groups at the graphene edge sites. This technique is already industrial and can be easily upscaled. Our methodology thus paves the way to the fabrication of high-performance macroscopic graphene fibers under optimal techno-economic and ecological conditions.
RESUMO
Flexible and wearable electronics have recently sparked intense interest in both academia and industry because they can greatly revolutionize human lives by impacting every aspect of our daily routine. Therefore, developing compatible energy storage devices has become one of the most important research frontiers in this field. Particularly, the development of flexible electrodes is of great significance when considering their essential role in the performance of these devices. Although there is no doubt that transition metal oxide nanomaterials are suitable for providing electrochemical energy storage, individual oxides generally cannot be developed into freestanding electrodes because of their intrinsically low mechanical strength.Two-dimensional sheets with genuine unilamellar thickness are perfect units for the assembly of freestanding and mechanically flexible devices, as they have the advantages of low thickness and good flexibility. Therefore, the development of metal oxide materials into a two-dimensional sheet morphology analogous to graphene is expected to solve the above-mentioned problems. In this Account, we summarize the recent progress on two-dimensional molecular sheets of transition metal oxides for wearable energy storage applications. We start with our understanding of the principle of producing two-dimensional metal oxides from their bulk-layered counterparts. The unique layered structure of the precursors inspired the exploration of their interlayer chemistry, which helps us to understand the processes of swelling and delamination. Rational methods for tuning the chemical composition, size/thickness, and surface chemistry of the obtained nanosheets and how physicochemical properties of the nanosheets can be modulated are then briefly introduced. Subsequently, the orientational alignment of the anisotropic sheets and the origins of their liquid-crystalline characteristics are discussed, which are of vital importance for their subsequent macroscopic assembly. Finally, macroscopic electrodes with geometric diversity ranging from one-dimensional macroscopic fibers to two-dimensional films/papers and three-dimensional monolithic foams are summarized. The intrinsically low mechanical stiffness of metal oxide sheets can be effectively overcome by wisely designing the assembly mode and sheet interfaces to obtain decent mechanical properties integrated with superior electrochemical performance, thereby providing critical advantages for the fabrication of wearable energy storage devices.We expect that this Account will stimulate further efforts toward fundamental research on interface engineering in metal oxide sheet assembly and facilitate wide applications of their designed assemblies in future new-concept energy conversion devices and beyond. In the foreseeable future, we believe that there will be a big explosion in the application of transition metal oxide sheets in flexible electronics.
