3D Printing of Graphene Aerogel Microspheres to Architect High‐Performance Electrodes for Hydrogen Evolution Reaction

Abstract The hydrogen evolution reaction (HER) efficiency is highly dependent on the electrocatalysts microstructure and the macrostructure of the electrodes. Herein, the graphene aerogel microspheres loaded with well‐dispersed ultrafine Ni/Co nanoparticles catalyst is prepared through electro‐spraying, in‐situ crosslinking, freeze‐drying, and pyrolysis, and then is utilized to print the HER electrode via direct ink writing (DIW). The obtained graphene‐based aerogel microspheres possess peculiar cabbage‐like mesoporous structures which allow ready access of reaction species to active sites, optimal mass transfer, and proton diffusion within the microspheres. DIW 3D printing achieves the ordered control on the periodic lattice macro‐geometry and thus facilitates the fast gas bubble evolution and release from the electrode surface. The as‐fabricated 3D electrode possesses a low overpotential of 341 mV at 10 mA cm −2 , a decrease by 31.5% compared to 3D printed electrode directly from 2D graphene, and a low Tafel slope of 119.1 mV dec −1 , 40% lower than that of the electrodes fabricated via directly casting the aerogel microspheres. Furthermore, the 3D‐printed electrode of aerogel microspheres displays good HER stability. This work provides a good approach for constructing high‐performance HER electrodes through 3D printing of graphene aerogel microspheres.