3D Printed Nitrogen‐Doped Thick Carbon Architectures for Supercapacitor: Ink Rheology and Electrochemical Performance

The 3D printing technique offers huge opportunities for customized thick-electrode designs with high loading densities to enhance the area capacity in a limited space. However, key challenges remain in formulating 3D printable inks with exceptional rheological performance and facilitating electronic/ion transport in thick bulk electrodes. Herein, a hybrid ink consisting of woody-derived cellulose nanofibers (CNFs), multiwalled carbon nanotubes (MWCNTs), and urea is formulated for the 3D printing nitrogen-doped thick electrodes, in which CNFs serve as both dispersing and thickening agents for MWCNTs, whereas urea acts as a doping agent. By systematically tailoring the concentration-dependent rheological performance and 3D printing process of the ink, a variety of gel architectures with high geometric accuracy and superior shape fidelity are successfully printed. The as-printed gel architecture is then transformed into a nitrogen-doped carbon block with a hierarchical porous structure and superior electrochemical performance after freeze-drying and annealing treatments. Furthermore, a quasi-solid-state symmetric supercapacitor assembled with two interdigitated carbon blocks obtained by a 3D printing technique combined with a nitrogen-doping strategy delivers an energy density of 0.10 mWh cm^-2 at 0.56 mW cm^-2 . This work provides guidance for the formulation of the printable ink used for 3D printing of high-performance thick carbon electrodes.