High Areal Capacitance and Rate Capability of 3D-Printed Thick Electrodes with Optimized Conductive Networks from the Core–Sheath Structure

Material extrusion 3D printing has received enormous attention to potentially overcome its limits by tailoring and designing thick electrodes. In this work, we prepared a thick reduced graphene oxide/carbon nanotube-reduced graphene oxide/carbon nanotubes/manganese oxide@carbon nanotubes (rGC-rGCMC) electrode with controlled lattice architectures, core-sheath structure, and hierarchical porosity by material coaxial extrusion 3D printing, freeze-drying, and thermal treatment. The volume ratios of core to sheath, including 100%-0%, 0%-100%, 20%-80%, 30%-70%, 40%-60%, and 50%-50%, were designed to investigate the influences of the core-sheath structure on thick electrodes. The electrodes with a core-sheath volume ratio of 30%-70% electrodes exhibited an enhanced areal specific capacitance of 588.27 mF cm^-2 (39.48 F g^-1) at a scan rate of 0.5 mA cm^-2. All capacitance decays from core-sheath electrodes (20%-80%, 30%-70%, 40%-60%, and 50%-50%) were smaller than those from rGCMC (0%-100%) electrodes, indicating the improved rate capability from the core-sheath structure. On comparison of 30%-70% core-sheath electrodes with electrodes made of a homogeneous 30% rGC and 70% rGCMC mixture (30%+70%), lower capacitance (382.27 mF cm^-2 and 25.66 F g^-1 at 0.5 mA cm^-2) of the 30%+70% mixture electrode without a core-sheath structure suggested less efficiency to harvest electrons from the redox reactions. Electrochemical impedance spectroscopy (EIS) data further supported and explained the resistances of thick electrodes with different volume ratios.