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 (39.48 F g) at a scan rate of 0.5 mA cm. 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 and 25.66 F g at 0.5 mA cm) 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.