Rational Design of Porous Nanowall Arrays of Ultrafine Co₄N Nanoparticles Confined in a La₂O₂CN₂ Matrix on Carbon Cloth for a High-Performing Supercapacitor Electrode

Transition metal nitrides (TMNs) have received special concern as important energy storage materials, owing to their high conductibility, good mechanical strength, and superior corrosion resistance. However, their insufficient capacitance and poor cycling stability limit their practical applications for supercapacitors. Here, a novel three-dimensional (3D) self-supported integrated electrode consisted of porous nanowall arrays of ultrafine cobalt nitride (Co₄N) nanoparticles encapsulated in a lanthanum oxycyanamide (LOC) matrix on carbon cloth (Co₄N@LOC/CC) for outstanding electrochemical energy storage is rationally designed and fabricated. The 3D monolithic configuration of porous nanowall arrays facilitates the mass/charge transfer, the exposure of electroactive sites, and the enhancement of electrical conductivity. Meanwhile, the unique core-shell structure of Co₄N@LOC can prevent ultrafine Co₄N nanoparticles from sintering, agglomeration, and oxidation and promotes electron transfer dynamics during the redox reaction, meanwhile enhancing the stability of the electrode. Additionally, the synergy of Co₄N and LOC can result in an efficient electron/ion transport in the process of the charge-discharge. Because of these features, the Co₄N@LOC/CC electrode displays superior specific capacitance (895.6 mF cm^-2 or 613.4 F g^-1 at 1 mA cm^-2) and admirable cycling durability (87.9% capacitance reservation after 10 000 cycles), surpassing the majority of nitride-based electrodes reported thus far. Furthermore, after being assembled into an asymmetric supercapacitor using active carbon (AC) as an anode, the obtained Co₄N@LOC/CC//AC/CC device displays a high energy density of 41.7 Wh kg^-1 at the power density of 875.8 W kg^-1 with a high capacitance reservation of 87.6% after 5000 cycles at 2 mA cm^-2. This work offers an efficient approach of combining TMNs with rare earth compounds to enhance the capacitance and stability of TMNs for supercapacitor electrodes.