Monodisperse Co₉S₈ nanoparticles in situ embedded within N, S-codoped honeycomb-structured porous carbon for bifunctional oxygen electrocatalyst in a rechargeable Zn–air battery

The exploitation of cost-effective, highly active, and robust non-precious metal bifunctional oxygen electrocatalysts for both the oxygen reduction reaction (ORR) and oxygen revolution reaction (OER) is the key to promoting the application of regenerative fuel cells and metal–air batteries. Co₉S₈ is considered a promising non-precious metal bifunctional oxygen electrocatalyst. However, the electrocatalytic performance of cobalt sulfide-based nanocatalysts is still far from satisfactory because of their poor conductivity, insufficient exposed active sites, and aggregation-prone during continuous work. Herein, based on the inspiration from honeycombs in nature, we synthesized Co₉S₈/N, S-codoped honeycomb-structured porous carbon (Co₉S₈/NSC) in situ composites via a simple method. Benefiting from the unique honeycomb composite structure composed of monodisperse Co₉S₈ nanoparticles in situ embedded within the three-dimensional interconnected network carbon matrix with high conductivity, which facilitates not only the electron transport and charge transfer across the interface but also the exposure of active sites and rapid transport of ORR/OER-related species, the obtained Co₉S₈/NSC in situ composites exhibit high stability and activity in both the ORR in terms of more a positive half-wave potential (0.88 V vs. RHE) than that (0.86 V vs. RHE) of commercial 20% Pt/C and the OER in terms of a small overpotential (0.41 V vs. RHE) approaching that of commercial IrO₂ (0.39 V vs. RHE) in alkaline electrolytes at 10 mA cm⁻². Thus, as expected, the assembled rechargeable Zn–air batteries based on the bifunctional electrocatalysts exhibit a small discharge/charge overpotential (0.96 V) with a high voltaic efficiency of 55.1% at 10 mA cm⁻² and a long-term cycling stability of over 4000 min.