Coordination Engineering of Dual Co, Ni Active Sites in N-Doped Carbon Fostering Reversible Oxygen Electrocatalysis

The development of affordable and non-noble-metal-based reversible oxygen electrocatalysts is required for renewable energy conversion and storage systems like metal-air batteries (MABs). However, the nonbifunctionality of most of the catalysts impedes their use in rechargeable MAB applications. Moreover, the loss of active sites also affects the long-term performance of the electrocatalyst toward oxygen electrocatalysis. In this work, we report a simplistic yet controllable chemical approach for the synthesis of dual transitional metals such as cobalt, nickel, and nitrogen-doped carbon (CoNi-NC) as bifunctional electrode materials for rechargeable zinc-air batteries (ZABs). The spatially isolated Ni-N₄ and Co-N₄ active units were rendered for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), respectively. The individual efficacy of both reversible reactions enables an ΔE value of ∼0.72 V, which outperforms several bifunctional electrocatalysts reported in the literature. The half-wave potential (E_1/2) and overpotential were achieved at 0.83 V and 330 mV (vs RHE) for ORR and OER, respectively. The peak power density of ZAB equipped with the CoNi-NC catalyst was calculated to be 194 mW cm^-2. The present strategy for the synthesis of bifunctional electrocatalysts with dual active sites offers prospects for developing electrochemical energy storage and conversion systems.