Cu/S-Occupation Bifunctional Oxygen Catalysts for Advanced Rechargeable Zinc–Air Batteries

The design and synthesis of low-cost and highly efficient bifunctional catalysts is an inevitable path for rechargeable zinc–air batteries (rZABs). In this work, double-carbon co-supported Co-based oxide with the Cu and S substitutions are synthesized by a one-step hydrothermal method and formed a unique honeycomb structure. As expected, the (Cu, Co)3OS3@CNT-C3N4 exhibits high oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity with low overpotential (0.86 V), high power density (215 mW cm–2), and long-term discharge stability (115 h). The (Cu, Co)3OS3@CNT-C3N4-based rZAB also shows a stronger charge–discharge durability with a very low voltage gap of merely 0.5 V than that of Pt/C+RuO2. The high catalytic performances are attributed to these following reasons: (i) the porous morphology and hierarchical structure with plentiful “catalytic buffer”, which accelerates the mass transfer; (ii) a high-speed electronic transmission network established by C3N4 and carbon nanotube (CNT), enhancing the conductivity; (iii) the strong synergistic effect between (Cu, Co)3OS3@CNT and C3N4, which improves the kinetics of ORR/OER; and (iv) the controllable occupation of Cu ions and S ions, which effectively regulates the CoO6 surface and increases the active site density. This work not only offers a promising ORR/OER electrode for rZAB but also provides a new pathway to understand the improvement mechanism for catalysts by the bi-ion substitutions.