Rational design of efficient and durable bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalysts is critical for rechargeable metal–air batteries. Here, we developed a facile strategy for fabricating three-dimensional phosphorus and sulfur codoped carbon nitride sponges sandwiched with carbon nanocrystals (P,S-CNS). These materials exhibited high surface area and superior ORR and OER bifunctional catalytic activities than those of Pt/C and RuO2, respectively, concerning its limiting current density and onset potential. Further, we tested the suitability and durability of P,S-CNS as the oxygen cathode for primary and rechargeable Zn–air batteries. The resulting primary Zn–air battery exhibited a high open-circuit voltage of 1.51 V, a high discharge peak power density of 198 mW cm–2, a specific capacity of 830 mA h g–1, and better durability for 210 h after mechanical recharging. An extraordinary small charge–discharge voltage polarization (∼0.80 V at 25 mA cm–2), superior reversibility, and stability exceeding prolonged charge–discharge cycles have been attained in rechargeable Zn–air batteries with a three-electrode system. The origin of the electrocatalytic activity of P,S-CNS was elucidated by density functional theory analysis for both oxygen reactions. This work stimulates an innovative prospect for the enrichment of rechargeable Zn–air battery viable for commercial applications such as armamentaria, smart electronics, and electric vehicles.

Scalable 3-D Carbon Nitride Sponge as an Efficient Metal-Free Bifunctional Oxygen Electrocatalyst for Rechargeable Zn–Air Batteries