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

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.