Active and durable bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) on the cathode are required for high-performance rechargeable metal-air batteries. Herein, the synthesis of hierarchically porous nitrogen-doped carbon (HPNC) with bifunctional oxygen electrocatalysis for Zn-air batteries is reported. The HPNC catalyst possesses a large surface area of 1459 m2 g-1 and exhibits superior electrocatalytic activity toward ORR and OER simultaneously with a low OER/ORR overpotential of 0.62 V, taking the difference between the potential at 10 mA cm-2 for OER and half-wave potential for ORR in 0.1 m KOH. Adopting HPNC as the air cathode, primary and rechargeable Zn-air batteries are fabricated. The primary batteries demonstrate a high open-circuit potential of 1.616 V, a specific capacity of 782.7 mAh gZn -1 and a superb peak power density of 201 mW cm-2 . The rechargeable batteries can be cycled stably for over 360 cycles or 120 h at the current density of 5 mA cm-2 . As elucidated by density functional theory, N-doping is preferred on defective sites with pentagon configuration and on the edge in the form of pyridinic-N-type. The high content of these two motifs in HPNC leads to the superior ORR and OER activities, respectively.
Keywords: bifunctional electrocatalysis; hierarchically porous; metal-free catalysts; nitrogen doping; zinc-air batteries.
© 2021 Wiley-VCH GmbH.