The millisecond fabrication of medium-entropy alloy as a high-performance bifunctional electrocatalyst for ultralong-term rechargeable zinc–air batteries

Abstract

Zinc air battery (ZAB) has widely recognized advantages such as high theoretical energy density, environmental friendliness, and safety. However, its cathodic reactions involve sluggish four-electron process oxygen reduction and oxygen evolution reactions (ORR and OER). Therefore, developing a cheap, efficient and durable dual functional oxygen electrocatalyst has important scientific significance and practical value for the development of ZAB. Herein, we applied noble metal free medium-entropy alloy (CoFeNi) nanoparticles which were in embedded nitrogen doped carbon framework (N-PCF) as a highly active and ultra-stable bifunctional electrocatalyst. The CoFeNi@N-PCF was prepared by high temperature thermal shock approach from ion-exchanged ZIF percussor to ensure the uniform dispersion of medium-entropy alloy, hierarchical porosity and strong metal-support interaction. Due to the medium-entropy induced synergistic effects, the as-prepared bifunctional electrocatalyst has a large ORR onset potential (Eonset) of 0.92 V and half-wave potential (E1/2) of 0.85 V (vs. RHE) in 0.1 M KOH. And the overpotential of OER in 1.0 M KOH is only 320 mV at 10 mA cm−2. When used in ZAB, the as-assembled rechargeable ZAB with the self-supported air electrode provides an extremely high-power density of 203 mW cm−2, a superior specific capacity of 812 mAh g−1, and amazing cycled steadily for 600 h. The assembled flexible ZAB with CoFeNi@N-PCF exhibits an excellent stability (over 45 h) and the excellent bending ability under different angles. This work can provide some new insights into the design and preparation of advanced bifunctional oxygen electrocatalysts for next-generation metal-air batteries.