Fe–Ni Alloy Nanoclusters Anchored on Carbon Aerogels as High-Efficiency Oxygen Electrocatalysts in Rechargeable Zn–Air Batteries

In this work, Fe–Ni alloy nanoclusters (Fe–Ni ANCs) anchored on N, S co-doped carbon aerogel (Fe–Ni ANC@NSCA catalysts) are successfully prepared by the optimal pyrolysis of polyaniline (PANI) aerogels derived from the freeze-drying of PANI hydrogel obtained by the polymerization of aniline monomers in the co-presence of tannic acid (TA), Fe 3+ , and Ni 2+ ions. In addition, the optimal molar ratio of the TA, Fe 3+ , and Ni 2+ ions for synthesis of Fe–Ni ANC@NSCA catalysts are 1:2:5, which can guarantee the formation of carbon aerogel composed of quasi-2D porous carbon sheets and the formation of high-density Fe–Ni ANCs with an ultrasmall size between 2 to 2.8 nm. These Fe–Ni ANCs consisting of N 4 –Fe–O–Ni–N 4 moiety are proposed as a new type of active species for the first time, to the best of the authors’ knowledge. Thanks to their unique features, the Fe–Ni ANC@NSCA catalysts show excellent performance in oxygen reduction reaction with a half-wave potential ( E 1/2 ) of 0.891 V and oxygen evolution reaction (260 mV @ 10 mA cm −2 ) in alkaline media as bifunctional catalysts, which are better than the state-of-the-art commercial Pt/C catalysts and RuO 2 catalysts. Moreover, Zn–air battery assembled with the Fe–Ni ANC@NSCA catalysts also shows a remarkable performance and exceptionally high stability over 500 h at 5 mA cm −2 .