In situ produced Co9S8 nanoclusters/Co/Mn-S, N multi-doped 3D porous carbon derived from eriochrome black T as an effective bifunctional oxygen electrocatalyst for rechargeable Zn-air batteries.

Construction of high-efficiency, low cost and stable non-noble metal catalyst on air cathode is of great importance for design and assembly of rechargeable Zn-air battery. Eriochrome black T (EBT) has phenolic hydroxyl and -N=Ν- groups, which provides multiple coordination sites for metal ions. Herein, Co9S8 nanoclusters implanted in Co/Mn-S,N multi-doped porous carbon (Co9S8@Co/Mn-S,N-PC) are fabricated with the mixture (i.e. EBT, metal precursors and dicyandiamide) by a coordination regulated pyrolysis strategy. Specifically, EBT effectively chelates with the Co and Mn ions, resulting in multiple incorporation and fine modulation of the carbon electronic structures. Meanwhile, its sulfonic acid groups are reduced at such high temperature, accompanied by simultaneously embedding S element in the carbon, ultimately in situ forming Co9S8 nanoclusters. The Co9S8@Co/Mn-S,N-PC performs as an effective bifunctional oxygen catalyst, displaying a positive half-wave potential of 0.85 V and a large limiting current density of 5.89 mA cm-2 for oxygen reduction reaction (ORR) in alkaline media, coupled with a small overpotential of 320 mV at 10 mA cm-2 towards oxygen evolution reaction (OER), outperforming commercial Pt/C and RuO2 catalysts, respectively. Furthermore, the assembled rechargeable Zn-air battery with Co9S8@Co/Mn-S,N-PC exhibits the much better charge/discharge performance and long-term durability (210 h, 630 cycles). This research opens an instructive avenue to develop high-efficient and stable bifunctional oxygen electrocatalysts in energy transformation and storage devices.