Alloying Co Species into Ordered and Interconnected Macroporous Carbon Polyhedra for Efficient Oxygen Reduction Reaction in Rechargeable Zinc-Air Batteries

Engineering non-precious transition metal (TM)-based electrocatalysts to simultaneously achieve an optimal intrinsic activity, high density of active sites, and rapid mass transfer ability for the oxygen reduction reaction (ORR) remains a significant challenge. To address this challenge, a hybrid composite consisting of FexCo alloy nanoparticles uniformly implanted into hierarchically ordered macro-/meso-/microporous N-doped carbon polyhedra (HOMNCP) is rationally designed. The combined results of experimental and theoretical investigations indicate that the alloying of Co enables a favorable electronic structure for the formation of the *OH intermediate, while the periodically trimodal-porous structured carbon matrix structure not only provides highly accessible channels for active site utilization but also dramatically facilitates mass transfer in the catalytic process. As expected, the Fe0.5Co@HOMNCP composite catalyst exhibits extraordinary ORR activity with a half-wave potential of 0.903 V (vs reversible hydrogen electrode), surpassing most Co-based catalysts reported to date. More remarkably, the use of the Fe0.5Co@HOMNCP catalyst as the air electrode in a zinc-air battery results in superior open-circuit voltage and power density compared to a commercial Pt/C + IrO2 catalyst. The results of this study are expected to inspire the development of advanced TM-based catalysts for energy storage and conversion applications.

Automated summary

This study successfully addresses the challenges in engineering non-precious transition metal-based electrocatalysts for achieving optimal intrinsic activity, high density of active sites, and rapid mass transfer ability. The Fe0.5Co@HOMNCP composite catalyst exhibits extraordinary ORR activity and outperforms most Co-based catalysts reported to date. Moreover, it shows superior open-circuit voltage and power density when used as the air electrode in a zinc-air battery compared to a commercial Pt/C + IrO2 catalyst.