Single-atom Mn sites confined into hierarchically porous core-shell nanostructures for improved catalysis of oxygen...

Applications of zinc-air batteries are partially limited by the slow kinetics of oxygen reduction reaction (ORR); Thus, developing effective strategies to address the compatibility issue between performance and stability is crucial, yet it remains a significant challenge. Here, we propose an in situ gas etching-thermal assembly strategy with an in situ-grown graphene-like shell that will favor Mn anchoring. Gas etching allows for the simultaneous creation of mesopore-dominated carbon cores and ultrathin carbon layer shells adorned entirely with highly dispersed Mn-N₄ single-atom sites. This approach effectively resolves the compatibility issue between activity and stability in a single step. The unique core-shell structure allows for the full exposure of active sites and effectively prevents the agglomerations and dissolution of Mn-N₄ sites in cores. The corresponding half-wave potential for ORR is up to 0.875 V (vs. reversible hydrogen electrode (RHE)) in 0.1 M KOH. The gained catalyst (Mn-N@Gra-L)-assembled zinc-air battery has a high peak power density (242 mW cm^-2) and a durability of ∼ 115 h. Furthermore, replacing the zinc anode achieved a stable cyclic discharge platform of ∼ 20 h at varying current densities. Forming more fully exposed and stable existing Mn-N₄ sites is a governing factor for improving the electrocatalytic ORR activity, significantly cycling durability, and reversibility of zinc-air batteries.