Longevous Cycling of Rechargeable Zn‐Air Battery Enabled by “Raisin‐Bread” Cobalt Oxynitride/Porous Carbon Hybrid Electrocatalysts

Developing commercially viable electrocatalyst lies at the research hotspot of rechargeable Zn‐air batteries, but it is still challenging to meet the requirements of energy efficiency and durability in realistic applications. Strategic material design is critical to addressing its drawbacks in terms of sluggish kinetics of oxygen reactions and limited battery lifespan. Herein, a “raisin‐bread” architecture is designed for a hybrid catalyst constituting cobalt nitride as the core nanoparticle with thin oxidized coverings, which is further deposited within porous carbon aerogel. Based on synchrotron‐based characterizations, this hybrid provides oxygen vacancies and Co‐Nx‐C sites as the active sites, resulting from a strong coupling between CoOxNy nanoparticles and 3D conductive carbon scaffolds. Compared to the oxide reference, it performs enhanced stability in harsh electrocatalytic environments, highlighting the benefits of the oxynitride. Furthermore, the 3D conductive scaffolds improve charge/mass transportation and boost durability of these active sites. Density functional theory calculations reveal that the introduced N species into hybrid can synergistically tune the d‐band center of cobalt and improve its bifunctional activity. As a result, the obtained air cathode exhibits bifunctional overpotential of 0.65 V and a battery lifetime exceeding 1350 h, which sets a new record for rechargeable Zn‐air battery reported so far. The design of “Raisin‐bread” architecture for bifunctional hybrid electrocatalyst enables the Zn‐air battery to exhibit a longevous cyclability exceeding 1350 h. It is realized through synergistic combination of (i) cobalt oxynitride as the protective shell, (ii) defect‐rich active sites resulting from in‐situ nitridation and strong coupling between cobalt raisin and surrounding 3D conductive bread, and (iii) enhanced mass and charge transportation via the boosted active surface and porosity.