LAUSR

Lithium–air batteries (LABs), owing to their ultrahigh theoretical energy density, are recognized as one of the next‐generation energy storage techniques. However, it remains a tricky problem to find highly active cathode catalyst operating within ambient air. In this contribution, a highly active Fe2Mo3O12 (FeMoO) garnet cathode catalyst for LABs is reported. The experimental and theoretical analysis demonstrate that the highly stable polyhedral framework, composed of FeO octahedrons and MO tetrahedrons, provides a highly effective air catalytic activity and long‐term stability, and meanwhile keeps good structural stability. The FeMoO electrode delivers a cycle life of over 1800 h by applying a simple half‐sealed condition in ambient air. It is found that surface‐rich Fe vacancy can act as an O2 pump to accelerate the catalytic reaction. Furthermore, the FeMoO catalyst exhibits a superior catalytic capability for the decomposition of Li2CO3. H2O in the air can be regarded as the main contribution to the anode corrosion and the deterioration of LAB cells could be attributed to the formation of LiOH·H2O at the end of cycling. The present work provides in‐depth insights to understand the catalytic mechanism in air and constitutes a conceptual breakthrough in catalyst design for efficient cell structure in practical LABs.