Electronic State Synergy of Dinuclear Catalytic Center in Wolframite‐type (CoMo)octMotetO Activates Efficient d‐p/π* Interaction During Multiphasic Electrocatalysis in Full Range Ambient Air for Li‐Air Battery

Li‐air batteries (LABs) have attracted intense interest due to ultrahigh energy density. However, the performance enhancement of LABs has to depend on systemic assistance to prevent side reactions only at low humidity, because of the lack of a highly active catalyst to handle the complicated full range of ambient air conditions. Herein, a relaxed wolframite structured CoMoO 4 with multiphasic catalytic capabilities was fabricated, which achieved efficient d‐p/π * coupling for ORR/OER process on a single catalytic center with modulated d‐band center and generated dinuclear Co sites activating CORR/COER process through a CO 2 +Li route. Further, its hydrophobic substrate and unstable adsorption of LiOH delay the formation of LiOH and accelerate the conversion from LiOH to Li 2 CO 3 in ambient air. Without any protection, the LABs delivered ultralong cycle performance at full range humidity of ambient air with 650 cycles at relative humidity (RH) range < 50% and 400 cycles at RH range of 50–100% and CO 2 environment. In punch cell, it delivered impressive energy density of 1217.6 Wh kg −1 and a long cycle life over 1300 h. This contribution demonstrates high energy density and long cycle life of LABs at full range air conditions, giving concept guidance for advanced catalysts and exhibiting future potential for practical application.