Integrated and Binder‐Free Air Cathodes of Co3Fe7 Nanoalloy and Co5.47N Encapsulated in Nitrogen‐Doped Carbon Foam with Superior Oxygen Reduction Activity in Flexible Aluminum‐Air Batteries

All‐solid‐sate Al‐air batteries with features of high theoretical energy density, low cost, and environmental‐friendliness are promising as power sources for next‐generation flexible and wearable electronics. However, the sluggish oxygen reduction reaction (ORR) and poor interfacial contact in air cathodes cause unsatisfied performance. Herein, a free‐standing Co3Fe7 nanoalloy and Co5.47N encapsulated in 3D nitrogen‐doped carbon foam (Co3Fe7@Co5.47N/NCF) is prepared as an additive‐free and integrated air cathode for flexible Al‐air batteries in both alkaline and neutral electrolytes. The Co3Fe7@Co5.47N/NCF outperforms commercial platinum/carbon (Pt/C) toward ORR with an onset potential of 1.02 V and a positive half‐wave potential of 0.92 V in an alkaline electrolyte (0.59 V in sodium chloride solution), which is ascribed to the unique interfacial structure between Co3Fe7 and Co5.47N supported by 3D N‐doped carbon foam to facilitate fast electron and mass transfer. The high ORR performance is also supported by in‐situ electrochemical Raman spectra and density functional theory calculation. Furthermore, the fabricated Al‐air battery displays good flexibility and delivers a power density of 199.6 mW cm−2, and the binder‐free and integrated cathode shows better discharge performance than the traditionally slurry casting cathode. This work demonstrates a facile and efficient approach to develop integrated air cathode for metal‐air batteries.