Regulation of Atomic Fe‐Spin State by Crystal Field and Magnetic Field for Enhanced Oxygen Electrocatalysis in Rechargeable Zinc‐Air Batteries

Abstract Highly‐active and low‐cost bifunctional electrocatalysts for oxygen reduction and evolution are essential in rechargeable metal‐air batteries, and single atom catalysts with Fe−N−C are promising candidates. However, the activity still needs to be boosted, and the origination of spin‐related oxygen catalytic performance is still uncertain. Herein, an effective strategy to regulate local spin state of Fe−N−C through manipulating crystal field and magnetic field is proposed. The spin state of atomic Fe can be regulated from low spin to intermediate spin and to high spin. The cavitation of d xz and d yz orbitals of high spin Fe III can optimize the O 2 adsorption and promote the rate‐determining step (*O 2 to *OOH). Benefiting from these merits, the high spin Fe−N−C electrocatalyst displays the highest oxygen electrocatalytic activities. Furthermore, the high spin Fe−N−C‐based rechargeable zinc‐air battery displays a high power density of 170 mW cm −2 and good stability.