Aerobically Autoxidized Self‐Charge Concept Derived from Synergistic Pyrrolic Nitrogen and Catechol Configurations in N, O Co‐Doped Carbon Cathode Material

Abstract Aerobically autoxidized self‐charging concept has drawn significant attraction due to its promising chemical charge features without external power supply. Particularly, heteroatom‐doped carbon materials with abundant oxidizable sites and good conductivity are expected to be ideal cathode materials. However, there is no well‐defined aerobically autoxidized self‐charging concept based on heteroatom‐doped carbon materials, significantly hindering the design of related carbon cathodes. An aerobically autoxidized self‐chargeable concept derived from synergistic effect of pyrrolic nitrogen and catechol configuration in carbon cathode using model single pyrrolic nitrogen and oxygen (N‐5, O) co‐doped carbon and O‐enriched carbon is proposed. First, self‐charging of N‐5, O co‐doped carbon cathode can be achieved by aerobic oxidation of pyrrolic nitrogen and catechol to oxidized pyrrolic nitrogen and ortho ‐quinone configurations, respectively. Second, introducing a single pyrrolic nitrogen configuration enhanced acidic wettability of N‐5, O co‐doped carbon facilitating air self‐charge/galvanic discharge involving proton removal/introduction. Third, synergistic effect of pyrrolic nitrogen and hydroxyl species with the strong electron‐donating ability to conjugated carbon‐based backbone endows N‐5, O co‐doped carbon with a higher highest occupied molecular orbital (HOMO) energy level more susceptible to oxidation charging. The assembled Cu/Carbon batteries can drive a timer after every air‐charging run. This promising aerobically autoxidized self‐charging concept can inspire exploring high‐efficiency self‐charging devices.