High‐Performance Azo Cathodes Enabled by N‐Heteroatomic Substitution for Zinc Batteries with a Self‐Charging Capability.

Redox‐active azo compounds are emerging as promising cathode materials due to their multi‐electron redox capacity and fast redox response. However, their practical application is often limited by low output voltage and poor thermal stability. Herein, we use a heteroatomic substitution strategy to develop 4,4′‐azopyridine. This modification results in a 350 mV increase in reduction potential compared to traditional azobenzene, increasing the energy density at the material level from 187 to 291 Wh kg−1. The introduced heteroatoms not only raise the melting point of azo compounds from 68 °C to 112 °C by forming an intermolecular hydrogen‐bond network but also improves electrode kinetics by reducing energy band gaps. Moreover, 4,4′‐azopyridine forms metal‐ligand complexes with Zn2+ ions, which further self‐assemble into a robust superstructure, acting as a molecular conductor to facilitate charge transfer. Consequently, the batteries display a good rate performance (192 mAh g−1 at 20 C) and an ultra‐long lifespan of 60,000 cycles. Notably, we disclose that the depleted batteries spontaneously self‐charge when exposed to air, marking a significant advancement in the development of self‐powered aqueous systems. [ABSTRACT FROM AUTHOR]