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.