Unveiling Phenoxazine's Unique Reversible Two‐Electron Transfer Process and Stable Redox Intermediates for High‐Performance Aqueous Zinc‐ion Batteries

Abstract The low specific capacity determined by the limited electron transfer of p‐type cathode materials is the main obstruction to their application towards high‐performance aqueous zinc‐ion batteries (ZIBs). To overcome this challenge, boosting multi‐electron transfer is essential for improving the charge storage capacity. Here, as a typical heteroaromatic p‐type material, we unveil the unique reversible two‐electron redox properties of phenoxazine in the aqueous electrolytes for the first time. The second oxidation process is stabilized in the aqueous electrolytes, a notable contrast to its less reversibility in the non‐aqueous electrolytes. A comprehensive investigation of the redox chemistry mechanism demonstrates remarkably stable redox intermediates, including a stable cation radical PNO⋅ + characterized by effective electron delocalization and a closed‐shell state dication PNO 2+ . Meanwhile, the heightened aromaticity contributes to superior structural stability during the redox process, distinguishing it from phenazine, which features a non‐equivalent hybridized sp 2 ‐N motif. Leveraging these synergistic advantages, the PNO electrodes deliver a high capacity of 215 mAh g −1 compared to other p‐type materials, and impressive long cycling stability with 100 % capacity retention over 3500 cycles. This work marks a crucial step forward in advanced organic electrodes based on multi‐electron transfer phenoxazine moieties for high‐performance aqueous ZIBs.