Abstract

Abstract The aqueous zinc‐iodine battery is a promising energy storage device, but the conventional two‐electron reaction potential and energy density of the iodine cathode are far from meeting practical application requirements. Given that iodine is rich in redox reactions, activating the high‐valence iodine cathode reaction has become a promising research direction for developing high‐voltage zinc‐iodine batteries. In this work, by designing a multifunctional electrolyte additive trimethylamine hydrochloride (TAH), a stable high‐valence iodine cathode in four‐electron‐transfer I − /I 2 /I + reactions with a high theoretical specific capacity is achieved through a unique amine group, Cl bidentate coordination structure of (TA)ICl. Characterization techniques such as synchrotron radiation, in situ Raman spectra, and DFT calculations are used to verify the mechanism of the stable bidentate structure. This electrolyte additive stabilizes the zinc anode by promoting the desolvation process and shielding mechanism, enabling the zinc anode to cycle steadily at a maximum areal capacity of 57 mAh cm −2 with 97 % zinc utilization rate. Finally, the four‐electron‐transfer aqueous Zn−I 2 full cell achieves 5000 stable cycles at an N/P ratio of 2.5. The unique bidentate coordination structure contributes to the further development of high‐valence and high capacity aqueous zinc‐iodine batteries.