Interrupting the Hydroxide Enrichment‐Induced Electrode Degradation Loop for Achieving Stable Aqueous Zn‐I 2 Batteries

Abstract Severe adverse reactions, including hydrogen evolution reaction (HER) and polyiodide shuttle, lead to short lifetimes of rechargeable aqueous zinc‐iodine (Zn‐I 2 ) batteries and have aroused widespread attention. However, few studies have specifically investigated the impact of hydroxide ion (OH − ) disturbance generated by side reactions on the Zn anode and I 2 cathode in aqueous electrolytes. Herein, a facile electrolyte additive strategy was introduced to break the OH − enrichment‐induced bidirectional electrode degradation loop toward achieving stable Zn‐I 2 cells. Particularly, the bidirectional additive restricts the crossover of OH − , suppressing the iodine hydrolysis reaction‐induced polyiodide formation and capturing polyiodides to prevent shuttling. It also preferentially interacts with Zn, simultaneously reconstructing the solvation shell and promoting the formation of a hybrid ZnS‐rich solid electrolyte interface (SEI) to improve Zn kinetics and inhibit HER. Therefore, a stable cycling of Zn//Zn cells can be sustained for 1700 and 400 h in acidic and alkaline electrolytes, respectively. Impressively, the Zn‐I 2 cell achieved a cycle life of 9000 cycles at a high mass loading of 12 mg cm −2 . The concept of bi‐directional synergetic regulation for accounting for the aqueous environment is expected to provide a new approach for highly stable aqueous Zn‐I 2 batteries.