Bio‐Inspired Zymogen‐Activation Strategy for On‐Demand and Bilateral Interphase Formation in Aqueous Zinc‐Ion Batteries

ABSTRACT Aqueous zinc‐ion batteries (AZIBs) possess distinct benefits in cost and safety, but bilateral interfacial failures on Zn anodes and MnO 2 cathodes constrain their practical applications. Inspired by zymogen‐to‐enzyme activation, this work proposes a biomimetic, intelligent electrolyte additive strategy that enables on‐demand protection on both electrodes. This strategy employs an inert additive, 1,4‐butane sultone (BS), which preferentially adsorbs on the electrode surfaces. Upon water attack and localized pH increase, BS can be activated, generating open‐ring derivatives (OBS) to facilitate the in situ construction of bilateral protective interphases with organic–inorganic composite components. Concurrently, it optimizes Zn 2+ solvation structures to lower the desolvation energy barrier. Residual BS further traps SO 4 2− and H 2 O and sustains the OBS formation for preventing interfacial alkalization. Consequently, the BS‐modified Zn//Zn cell delivers a lifespan exceeding 4000 h, and the Zn//Cu cell attains an ultrahigh initial Coulombic efficiency of 97.62%. Zn//MnO 2 full cells maintain capacity retention of 92.7% and 80.5% after 100 cycles at 0.2 A g −1 and 8000 cycles at 6 A g −1 , respectively. Such a strategy not only delivers a high‐performance electrolyte additive for AZIBs but also offers biomimetic inspiration for the development of electrolytes in other metal‐based battery systems.