Configuring a Robust Sulfur‐Rich Shielding Interphase for Suppressing Electric‐Field‐Driven Zinc Corrosion

ABSTRACT Electric‐field‐driven zinc corrosion fundamentally restricts the durability of aqueous zinc‐ion batteries (AZIBs), yet its underlying mechanism remains challenging. Herein, the governing role of electric field intensity in Zn corrosion is elucidated by integrating electrochemical analysis with nanoscale surface and interfacial probes. Strong electric fields are revealed to accelerate corrosion through amplified surface heterogeneity, hydrogen evolution, and by‐product accumulation, leading to unstable Zn deposition. To mitigate these effects, a sulfur‐rich anticorrosive shielding layer is in situ configured onto Zn surface. This interphase comprises a ZnS‐rich inner layer, a ZnN‐rich outer layer, and uniformly distributed ZnSO 3 . This unique structure endows the electrode with mechanical robustness, homogenizes Zn‐ion flux, and suppresses electric‐field‐driven corrosion. Consequently, Zn//Zn symmetrical cells achieve an extended lifespan of 1250 h at 20 mA·cm −2 and 5 mAh·cm −2 , and Zn//Cu half cells deliver 690 cycles with 99.7 % Coulombic efficiency. Furthermore, Zn–I 2 full cells retain 93.8 % capacity over 20000 cycles at 8 A·g −1 , while a 7.5 × 7.5 cm 2 pouch cell sustains a discharge capacity of 180.6 mAh after 1200 cycles without attenuation. These findings clarify the role of the electric field in Zn corrosion and provide a practical interphase‐engineering strategy toward durable Zn anodes for high‐performance AZIBs.