Wendan Zhang, Jiaming Gong, Leiqian Zhang, Zeng Liu, Jia You, Z. Wang, Yang Zhou, C. Y. Zhang, Elke Debroye, Jean‐François Gohy, Prof. Dr. Johan Hofkens, Yue‐E Miao, Feili Lai, Tianxi Liu
ABSTRACT Aqueous zinc‐iodine batteries (ZIBs) have attracted extensive attention due to their advantages of high theoretical specific capacity, abundant reserves, high safety, and low cost, while the Zn anodes are still suffering from dendrite growth, side reactions, and polyiodide corrosion, seriously affecting the service life of ZIBs. Herein, sulfonated cellulose acetate (SCA) nanofiber membrane with zincophilic‐hydrophobic property is constructed on the Zn anode as a protective layer by electrospinning to circumvent the above problems and achieve a stable Zn anode. Attributing to both the hydrophobicity and zincophilicity, the SCA nanofiber membrane not only reduces the activity of water but also promotes the Zn 2+ desolvation. Moreover, negatively‐charged groups of the SCA nanofiber membrane cause electrostatic repulsion with polyiodide. Density functional theory calculations and COMSOL simulations further reveal that the SCA nanofiber membrane can tune the uniform 3D deposition behavior of Zn 2+ by chemisorption and physical structure, respectively. The obtained ZIBs can achieve ultra‐long life span (> 13000 cycles) with high‐capacity retention (96.74%) and reversibility (average CE: 99.83%), demonstrating the reliability of our proposed strategy for achieving stable and high‐performance ZIBs.