Hierarchical Carbon Aerogel With Polarized Zr─O Interfaces Enables Dynamic Iodine Regulation in Aqueous Zn‐I 2 Batteries

The shuttle effect of soluble polyiodides limits the cycling stability and rate capability of aqueous Zn‐I 2 batteries. Herein, a ZrO 2 ‐decorated cellulose‐derived carbon aerogel (ZCA) is developed by integrating hierarchical pore confinement with polarized Zr─O/carbon interfacial regulation. Spectroscopic analyses and density functional theory calculations reveal moderate O···I─I coupling with halogen‐bond‐like character for neutral I 2 at Zr‐adjacent oxygen sites, while reduced iodine species are stabilized through species‐dependent interfacial regulation within the polarized Zr─O‐containing environment. This structural‐interfacial synergy suppresses polyiodide diffusion while preserving reversible I − /I 3 − /I 2 conversion. Consequently, ZCA@I 2 delivers 187.2 mAh g −1 after 5000 cycles at 1 A g −1 and sustains 123.2 mAh g −1 after 50 000 cycles at 10 A g −1 , with a per‐cycle decay of only 0.000052%. At an iodine areal loading of 6.7 mg cm −2 , it retains 93.1% of its capacity after 6000 cycles at 1 A g −1 . These results provide a structure‐interface design strategy for durable, high‐rate, and high‐loading aqueous Zn‐I 2 batteries.