Introducing <i>p</i> ‐Band Center to Promote <i>p/p</i> ‐π* Orbital Hybridization for High‐Performance Aqueous Zinc‐Iodine Batteries Toward Flexible Wearable Devices and Seawater Electrolyte Applications

Abstract Aqueous zinc‐iodine (Zn‐I 2 ) batteries represent attractive candidates for flexible electronics and advanced energy storage due to their environmental benignity, inherent safety, and low cost. However, severe zinc dendrite formation, parasitic side reactions, and rapid polyiodide shuttling coupled with sluggish redox kinetics impede practical deployment. To overcome these limitations, a novel (1,4‐dioxan‐2‐yl)methanol (DXm) is introduced as a multifunctional electrolyte additive. The p ‐band center of ─O─ groups in DXm covalently coordinates with Zn 2 ⁺, enabling uniform zinc deposition and suppressing interfacial side reactions. Meanwhile, DXm introduces p / p ‐π* orbital hybridization with iodine species, accelerating polyiodide redox kinetics. Consequently, DXm‐modified flexible cells exhibit exceptional cyclability and stable performance across a broad temperature range (0–25 °C), even under mechanical deformation. Furthermore, cells employing DXm‐containing seawater electrolyte present 187 mAh g −1 capacity with 1000 cycles at a current density of 25 C. This work provides fundamental insights into p ‐band center modulation for enhanced p / p ‐π* hybridization in electrochemical redox reactions, establishing design principles for sustainable Zn‐I 2 batteries in flexible, wearable, and seawater‐based applications.