Energetic Hypervalent Organoiodine Electrochemistry for Aqueous Zinc Batteries.

Hypervalent organoiodine compounds have been extensively utilized in organic synthesis, yet their electrochemical properties remain unexplored despite their theoretically high redox potential compared with inorganic iodine, which primarily relies on the I - /I 0 redox couple in battery applications. Here, the fundamental redox mechanism of hypervalent organoiodine in a ZnCl 2 aqueous electrolyte is established for the first time using the simplest iodobenzene (PhI) as a model compound. We validated that the PhI to PhICl 2 transition is a single-step and reversible reaction, enabling two-electron transfer of I + /I 3+ redox chemistry (1.9 V vs Zn 2+ /Zn) with high capacity (422 mAh g iodine -1 , and 262.6 mAh g -1 based on PhI) and high theoretical energy density (801.8 Wh kg -1 ). It was also elucidated that such organoiodine electrochemistry exhibits rich tunability in terms of the global reactivity of various PhI derivatives, including multiple iodine-substituted isomers and functional substituents. Additionally, the stabilizing anion ligands affect the reversibility and stability of trivalent organoiodine compounds. By limiting side reactions and improving the stability of trivalent organoiodine at low temperatures, the zinc-PhI battery demonstrated the feasibility of I + /I 3+ conversion and sustained stable performance over 400 cycles. This work bridges the gap between hypervalent organoiodine chemistry and battery technology, highlighting the potential for future high-performance battery applications.