Polymeric Iodine Transport Layer Enabled High Areal Capacity Dual Plating Zinc‐Iodine Battery

Iodine cathode in aqueous battery has drawn great attention due to its high energy density and high safety. However, iodine has extremely low conductivity of 1×10−7 S cm−1, which usually results in low specific capacity. In this work, a PVA‐hydrogel layer was designed to enhance the areal capacity of zinc‐iodine cell. The areal capacity of PVA‐hydrogel layer modified CNT cathode showed twice as higher capacity than that of pure CNT film in a dual‐plating cell, The significant enhancement of the capacity was attributed to the fast iodine transport in the PVA‐hydrogel layer. Besides, the strong interaction between PVA chain and polyiodide anions prevented the shuttle effect. The PVA modified CNT cathode could stably operate for over 3000 hours with remarkably higher capacity and cycle life. We analyzed the uniquely fast transport behavior of polyiodides in PVA hydrogel by in situ Raman spectroscopy, in situ optical micrography, as well as DFT calculations. It was found that the strong binding force together with lower dissociation energy of iodine on PVA chain is the dominate reason for reduced shuttle effect and fast polyiodide transport. As a result, the assembled PVA‐I2 pouch cells showed excellent performance in both dual‐plating cells and conventional‐type cells. The capacity of zinc‐iodine battery is limited by the low conductivity of iodine. In this work, a polymeric conductive PVA hydrogel cathode was proposed. The unique “confined transport” of iodide/polyiodides ions in the hydrogel can effectively enhance the areal capacity with suppressed polyiodide shuttle effect.