Efficient Charge Storage in Zinc–Iodine Batteries based on Pre‐Embedded Iodine‐Ions with Reduced Electrochemical Reaction Barrier and Suppression of Polyiodide Self‐Shuttle Effect

Abstract Aqueous zincIodine batteries are considered as a promising energy storage system due to their high energy/power density, and safety. However, polyiodide shuttling leads to severe active mass loss, which results in lower Coulombic efficiency and limits the cyclic life. Herein, a novel structure‐limiting strategy to pre‐embed iodide ions into Prussian blue (PBI) is proposed. The DFT calculations and electrochemical characterization reveal that the formation of FerrumIodine bond reduces the electrochemical reaction energy barrier of subsequent iodide‐ions at the pre‐embedding sites, improves the I − oxidation reaction kinetic process, and suppresses the polyiodide self‐shuttle. The PBI//Zn batteries exhibit a low Tafel slope (155 mV dec −1 ). Moreover, UV–vis spectroscopy confirms that the proposed strategy suppresses the polyiodide self‐shuttle. As a result, the PBI//Zn battery achieves high iodide utilization and Coulomb efficiency (242 mAh g −1 at 0.2 A g −1 , CEs ≈ 100%), as well as high multiplicity performance of 197.2 mAh g −1 even at 10 A g −1 (82% of initial capacity). The PBI//Zn battery also renders excellent cyclic stability with a capacity retention of 94% at 4 A g −1 after 1500 cycles. The device exhibits a high energy density of 142 W h kg −1 at a power density of 5538 W kg −1 .