AbstractThe chlorine-based redox reaction (ClRR) could be exploited to produce secondary high-energy aqueous batteries. However, efficient and reversible ClRR is challenging, and it is affected by parasitic reactions such as Cl₂ gas evolution and electrolyte decomposition. Here, to circumvent these issues, we use iodine as positive electrode active material in a battery system comprising a Zn metal negative electrode and a concentrated (e.g., 30 molal) ZnCl₂ aqueous electrolyte solution. During cell discharge, the iodine at the positive electrode interacts with the chloride ions from the electrolyte to enable interhalogen coordinating chemistry and forming ICl₃^-. In this way, the redox-active halogen atoms allow a reversible three-electrons transfer reaction which, at the lab-scale cell level, translates into an initial specific discharge capacity of 612.5 mAh g_I2⁻¹ at 0.5 A g_I2⁻¹ and 25 °C (corresponding to a calculated specific energy of 905 Wh kg_I2⁻¹). We also report the assembly and testing of a Zn | |Cl-I pouch cell prototype demonstrating a discharge capacity retention of about 74% after 300 cycles at 200 mA and 25 °C (final discharge capacity of about 92 mAh).