Precipitated Iodine Cathode Enabled by Trifluoromethanesulfonate Oxidation for Cathode/Electrolyte Mutualistic Aqueous Zn–I Batteries

Abstract Aqueous Zn–I batteries hold great potential for high‐safety and sustainable energy storage. However, the iodide shuttling effect and the hydrogen evolution reaction that occur in the aqueous electrolyte remain the main obstacles for their further development. Herein, the design of a cathode/electrolyte mutualistic aqueous (CEMA) Zn–I battery based on the inherent oxidation ability of aqueous trifluoromethanesulfonate ((OTf)⁻) electrolyte toward triiodide species is presented. This results in the formation of iodine sediment particles assembled by fine iodine nanocrystals (≈10 nm). An iodine host cathode with high areal iodine loading is realized via a spontaneous absorption process that enriched redox‐active iodine and iodide species from aqueous electrolyte onto nanoporous carbon based current collector. By tuning iodide redox process and suppressing competitive hydrogen evolution reaction, the assembled CEMA Zn–I batteries demonstrate a remarkable capacity retention of 76.9% over 1000 cycles at 0.5 mA cm⁻². Moreover, they exhibit a notable rate capability, with a capacity retention of 74.6% when the current density is increased from 0.5 to 5.0 mA cm⁻². This study demonstrates the feasibility of using the oxidation effect to repel redox‐active species from the electrolyte to the cathode, paving a new avenue for high‐performance aqueous Zn–I batteries.