Initiating a composite membrane with a localized high iodine concentration layer based on adduct chemistry to enable highly reversible zinc-iodine flow batteries.

The issue of polyiodide crossover at an iodine cathode significantly diminishes the efficiency and practicality of aqueous zinc-iodine flow batteries (ZIFBs). To address this challenge, we have introduced a localized high iodine concentration (LHIC) coating layer onto a porous polyolefin membrane, which featured strong chemical adsorption by exploiting adduct chemistry between the iodine species and a series of low-cost oxides, , MgO, CeO, ZrO, TiO, and AlO. Leveraging the LHIC based on the potent iodine adsorption capability, the as-fabricated MgO-LHIC composite membrane effectively mitigates iodine crossover Donnan repulsion and concentration gradient effects. At a high volumetric capacity of 17.8 Ah L, ZIFBs utilizing a MgO-LHIC composite membrane exhibited improved coulombic efficiency (CE) and energy efficiency (EE) of 96.3% and 68.6%, respectively, along with long-term cycling stability of 170 cycles. These results significantly outperform those of ZIFBs based on a blank polyolefin membrane (78.2%/61.9% after 60 cycles) and the widely used commercial Nafion N117 (67.8%/53.0% after 23 cycles). Even under high-temperature conditions (60 °C), the LHIC-based battery still demonstrates superior CE/EE of 95.1%/67.5% compared to those of the blank polyolefin membrane (CE/EE: 61.1%/46.8%). Our pioneering research showcases enormous prospects for developing high-efficiency and low-cost composite membranes based on adduct chemistry for large-scale energy storage applications.