| Summary: | The iron–chromium flow battery (ICFB), the earliest flow battery, shows promise for large-scale energy storage due to its low cost and inherent safety. However, there is no specific membrane designed that meets the special requirements of ICFBs. To match the harsh operation parameters of ICFBs, we designed and fabricated a composite membrane with high mechanical, chemical, and thermal stability. In the design, a commercial porous polyethylene membrane is selected as the framework material, offering high mechanical stability and reducing the cost. Meanwhile, the Nafion resin is filled in the pores of a porous membrane, which inhibits the transfer of redox-active ions and creates the proton channels via hydrophobic/hydrophilic phase separation. As a result, the composite membrane exhibits high conductivity, selectivity, and stability, especially with almost no swelling at high operating temperatures. Thus, an ICFB with the prepared membrane exhibits a coulombic efficiency of 93.29% at the current density of 80 mA cm<sup>−2</sup> and runs stably for over 300 cycles. This work provides an easy method to fabricate high-performance and low-cost membranes specifically for ICFBs and has the potential to promote the development of ICFBs.
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