The ion exchange membrane of the Nafion series widely used in vanadium flow batteries (VFBs) is characterized by its high cost and high vanadium permeability, which limit the further commercialization of VFBs. Herein, a thin composite membrane enabled by a low-cost microporous polyethylene (PE) substrate and perfluorosulfonic acid (PFSA) resin is proposed to reduce the cost of the membrane. Meanwhile, the rigid PE substrate limits the swelling of the composite membrane, which effectively reduces the penetration of vanadium ions and improves the ion selectivity of the composite membrane. Benefiting from such a rational design, a VFB assembled with the PE/PFSA composite membrane exhibited a higher coulombic efficiency (CE ≈ 96.8%) compared with commercial Nafion212 at 200 mA cm−2. Significantly, the energy efficiency maintained stability within 200 cycles with a slow decay rate. In practical terms, the thin PE/PFSA composite membrane with low cost and high ion selectivity can make an ideal membrane candidate in VFBs.
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