Proton conductivity of proton exchange membranes (PEMs) strongly relies on microscopic morphology, which can be modulated by engineering the distribution of ionic groups. Herein, poly(arylene ether)s with densely distributed allyl functionalities are polymerized from a tetra-allyl bisphenol A monomer. The subsequent thiol-ene addition with sodium 3-mercapto-1-propanesulfonate yields comb-shaped sulfonated fluorinated poly(arylene ether)s (SFPAEs) with ion exchange capacities (IECs) ranging from 1.29 mmol·g⁻¹ to 1.78 mmol·g⁻¹. These SFPAEs exhibit superior proton conductivity over the whole temperature range, which is attributed to the enhanced hydrophilic/hydrophobic phase separation as evidenced by small angle X-ray scattering characterizations. The SFPAE-4-40 with an IEC of 1.78 mmol·g⁻¹ shows the largest proton conductivity of 93 mS·cm⁻¹ at room temperature under fully hydrated condition, higher than that of Nafion 212. Furthermore, the vanadium redox flow battery (VRFB) assembled with SFPAE-4-40 separator exhibits higher energy efficiency than the VRFB assembled with Nafion 212.

质子交换膜（PEMs）的质子传导性强烈依赖于微观形态，可以通过工程化离子基团的分布来对其进行调节。在此，具有高分布烯丙基官能度的聚（亚芳基醚）由四烯丙基双酚A单体聚合。随后用3-巯基-1-丙烷磺酸钠加成硫醇烯，得到梳形磺化氟化聚亚芳基醚（SFPAE），离子交换容量（IEC）为1.29 mmol·g ^-1至1.78 mmol·g ^-1。这些SFPAE在整个温度范围内均表现出优异的质子传导性，这归因于亲水/疏水相分离的增强，如小角度X射线散射特征所证明。该SFPAE-4-40IEC为1.78 mmol·g ^-1时，在完全水合的条件下，室温下的最大质子传导率为93 mS·cm ^-1，高于Nafion 212的质子传导率。此外，装配有SFPAE的钒氧化还原液流电池（VRFB）-4-40分离器比与Nafion 212组装的VRFB具有更高的能效。