Fluorine-free proton exchange membranes (PEMs) capable of healing from physical damage are important for PEM fuel cells (PEMFCs) with extended service life and enhanced reliability. Herein, highly elastic fluorine-free PEMs with excellent self-healing ability and high proton conductivity are fabricated through complexation of phytic acid (PA) with sulfonated polyvinyl alcohol (SPVA), followed by subsequent grafting of SPVA with positively charged 4-(1H-imidazol-1-yl)benzenecarbaldehyde (IBZ). Compared with recast Nafion membranes, the as-prepared SPVA-IBZ/PA membranes exhibit an enhanced mechanical strength and elasticity and can spontaneously recover from a ∼50% strain to their initial states within ∼30 s at room temperature. Meanwhile, the SPVA-IBZ/PA membranes have a proton conductivity of ∼0.095 S cm⁻¹ at ∼70°C, which is higher than that of recast Nafion membranes. The hydrogen-powered PEMFCs using the SPVA-IBZ/PA membranes, which show an open circuit voltage of ∼0.98 V and maximum power density of ∼609 mW cm⁻², exhibit a satisfactory cell performance. Importantly, the SPVA-IBZ/PA membranes can spontaneously heal mechanical damage of several tens of micrometers in size and restore their original proton conductivity and cell performance under the working conditions of PEMFCs.

能够消除物理损伤的无氟质子交换膜（PEM）对于延长使用寿命和增强可靠性的PEM燃料电池（PEMFC）至关重要。在此，通过将植酸（PA）与磺化聚乙烯醇（SPVA）络合，随后将SPVA与带正电荷的4-（1H-）接枝，制得具有出色的自愈能力和高质子传导性的高弹性无氟PEM。咪唑-1-基）苯甲醛（IBZ）。与重铸的Nafion膜相比，所制备的SPVA-IBZ / PA膜具有增强的机械强度和弹性，并且在室温下约30 s内可从约50％的应变自发恢复到其初始状态。同时，SPVA-IBZ / PA膜的质子传导率为〜0.095 S cm ^-1温度约为70°C，高于重铸的Nafion膜的温度。使用SPVA-IBZ / PA膜的氢动力PEMFC的开路电压约为0.98 V，最大功率密度约为609 mW cm ^-2，显示出令人满意的电池性能。重要的是，在PEMFC的工作条件下，SPVA-IBZ / PA膜可自发地修复数十微米大小的机械损伤，并恢复其原始质子传导性和电池性能。