The perfluorosulfonic acid (PFSA) polymers have achieved great success as proton exchange membranes (PEMs) in various energy storage and conversion devices; nevertheless, the improvements regarding PEMs' synthetic cost, mechanical properties, stability and processability are still urgently required. Herein, 1 nm super acidic metal oxide cluster, HPWO (PW), is complexed with the blends of polyvinylpyrrolidone (PVP) and polyvinylidene fluoride (PVDF) to afford nanocomposite PEMs that enables the stable and effective operation of hydrogen fuel cell devices. As the polymer matrix, the PVDF is blended with PVP via inter-chain hydrogen bonding to provide mechanical support for the nanocomposite PEMs. The further introduced PW clusters can interact strongly with PVP via electrostatic attraction to enhance the PEMs' mechanical strength (E = 231 MPa) and prevent the leaching of PW for long-term stability. Meanwhile, the incorporation of the super acidic PW can facilitate the fast proton transportation and therefore, lead to the significant increasement of proton conductivity to 9.8 × 10 S cm at 70 °C and 100% RH. Due to the excellent mechanical properties and the supramolecular interaction among the components, the PEMs’ thickness can be controlled to be challenging ∼10μm for feasible large-scale continuous processing. Finally, the molecular design enables the successful fabrication of the nanocomposite PEMs into fuel cell devices with the power density as 342.8 mW cm. The studies not only shed light on the structure-properties of polymer nanocomposites, but also pave avenues to the design of robust composite PEMs for fuel cell appliacations.

中文翻译：

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PVDF-PVP 共混物中金属氧化物簇的超分子络合，用于大规模制造燃料电池质子交换膜

全氟磺酸（PFSA）聚合物作为质子交换膜（PEM）在各种能量存储和转换装置中取得了巨大成功；尽管如此，质子交换膜的合成成本、机械性能、稳定性和加工性能仍然迫切需要改进。在此，1 nm超酸性金属氧化物簇HPWO (PW)与聚乙烯吡咯烷酮(PVP)和聚偏二氟乙烯(PVDF)的混合物复合，形成纳米复合质子交换膜，使氢燃料电池装置能够稳定有效地运行。作为聚合物基体，PVDF 通过链间氢键与 PVP 共混，为纳米复合材料 PEM 提供机械支撑。进一步引入的PW簇可以通过静电引力与PVP发生强烈相互作用，从而增强PEM的机械强度（E = 231 MPa）并防止PW的浸出，从而实现长期稳定性。同时，超酸性PW的加入可以促进质子的快速传输，从而使质子电导率在70℃和100%RH下显着增加至9.8×10Scm。由于优异的机械性能和组分之间的超分子相互作用，PEM 的厚度可以控制在~10μm，这对于可行的大规模连续加工来说是具有挑战性的。最后，分子设计使得纳米复合质子交换膜成功制造成功率密度为342.8 mW cm的燃料电池装置。这些研究不仅揭示了聚合物纳米复合材料的结构特性，而且为设计用于燃料电池应用的坚固复合质子交换膜铺平了道路。