Heteropolyacid-doped Proton-exchange Membranes:Preparation, Structure and Properties
GAO Xuesong1,2,3, LUO Feng3, YANG Yehua3, GONG Xinghou1,2,3, HU Tao1,2,3, WU Chonggang1,2,3
1 Hubei Provincial Key Laboratory of Green Materials for Light Industry, Hubei University of Technology, Wuhan 430068; 2 Collaborative Innovation Center of Green Light-weight Materials and Processing, Hubei University of Technology, Wuhan 430068; 3 School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan 430068
Abstract: As a strong solid-acid with a Keggin molecular-configuration of polyoxometalate, heteropolyacids (HPAs) exhibit superior hygroscopy, proton conductivity (cp), as well as mechanical, thermal and chemical stabilities. Doping of ceramics or polymers with an HPA endows the resulting composite proton-exchange membranes (PEMs) with efficiently improved hydrophily, cp, fuel barrier property, as well as mechanical, thermal and chemical stabilities, and also the considerably decreased dependencies of their cp and fuel barrier property on temperature and humidity. When HPA is doped with ceramics, the hydrogen bonding between the two components results in a low rate of the HPA running-off, high dispersion and high doping capacity of the HPA in the matrix, and the cp of the composite PEMs(10-1 S/cm) is significantly enhanced compared to that of the matrix PEMs(ca.10-3-10-2 S/cm). When HPA is doped with sulfonated polymers, the electrostatic repulsion between the two components leads to more HPA run-off, much lower dispersion and low doping capacity of the HPA in the polymeric matrix, and the cp of the composite PEMs(10-1 S/cm) is only slightly higher than that of the matrix PEMs (ca. 10-2-10-1 S/cm). To reduce the running-off rate of an HPA from polymeric matrices, different approaches can be employed, such as use of sandwiching polymer membranes to protect the composite PEMs, salination of the HPA, modification of the matrices or support of the HPA on the third component to form hydrogen bonding/electrostatic attractions between the HPA and the matrices or the support. For the modification of the HPA support, the dispersion and doping capacity of the HPA are not improved in the matrices because the ceramic or polymeric support tends to form cluster within the matrices. Occasionally, an HPA and hygroscopic phosphoric-acid are jointly employed to dope ceramic matrices or supports to synergistically enhance the cp of composite PEMs, which has no obvious effect. The aforementioned HPA-doped PEMs of various structures generally are prepared by solution-casting, self-assembly, sol-gel and infiltration methods, and a preparation process possibly involves two or three types of methods. To modify an HPA or its support for higher dispersion and doping capacity of the HPA within sulfonated-polymer matrices, and construct an original, efficient proton-transport channel configurations to accomplish an ultrahigh cp (100 S/cm) for composite PEMs, is one of the key future development directions for the PEMs technology.
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2017, Vol. 31 
