含氨基聚芳醚酮/磺化聚芳醚酮砜中高温质子交换复合膜的制备与性能研究

以自制的高磺化度磺化聚芳醚酮砜(SPAEKS)和含有氨基的聚芳醚酮(Am-PAEK)为原料,通过共溶剂涂膜法制备了不同重量比例的Am-PAEK/SPAEKS复合膜.通过高温(160℃)处理使氨基和磺酸基团在复合膜内形成交联,制得交联型复合膜.复合膜的热性能、尺寸稳定性、阻醇性能有所提高,而且交联型复合膜中的Am-PAEK/SPAEKS-C-3质子传导率在120℃时达到了0.0892 S/cm,高于在相同测试条件下SPAEKS膜的0.0654 S/cm和Nafion膜的0.062 S/cm,而其甲醇渗透系数在25℃时达到0.14×10-6cm2/s,低于SPAEKS膜的0.85×10-6cm2/s和Nafion膜的2×10-6cm2/s.实验结果表明,Am-PAEK/SPAEKS交联型复合膜有望在中高温质子交换膜燃料电池中得到应用.

PREPARATION AND PROPERTIES OF AMINO-CONTAINING POLY (ARYLE ETHER KETONE)/POLY (ARYLE ETHER KETONE SULFONE) MIDDLE-HIGH TEMPERATURE COMPOSITE PROTON EXCHANGE MEMBRANE

In order to meet the requirements of middle-high temperature proton exchange membrane full cells,different weight ratio(Am-PAEK/SPAEKS) composite membranes are prepared by solution casting of the high degree sulfonated poly(aryle ether ketone sulfone)(SPAEKS) and poly(aryle ether ketone) with amino groups(Am-PAEK) as raw material.Cross-linked composite membranes are obtained by a heating reaction at 160℃.The cross-linked structure is formed in the membrane by acid-base cross-linking reaction between amino and sulfonic acid groups.The composite membranes show good thermal stability,dimensional stability and methanol permeability.The Am-PAEK/SPAEKS-C-3 membrane exhibits excellent proton conductivity up to 0.0892 S/cm at 120℃,which is superior to that of Nafion membrane(0.062 S/cm) and SPAEKS membrane(0.0654 S/cm) under the same test conditions.The water diffusion coefficient of the Am-PAEK/SPAEKS-C-3 membrane reaches 3.51×10-9 cm2/s that is lower than that of SPAEKS membrane(8.96×10-8 cm2/s).The methanol diffusion coefficient(0.14×10-6 cm2/s) of Am-PAEK/SPAEKS-C-3 membrane is lower than that of pure SPAEKS membranes(0.85×10-6 cm2/s) and the Nafionmembrane(2×10-6cm2/s).Experimental data confirm that Am-PAEK/SPAEKS-C-3 membrane has high proton conductivity and low methanol diffusion coefficient in middle-high temperatures.All the results indicate that Am-PAEK/SPAEKS-C-3 crosslinked composite membrane may be a potential material for middle-high temperature proton exchange membrane fuel cells applications.