Asano Naoki, Aoki Makoto, Suzuki Shinsuke, Miyatake Kenji, Uchida Hiroyuki, Watanabe Masahiro
Clean Energy Research Center, and Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi, 4 Takeda, Kofu 400-8510, Japan.
J Am Chem Soc. 2006 Feb 8;128(5):1762-9. doi: 10.1021/ja0571491.
To produce a proton conductive and durable polymer electrolyte membrane for fuel cell applications, a series of sulfonated polyimide ionomers containing aliphatic groups both in the main and in the side chains have been synthesized. The title polyimide ionomers 1 with the ion exchange capacity of 1.78-2.33 mequiv/g were obtained by a typical polycondensation reaction as transparent, ductile, and flexible membranes. The proton conductivity of 1 was slightly lower than that of the perfluorinated ionomer (Nafion) below 100 degrees C, but comparable at higher temperature and 100% RH. The highest conductivity of 0.18 S cm(-)(1) was obtained for 1 at 140 degrees C. Ionomer 1 with high IEC and branched chemical structure exhibited improved proton conducting behavior without sacrificing membrane stability. Microscopic analyses revealed that smaller (<5 nm) and well-dispersed hydrophilic domains contribute to better proton conducting properties. Hydrogen and oxygen permeability of 1 was 1-2 orders of magnitude lower than that of Nafion under both dry and wet conditions. Fuel cell was fabricated with 1 membrane and operated at 80 degrees C and 0.2 A/cm(2) supplying H(2) and air both at 60% or 90% RH. Ionomer 1 membrane showed comparable performance to Nafion and was durable for 5000 h without distinct degradation.
为了制备用于燃料电池应用的质子传导且耐用的聚合物电解质膜,合成了一系列主链和侧链均含有脂肪族基团的磺化聚酰亚胺离聚物。通过典型的缩聚反应获得了离子交换容量为1.78 - 2.33 mequiv/g的标题聚酰亚胺离聚物1,制成透明、可延展且柔韧的膜。在100℃以下,1的质子传导率略低于全氟离聚物(Nafion),但在较高温度和100%相对湿度下相当。在140℃时,1的最高传导率为0.18 S cm⁻¹。具有高IEC和支化化学结构的离聚物1在不牺牲膜稳定性的情况下表现出改善的质子传导行为。微观分析表明,较小(<5 nm)且分散良好的亲水域有助于更好的质子传导性能。在干燥和潮湿条件下,1的氢气和氧气渗透率均比Nafion低1 - 2个数量级。用1膜制造燃料电池,并在80℃和0.2 A/cm²下运行,分别以60%或90%相对湿度供应氢气和空气。离聚物1膜表现出与Nafion相当的性能,并且耐用5000小时无明显降解。