SPEEK/PES-C、SPEEK/SPES-C共混质子交换膜研究  

STUDIES ON SPEEK/PES-C AND SPEEK/SPES-C BLEND PROTON-EXCHANGE MEMBRANES

作　　者：高启君[1,2] 王宇新[1,2] 许莉[1] 卫国强[1,2] 王志涛[1,2] 

机构地区：[1]天津大学化工学院 [2]天津大学化学工程联合国家重点实验室,天津300072

出　　处：《高分子学报》2009年第1期45-52,共8页Acta Polymerica Sinica

基　　金：国家重点基础研究发展计划(项目号2008CB617502);国家自然科学基金(基金号20606025)资助项目

摘　　要：通过在磺化聚醚醚酮(SPEEK,DS=61.68%)中分别混入酚酞型聚醚砜(PES-C)、磺化酚酞型聚醚砜(SPES-C,DS=53.7%)制备出SPEEK/PES-C、SPEEK/SPES-C共混质子交换膜.结果表明,共混的两种聚合物之间均具有较好的相容性.PES-C、SPES-C的混入能有效降低膜的溶胀及甲醇透过,且随着共混量的增加,这种作用越趋明显.纯SPEEK膜在75℃左右溶解,而SPEEK/PES-C(30wt%)、SPEEK/SPES-C(30wt%)共混膜在80℃时溶胀度仅为22.5%、26.32%.在室温至80℃范围内,纯SPEEK及共混膜的甲醇透过系数都在10-7cm2.s-1数量级上,远小于Nafion115膜.在饱和湿度下,温度大于90℃时,SPEEK/PES-C(20wt%)共混膜电导率超过Nafion115膜;温度大于110℃时,SPEEK/SPES-C(30wt%)共混膜电导率与Nafion115膜相当,达到0.11S.cm-1.高电导率,低透醇系数以及明显提高了的可使用温度表明该类共混膜有望在DMFC中使用.Sulfonated poly （ether ether ketone）（SPEEK） is a very promising alternative membrane material for direct methanol fuel cells （DMFC）. The demand of high proton conductivity calls for the membranes to have a high degree of sulfonation （DS） and work at elevated temperatures. However, with a fairly high DS, SPEEK membrane can swell excessively and even dissolve at high temperatures. To deal with this contradictory situation, phenolphthalein poly（ether sulfone） （PES-C） and sulfonated phenolphthalein poly （ ether sulfone） （ SPES-C, DS = 53.7 % ） were respectively blended into SPEEK polymer to prepare SPEEK/PES-C and SPEEK/SPES-C blend membranes. DSC resuhs revealed that the two blended polymers showed good miscibility. The effect, that both PES-C and SPES-C can decrease effectively the swelling degree and methanol permeability of blend membranes, became evident with the increment of PES-C and SPES-C contents. Pure SPEEK membrane dissolved completely at 75℃, however, the swelling degree of SPEEK/PES-C （30%） and SPEEK/SPES-C （30%） were 22.5% and 26.32% at 80℃,respectively. From room temperature to 80℃, the blend membranes presented methanol permeability of around 10^-7 cm^2· s^-1 , which was about one order of magnitude lower than that of Nation 115. Under 100% relative humidity, the proton conductivity of blend membranes with 20 wt% PES-C exceeded that of Nation 115 above 90℃, the proton conductivity of blend membranes with 30 wt % SPES-C reached 0.11 S· cm^-1 of Nation 115 at 110℃. The blend membranes are promising for DMFC application because of their improved applicable temperature, high conductivity and low methanol permeability.

关 键 词：磺化聚醚醚酮 酚酞型聚醚砜 磺化酚酞型聚醚砜 共混膜 直接甲醇燃料电池 

分 类 号：O631.3[理学—高分子化学]