摘要质子交换膜是聚合物电解质膜燃料电池的关键部件之一，要求具有高的电导率，热、化学稳定性，机械强度且成本经济。本论文采用先分别合成聚合物主链和侧链再以一定的比例合成产物，进一步浇筑成膜。首先，以十氟联苯（HFBP）、4,4’-联苯二酚(BP)及双酚芴以及溶剂DMAC，碳酸钾和环己烷反应制备了含氟聚芳醚砜，再用4，4’-二氟二苯砜(DFDPS),BP以及3,3’-二磺化-4,4’-二氟二苯砜二钠（SDFDPS）以及溶剂DMSO，碳酸钾以及甲苯合成了聚合物侧链，合成了一系列侧链磺化型含氟聚芳醚砜质子交换膜（sSPFAES）。制备的sSPFAES膜离子交换容量（IEC）为0.85-1.60 mmol/g，柔韧结实，杨氏模量均高于1.33 GPa，拉伸强度达到35.8-42.2 MPa，断裂伸长率为18.6-50%；同时膜的热、氧化稳定性良好。水解稳定性也很好，在140℃，24h水中处理后，膜仍然具有很好的强度。吸水性及膨胀性测试结果表明该系列膜具有较低的吸水率和良好的尺寸稳定性，在测试温度范围内（30-90℃）吸水率为11.7-75.7%，横向尺寸变化率在0.2-13.9%厚度尺寸变化为5.3-26.6%。该系列膜也表现出很规律的电导率水平，随着温度或IEC的增大，质子电导率也随之增大。42428
毕业论文关键词 燃料电池，质子交换膜，侧链磺化，磺化聚芳醚，含氟聚合物
Title Preparation and properties of proton exchange membranes basedon side-chain type fluorinated poly(arylether)s bearing sulfonatednaphthanoxyl pendants
Abstract Proton exchange membrane is one of the key components for the polymer electrolytemembrane fuel cell, which requires high conductivity, thermal and chemicalstability, mechanical toughness as well as low cost. Borrowing ideas from theunique structure of perfluoro-hydrophobic backbone and sulfonated hydrophilicside chain for perfluorosulfonic acid membranes, several proportion of backboneand side-chain type sulfonated partially fluorinated poly(aryl ether) copolymerswere developed.A series of novel side-chain type partially fluorinated sulfonated poly(ethersulfone)s (sSPFAES) copolymers were successfully synthesized mainly bynucleophilic substitution reaction from decafluorobiphenyl(HFBP),4,4’-biphenol, 9,9’-biphenylfluorene,BP,SDFDPS,potash,etc. Ion exchangecapacities (IECs) of the sSPFAES membranes were about0.85~1.60 mmol/g, all weretough and ductile, exhibiting Young’s modulus higher than 1.33 GPa, tensilestrength of 35.8-42.2 MPa and elongation at break of 18.6-50%. They also showedgood thermal and oxidative stability.They also showed good hydrolyticstability,after 24h inthe water which is 140℃,the membranes still showed good strength.The water absorbing and swelling behavior tests indicate that the obtained sSPFAESmembranes had rather low water uptakes and good dimensional stability, with wateruptake of 11.7-75.7%, swelling ratios of 0.2-13.9%(△l) and 5.3-26.6%(△t) atthe testing temperature range of 30~90℃. They all also showed good protonconductivity .
Keywords Fuel cell, proton exchange membrane, side-chain sulfonation, sulfonatedpoly(aryl ether), fluorinated polymers
目次
1绪论1
1.1燃料电池的分类1
1.2燃料电池特点2
1.3燃料电池的应用2
1.5本课题拟解决的问题6
2实验材料与试验方法7
2.1实验药品与试剂7
2.2实验仪器及设备7
2.2药品提纯及试剂精制8
2.3实验表征方法8
2.4侧链型含氟磺化聚芳醚砜质子交换膜的制备10
3结果与讨论.13
3.1IEC，吸水率和尺寸变化.13
3.2质子导电率16
3.3机械性能16
3.4抗氧化稳定性17
3.5水解稳定性17
3.6溶解性18
结论19
致谢20
参考文献21
1 绪论20 世纪以来，石油等能源危机日益严重，人们开始重视高效环保的能源，很多国家积极地投入人力物力研发各种民用燃料电池。直到现在，燃料电池已经在汽车，飞机等方面得到应用（2010 年3 月在第六届国际氢燃料电池展上，来自世界各地的多家公司展示了大量的便携或小型发电式燃料电池产品） 。 接枝侧链型磺化聚芳醚质子交换膜的制备及其性能研究:http://www.751com.cn/huaxue/lunwen_42859.html