新型磷酸掺杂交联型聚苯并咪唑高温质子交换膜材料的制备与性能研究

发布时间：2019-06-10 12:03

【摘要】：聚苯并咪唑（PBI）具有优异的热稳定性和化学稳定性，利用掺杂磷酸将其质子化后，可作为高温燃料电池的质子交换膜。磷酸吸附含量不仅影响PBI膜材料的质子传导率，也影响膜材料的机械性能。针对高磷酸含量条件下，膜材料力学强度差的缺点，，我们采用了以下方法进行改性：（i）采用具有柔性结构的小分子交联剂——新戊二醇二缩水甘油醚（NGDE），利用程序升温加热制备了一系列交联度不同的交联膜，交联网络的引入在一定程度上提高了磷酸掺杂膜的力学强度、化学稳定性和抗氧化稳定性。（ii）为了进一步提高磷酸吸附含量，制备多孔膜的同时引入交联网络是一种有效的方法，我们采用具有刚性结构的四甲基联苯二酚型环氧树脂（TMBP）作为交联剂，邻苯二甲酸二丁酯（DBP）作为致孔剂，制备了一系列交联多孔膜，其质子传导率得到了显著提升。（iii）向PBI体系中引入纳米粒子填充物（如SiO2），可以同时赋予材料高的质子传导率和足够的力学强度。尤其是引入硅烷功能化的SiO2纳米粒子，可以显著地提高PBI膜的质子传导率。我们采用硅烷偶联剂（KH560）作为交联剂，制备了一系列交联膜，其质子传导率和机械性能均有所提高。（iv）交联剂的结构对交联膜的整体性能具有显著的影响，我们采用溴代聚芳醚酮（BrPAEK）作为大分子交联剂，利用交联剂的刚性结构来提高交联膜的磷酸吸附含量和力学强度，制备了一系列交联膜。
[Abstract]:Polybenzimidazole (PBI) has excellent thermal stability and chemical stability. It can be used as proton exchange membrane of high temperature fuel cell after protonation by doping phosphate. The adsorption content of phosphate not only affects the proton conductivity of PBI membrane material, but also affects the mechanical properties of the membrane material. In order to solve the problem that the mechanical strength of membrane materials is poor under the condition of high phosphate content, we used the following method to modify: (i) by using a small molecular crosslinker with flexible structure, neopentanediol Diglycidyl ether (NGDE),. A series of crosslinked films with different degree of cross-linking were prepared by temperature programmed heating. The introduction of crosslinked network improved the mechanical strength of phosphate doping films to a certain extent. In order to further increase the adsorption content of phosphate, the introduction of cross-linking network into porous membrane is an effective method to prepare porous membrane with chemical stability and antioxidant stability. (ii). A series of crosslinked porous membranes were prepared by using tetramethylbihydrophenol epoxy resin (TMBP) with rigid structure as cross-linking agent and dibutylphthalate (DBP) as pore-forming agent. The proton conductivity of. (iii) can be significantly improved by introducing nanoparticles (such as SiO2) into PBI system, which can give the material high proton conductivity and enough mechanical strength at the same time. In particular, the proton conductivity of PBI membranes can be significantly improved by introducing SiO2 nanoparticles functionalized by silane. A series of crosslinked membranes were prepared by using silane coupling agent (KH560) as crosslinker. The proton conductivity and mechanical properties of the crosslinked membranes were improved. The structure of. (iv) crosslinker has a significant effect on the overall properties of the crosslinked membranes. A series of crosslinked membranes were prepared by using brominated polyaryl ether ketone (BrPAEK) as macromolecular crosslinker and using the rigid structure of crosslinker to improve the phosphate adsorption content and mechanical strength of crosslinked membranes.
【学位授予单位】：吉林大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：TM911.4;O633.5

【共引文献】