Polymer membranes for high temperature proton exchange membrane fuel cell: Recent advances and challenges

Proton-exchange membrane fuel cells (PEMFCs) are considered to be a promising technology for efficient power generation in the 21st century. Currently, high temperature proton exchange membrane fuel cells (HT-PEMFC) offer several advantages, such as high proton conductivity, low permeability to fuel, low electro-osmotic drag coefficient, good chemical/thermal stability, good mechanical properties and low cost. Owing to the aforementioned features, high temperature proton exchange membrane fuel cells have been utilized more widely compared to low temperature proton exchange membrane fuel cells, which contain certain limitations, such as carbon monoxide poisoning, heat management, water leaching, etc. This review examines the inspiration for HT-PEMFC development, the technological constraints, and recent advances. Various classes of polymers, such as sulfonated hydrocarbon polymers, acid-base polymers and blend polymers, have been analyzed to fulfill the key requirements of high temperature operation of proton exchange membrane fuel cells (PEMFC). The effect of inorganic additives on the performance of HT-PEMFC has been scrutinized. A detailed discussion of the synthesis of polymer, membrane fabrication and physicochemical characterizations is provided. The proton conductivity and cell performance of the polymeric membranes can be improved by high temperature treatment. The mechanical and water retention properties have shown significant improvement., However, there is scope for further research from the perspective of achieving improvements in certain areas, such as optimizing the thermal and chemical stability of the polymer, acid management, and the integral interface between the electrode and membrane.     

Theoretical and experimental infrared spectra of hydrated and dehydrated sulfonated poly(ether ether ketone)

Time-dependent FT-IR spectra of sulfonated poly(ether ether ketone) during dehydration show diminishing 1081 cm⁻¹ and 1023 cm⁻¹ band intensities concurrent with the emergence and shifting of bands at 1362 cm⁻¹ and 898 cm⁻¹. Animations of density functional theory calculated normal modes enable assignment of the 1081 cm⁻¹ and 1023 cm⁻¹ bands as group modes that include a sulfonate exchange site with C_3v local symmetry, while the 1362 cm⁻¹ and 898 cm⁻¹ bands are assigned as group modes that include an associated sulfonic acid with no local symmetry (C₁). In contrast to analogously assigned Nafion group mode bands, the SPEEK C_3v and C₁ bands coexist throughout the entire dehydration–hydration cycle, suggesting the presence of associated and dissociated exchange sites in SPEEK at all states-of-hydration. This supports a morphological model for SPEEK featuring branched hydrophilic domains and dead-end aqueous confines.     

流延法制备的SPEEK/SiO2/SiWA复合膜

用流延法制备了磺化聚醚醚酮(SPEEK)/二氧化硅(Si O2)/硅钨酸(Si WA)复合膜,并分析了复合膜的形貌、质子传导性能、阻醇性能及溶胀性能。m(SPEEK)∶m(Si O2)∶m(Si WA)=70∶10∶20的复合膜性能良好:在90℃时的质子传导率为0.018 S/cm;在30℃和90℃时的甲醇渗透率分别为3.4×10-8cm2/s和5×10-7cm2/s;温度从30℃升高到80℃,吸水率仅增加了17.9%,溶胀率仅增加了0.9%;Si O2和Si WA在复合膜中分散均匀,颗粒细小,没有团聚。     

直接甲醇燃料电池用磺化聚醚醚酮质子交换膜

在回顾近年来直接甲醇燃料电池用磺化聚醚醚酮(SPEEK)质子交换膜的发展历程基础上,分别综述了制膜材料SPEEK的合成和SPEEK质子交换膜的制备研究进展,重点总结了SPEEK质子交换膜的电导率和阻醇性能及其稳定性的影响因素和影响规律,其中包括制膜材料和溶剂以及工艺、SPEEK的共混改性、SPEEK的填充改性或多层复合结构的影响,进而分析了高性能SPEEK质子交换膜的开发研究前景.     

聚乙烯醇/磺化聚醚醚酮/对氨基二苯胺电活性复合膜的制备与性能

以聚乙烯醇(PVA)、磺化聚醚醚酮(SPEEK)和对氨基二苯胺(p-ADA)为原料,通过水溶液流延成膜法制备了PVA/SPEEK/p-ADA电活性复合膜。借助核磁共振谱(1 H-NMR)、红外光谱(FTIR)和X射线光电子能谱(XPS)分别对SPEEK和复合膜的化学结构进行了表征。采用万能材料试验机和电化学综合站分别对复合膜的力学性能和电性能进行分析测试。结果表明,当PVA含量为60%(质量分数)、SPEEK含量为35%(质量分数)、p-ADA含量为5%(质量分数)时复合膜的力学性能最佳,拉伸强度和弹性模量分别达到64 MPa和2 538 MPa,较纯PVA分别提高了52%和122%。电压窗口为-0.8~0.8 V时,PVA-60%/SPEEK-35%/p-ADA-5%复合膜具有明显的电活性,并且该电活性复合膜在外界酸碱环境发生改变时具有变色性。     

燃料电池质子交换膜电导与阻醇性能测试方法研究

质子交换膜（PEM）是直接甲醇燃料电池（DMFC）的核心部件,而PEM的电导率和阻醇性能是决定PEM乃至DMFC性能的关键因素。采用自行建立的改进型交流两电极法测量磺化聚醚醚酮（SPEEK）材料PEM的电导率,采用扩散池和折光仪测试PEM甲醇透过性能。结果表明,这些测试装置简易可靠,数据重现性较好,膜的电导率测试对30℃至90℃之间不同的测试温度条件灵敏度较高,膜的电导率和甲醇透过性能测试对不同成膜材料和制膜溶剂均具有较高的分辨率。     

燃料电池用磺化聚醚醚酮薄膜的研究进展

概述了近几年来燃料电池用磺化聚醚醚酮(SPEEK)质子交换膜的研究进展,分别从聚醚醚酮(PEEK)磺化制备SPEEK、SPEEK薄膜的制备和改性SPEEK薄膜等几个方面总结了SPEEK质子交换膜的研究结果,并分析展望了研究工作的发展趋势.     

磺化聚醚醚酮上浆剂的制备及其对碳纤维性能的影响

目的 制备一种热塑性上浆剂,以期改善碳纤维的表面性能以及单丝拉伸性能。方法 通过直接磺化法制备磺化聚醚醚酮水性上浆剂,并通过喷涂法对未上浆的T300碳纤维进行上浆处理,研究制得上浆剂的结构特征、性能以及其对碳纤维性能的影响。结果 制得磺化聚醚醚酮的磺化度约为74%,以此为主浆料配制的水性上浆剂具有良好的成膜性和储存稳定性。经上浆处理后,碳纤维表面形成了连续的磺化聚醚醚酮上浆层,表面官能团含量明显增加,树脂微滴在纤维表面的接触角降低。此外,上浆层可以弥补纤维表面的部分缺陷,使得上浆后碳纤维的单丝拉伸强度提高了5%。结论 磺化聚醚醚酮上浆剂可以有效改善碳纤维的表面性能及单丝拉伸性能。     

Sulfonated polyether ether ketone and hydrated tin oxide proton conducting composites for direct methanol fuel cell applications

Composite membranes based on sulfonated polyether ether ketone (SPEEK) and hydrated tin oxide (SnO₂·nH₂O) were prepared and characterized. The formation of the composite substantially modified the properties of SPEEK in terms of durability and electrochemical performance. The structural and electrochemical performance of the samples were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis, electrochemical impedance spectroscopy (EIS), water and methanol uptake (WU, MU), and direct methanol fuel cell (DMFC) tests. The polymer electrolyte membrane doped with 50 wt% SnO₂·n(H₂O) possess good proton transport characteristics, reduced methanol uptake and improved stability with respect to a reference unfilled membrane and it is then suitable for application as electrolyte in DMFCs.     

Study on improvement of the selectivity of proton exchange membrane via incorporation of silicotungstic acid-doped silica into SPEEK

Nafion based proton exchange membrane (PEM) has long been used as conventional PEM in direct methanol fuel cell (DMFC) industry. However, the high cost of Nafion membrane and other drawbacks like high methanol crossover hinder the advancement of this industry. This study aims to develop a low cost membrane using sulfonated poly ether ether ketone (SPEEK) polymer. Silica and silicotungstic acid (SiWA) were incorporated into the membrane matrix using solution casting method. The optimum loading of the additives was tuned and it is discovered that the SPEEK membrane containing 10 wt% of silica and 5 wt% of SiWA has the best performance due to its high proton conductivity and moderately low methanol permeability. The performance of the membrane can further be enhanced by adding (3-aminopropyl)triethoxysilane (APTES) and carbonyldiimidazole (CDI) as coupling agents. Inclusion of APTES and CDI in SPEEK could not only improve the compatibility between organic SPEEK and inorganic additives, but also improve the homogeneity and dispersity of the additives. As a result, the resultant membrane with a better dimensional stability achieves high selectivity (10.60 × 10⁴ S.s/cm³) up to 6.5 times more than pristine SPEEK membrane and 1.3 times higher than the commercial Nafion 117 membrane.