DMFC用磺化聚酰亚胺质子交换膜的合成与性能

以一种磺化二胺单体2,2′-二磺酸基-4,4′-二苯醚二胺(S-ODA)与非磺化单体4,4′-二苯醚二胺(ODA),及二酐单体3,3′,4,4′-二苯甲酮四羧酸二酐(BTDA)为原料,采用高温一步法直接聚合,得到了一系列磺化聚酰亚胺(SPI)质子交换膜材料,并用红外光谱对聚合物进行了表征.通过改变聚合体系中磺化单体与非磺化单体的比例控制聚合物的磺化度,并研究了材料的组成对膜的电导率、吸水率等性能的影响。     

一种新型的燃料电池用质子交换膜--磺化聚酰亚胺膜

综述了磺化聚酰亚胺作为质子交换膜燃料电池中膜材料的研究概况。介绍了其制备方法,总结了磺化聚酰亚胺结构对膜性能的影响。重点讨论了提高磺化聚酰亚胺质子交换膜电导率的途径和影响水解稳定性的因素,结果表明：纳米孔和相分离结构有助于提高质子电导率;磺化聚酰亚胺的水解稳定性不仅与吸水率有关,还与分子链的柔性和二胺单体的碱性有关。     

六元环型磺化聚酰亚胺类质子交换膜

磺化聚酰亚胺是一类很有希望在燃料电池中获得应用的质子交换膜材料。本文对近年来六元环型磺化聚酰亚胺的制备、磺化聚酰亚胺质子交换膜的各项性能做了一定的归纳与分析。重点介绍了耐水性、耐久性、离子交换容量、质子电导率四个方面的测试方法及影响因素,指出目前存在的问题并预测了今后重点研究的方向。     

新型细菌纤维素基阻醇质子交换膜的制备及表征

以凝胶贴附法,在Nation膜两侧贴附细菌纤维素（BC）膜,制备出BC／Nation／BC夹心复合膜,以期结合Nation膜的良好导电性和BC膜的优秀阻醇性,制备新型阻醇质子交换膜。利用扫描电镜、热重分析对其形态结构和热稳定性进行研究,并对夹心膜的尺寸稳定性、质子传导率和甲醇渗透率进行表征。结果发现,复合膜的夹心结构紧密,热稳定性良好,尺寸稳定性比市售的Nation膜有很大改善,提高了43％。夹心膜的质子传导率随温度的升高明显上升,虽略低于Nation膜,但是甲醇渗透率明显降低一个数量级,阻醇性能得到了很大改善。组装成电池后,单电池开路电压达到922mV,最大发电功率密度为7．2mW／cm^2。该结果表明夹心复合膜作为新型质子交换膜应用于直接甲醇燃料电池中具有很大潜力。     

磺化聚苯醚质子交换膜的制备与性能研究

以氯磺酸为磺化剂制备了一系列不同磺化度的磺化聚苯醚(SPPO)膜,通过热重-红外联用分析、差示扫描量热分析、含水率测试、力学性能和电导率测试,探讨了SPPO膜作为质子交换膜用于燃料电池的可能性。结果表明,SPPO存在3个阶段的失重,分别归属于吸收的水分、磺酸基团及主链的降解,磺化之后热稳定性虽有所下降,但主链的降解温度基本保持不变,玻璃化转变温度明显升高;SPPO的含水率随着磺化度和温度的增加而增加;膜的拉伸强度则随着磺化度的增加而降低,且膜在湿态时的强度较干态时的要低,但与商业化的Nafion 112膜相比仍具有较高的强度;磺化度为40.1%的SPPO膜在室温下的电导率为1.16×10-2S/cm,与Nafion 112膜为同一数量级。     

磺化聚酰亚胺的合成及其膜性能研究

采用2,2'-双苯氧基对二氨基联苯(PHOB)制备了2,2'-双(4-磺酸基苯氧基)对二氨基联苯(2,2′-BSPOB),以2,2′-BSPOB、1,3-双(4-氨基苯氧基)苯(BAPBz)和1,4,5,8-萘四甲酸二酐(NTDA)为原料,经缩聚反应生成磺化聚酰亚胺(SPIs)。以间甲酚为溶剂,通过溶液浇铸法成膜,研究了合成聚合物膜的吸水率、尺寸变化、机械性能和质子导电率。NTDA-BSPOB-BAPBz(3/2/1)聚合物膜在水中的质子导电率达到了198.3 mS/cm。     

磺化聚酰亚胺质子导电材料的研究进展

由于Nafion膜在工作温度超过90℃的燃料电池中，或者是在直接甲醇燃料电池中的种种不良表现使得燃料电池的应用得到制约，所以发展新型导电聚合物电解质膜就与聚台物燃料电池的发展紧密联系在一起。近些年来这个领域的研究成果包括新的离子聚合物、用于控制形态及保水能力的纳米无机颗粒复合膜，以及碱性聚合物与含氧酸的络合物等。而聚酰亚胺，作为一种耐高温的含氮杂环碱性聚合物，在电解质燃料电池中正表现出广阔的应用前景。     

高温质子交换膜研究进展

高温质子交换膜燃料电池解决了传统质子交换膜燃料电池催化剂易受CO等杂质气体毒化、水热管理复杂等问题,成为当今燃料电池发展的主要方向。高温质子交换膜是实现高温操作的关键部分。本文结合质子传递机理,分析了以水作为质子溶剂、非水质子溶剂质子交换膜以及无机固态质子导体膜的研究现状,认为有机/无机复合膜和非水质子溶剂膜,尤其是其中的磷酸掺杂的PBI膜是高温质子交换膜的发展方向。     

磷酸化二氧化硅填充磺化聚醚醚酮质子交换膜的制备及表征

制备了两种磷酸化改性的介孔二氧化硅亚微米球形颗粒,分别为仅外表面接枝磷酸根基团的颗粒(PMPS-Ⅰ)和内外表面均接枝磷酸根基团的颗粒(PMPS-Ⅱ)。颗粒具有均一的尺寸和规则排布的六面体一维贯通孔道。将制备的二氧化硅颗粒与磺化聚醚醚酮(SPEEK)溶液共混制备杂化膜。与填充PMPS-Ⅰ的杂化膜相比,填充PMPS-Ⅱ的杂化膜显示出较好的质子传导性能。当PMPS-Ⅱ的填充量为5%(质量)时,杂化膜在60℃、100%相对湿度下最高质子传导率为0.241 S·cm^-1。研究结果表明,连续贯通的质子传递通道有助于提高杂化膜的质子传导率。     

磺化聚砜/黑磷复合质子交换膜制备及性能研究

以聚醚砜(PES)为原料,采用氯磺酸(CSA)为磺化剂,通过控制反应温度和时间制备系列磺化聚砜(SPES),并以SPES为基质,二维黑磷(BP)为功能填料,采用溶液铸膜法制备了复合质子交换膜。采用红外光谱分析仪(FTIR)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)等对材料结构进行表征,研究了复合膜的吸水率、质子交换性、阻醇性等。结果表明,SPES的磺化度随反应温度、时间、磺化剂浓度的升高而增大。BP的添加增强了复合膜的热稳定性、氧化稳定性、质子交换性、阻醇性等综合性能。在相同测试条件下SPES基膜的甲醇渗透率为1.185×10^-6 cm²/s,而5%(质量分数,下同)SPES/BP复合膜的甲醇渗透率仅为2.88×10^-7 cm²/s。     

氧化石墨烯/磺化聚苯并咪唑高温质子交换膜的制备和表征

通过共混法和原位聚合法成功制备氧化石墨烯（GO）/磺化聚苯并咪唑（SPBI）质子交换复合膜。用FTIR及TEM表征了复合膜的结构,并测试了复合膜的热稳定性、力学性能、尺寸稳定性、含水率、酸掺杂率、氧化稳定性及质子电导率,重点考察不同制备方法、GO的加入对GO/SPBI质子交换复合膜结构和性能的影响。实验结果表明,GO在Y-GO/SPBI-1%复合膜中呈薄片状并良好分散。添加GO后复合膜的力学性能大幅提高,拉伸强度相较于Nafion 117膜（26.65MPa）提高了2.5倍。Y-GO/SPBI-1%复合膜热稳定性稍高于G-GO/SPBI-1%复合膜。Y-GO/SPBI-1%复合膜拥有与SPBI膜相当的含水率,比G-GO/SPBI-1%复合膜的含水率提高了51.36%,表明原位聚合法制备的膜具有良好的保水能力。原位聚合法制备的复合膜具有更高的酸掺杂率和更低的酸溶胀度,提高了膜的尺寸稳定性。Y-GO/SPBI-1%质子交换复合膜在相对湿度40%、160℃下具有最高的质子电导率0.113S/cm。GO上的含氧官能团有助于复合膜中质子的跳跃,原位聚合法使GO更均匀地分散在SPBI基质中,对复合膜质子电导率的提高起到关键作用。     

主链组成对低磺化度磺化芳香族聚合物质子交换膜性能的影响

通过改变共聚单体种类,探究主链元素种类对聚合物质子交换膜性能的影响。以3,3'-二磺酸基钠盐-4,4'-二氟二苯砜为磺化单体,4,4'-二氟二苯砜为非磺化单体,4,4'-二羟基二苯醚或4,4'-二巯基二苯硫醚为共聚单体,通过亲核缩聚反应成功可控制备出磺化度分别为30%和50%的磺化聚芳醚砜（SPES）与磺化聚芳硫醚砜（SPTES）。采用流延法制备了两种聚合物的透明坚韧的质子交换膜。研究发现两种聚合物膜均显示出了良好的力学性能以及较为适中的吸水率与溶胀度。两种聚合物质子交换膜的起始分解温度达到250℃,具有良好的热稳定性。随磺化度的升高,两种聚合物膜的吸水率、溶胀率以及质子传导率均升高。由于主链硫较氧原子与苯环的共轭作用更强以及供电子硫原子与吸电子基团的相互作用,SPTES膜较SPES膜表现出更高的玻璃化转变温度（T _g）、更低的溶胀率以及更高质子传导率。其中SPES-50与SPTES-50在80℃、100%RH条件下,质子传导率分别为0.136S/cm与0.142S/cm,表明其作为质子交换膜具有潜在的应用前景。     

Preparation and characterization of sulfonated poly(arylene‐co‐naphthalimide)s for use as proton exchange membranes

In this study, conductive porous composites were fabricated using the host substrate with an interconnected porous network, followed by the penetration and deposition of polypyrrole (PPy) to create a continuous conductive network. The open‐porous host substrate was processed using polylactide (PLA) with compression molding and salt leaching techniques. Three different salt contents were varied from 75 wt %, 85 wt %, and 90 wt %, which were referred to by their salt‐to‐polymer mass ratios of 3, 6, and 9, respectively. The porous network was made conductive by coating its interior surfaces through in situ polymerization of PPy using iron (III) chloride as the oxidant species. These porous composites were then characterized to analyze the relationships between their morphology and their physical, conductive, and mechanical properties. The mechanical properties were then fitted with numerically simulated results from finite element modeling (FEM). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of new sulfonated copolytriazoles and their proton exchange membrane properties

This work reports the synthesis and characterization of a series of new sulfonated copolytriazoles. The polymers were prepared by CuI catalyzed 1,3-cycloaddition reaction of an equimolar amount of a dialkyne monomer, 1,3-diethynylbenzene and a mixture of two diazide monomers, namely, 4,4′-diazidodiphenyl ether and 4,4′-diazido-2,2′-stilbenedisulfonic acid disodium salt. The copolymers showed high inherent viscosity indicating the formation of high molar mass product. The copolymers were characterized by Fourier transform infrared and proton nuclear magnetic resonance spectroscopic techniques. The copolymer membranes displayed moderate water uptake, high dimensional, mechanical, and thermal stability. Transmission electron microscopy micrographs displayed excellent phase-separated morphology along with very fine ionic clusters. The copolymer PTEOSH-90 (90% degree of sulfonation) showed much higher proton conductivity value which is up to 196 mS cm⁻¹ at 80 °C in completely hydrated condition compared to that of Nafion (165 mS cm⁻¹). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48514.     

SPTES-b-PI质子交换膜的制备及表征

质子交换膜作为质子交换膜燃料电池的核心部件具有提供离子通道传递质子和隔绝两极气体的双重作用,其性能的好坏直接影响着电池性能的优劣。主链引入亲水和疏水段的嵌段芳香族共聚物,由于各嵌段之间具有热力学不相容性会产生微相分离结构,进而形成高效的质子传导通道。本文以磺化双（4-氟苯基）砜（SDFDPS）和4,4'-硫代双苯硫酚（TBBT）为单体,以间羟基苯胺为封端剂合成了带有氨端基的磺化聚芳硫醚砜（SPTES-NH₂）。嵌段聚合物SPTES-b-PI通过亲水段SPTES-NH₂与以1,4,5,8-萘四羧酸二酐（NDA）和4,4'-双（3-氨基苯氧基）二苯基砜（m-BAPS）为单体缩聚而成的疏水段聚酰亚胺（PI）的酰亚胺化偶联反应来合成,制备出了PI分子量不同的SPTES-b-PIx（x=5~20kg/mol）。SPTES-b-PIx膜显示出优异的热力学稳定性,SPTES-b-PIx膜的脱磺化反应开始于290℃高于260℃的SPTES膜,与SPTES-70相比吸水率降低。随着聚酰亚胺分子量的增大,热稳定性增加,质子传导率增加。SPTES-b-PIx的质子传导率25℃下达到0.045~0.124S/cm。     

Performance of the sulfonated poly ether ether ketone proton exchange membrane modified with sulfonated polystyrene and phosphotungstic acid for microbial fuel cell applications

In this research, the preparation of low cost proton exchange membranes (PEMs) based on sulfonated poly ether ether ketone (SPEEK) for application in the microbial fuel cells (MFCs) is studied. Sulfonated polystyrene (SPS) and phosphotungstic acid (PWA) were employed to improve the performance of PEM through the creation of more proton pathways. At first, the sulfonation of PEEK and polystyrene were performed through two modified methods to obtain uniform and high degree of sulfonation (DS) of the polymers and then, the PEMs were prepared through the solution casting method. Accordingly, the formation of uniform skin layer was confirmed by the SEM micrographs. Blending the aforementioned additives to the SPEEK polymer solution significantly enhanced the proton conductivity, water uptake and durability of the modified membranes. The proton conductivities of SPEEK/SPS and SPEEK/PWA membranes at additive/SPEEK weight ratio of 0.15 were 45.3% and 26.2% higher than that of the commercial Nafion117 membrane, respectively. Moreover, the degradation times for the abovementioned modified membranes were 140 and 350 min which indicated satisfactory oxidation stability. Besides, the aforementioned membranes exhibited two times more water uptake compared to the neat SPEEK membrane. Finally, SPEEK/SPS and SPEEK/PWA membranes produced 68% and 36% higher maximum power in the MFC, compared to the commercial Nafion117 membrane. Therefore, the fabricated PEMs are potentially suitable alternatives to be used in the fuel cell applications.     

Fabrication and characterization of sulfonated polybenzimidazole/sulfonated imidized graphene oxide hybrid membranes for high temperature proton exchange membrane fuel cells

The sulfonated polybenzimidazole (sPBI)/sulfonated imidized graphene oxide (SIGO) was evaluated to be a potential candidate for high temperature proton exchange membranes fuel cells (HT-PEMFCs). Multifunctionalized covalently bonded SIGO is incorporated in sPBI matrix to resolve the drawbacks such as low proton conductivity, poor water uptake, and ion-exchange capacity (IEC) of sPBI polymer, synthesized by direct polycondensation in phosphoric acid for the application of proton exchange membranes. Strong hydrogen bonding among multifunctional groups established a neighborhood of interconnected hydrophobic graphene sheets and organic polymer chains. It provides hydrophobic–hydrophilic phase separation and facile proton hopping architecture. The optimized sPBI/SIGO (15 wt %) revealed 2.45 meq g⁻¹ IEC; 5.81 mS cm⁻¹ proton conductivity [120 °C and 10% relative humidity (RH)] and 2.45% bound water content. The maximum power density of the sPBI/SIGO-15 membrane was 0.40 W cm⁻² at 160 °C (5% RH) and ambient pressure with stoichiometric feed of H₂/air. This recommends that sPBI/SIGO composite membranes are compatible candidate for HT-PEMFCs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47892.     

Facile in situ template synthesis of sulfonated polyimide/mesoporous silica hybrid proton exchange membrane for direct methanol fuel cells

Highly conductive and hydration retentive organic-inorganic hybrid proton exchange membranes for direct methanol fuel cells were synthesized by in situ sol-gel generation of mesoporous silica (mSiO₂) in sulfonated polyimide (SPI) via self-assembly route of organic surfactant templates for the tuning of the architecture of silica. The microstructure and properties of the resulting hybrid membranes were extensively characterized. The mesopores of about 3 nm in silica dispersion phase were formed in the SPI matrix. The existence of the mesoporous structure of silica improved the thermal stability, water-uptake and proton conductivity as well as methanol resistance of the hybrid membranes. The hybrid membrane with 30 wt.% mSiO₂ exhibited the water-uptake of 44.8% at 25 °C, and proton conductivity of 0.214 S cm⁻¹ at 80 °C at RH = 100%, while pure SPI exhibited the values of 40.6% and 0.179 S cm⁻¹ in the same test conditions, respectively. The results suggested that the highly hydrophilic character of Si-OH groups and the large surface area of mSiO₂ should contribute to the improvement of the water-uptake, meanwhile the mesoporous channels may supply the continuous proton conductive pathway in the hybrid membranes.     

Preparation and characterization of poly(vinylidene fluoride)/sulfonated poly(phthalazinone ether sulfone ketone) blends for proton exchange membrane

Poly(vinylidene fluoride)/sulfonated poly(phthalazinone ether sulfone ketone) (PVdF/SPPESK) blend membranes are successfully prepared by solution blending method for novel proton exchange membrane (PEM). PVdF crystallinity, FTIR‐ATR spectroscopy, thermal stability, morphology, water uptake, dimension stability, and proton conductivity are investigated on PVdF/SPPESK blends with different PVdF contents. XRD and DSC analysis reveal that the PVdF crystallinity in the blends depends on PVdF content. The FTIR‐ATR spectra indicate that SPPESK remains proton‐conducting function in the blends due to the intactness of ? SO₃H group. Thermal analysis results show a very high thermal stability (T_d1 = 246–261°C) of the blends. PVdF crystallinity and morphology study demonstrate that with lower PVdF content, PVdF are very compatible with SPPESK. Also, with lower PVdF content, PVdF/SPPESK blends possess high water uptake, e.g., P/S 10/90 and P/S 15/85 have water uptake of 135 and 99% at 95°C, respectively. The blend membranes also have good dimension stability because the swelling ratios are at a fairly low level (e.g., 8–22%, 80°C). PVdF/SPPESK blends with low PVdF content exhibit very high proton conductivity, e.g., at 80°C, P/S 15/85 and P/S 10/90 reach 2.6 × 10^?2 and 3.6 × 10^?2 S cm^?1, respectively, which are close to or even higher than that (3.4 × 10^?2 S cm^?1) of Nafion115 under the same test condition. All above properties indicate that the PVdF/SPPESK blend membranes (particularly, with 10–20% of PVdF content) are very promising for use in PEM field. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010