车用燃料电池质子交换膜的制备及性能

合成了一系列具有不同支化度的磺化聚芳醚砜材料,并对其结构和性能进行了表征。所制备的磺化的支化聚芳醚砜材料的分子量可达7.00×105以上,并且分子量分布在1.17左右,拉伸强度可达20.55~28.81 MPa。随着聚合物支化度的增加,聚合物的热稳定性得到改善,在550℃下的热失重可降低至39%~45%。高支化的磺化聚芳醚砜薄膜的氧化稳定性也得到改善,80℃下的使用寿命可提高至7.25 h。支化的磺化聚芳醚砜薄膜的吸水率和质子传导率都较高。80℃下高支化度的聚芳醚砜薄膜的质子传导率可达0.33 S/cm。对其微观形貌进行观测发现,支化聚芳醚砜中的支化结构可对周围的亲水磺酸基团起支撑作用,促使其发生团聚而形成连续的质子通道。     

高温质子交换膜燃料电池机理模型研究进展

建立高温质子交换膜燃料电池的机理模型可以加深对其内部传递现象和反应机理的认识,同时可以预测不同参数下燃料电池的性能,对优化电池的操作条件和结构参数等具有重要的指导意义。对现有的高温质子交换膜燃料电池机理模型进行了评述,分析了基于磷酸掺杂聚苯并咪唑膜(H3PO4/PBI)不同维数的稳态和动态模型及基于其他复合膜模型的优点和不足,并指出了高温质子交换膜燃料电池模型的研究方向。     

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。     

高温质子交换膜研究进展

高温质子交换膜燃料电池（HT-PEMFCs）因其具有催化剂CO耐受性良好,能量转化率高,水热管理简单等优点,成为了能源领域重要的研究方向之一。高温质子交换膜（HTPEM）是它的主要部件之一,分别以水、磷酸分子和咪唑分子为质子传导载体分析了目前HTPEM的研究现状,比较后得出了以磷酸为质子载体的HTPEM性能最佳的结论,指出了研究中尚存的问题,并展望了未来HTPEM可能的研究方向。     

磺化聚苯并咪唑/磺化聚醚砜酸碱复合质子交换膜的制备与表征

为提高膜的尺寸稳定性和阻醇性能,以磺化聚苯并咪唑(S-PBI)与高磺化度聚醚砜(ABPS)两种聚合物为原料,采用溶液共混的方法,制备了系列酸碱复合质子交换膜。研究了复合膜的甲醇溶胀性、吸水率、甲醇渗透系数、质子传导率随S-PBI含量的变化规律。研究表明,随着S-PBI含量的增加,膜的阻醇性能和尺寸稳定性明显提高;同时,复合膜具有较好的质子传导率,有望应用于直接甲醇燃料电池。     

质子交换膜燃料电池关键技术研究进展

简述了质子交换膜燃料电池(PEMFC)的工作原理及特点;综述了PEMFC关键技术的最新研究进展,包括质子交换膜合成、电催化剂制备、膜电极工艺及水管理和热控制;并简介了我国PEMFC的开发情况。     

燃料电池质子交换膜研究进展

质子交换膜作为燃料电池的关键材料之一,得到世界各国学者的广泛关注和深入研究,已先后研发出含氟高分子类、芳香烃聚合物类以及有机/无机杂化材料的质子交换膜.本文对燃料电池工作原理进行简要概述,并针对质子交换膜的应用前景及研究现状进行分析.     

用于高温质子交换膜燃料电池的聚合物电解质膜研究进展

高温质子交换膜燃料电池在降低燃料电池水热管理复杂性、催化剂中毒方面有明显优势;可改善电池阴阳两极尤其是阴极氧气还原反应的动力学特性,提高电池的效率。聚合物电解质膜作为关键材料之一,在高温时易失水导致质子传导率降低、机械强度和热稳定性不高等问题。本文基于磺酸、磷酸和离子液体等不同质子传递介质,对高温聚合物电解质膜进行综述,比较了各类聚合物电解质膜的优缺点及应用时存在的问题,着重探讨嵌段共聚物在高温聚合物电解质膜方面的潜在应用,指出离子液体的添加不但可作为质子载体,而且在构建嵌段聚合物结构方面可发挥"诱导剂"作用。提出通过分子设计可更好了解嵌段聚合物的空间构效关系,进而通过结构设计提高膜的质子传导性能和稳定性。     

硫酸化SnO2/SPPESK复合质子交换膜的制备及燃料电池性能

非氟聚合物磺化聚芳醚砜酮（SPPESK）具有甲醇渗透率低、化学、热稳定性高等优点,但其高的电导率需通过提高磺化度获得,导致膜因过度溶胀而失去尺寸稳定性。添加无机纳米颗粒可以有效提高膜性能,但因其表面缺少功能化基团,导致颗粒有机相容性差,阻醇性能和质子传导率不易同时提高。硫酸化改性的纳米颗粒因其表面具有酸性位点和硫酸基团,能够有效克服这一问题。本文制备表面硫酸化改性的SnO₂（SSnO₂）纳米颗粒并引入SPPESK基质制备有机无机复合质子交换膜。当SSnO₂含量不大于7.5%时,纳米颗粒具有良好的有机相容性,可均匀分散于聚合物基质。SSnO₂含量为7.5%时,80℃下复合膜吸水率（19.6%）比SPPESK原膜提高19%,接近Nafion115。颗粒诱导膜内离子簇的聚集扩大,降低了质子的传导阻力,质子传导率分别比SPPESK原膜和Nafion115膜提高48%和30%。同时,纳米颗粒增大了甲醇传递空间位阻,甲醇渗透率较SPPESK原膜和Nafion115膜分别降低46%和71%。直接甲醇燃料电池0.5V处功率密度分别比SPPESK原膜和Nafion115膜高205%和50%。     

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     

Preparation and properties of bisphenol A‐based sulfonated poly(arylene ether sulfone) proton exchange membranes for direct methanol fuel cell

Novel bisphenol A‐based sulfonated poly(arylene ether sulfone) (bi A‐SPAES) copolymers were successfully synthesized via direct copolymerization of disodium 3,3′‐disulfonate‐4,4′‐dichlorodiphenylsulfone, 4,4′‐dichlorodiphenylsulfone, and bisphenol A. The copolymer structure was confirmed by Fourier transform infrared spectra and ¹H NMR analysis. The series of sulfonated copolymers based membranes were prepared and evaluated for proton exchange membranes (PEM). The membranes showed good thermal stability and mechanical property. Transmission electron microscopy was used to obtain the microstructures of the synthesized polymers. The membranes exhibit increased water uptake from 8% to 66%, ion exchange capacities from 0.41 to 2.18 meq/g and proton conductivities (25°C) from 0.012 to 0.102 S/cm with the degree of sulfonation increasing. The proton conductivities of bi A‐SPAES‐6 membrane (0.10–0.15 S/cm) with high‐sulfonated degree are higher than that of Nafion 117 membrane (0.095–0.117 S/cm) at all temperatures (20–100°C). Especially, the methanol diffusion coefficients of membranes (1.7 × 10^?8 cm²/s–8.5 × 10^?7 cm²/s) are much lower than that of Nafion 117 membrane (2.1 × 10^?6 cm²/s). The new synthesized copolymer was therefore proposed as a candidate of material for PEM in direct methanol fuel cell. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Sulfonation of poly(phthalazinone ether sulfone ketone) by heterogeneous method and its potential application on proton exchange membrane (PEM)

A series of sulfonated PPESK (SPPESKs) were synthesized through a heterogeneous sulfonation process with fuming sulfuric acid as sulfonating agent in a chloroform solvent. Membranes prepared from SPPESKs were investigated and proved to be candidates of proton exchange membrane in fuel cell operating at high temperature and low humidity. The heterogeneous sulfonation reaction is verified to first occur on the interface of the acid phase and the chloroform phase, then went on in the acid phase. SPPESKs with sulfonation degree (DS) up to 2.0 are obtained through a new reprecipitation method. Effects of reaction temperature, reaction time, acid/polymer ratio, and chloroform/polymer ratio on the sulfonation reaction are reported in details. An increase in sulfonation degree results in the increase of hydrophilicity, bringing about a substantial gain in proton conductivity. SPPESK membranes exhibit high water uptake of about 105.4% with DS of 1.01, almost two times higher than that of Nafion® with similar dimensional variation. Conductivity values at 35°C, 60% R.H. ranging from 10^?3 to 10^?2 S/cm were measured, which are comparable to or higher than that of Nafion® 112 (1.635 × 10^?2 S/cm) under the same test condition. Thermogravimetric analysis shows that SPPESK membranes are stable up to 290°C in N₂. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1002–1009, 2007     

A modified poly(aryle ether ketone sulfone) proton exchange membrane with in situ polymerized polypyrrole for the direct methanol fuel cells

Bone tissue interfacial scaffolds, which encourage cell growth, are critical determinants for clinical success after implant surgery. Over the years, a number of resorbable configurations have emerged for bone cell support and growth, but only a few have demonstrated clinical efficacy. Polymer coatings produced by electrospinning are regarded as very promising bone interfaces because of the ultrathin‐scaled dimensions of its physical structure. In this study, the morphology, composition, thermal properties, and cell growth viability of a number of polylactide‐based systems containing different binary and ternary formulations of this biomaterial with collagen and commercial hydroxyapatite nanoparticles were characterized. The best performance in terms of biocompatibility was obtained for the tricomponent system in which the submicron fibers were further subjected to uniaxial orientation process during formation. The in vitro proliferation of the cells, which harbored on these ultrathin‐structured mats, was examined by means of a metabolic activity indicator and ensured by means of scanning electron microscopy, and cell anchorage was checked by fluorescent optical microscopy. Finally, the optimum tricomponent material was successfully sterilized for the first time by gamma radiation without noticeable losses in cell‐seeding capacity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

磺化含酚酞侧基聚芳醚酮/氧化石墨烯复合质子交换膜的性能

采用共混制备了一系列磺化含酚酞侧基聚芳醚酮(SPEK-C)/氧化石墨烯(GO)复合质子交换膜,系统地研究了GO含量对复合膜性能的影响。结果表明,GO含量对膜的离子交换容量、稳定性、质子电导率和甲醇渗透率等有重要影响。复合膜质子电导率随GO含量增加而提高,GO含量为2%和5%的复合膜在80℃下质子电导率均在10^-1 S·cm^-1以上。80℃下,GO含量为5%的复合膜甲醇渗透率为6.69×10^-7 cm²·s^-1,低于同温度下复合前SPEK-C膜1个数量级。复合后膜的化学稳定性增强,离子交换容量和含水率均有提高,相对选择性明显增大,最高达SPEK-C的18.2倍。     

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.     

Air-breathing microbial fuel cell with enhanced performance using nanocomposite proton exchange membranes

This work aims to improve the performance of air-breathing microbial fuel cells (MFCs) through using hydrocarbon polymer based nanocomposite proton exchange membranes. Accordingly, nanocomposite membranes based on sulfonated poly(ether ether ketone) (SPEEK) and montmorillonite (MMT) were investigated for such an application. Although the incorporation of MMT into SPEEK membranes resulted in reduced oxygen permeability as well as proton conductivity, but the overall selectivity was found to be improved. MFC tests revealed that using the optimized nanocomposite membrane (SPEEK-70/MMT-3 wt%) results in a considerably higher open circuit voltage (OCV) compared to the corresponding neat membrane. Moreover, it was found that the SPEEK-70/MMT-3 wt% membrane is able to provide about 40% more power output than Nafion^®117. On the account of high proton conductivity, low oxygen permeability, high electrochemical performance, ease of preparation and low cost, hydrocarbon based nanocomposite PEMs could be considered as promising electrolytes to enhance the performance of MFCs.