SPPO/SiO2/PWA复合质子交换膜的制备及性能

利用溶胶-凝胶法制备出了SPPO/SiO2/PWA复合质子交换膜,对膜的离子交换容量(IEC)、平均当量重量(EW)、磺化度(SD)、吸水性、溶胀率、质子电导率、Tg进行了表征,此外,还对膜的结构进行了FT-IR、SEM表征,结果表明,所制得的掺杂2%～5%SiO2和3%PWA的SPPO复合膜在100℃、100%相对湿度时的质子电导率与Nafion-117?膜相近,有望作为质子交换膜使用。     

Ionic polymer–metal composite actuators obtained from sulfonated poly(ether ether sulfone) ion-exchange membranes

The cost-effective and high-performance ionic polymer–metal composites (IPMC) were designed and prepared from ion-exchange membranes based on sulfonated poly(ether ether sulfone) (SPEES) with different degrees of sulfonation (DS). The precursor of SPEES, namely PEES, is commercially available and industrial grade. Moreover, the PEES can be transformed easily into ion-conductive SPEES through a simple sulfonation reaction. The ion exchange capacity (IEC) and water uptake (WU) of SPEES membranes increase with increasing their DS, and the proton conductivities of these hydrated SPEES membranes are subsequently enhanced. Compared with the commercial Nafion ion-exchange membrane, the SPEES membranes have higher IEC and WU. The IPMC actuators made of the SPEES membranes show the large bending strain and fast response under electric stimulation. The SPEES membrane with the highest DS (SPEES4) shows the best performance of IPMC actuators. The electromechanical behaviors of these IPMC actuators indicate that the SPEES is a candidate to substitute Nafion.     

磺化聚苯醚/聚醚酰亚胺共混质子交换膜的制备与性能

以磺化聚苯醚(SPPO)和聚醚酰亚胺(PEI)为原料,采用溶液共混法制备了SPPO/PEI共混质子交换膜,并经扫描电镜(SEM)、热重分析、拉伸测试等对膜的结构和性能进行了表征。结果表明,共混膜较纯SPPO膜具有更高的热稳定性、力学性能和尺寸稳定性;SPPO与PEI之间的强烈氢键相互作用使两组分之间并未发生明显的相分离。PEI的引入虽使得共混膜的质子传导率有所下降,但对于PEI含量在40%以下的共混膜,其质子传导率仍维持在约10-2S/cm的数量级水平,能满足质子交换膜的要求。     

Synthesis,characterization of novel silicotungstic acid incorporated SPEEK/PVA-co-ethylene-based composite membranes for fuel cell

Sulfonated polyether ether ketone (SPEEK) is prepared by the sulfonation of polyether ether ketone (PEEK). Five of the composite membranes (PSW1–PSW5) with various percentage compositions of the SPEEK, PVA-co-ethylene, and silicotungstic acid (SWA) were prepared. The prepared composite membranes were characterized using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). Surface morphology of the composite membranes was analyzed using scanning electron microscopy (SEM). Other evaluations related to conductivities (ion exchange capacity, IEC), proton conductivity), absorptivity (water and methanol absorption), durability and mechanical properties (tensile strength and percentage elongation) were also evaluated for the composite membranes. Among the five composite membranes, composite membrane with higher SWA content, PSW5 (which has 10% SWA) showed more conductivity compared to other membranes. These composites also showed very good conductivities, mechanical properties, and durabilities. Hence, these composite membranes have the potential to be used in the development of newer proton exchange membrane fuel cells (PEMFCs).     

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.     

聚乙二醇/磺化聚苯醚质子交换膜的制备与性能研究

采用溶液共混浇铸法制备了一系列的聚乙二醇/磺化聚苯醚(PEG/SPPO)共混膜SPPO的红外光谱图显示了磺酸基团的成功引入;X-射线衍射图表明,加入柔性的聚乙二醇,SPPO的有序程度降低;膜的离子交换容量(IEC值)、质子传导率和吸水率等理化性能结果表明:PEG/SPPO共混膜的质子传导率和离子交换容量虽然较纯SPPO膜有所下降,但是最大也分别达到了1.80mequiv.g-1和0.061S/cm(PEG/SPPO=10/90,90℃),仍然可以满足质子交换膜的使用要求,而复合膜的吸水率和溶胀率较SPPO膜大幅降低。整体来说,复合膜的各项综合性质良好,有望应用于直接甲醇燃料电池。     

Ion transport within random-sulfonated and block-sulfonated copolyimides

A series of sulfonated copolyimides was prepared from 4,4-oxydianiline, sulfonated 4,4′-oxydianiline, and 4,4′-(4,4′-isopropylidenediphenoxy) bis(phthalic anhydride). Both random- and block structures were prepared by varying the timing of monomer addition to the polymerization reaction. The polymers were converted to their acid forms and then cast into films. ¹H NMR, FTIR, and non-aqueous titration verified the degree of polymer sulfonation. The block copolymers showed higher water uptake and proton conductivities than random copolymers with similar ion exchange capacity (IEC) values. These differences became pronounced as the IEC value was increased.     

Dihydrogenimidazole modified silica-sulfonated poly(ether ether ketone) hybrid materials as electrolyte membranes for direct ethanol fuel cells

The present study reports on dihydrogenimidazole modified inorganic-organic mixed matrix membranes for possible application as a proton exchange membrane in direct ethanol fuel cells. The polymeric phase consisted mainly of sulfonated poly(ether ether ketone) (sPEEK) with a sulfonation degree of 55%. The inorganic phase was built up from hydrophilic fumed silica particles interconnected with partially hydrolyzed and condensed tetraethoxysilane with a total inorganic loading of 27.3%. This inorganic phase was further modified with N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole (DHIM), which consists of an hydrolyzable inorganic part and a functional organic group. The influence of the modifier on the mixed matrix system was studied by means of various modifier concentrations in various aqueous-ethanolic systems (water, 2 M and 4 M ethanol). Modifier concentration and ethanol concentration of the ethanol-water mixture exhibited significant but opposite effects on the liquid uptake of the mixed matrix membranes. The proton conductivity as well as the proton diffusion coefficient as a function of modifier content showed a linear decrease. The proton conductivity as a function of temperature showed Arrhenius behavior and the activation energy of the mixed matrix membranes was 43.9 ± 2.6 kJ mol⁻¹. High selectivity of proton diffusion coefficient to ethanol permeability coefficient was obtained with high modifier concentrations. At low modifier concentrations, this selectivity was dominated by ethanol permeation and at high modifier concentrations by proton diffusion. The main electrolyte properties can be optimized by setting the DHIM content in mixed matrix membrane. With this approach, tailor-made membranes can be prepared for possible application in direct ethanol fuel cells.     

化学交联法在质子交换膜制备中的应用

化学交联是提高质子交换膜性能的一种有效方法。交联质子交换膜具有较低的水溶胀性、甲醇渗透性,以及较高的热、力学稳定性。使用化学交联法制备质子交换膜时,通常采用交联聚合物磺化法、磺化聚合物交联法和共混聚合物交联法等三种方法。采用不同方法交联时,交联活性点的选取各不相同,制备的交联质子交换膜性能也有差异。深入研究交联程度、离子交换容量、交联剂种类等不同制备条件对交联膜的微观结构及性能的影响,才能使交联质子交换膜的综合性能得到优化。     

一种新型的磺化聚芳醚酮质子交换膜材料

利用先聚合后磺化的方法合成了一种新型磺化聚芳醚酮,FTIR和HNMR结构表征表明,其磺酸基只连在悬挂侧链上.利用浇铸法将该材料制备成膜,对膜的离子交换容量(IEC)、平均当量重量(EW)、磺化度(SD)、吸水性、线性膨胀率及其电导率进行了表征,结果表明这种膜材料具有良好的吸水性和较低的线性溶胀率,所制得的膜在100℃、100%相对湿度时的质子电导率与Nafion-117~(R)膜相近,有望作为质子交换膜使用.     

Synthesis and characterization of poly(ether sulfone ether ketone ketone) grafted poly(sulfopropyl methacrylate) for proton exchange membranes via atom transfer radical polymerization

A series of copolymers of poly(ether sulfone ether ketone ketone) grafted poly(sulfopropyl methacrylate) (PESEKK-g-PSPMA) were successfully synthesized by atom transfer radical polymerization (ATRP) of sulfopropyl methacrylate (SPMA) after chloromethylation of poly(ether sulfone ether ketone ketone) (PESEKK) backbone. The structure of the chloromethyl PESEKK and the copolymers were carefully investigated. Variation of the polymerization time leads to the formation of copolymers with different degree of sulfonation (DS). The properties of the proton exchange membranes such as water uptake, ion exchange capacity, proton conductivity, and methanol permeability are studied with compared to those of Nafion 117 membranes and could be modulated simply by control of the ATRP time. The copolymers exhibited much lower methanol permeability and higher proton conductivity as compared with Nafion 117.     

DMFC用磺化聚醚醚酮/聚苯胺共混型质子交换膜的研究

磺化聚醚醚酮膜(SPEEK)是直接甲醇燃料电池(DM FC)用质子交换膜的候选材料之一,但是当温度和磺化度(D S)较高时,该膜在甲醇水溶液中溶胀非常严重,甚至溶解,其使用温度受到限制。将磺化度为50.11%的SPEEK和聚苯胺(PAN I)共混制膜,希望利用酸碱之间的相互作用对SPEEK进行改性。研究结果表明,PAN I的加入使SPEEK/PAN I共混膜的使用温度有较大提高,并且该膜还具有较高的电导率和较好的阻醇性能。     

全钒液流电池用新型全氟磺酸离子交换膜制备及性能研究

通过溶液流延成膜法制备了具有不同离子交换容量(IEC)的全氟磺酸(PFSA)离子交换膜,并测试了其吸水率、电导率、钒离子(Ⅴ(Ⅳ))透过率和选择性系数。研究发现,具有高IEC值的PFSA离子交换膜具有相对较低的Ⅴ(Ⅳ)离子透过率和较高的质子电导率。其中IEC值为1.10mmol/g的PFSA离子交换膜对Ⅴ(Ⅳ)离子具有最高的选择性,其选择性系数为Nafion 117膜的2.97倍。     

Toxic metal ion separation by cellulose acetate/sulfonated poly(ether imide) blend membranes: effect of polymer composition and additive

Toxic heavy metal ion removal from industrial effluents are gaining increased visibility owing to environmental concern and saving precious materials. In this work, an attempt has been made to remove the valuable metal ions using modified ultrafiltration (UF) blend membranes based on cellulose acetate (CA) and sulfonated poly(ether imide) (SPEI) were prepared in the presence and absence of additive, poly(ethylene glycol) 600 (PEG600) in various compositions. Prepared membranes were characterized in terms of pure water flux (PWF), water content and membrane hydraulic resistance. High flux UF membranes were obtained in the range of 15-25 wt% SPEI and 2.5-10 wt% PEG600 in the polymer blend. The molecular weight cut-off (MWCO) of the blend membranes were determined using protein separation studies found to vary from 20 to greater than 69 kDa. Surface morphology of the blend membranes were analysed with scanning electron microscopy. Studies were carried out to find the rejection and permeate flux of metal ions such as Cu(II), Ni(II), Zn(II) and Cd(II) using polyethyleneimine as the chelating ligand. On increasing the composition of SPEI and PEG600, the rejection of metal ions is decreasing while the permeate flux has an increasing trend. These effects are due to the increased pore formation in the CA/SPEI blend membranes because of the hydrophilic SPEI and polymeric additive PEG600. In general, it was found that CA/SPEI blend membranes displayed higher permeate flux and lower rejection compared to pure CA membranes. The extent of separation of metal ions depends on the affinity of metal ions to polyethyleneimine to form macromolecular complexes and the stability of the formed complexes.     

测试介质对纳米CeO_2改性SPEEK膜质子电导率的影响

采用纳米氧化铈(CeO2)改性磺化度48.3%的磺化聚醚醚酮(SPEEK),通过溶液浇铸法制备用于直接甲醇燃料电池的质子交换膜.在两种介质中测试改性膜的电导率均随温度的升高而增大,与未改性膜相比却大小正好相反:在1 mol/L以盐酸溶液为电解液的测试介质中,改性膜的电导率是未改性膜的15倍,在水蒸气测试介质中,却仅为40%.红外光谱分析表明,CeO2中的铈原子与—SO3H基团中的氧原子发生配位作用.X射线衍射仪(XRD)分析可见,当复合膜浸入1 mol/L盐酸4 h前后,纳米CeO2的晶体结构未见明显变化,表明所发生的配位作用仅处于CeO2和SPEEK两个固相界面上.扫描电子显微镜(SEM)观察改性膜和未改性膜均无网络结构和微相分离,质子在膜内通过—SO3H基团之间的跃迁传导,酸溶液介质远比水蒸气有利于质子在纳米CeO2改性SPEEK膜内磺酸基团之间的跃迁.     

新型燃料电池质子交换膜的研究进展

由于当前所使用的质子交换膜材料存在成本高、无法高温操作和不够环保等缺点,开发新型的成本低、性能高的质子交换膜越来越引起人们的重视．对于新型质子交换膜的研制主要体现在两个方面,一个是对于全氟磺酸型膜的改进和增强,包括加入支撑材料或掺杂增强材料等方法;另一个是彻底抛开全氟树脂,开发新型的质子交换膜材料,其中包括直接磺化、直接聚合、接枝、掺杂等制备方法,简要评述了这些方法的优缺点和这些膜材料的性能,并附以实例说明．     

Proton conductivity of Nafion/ex situ Stöber silica nanocomposite membranes as a function of silica particle size and temperature

In the first systematic study of the influence of the size of silica particles on ion exchange capacity (IEC) and proton conductivity of Nafion–silica nanocomposite membranes, thin films cast from mixtures of silica particles (5 wt%) with varying diameters ranging from 10 to 400 nm and Nafion in alcohol were examined. IECs decreased exactly as expected with the dilution of Nafion and its sulfonic acid groups with added silica. At 80 °C, the proton conductivity was also less with silica particles. However, at higher temperatures (120 °C), there was a 58 % improvement in proton conductivity at low relative humidity and a 45 % improvement at higher relative humidity for nanocomposite membranes prepared with silica particles <50 nm in size. The improvement was less significant with larger silica particles in the membranes.     

磺化来瓦希尔骨架(MIL-101(Cr)-SO3H)/磺化酚酞侧基聚芳醚砜杂化质子交换膜的制备及性能

应用水热合成法制备了来瓦希尔骨架材料（MIL-101（Cr））,通过后磺化法将磺酸（SO₃H）基团引入MIL-101（Cr）的笼状结构中,得到具有质子传导功能的MIL-101（Cr）-SO₃H。FTIR结果表明,磺酸基团成功引入到MIL-101（Cr）中。SEM和XRD结果表明,磺化前后材料的粒径在纳米尺寸范围,且MIL-101（Cr）-SO₃H颗粒的晶体结构无坍塌。元素分析结果表明,MIL-101（Cr）-SO₃H的磺化度为0.36。然后将MIL-101（Cr）-SO₃H掺杂到磺化酚酞侧基聚芳醚砜（SPES-C）中制备了MIL-101（Cr）-SO₃H/SPES-C燃料电池用杂化质子交换膜。SEM结果说明,MIL-101（Cr）-SO₃H/SPES-C杂化膜内MIL-101（Cr）-SO₃H分散均匀,SPES-C与MIL-101（Cr）-SO₃H两相相容性较好,膜内无缺陷。TGA分析结果表明,MIL-101（Cr）-SO₃H/SPES-C杂化膜热稳定性优良。MIL-101（Cr）-SO₃H的引入可以提高MIL-101（Cr）-SO₃H/SPES-C杂化膜吸水率并降低甲醇渗透性。随填充物MIL-101（Cr）-SO₃H的含量增加和测试温度升高,MIL-101（Cr）-SO₃H/SPES-C杂化膜的质子传导率随之增大。当温度为80℃时,MIL-101（Cr）-SO₃H填充量为5wt%的MIL-101（Cr）-SO₃H/SPES-C杂化膜的质子传导率达到0.162 S·cm-1,比商用Nafion膜的质子传导率（0.134 S·cm-1）提高了20.1%。      

The importance of orientation in proton transport of a polymer film based on an oriented self-organized columnar liquid-crystalline polyether

We prepared membranes based on a liquid-crystalline side-chain polyether obtained by chemical modification of commercial poly(epichlorohydrin) (PECH) with dendrons. This polymer exhibited a columnar structure, which could form an ion channel in the inner part. The columns were successfully oriented by taking advantage of surface interactions between the polymer and hydrophilic substrates, as confirmed by X-ray diffraction analysis (XRD), environmental scanning electron microscopy (ESEM) and optical microscopy between crossed polars (POM). Column orientation was found to be crucial for effective transport: the oriented membranes exhibited proton transport comparable to that of Nafion® N117 and no water uptake. An increase in sodium ion concentration in the feed phase suggested a proton/cation antiport. On the contrary, no proton transport was detected on unoriented membranes based on the same liquid-crystalline side-chain polyether or on unmodified PECH.     

Poly (ether ether ketone) derivatives: Synthetic route and characterization of nitrated and sulfonated polymers

Nitrated and sulfonated poly (ether ether ketone) [SNPEEK] samples were prepared through sulfonation of nitrated PEEK (NPEEK) at different temperatures resulting in polymers with distinct sulfonation degrees (SD). The sulfonation occurred preferentially in the hydroquinone segment even after 81% of this moiety had been nitrated. Sulfonation in the benzophenone moiety was achieved only in 16% of this segment at the reaction temperature of 80 °C. The substitution degree was obtained through the TG curves, and values were in agreement with ¹H NMR data when SD is much higher as ND (nitration degree). The highest SD obtained was 72%. Membranes of the sulfonated and nitrated PEEK (SNPEEK) were prepared by casting and showed good ductility depending on the substitution degree, with proton conductivity in the order of 10^? 2 S cm^? 1, an important characteristic in some applications, such as in fuel cells.