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。     

一类含柔性侧链结构质子交换膜的制备与性能

通过利用含侧甲基结构聚芳醚砜的溴化和接枝磺化反应，制备得到一系列结构单元中含有4个柔性侧链结构的磺化聚芳醚砜质子交换膜（4SPAES-x）。通过1HNMR表征其化学结构，并利用原子力显微镜对膜材料的相分离形态结构进行分析，证实所制膜材料具有良好的亲水/疏水相分离形态结构。4SPAES-x膜的离子交换容量在1.12~1.74 mmol/g，30 ℃时的吸水率、溶胀率和质子传导率分别在11%~32%、7%~22%和21~86 mS/cm，均随磺化比例的增大而增大。4SPAES-25膜组装的钒流单电池在40 mA/cm2电流密度下最高能量效率为83.3%，高于Nafion 115的81.5%。此外，该单电池的效率还具有良好的循环稳定性。     

季铵型交联聚芳醚砜薄膜的制备及其性能研究

以甲基丙烯酸二甲氨基乙酯(DMAEMA)为铵化试剂,合成了含有双键的季铵型聚芳醚砜共聚物,通过流延技术,在热处理条件下挥发溶剂并交联,制备了季铵型交联聚芳醚砜(cPAES-N)薄膜。论文研究了聚芳醚砜的基本结构、交联情况、热稳定性和不同温度下的吸水溶胀情况。研究发现,交联聚芳醚砜薄膜可在流延溶剂中稳定存在,而且其热稳定性优于非交联聚芳醚砜(PAES-N);交联聚芳醚砜薄膜的吸水率与溶胀率均低于非交联聚芳醚砜薄膜,尺寸稳定性良好。     

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。     

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%。     

静电层层自组装改性SPPESK/PWA质子交换膜

运用直接掺杂法制备的磺化聚芳醚砜酮/磷钨酸(SPPESK/PWA)复合质子交换膜存在PWA流失严重的问题,影响了膜的正常使用。为了解决这一问题,以壳聚糖(CS)和PWA为聚阴阳离子电解质对,对复合膜进行静电层层(LBL)自组装改性研究,对膜的吸水率、溶胀度、质子传导率等性能进行了表征,并测试了膜中PWA的稳定性。经测定,SPPESK/PWA/(CS/PWA)₂的质子传导率达到154mS/cm(80℃),高于相应的SPPESK膜(118mS/cm)及SPPESK/PWA膜(147mS/cm);SPPESK/PWA/(CS/PWA)₄在80℃水中浸泡30天后,膜的质量损失率由18.45%降为11.81%,电导率损失率由32.20%降为16.77%。结果表明,该方法不仅提高了复合膜的质子传导率,并且有效抑制了PWA的流失。     

季铵盐化氧化石墨烯复合磺化聚磷腈质子交换膜的制备与表征

制备了一系列含有季铵盐化氧化石墨烯(QGO)的磺化聚磷腈类复合质子交换膜。通过对复合膜的稳定性能和电化学性能测试发现,复合膜(SP-x-QGO)的吸水率和溶胀度都低于纯磺化聚磷腈膜(SPFPP)。复合膜具有较好的抗氧化性能;复合膜SP-3-QGO在80℃完全吸水条件下的质子传导率为0.092 S/cm。结果表明,季铵盐化的氧化石墨烯(QGO)复合磺化聚磷腈类质子交换膜(SP-x-QGO)在燃料电池领域具有很大的发展前景。     

氯甲基化/季铵化新型聚芳醚砜酮超滤膜的研制

本文对含二氮杂萘结构聚芳醚砜酮进行改性制得氯甲基化聚芳醚砜酮。选用N-甲基一2-吡咯烷酮作制膜溶剂，依据正交设计方法制得了一系列氯甲基化聚芳醚砜酮超滤膜。考察了聚合物浓度、添加剂种类和添加量以及制膜蒸发时间等对膜性能的影响。将氯甲基化聚芳醚砜酮超滤膜浸入三甲胺溶液进行季铵化反应，得季铵化聚芳醚砜酮超滤膜。并考察了膜的抗污染性。     

壳聚糖与磺化聚芳醚砜复合膜材料研究进展

基于利用壳聚糖中氨基和磺化聚芳醚砜中的磺酸基团之间的静电力制备复合膜材料。综述了该类复合材料的材质选择、成膜方式以及在超微滤、纳滤、反渗透以及质子交换膜领域的应用状况,并展望了未来的发展方向。     

磺化聚醚醚酮复合膜的制备及其性能研究

采用共混溶液浇铸法制备了磺化聚醚醚酮(SPEEK)/季铵化聚降冰片烯聚合物(TAPNM)复合质子交换膜,并对其力学性能、尺寸稳定性、离子交换容量和质子传导率进行表征。结果表明,制备的复合膜具有良好的透明性和均匀性,且致密无明显缺陷,具有良好的相容性。复合膜的尺寸稳定性测试和力学性能测试结果表明,TAPNM的引入显著增强了复合膜的尺寸稳定性和力学性能。在TAPNM质量分数为5%左右时,可以有效提升复合膜的质子传导率,30℃条件下质子传导率达到53.19 mS/cm,是SPEEK膜的1.2倍。     

DMFCs用磺化聚醚醚酮/磺化酚酞型聚醚砜共混质子交换膜

A sulfonated poly(ether ether ketone) (SPEEK) membrane with fairly high degree of sulfonation (DS) swells excessively and even dissolves at high temperature. To solve these problems, sulfonated phenolphthalein poly(ether sulfone) (SPES-C, DS 53.7%) is blended with the SPEEK matrix (DS 55.1%, 61.7%) to prepare SPEEK/SPES-C blend membrane. The decrease in swelling degree and methanol permeability of the membrane is dose-dependent. Pure SPEEK (DS 61.7%) membrane dissolves completely in water at 70ºC, whereas the swelling degree of the SPEEK (DS 61.7%)/SPES-C (40%, by mass) membrane is 29.7% at 80ºC. From room temperature to 80ºC, the methanol permeability of all SPEEK (DS 55.1%)/SPES-C blend membranes is about one order of magnitude lower than that of Nafion®115. At higher temperature, the addition of SPES-C polymer increases the dimensional stability and greater proton conductivity can be achieved. The SPEEK (DS 55.1%)/SPES-C (40%, by mass) membrane can withstand temperatures up to 150ºC. The proton conductivity of SPEEK (DS 55.1%)/SPES-C (30%, by mass) membrane approaches 0.16 S•cm－1, matching that of Nafion115 at 140ºC and 100% RH, while pure SPEEK (DS 55.1%) membrane dissolves at 90ºC. The SPEEK/SPES-C blend membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.     

Preparation and DMFC performance of a sulfophenylated poly(arylene ether ketone) polymer electrolyte membrane

A sulfonated poly(aryl ether ether ketone ketone) (PEEKK) having a well-defined rigid homopolymer-like chemical structure was synthesized from a readily prepared PEEKK by post-sulfonation with concentrated sulfuric acid at room temperature within several hours. The polymer electrolyte membrane (PEM) cast from the resulting polymer exhibited an excellent combination of thermal resistance, oxidative and dimensional stability, low methanol fuel permeability and high proton conductivity. Furthermore, membrane electrode assemblies (MEAs) were successfully fabricated and good direct methanol fuel cell (DMFC) performance was observed. At 2 M MeOH feed, the current density at 0.5 V reached 165 mA/cm, which outperformed our reported similarly structured analogues and MEAs derived from comparative Nafion^® membranes.     

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。     

Synthesis and characterization of partially fluorinated poly(fluorenyl ether ketone)s with different degrees of sulfonation as proton exchange membranes

Partially fluorinated poly(fluorenyl ether ketone)s with different degree of sulfonation were successfully synthesized by the sulfonation of the designed parent polymer. The sulfonation took place only at the specific (2, 7)-position on the fluorenyl groups due to the positions adjacent to the ether bond occupied by methyl groups. The sulfonated polymers are soluble in common organic solvents and can readily be cast into tough and smooth films from their solutions. The properties of proton conductivity, water uptake, thermal and oxidative stability for the membranes were investigated. It was found that the oxidative stability of the membrane decreased with increasing the degree of sulfonation. However, the partially fluorinated membrane with high degree of sulfonation exhibited better oxidative stability compared to the non-fluorinated analogy with low degree of sulfonation. The proton conductivity of the membranes increased with increasing the degree of sulfonation and temperature. Moreover, the membranes also showed good thermal and hydrolytic stabilities.     

DMFCs用SPEEK/SiOx-S复合质子交换膜

A sulfonated poly(ether ether ketone) (SPEEK) membrane with a fairly high degree of sulfonation (DS) can swell excessively and even dissolve at high temperature. To solve these problems, insolvable functionalized silica powder with sulfonic acid groups (SiOx-S) was added into the SPEEK matrix (DS 55.1%) to prepare SPEEK/ SiOx-S composite membranes. The decrease in both the swelling degree and the methanol permeability of the membranes was a dose-dependent result of addition of the SiOx-S powder. Pure SPEEK membrane swelled 52.6% at 80°C, whereas the SPEEK/SiOx-S (15%, by mass) membrane swelled only 27.3% at the same temperature. From room temperature to 80℃, all SPEEK/SPEEK/SiOx-S composite membranes had methanol permeability of about one order of magnitude lower than that of Nafion115. Compared with pure SPEEK membranes, the addition of the SiOx-S powder not only leads to higher proton conductivity, but also increases the dimensional stability at higher temperatures, and greater proton conductivity can be achieved at higher temperature. The SPEEK/SiOx-S (20%, by mass) membrane could withstand temperature up to 145°C, at which in 100% relative humidity (RH) its proton conductivity exceeded slightly that of Nafion115 membrane and reached 0.17 S•cm－1, while pure SPEEK mem-brane dissolved at 90°C. The SPEEK/SiOx-S composite membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.     

直接甲醇燃料电池用新型质子交换膜的研究

以聚醚醚酮(PEEK)为原料,浓硫酸为磺化剂制备了不同磺化度的磺化聚醚醚酮(SPEEK)膜,以及磺化聚醚醚酮与聚乙烯醇(PVA)、正硅酸乙酯(TEOS)、磷钨酸的复合膜.分别对膜的电导率、阻醇性能和吸水率进行了研究.随着SPEEK膜磺化度的增大,膜的电导率有所提高,然而甲醇渗透系数也增大,膜的机械强度明显降低.SPEEK膜的吸水率低于Nafion 115膜,而PVA膜的吸水率则过高.     

Sulfonated poly(arylene ether ketone)s prepared by direct copolymerization as proton exchange membranes: Synthesis and comparative investigation on transport properties

Sulfonated poly(aryl ether ketone)s (SPAEK) copolymers were synthesized by aromatic nucleophilic polycondensation from 3,3′, 5,5′‐tetramethyl‐4, 4′–biphenol, 1,4‐bis(4‐fluorobenzoyl) benzene, and disulfonated difluorobenzophenone. The SPAEK membranes did not exhibit excessive swelling in hot water and at the same time show the proton conductivities in the range of 0.030 S/cm to 0.099 S/cm at 80°C. The methanol diffusion coefficients of the SPAEK membranes were in the range of 4.7 × 10^?7 to 8.1 × 10^?7cm²/s measured at 25°C. The transport properties of this series of SPAEK copolymers were compared to poly(aryl ether ether ketone)s (SPEEK), poly(aryl ether ether ketone ketone)s (SPEEKK), and Nafion® membranes. It was found that the transport properties (including proton conductivity and methanol permeability) follows the trend of SPEEKK‐60 < SPAEK‐60 < SPEEK‐60 < Nafion® 117, the order of which is also attributed to the differences in the chemical structure of the polymers and the membrane morphology. In general, this novel series of SPAEK membranes possess various advantages, such as low cost of the initial monomers, high thermal and mechanical stability, and low methanol permeability while simultaneously possessing sufficient proton conductivity, which makes them notably promising as proton exchange membrane (PEM) materials in direct methanol fuel cell (DMFC) applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

质子交换膜燃料电池用磺化聚醚醚酮膜的研究进展

Nafion膜具有优良的化学稳定性和导电性能,但是它成本高,高温下几乎不导电。本文回顾了Nafion替代膜之一——磺化聚醚醚酮（SPEEK）膜及SPEEK/离子液体（IL）复合膜的研究进展。介绍了SPEEK制备的两种方法：直接磺化法和磺化单体聚合法,其中直接磺化法工艺简单,但磺化度（DS）≤1.0,反应较难控制;磺化单体聚合法DS可控,但工艺复杂,原料有毒。简述了温度、反应时间、原料配比、磺化单体种类、制膜工艺及溶剂对SPEEK膜性能的影响：直接磺化法中DS与温度成负相关,与反应时间成正相关,与原料配比关系不大;磺化单体聚合法中DS受磺化单体的种类和氟酮与磺化氟酮的比例影响较大。着重介绍了SPEEK/咪唑离子液体复合膜和SPEEK/季铵盐离子液体复合膜的研究现状及应用于质子交换膜燃料电池（PEMFC）时存在的问题。最后对SPEEK/IL复合膜未来的研究方向进行了展望,即解决燃料电池运行过程中复合膜中离子液体流失及与Pt基催化剂相容性等关键问题,以提高PEMFC的性能。     

Synthesis and characterization of sulfonated fluorene-containing poly(arylene ether ketone) for high temperature proton exchange membrane

A novel fluorene-containing poly(arylene ether ketone) were synthesized followed by sulfonating into a series of sulfonated fluorene-containing poly(arylene ether ketone)s using chlorosulfonic acid. The sulfonated polymers were thereafter cast into membranes from their solutions. The properties of the ionic exchange capacity, sulfonation degree, water-uptake, mechanical properties, thermal and oxidative stabilities as well as proton conductivities of the membranes were fully investigated. It was found that their proton conductivities increased continuously with increasing testing temperature up to 130 °C at 100% relative humidity. The membrane exhibited a higher proton conductivity and other comprehensive properties for proton exchange membrane than Nafion-117 at 130 °C under same testing conditions.