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。     

直接甲醇燃料电池用SPES/SiO_2复合膜的研究

采用溶胶-凝胶法成功制备出新型磺化聚醚砜(SPES)/二氧化硅(SiO_2)复合质子交换膜,并对复合膜的结构和性能进行了表征。结果表明,SiO_2在复合膜中分布十分均匀,并且由于SPES与SiO_2之间的氢键相互作用使复合膜的热稳定性明显提高。SiO_2的引入虽使得复合膜的质子传导率有所下降,但其阻醇性能得到了明显改善。     

基于微孔聚四氟乙烯的复合质子交换膜

研究了基于微孔聚四氟乙烯（PTFE）的复合方式,通过将自制ABPSH40树脂——N,N-二甲基乙酰胺溶液流延在用液相介质表面处理法改性过的聚四氟乙烯微孔膜表面上,制得了均匀的ABPSH40/PTFE 增强复合质子交换膜。采用扫描电镜（SEM）观察复合膜的表面及断面形态,采用气相色谱仪（GC）测定了复合膜的甲醇渗透性,利用交流阻抗（AC）测定了膜的质子传导率。结果表明,ABPSH40树脂在复合膜内分布均匀,而且PTFE膜微孔填堵充分;复合膜具有优越的尺寸稳定性,较低的甲醇渗透率和接近Nafion膜的质子传导率,和ABPSH40均质膜进行比较后的优点明显。ABPSH40/PTFE 增强复合质子交换膜可望成为一种直接甲醇燃料电池用质子交换膜。     

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%。     

原位合成法磷钨酸/聚乙烯醇质子交换膜的制备与性能研究

以原位合成法制备出磷钨酸/聚乙烯醇(PTA/PVA)质子交换膜.采用多功能材料实验机表征了膜的机械强度,使用交流阻抗谱和气相色谱仪研究了钨酸钠含量对PTA/PVA膜的质子导电性能和阻醇性能的影响.结果表明:钨酸钠加入后,随着钨酸钠含量的增加,PTA/PVA膜的质子电导率σ增大,机械性能得到了改善.与Nation膜的电导率和甲醇渗透率相比,Na2WO4·2H2O含量为15％的PTA/PVA膜的电导率增加了2.5倍,甲醇渗透率降低了一个数量级.     

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。     

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。     

一种新型磺化聚酰亚胺质子交换膜的合成与表征

质子交换膜是质子交换膜燃料电池膜电极的核心部件之一,它的性能好坏对整个系统的运行起着至关重要的作用．目前在质子交换膜燃料电池中普遍采用的质子交换膜材料是全氟磺酸系列薄膜,这类材料具有较高的质子传导率、化学及机械稳定性,但用于直接甲醇燃料电池（DMFC）时则存在甲醇渗透、导致燃料电池输出性能大大降低的问题     

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。     

多孔有机笼在聚丙烯腈纳米纤维表面固载及其复合质子交换膜

质子交换膜（PEM）是质子交换膜燃料电池的核心部件,需具备选择性地快速传递质子的特性。多孔有机笼具有高比表面积、良好的化学稳定性和高吸水特性以及三维连通的质子传递路径,可提升PEM的质子传导性能。本文将多孔有机笼（CC3）原位固载到聚丙烯腈（PAN）纳米纤维表面,与Nafion复合制备了CC3/PAN-Nafion复合质子交换膜,对其结构和性能进行了研究,结果表明：CC3的固载改变了纤维的微观形貌,增加了纤维直径,使纳米纤维比表面积从9.57m²/g增加到113.6m²/g;将CC3/PAN引入复合膜显著提升了CC3/PAN-Nafion的热稳定性、吸水性、阻醇性以及质子传导性能,其中CC3/PAN-Nafion12在100%RH,80℃时质子传导率可达0.165S/cm,较Nafion膜提升了一倍。     

聚吡咯修饰Nafion膜直接甲醇燃料电池的性能

用FeCl3化学氧化法制备了PPy/Nafion改性膜,采用浸渍-还原法在PPy/Nafion阴极侧上沉积Co金属,制得Co-PPy/Nafion电解质膜。采用TG、CV及交流阻抗谱测试了Nafion膜及改性膜的热稳定性,质子电导性和甲醇渗透性能,结果表明:PPy/Nafion及Co-PPy/Nafion改性膜具有更好的热稳定性和抗甲醇渗透性。分别以Co-PPy/Nafion改性膜、PPy/Nafion改性膜和纯Nafion膜为电解质膜,PtRu/C为阳极催化剂,Pt/C为阴极催化剂组装DMFC并考察其性能。实验结果表明:Co-PPy/Nafion改性膜组装单电池在高浓度甲醇及大电流密度的测试条件下,表现出更优异的电池性能。     

Sulfonated poly(ether sulfone)/phosphotungstic acid/attapulgite composite membranes for direct methanol fuel cells

Novel composite sulfonated poly(ether sulfone)(SPES)/phosphotungstic acid (PWA)/attapulgite (AT) membranes were investigated for direct methanol fuel cells (DMFCs). Physical–chemical properties of the composite membranes were characterized by FTIR, DSC, TGA, SEM‐EDX, water uptake, tensile test, proton conductivity, and methanol permeability. Compared with a pure SPES membrane, PWA, and AT doping in the membrane led to a higher thermal stability and glass transition temperature (T_g) as revealed by TGA and DSC. Tensile test indicated that lower AT content (3%) in the composite can significantly increase the tensile strength, while higher AT loading demonstrated a smaller contribution on strength. Proper PWA and AT loadings in the composite membranes can increase the proton conductivity and lower the methanol cross‐over. The proton conductivity of the SPES‐P‐A 10% composite membrane reached 60% of the Nafion 112 membrane conductivity at room temperature while the methanol permeability was only one‐fourth of that of Nafion 112 membrane. This excellent performances of SPES/PWA/AT composite membranes could indicate a potential feasibility as a promising electrolyte for DMFC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Modification of Nafion membranes with ternary composite materials for direct methanol fuel cells

Composite membranes for direct methanol fuel cells (DMFCs) were prepared by using Nafion115 membrane modification with polyvinyl alcohol (PVA), polyimide (PI) and 8-trimethoxysilylpropyl glycerin ether-1,3,6-pyrenetrisulfonic acid (TSPS). The performance of the composite membranes was evaluated in terms of water sorption, dimensional stability, thermal stability, proton conductivity, methanol permeability and cell performance. The proton conductivity was slightly decreased by 1-3% compared with Nafion115, which still kept the high proton conduction of Nafion115. The methanol permeability of Nafion/PI-PVA-TSPS composite membranes was remarkably reduced by 35-55% compared with Nafion115. The power density of DMFCs with Nafion/PI-PVA-TSPS composite membranes reached to 100 mW/cm², exceeding that with Nafion115 (68m W/cm²).     

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.     

Composite Proton Exchange Membranes of Sulfonated Poly(ether ketone ether sulfone) (S-PEKES) and Molecular Sieve With High Mechanical Strength for Direct Methanol Fuel Cell

Composite proton exchange membranes are prepared by solvent casting via the incorporation of molecular sieves 3A, 4A, and 5A into the sulfonated poly(ether ketone ether sulfone) (S-PEKES) at the sulfonation degree of 0.66, with varying the ratio at of 3%, 6%, 9%, and 12% v/v. The influences of type and amount of the molecular sieves on the proton conductivity, methanol permeability, structural, thermal, and mechanical stabilities of the membranes are investigated. The composite membranes are characterized by FTIR, TGA, LCR meter, and GC techniques. All properties of the composite membrane are compared with the pristine S-PEKES and Nafion 117 membrane.     

PWA/silica doped sulfonated poly(ether sulfone) composite membranes for direct methanol fuel cells

A novel sulfonated poly(ether sulfone) (SPES)/phosphotungstic acid (PWA)/silica composite membranes for direct methanol fuel cells (DMFCs) application were prepared. The structure and performance of the obtained membranes were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), water uptake, proton conductivity, and methanol permeability. Compared to a pure SPES membrane, PWA and SiO₂ doped membranes had a higher thermal stability and glass transition temperature (T_g) as revealed by TGA‐FTIR and DSC. The morphology of the composite membranes indicated that SiO₂ and PWA were uniformly distributed throughout the SPES matrix. Proper PWA and silica loadings in the composite membranes showed high proton conductivity and sufficient methanol permeability. The selectivity (the ratio of proton conductivity to methanol permeability) of the SPES‐P‐S 15% composite membrane was almost five times than that of Nafion 112 membrane. This excellent selectivity of SPES/PWA/silica composite membranes indicate a potential feasibility as a promising electrolyte for DMFC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

PWA-13X-CS复合质子交换膜的性能研究

用13X分子筛负载无机质子导体-磷钨酸,然后加入壳聚糖(CS)中制备得到PWA-13X-CS复合质子交换膜,对其进行扫描电镜表征,测试了其吸水率、溶胀度、质子导电率、甲醇渗透系数等性质。结果表明PWA-13X-CS复合质子交换膜溶胀度较小,机械性能较好,质子导电率明显高于壳聚糖空白膜,且随温度升高呈上升趋势,其质子导电活化能低于壳聚糖空白膜,甲醇渗透系数小于Nafion117膜。将其与同样添加负载磷钨酸的13X分子筛的聚酰亚胺复合膜及聚乙烯醇复合膜性能进行对比,结果表明PWA-13X-CS复合质子交换膜综合性能较优,在直接甲醇燃料电池中具有较好的应用潜力。