磺化聚醚醚酮的合成及其性能表征

采用浓硫酸作为磺化剂,利用两种不同分子量的聚醚醚酮(PEEK)制备了具有不同磺化度的磺化聚醚醚酮(SPEEK)膜,用FTIR 和DSC对SPEEK进行了表征,通过质子交换容量(IEC)对磺化度进行了测定,并对SPEEK膜的质子导电性能进行了研究.结果表明,质子交换容量(IEC)与磺化度均随着反应时间的延长而增大,吸水率也随磺化度的增加而增大.     

SPEEK/B-SPEEK共混质子交换膜的制备及其性能

聚醚醚酮进行磺化,得到了磺化聚醚醚酮(SPEEK),再先后与氯化亚砜和对甲苯磺酰胺反应,制备侧链含磺酰亚胺基的聚醚醚酮(B-SPEEK)。将SPEEK和B-SPEEK以不同的比例共混制备质子交换膜,研究了共混膜的结构、质子交换容量、吸水率、电导率、力学性能和热性能等。结果表明:SPEEK与B-SPEEK按质量比为1.0∶1.0制备的共混膜具有较好的力学性能(拉伸强度25.3 MPa,断裂伸长率45.1%)和最高的电导率(在80℃的条件下,电导率为0.227 S/cm),是一类非常有潜力的质子交换膜。     

离子液体修饰磺化聚醚醚酮作为离子交换膜

通过NaBH₄还原磺化聚醚醚酮(SPEEK)得到羟基功能化的SPEEK后,采用酯化反应将离子液体1-羧甲基-3-甲基咪唑氯盐接枝到磺化聚醚醚酮上得到接枝聚合物。实验结果表明：离子液体修饰后的磺化聚醚醚酮离子交换膜吸水率和溶胀度降低,而导电率得到了显著提高。     

磺化聚醚醚酮共混膜的制备及其特性的研究

通过溶液共混的方法,以磺化聚醚醚酮(SPEEK)和聚醚砜(PES)为原料,N,N-二甲基甲酰胺(DMF)为溶剂,制备了一系列不同比例的SPEEK与PES的共混膜,并研究了膜的组成对膜的吸水率、电导率、甲醇渗透系数的影响,与目前所使用的Nafion117膜相比,这种共混膜既可以提高阻醇性能,同时又具有一定的电导率。     

SPEEK/改性MWCNT复合质子交换膜的制备与性能

制备了带有柔性有机侧链的改性碳纳米管(MWCNT-G),并与磺化聚醚醚酮(SPEEK)共混制得复合膜。扫描电镜(SEM)分析结果表明,MWCNT-G比原始MWCNT在SPEEK中分散更均匀。在1%的掺杂比例下对比分析了SPEEK/MWCNT膜及SPEEK/MWCNT-G膜的质子传导率、吸水率、溶胀度、机械性能、化学稳定性、热稳定性等。SPEEK/MWCNT-G膜未降低吸水率却降低了溶胀度,在机械强度及稳定性上均有所提高。SPEEK/MWCNT-G膜质子传递阻力更低,60℃时其质子传导率达0. 086 S/cm,是SPEEK/MWCNT膜的1. 46倍、SPEEK膜的1. 72倍。该方案使MWCNT与SPEEK相容性差的状况得以改善。     

聚醚砜/磺化聚醚醚酮共混膜的制备和性能

采用流延法制备了聚醚砜(PES)含量不同的PES/磺化聚醚醚酮(SPEEK)共混膜。PES与SPEEK具有良好的相容性。所制备PES/SPEEK共混膜的含水率、溶胀度和甲醇透过系数均随PES含量的增加而降低。虽然共混膜的质子传导性能有所降低.但阻醇性能和溶胀性能提高,这说明PES/SPEEK共混膜是一种很好的直接甲醇燃料电池用固体高分子电解质膜材料。     

磺化聚醚醚酮纳米纤维膜的制备及其吸附性能

通过静电纺丝法制备了不同磺化度的磺化聚醚醚酮(SPEEK)纳米纤维膜,运用扫描电镜、热重分析仪分别对纤维的形貌和热性能进行了分析,并利用紫外-可见分光光度计研究了纤维膜对亚甲基蓝染料的吸附行为。结果表明:随着磺化度的增加,纺丝束流的稳定性得到改善,纤维直径减小;纤维膜对亚甲基蓝具有良好的吸附能力,在p H值=7时其对亚甲基蓝的去除率最大,平衡吸附时间约为90min;热力学分析表明,使用Freundlich模型描述SPEEK纳米纤维膜对亚甲基蓝的吸附行为更加合理;动力学分析表明,SPEEK纳米纤维膜对亚甲基蓝的吸附遵循准二级动力学模型。     

磺化聚醚醚酮/接枝多壁碳纳米管复合膜的制备与表征

以浓硫酸为磺化剂,室温下制备了磺化聚醚醚酮(SPEEK)。以N,N-二环己基碳酰亚胺(DCC)为催化剂,将对氨基苯磺酸接枝到多壁碳纳米管(MWCNTs)的表面。采用溶液共混法制备了SPEEK/g-MWCNTs复合膜。采用傅里叶变换红外光谱仪(FT-IR)分析了复合膜的化学结构,采用光学显微镜以及扫描电子显微镜(FESEM)观察了膜的表面和断面结构,并采用交流阻抗法考察了膜的质子传导性能。结果表明:碳纳米管在复合膜中分散均匀,树脂基体包覆在碳管表面,复合膜的质子传导性和拉伸强度均优于磺化聚醚醚酮纯膜。     

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。     

BaCe0.8Al0.2O3掺杂的SPEEK复合质子交换膜制备与性能1

针对普通磺化聚醚醚酮(SPEEK)膜质子传导率较低的问题,提出无机掺杂的改善方法.采用共沉淀法制备BaCe0.8Al0.2O3复合氧化物,将其掺杂到SPEEK膜基体中,并通过溶液浇铸法制得了SPEEK/BaCe0.8Al0.2O3复合质子交换膜.对复合膜的尺寸稳定性、氧化稳定性、力学性能、质子传导率及微观形貌等进行了测...     

Proton conducting membranes based on sulfonated poly(ether ether ketone)/TiO2 nanocomposites for a direct methanol fuel cell

This paper presents an evaluation of the effects of titanium dioxide nanoparticles in sulfonated poly(ether ether ketone) (SPEEK) with a sulfonation degree of 57%. A series of inorganic/organic hybrid membranes was prepared with a systematic variation of titanium dioxide nanoparticle content. Their water uptake, methanol permeability and proton conductivity as a function of temperature were investigated. The results obtained show that the inorganic oxide network decreases the proton conductivity and water swelling. It is also found that increasing the inorganic oxide content leads to a decrease of methanol permeability. In terms of morphology, the membranes are homogeneous and exhibit good adhesion between inorganic domains and the polymer matrix. The proton conductivity and fuel cell performances of the nanocomposite membranes showed very good prospective in direct methanol fuel cell usages. The properties of the composite membranes are compared with those of standard Nafion membranes. Copyright © 2006 Society of Chemical Industry     

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.     

Effect of dispersion state of Cloisite15A® on the performance of SPEEK/Cloisite15A nanocomposite membrane for DMFC application

The introduction of 2,4,6‐triaminopyrimidine (TAP) into sulfonated poly(ether ether ketone) (SPEEK)/Cloisite15A® nanocomposite membranes were investigated for the purpose of maintaining low methanol permeability and suppressing swelling in direct methanol fuel cell (DMFC). SPEEK with 63% of degree of sulfonation (DS) was prepared by sulfonation of PEEK. Cloisite15A (7.5 wt %) along with various weight loading of TAP was incorporated into SPEEK matrix via solution intercalation method. The effect of TAP loading on the SPEEK/Cloisite15A/TAP morphology was studied. The beneficial impact of the SPEEK/Cloisite15A/TAP morphology on the physicochemical properties of the membrane was further discussed. Swelling behavior, ion exchange capacity (IEC), proton conductivity, and methanol permeability of the resultant membranes were determined as a function of Cloisite15A and TAP loadings. Uniform distribution of Cloisite15A particles in the SPEEK polymer matrix in the homogenous SPEEK/Cloisite15A/TAP nanocomposite membranes was confirmed by scanning electron microscopy and X‐ray diffraction. The water uptake of the SPEEK nanocomposite membranes decreased dramatically in the presence of TAP. The significant selectivity of SP/7.5/7.5 nanocomposite membranes could indicate a potential feasibility as a promising electrolyte for DMFC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

非溶剂对浇铸SPEEK膜性能的影响

首次采用磺化聚醚醚酮/N,N-二甲基甲酰胺(SPEEK/DMF)和非溶剂(四氯乙烯或对二甲苯)组成的铸膜液制备了SPEEK膜.采用交流阻抗法和隔膜扩散法分别考察了膜的质子传导性和透水性能.结果表明,由于在SPEEK/DMF中添加非溶剂,膜的透水率增加了约30％,质子导电率提高了50％左右.非溶剂的加入影响了铸膜液中聚合物的形态、尺寸和团聚情况,从而影响了成膜后膜的性能.本研究提出的控制膜微相结构的新方法将有助于提高SPEEK膜燃料电池性能.     

Proton conducting blend membranes: physical,morphological and electronic properties

Blend membranes of sulfonated poly(ether ether ketone) (SPEEK) and sulfonated polyetherimide (SPEI) have been prepared and investigated as a potential polymer electrolyte membrane (PEM) for direct methanol fuel cell (DMFC). Polymers were dissolved in N-methyl-2-pyrrolidone (NMP) in different mixing ratios and membranes were casted using a semi-automatic casting machine on a pre-cleaned glass plate. The influence of SPEI percentage on ion exchange capacity (IEC), water uptake, methanol permeability and proton exchange capacity have been investigated. Blend membranes showed slightly better IEC, water uptake and methanol crossover properties as compare to pure SPEEK; but proton conductivity was slightly lower than that of pure SPEEK membrane. Membrane morphology was investigated by FESEM, TGA and AFM. Overall, a homogeneous surface was observed for most of the blend membranes, with minor phase separation at higher SPEI contents samples. AFM image of the membrane surface shows nanoscale surface roughness.     

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.     

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.     

Sulfonated poly(ether ether ketone)/zirconium tricarboxybutylphosphonate composite proton-exchange membranes for direct methanol fuel cells

Sulfonated poly(ether ether ketone) (SPEEK) is a very promising alternative membrane material for direct methanol fuel cells. However, with a fairly high degree of sulfonation (DS), SPEEK membranes can swell excessively and even dissolve at high temperature. This restricts membranes from working above a high tolerable temperature to get high proton conductivity. To deal with this contradictory situation, insolvable zirconium tricarboxybutylphosphonate (Zr(PBTC)) powder was employed to make a composite with SPEEK polymer in an attempt to improve temperature tolerance of the membranes. SPEEK/Zr(PBTC) composite membranes were obtained by casting a homogeneous mixture of Zr(PBTC) and SPEEK in N,N-dimethylacetamide on a glass plate and then evaporating the solvent at 60°C. Many characteristics were investigated, including thermal stability, liquid uptake, methanol permeability and proton conductivity. Results showed significant improvement not only in temperature tolerance, but also in methanol resistance of the SPEEK/Zr(PBTC) composite membranes. The membranes containing 30 wt-% ∼ 40 wt-% of Zr(PBTC) had their methanol permeability around 10^-7 cm²·s^-1 at room temperature to 80°C, which was one order of magnitude lower than that of Nafion ^¯115. High proton conductivity of the composite membranes, however, could also be achieved from higher temperature applied. At 100% relative humidity, above 90°C the conductivity of the composite membrane containing 40 wt-% of Zr(PBTC) exceeded that of the Nafion ^¯115 membrane and even reached a high value of 0.36 S·cm^-1 at 160°C. Improved applicable temperature and high conductivity of the composite membrane indicated its promising application in DMFC operations at high temperature.     

Mass transport of direct methanol fuel cell species in sulfonated poly(ether ether ketone) membranes

Homogeneous membranes based on sulfonated poly(ether ether ketone) (sPEEK) with different sulfonation degrees (SD) were prepared and characterized. In order to perform a critical analysis of the SD effect on the polymer barrier and mass transport properties towards direct methanol fuel cell species, proton conductivity, water/methanol pervaporation and nitrogen/oxygen/carbon dioxide pressure rise method experiments are proposed. This procedure allows the evaluation of the individual permeability coefficients in hydrated sPEEK membranes with different sulfonation degrees. Nafion^® 112 was used as reference material. DMFC tests were also performed at 50 °C. It was observed that the proton conductivity and the permeability towards water, methanol, oxygen and carbon dioxide increase with the sPEEK sulfonation degree. In contrast, the SD seems to not affect the nitrogen permeability coefficient. In terms of selectivity, it was observed that the carbon dioxide/oxygen selectivity increases with the sPEEK SD. In contrast, the nitrogen/oxygen selectivity decreases. In terms of barrier properties for preventing the DMFC reactants loss, the polymer electrolyte membrane based on the sulfonated poly(ether ether ketone) with SD lower or equal to 71%, although having slightly lower proton conductivity, presented much better characteristics for fuel cell applications compared with the well known Nafion^® 112. In terms of the DMFC tests of the studied membranes at low temperature, the sPEEK membrane with SD = 71% showed to have similar performance, or even better, as that of Nafion^® 112. However, the highest DMFC overall efficiency was achieved using sPEEK membrane with SD = 52%.