Modeling and optimization of sulfonated poly (ether ether ketone) nanofibrous proton exchange membranes with response surface methodology

The morphological control of proton conductive nanofibrous mat used in proton exchange membranes (PEMs) is a key issue to improve proton conductivity of PEMs. In this study, response surface methodology (RSM) was utilized to investigate the morphological characterizations of electrospun sulfonated poly (ether ether ketone) (SPEEK) nanofibrous membranes. The effects of electrospinning parameters namely solution concentration, applied voltage and tip to collector distance were studied on the average diameter, its standard deviation and the degree of alignment of SPEEK nanofibers. The adequacy of the response surface models was verified by the validation experiments. Optimized conditions were obtained to meet the desired status of collecting more uniform and finer nanofibers with improved alignment. After obtaining the significant factors and optimal test level, an additional optimization was conducted at different take‐up speeds to fabricate high‐grade aligned nanofibers. The resultant nanofibers had the diameter of 107 ± 22 nm at the optimum point which was in good agreement with the predicted response values. The highest degree of alignment was yielded at the take‐up speed of 8.8 m/s with the maximum second‐order orientation parameter of 0.869. Electrochemical spectroscopy analysis showed that the aligning of proton conductive nanofibers improved in‐plane proton conductivity about 67%. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers     

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.     

Solution‐blown SPEEK/POSS nanofiber–nafion hybrid composite membranes for direct methanol fuel cells

This study aims to develop novel hybrid composite membranes (NHMs) by impregnating Nafion solution into the porous sulfonated poly(ether ether ketone)/polyhedral oligomeric silsesquioxanes (SPEEK/POSS) nanofibers (NFs). The composite membrane was prepared by solution blowing of a mixture of SPEEK/POSS solution. The characteristics of the SPEEK/POSS NFs and the NHMs, including morphology, thermal stability, and performance of membrane as PEMs, were investigated. The performance of NHMs was compared with that of Nafion117 and SPEEK/Nafion composite membranes. Results showed that the introduction of POSS improved the proton conductivity, water swelling, and methanol permeability of membranes. A maximum proton conductivity of 0.163 S cm^?1 was obtained when the POSS content was 6 wt % at 80°C, which was higher than that of Nafion117 and SPEEK/Nafion. NHMs could be used as proton exchange membranes (PEMs) for fuel cell applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42843.     

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.     

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     

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(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     

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&#61650;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&#61650;115 membrane and reached 0.17 S&#8226;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.     

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.     

Novel polymer electrolyte membranes based on semi‐interpenetrating blends of poly(vinyl alcohol) and sulfonated poly(ether ether ketone)

In this work, the properties of novel ionic polymer blends of crosslinked and sulfonated poly(vinyl alcohol) (PVA) and sulfonated poly(ether ether ketone) (SPEEK) are investigated. Crosslinking and sulfonation of PVA were carried out using sulfosuccinic acid (SSA) in the presence of dispersed SPEEK to obtain semi‐interpenetrating network blends. PVA–SSA/SPEEK blend membranes of different compositions were studied for their ion‐exchange capacity, proton conductivity, water uptake, and thermal and mechanical properties. The hydrated blend membranes show good proton conductivities in the range of 10^?3 to 10^?2 S/cm. When compared with pure component membranes, the PVA–SSA/SPEEK blend membranes also exhibit improvement in tensile strength, tensile modulus, and delay in the onset of thermal and chemical degradation. Semi‐interpenetrating nature of the blends is established from morphology and dynamic mechanical analysis. Morphology of the membranes was studied using scanning electron microscopy after selective chemical treatment. The dynamic mechanical properties of the membranes are examined to understand the miscibility characteristics of the blends. The relative proportions of PVA and SPEEK and the degree of crosslinking of PVA–SSA are important factors in determining the optimum properties for the blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

全钒液流电池用SPEEK／PES共混膜的制备

通过将PES掺入高磺化度的SPEEK进行共混改性,采用流延法制备了一系列不同PES含量的SPEEK／PES共混膜,获得了SPEEK／PES共混膜的离子交换容、含水率、质子电导率等参数,特别测定了在全钒液流电池工作条件下钒（IV）离子渗透率。综合考察发现,当磺化温度为45℃,磺化时间控制为4h,得到SPEEK的DS为55％,掺入10％的PES,此时共混膜的电导率为0．08S／cm,钒（IV）离子渗透率为0．38×10^-6cm2／min,对钒（IV）离子选择性为Nation膜的5倍,含水率为35％,共混膜综合性能最好,基本满足全钒液流电池（VRB）的使用需求。     

Effects of microstructural functional polyaniline layers on SPEEK/HPW proton exchange membranes

In this study, a method is developed to fabricate sulfonated poly (ether ether ketone)/phosphotungstic acid‐polyaniline (SPEEK/HPW‐PANI) membranes by in situ polymerization of aniline for the purpose of decreasing the weight loss of HPW in the membranes. The synthesis involves the production of a SPEEK/HPW hybrid membrane followed by different layer of PANI coatings on the membrane surface, and subsequent treatment using drying in vacuum procedures. The scanning electronic microscopy images showed that HPW had good compatibility with SPEEK polymers and energy dispersive X‐ray spectroscopy revealed the successfully doping with HPW and polymerization of PANI. The surface of SPEEK/HPW‐PANI becomes more compact than that of SPEEK/HPW and pure SPEEK, which may lead to reduce the water uptake and swelling property. The proton conductivity was found for the SPEEK/HPW‐PANI‐5 composite membrane (91.53 mS/cm at 80°C) higher than that of pure SPEEK membrane (68.72 mS/cm at 80°C). Better thermal stability was determined in both SPEEK/HPW and SPEEK/HPW‐PANI membranes than pristine SPEEK membrane. Therefore, PANI is a good potential coating for organic–inorganic hybrid e.g. SPEEK/HPW membrane materials to improve their hydrothermal stable properties and SPEEK/HPW PANI is a material that shows promise as a proton exchange membranes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41033.     

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.     

Effect of clay modification on the structure and properties of sulfonated poly(ether ether ketone)/clay nanocomposites

Sulfonated poly(ether ether ketone) (SPEEK)/clay hybrid membranes were prepared using three types of commercially available clays, the sodium montmorillonite (IC), hydrophobic organo‐clay with long alkyl chains (OC), and organo‐clay with carboxylic acid end groups (HC). It was found that the SPEEK/HC hybrid membranes achieved the best clay dispersion, with the exfoliation of the clay nano‐platelets when the filler loading was < 10 wt%. The incorporation of the carboxylic acid groups in clay layers also improved the connectivity between the ionic clusters in the membrane, resulting in higher proton conductivity without compromising the dimensional stability of membranes. The selectivity higher than the pristine SPEEK membranes was obtained for the SPEEK/HC hybrid membranes at low filler loading (<10 wt%), with higher proton conductivity and similar methanol permeability. POLYM. COMPOS., 37:2632–2638, 2016. © 2015 Society of Plastics Engineers     

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。     

Basicity‐based screening of aniline derivative for composite proton exchange membranes

The aim of this study was to find a suitable aniline derivative to develop composite sulfonated poly(ether ether ketone) (SPEEK) membranes and detail evaluation of their physico‐ and electrochemical properties. The hypothesis was high basicity of the aniline derivatives could form good composite membranes with better physicochemical and electrochemical properties. To assess the basicity we measured the zeta potentials of the polymers and correlated them with ion‐exchange capacities, water uptakes, transport numbers, water‐diffusion coefficients, conductivities, and methanol permeabilities. The obtained values of zeta potentials at pH 7 were 6.52, ?14.66, ?25.17, and ?28 for SPEEK/polynaphthalene (PNAPH), SPEEK/polyanisidine (PANIS), SPEEK/polyaniline (PANI), and SPEEK/polyxylindine (PXYL), respectively supports the hypothesis and strongly suggests polyaniline derivative's basicity‐dependent properties. Of the four derivatives (PNAPH, PANIS, PANI, and PXYL), the SPEEK/PXYL composite membrane had the lowest methanol permeability of 1 × 10^?4 cm²/s and highest proton conductivity of 161 mS/cm. These values are far better than the neat SPEEK and SPEEK/PANI composite. The suitability of SPEEK/PXYL can be explained by the high basicity of the PXYL composite membrane, which leads to the formation of effective Debye spheres, meaning that the ionic complex can interact with surrounding hydronium ions and form hydrophilic channels resulting in high proton conductivity and low methanol permeability. These results suggest that SPEEK/PXYL is a highly suitable membrane for methanol fuel cells or other electrochemical applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43978.     

Sulphonated Poly(ether ether ketone) Proton Exchange Membranes for Fuel Cell Applications

Polymer electrolyte membrane fuel cells (PEMFCs) are promising new power sources for automotive and portable devices. Nafion® is the currently used membrane in PEMFCs. Although these membranes show high proton conductivity and excellent chemical stability, their high cost makes them unpractical for commercial purposes. Sulphonated poly(ether ether ketone) (SPEEK) ionomers were synthesized using chlorosulphonic acid as the sulphonating agent in dichloromethane medium. Homogeneous proton-conducting membranes were developed from the obtained SPEEK by solvent casting method. Membranes were assessed for their suitability in fuel cell applications. The extent of sulphonation was controlled by varying the reaction time, concentration of polymer, and concentration of sulphonating agent. The SPEEK membranes exhibit degree of sulphonation from 10 to 66%, ion exchange capacity from 0.29 to 1.92 meq/g and maximum water and methanol uptake up to 54 and 22%, respectively, at 25°C. The membranes were characterized by FTIR to confirm sulphonation, and DSC and TGA to investigate the thermal stability. The proton conductivities of such membranes were found to be excellent in the order of 10^?2 S/cm in the fully hydrated condition at room temperature as measured by impedance spectroscopy. The durability of the membranes was also tested. The study revealed the possibility of a cheaper alternative membrane for use in PEMFC.     

Hydrophilic TiO2 decorated carbon nanotubes/sulfonated poly(ether ether ketone) composite proton exchange membranes for fuel cells

Sulfonated poly(ether ether ketone) (SPEEK) is currently considered to be one of the most potential candidates of commercial perfluorinated sulfonic acid proton exchange membranes. To balance the proton conductivity and mechanical properties of SPEEK, nano TiO₂ coated carbon nanotubes (TiO₂@CNTs) were prepared using a benzyl alcohol-assisted sol-gel method and then used as a new nanofiller to modify SPEEK to prepare SPEEK/TiO₂@CNTs composite membranes. The thick insulated TiO₂ coating layer can effectively avoid the risk of electronic short-circuiting formed by CNTs, while the hydrophilicity of TiO₂ can also reduce the polar difference between CNTs and SPEEK matrix, thus promoting the homogeneous dispersion of CNTs in the composites. As a result, the composite membranes demonstrated simultaneously improved strength and proton conductivity. Incorporating 5 wt% of TiO₂@CNTs exhibited 31% growth in mechanical strength when compared with pure SPEEK. Moreover, the maximum conductivity was 0.104 S cm⁻¹ (80°C) for the composite membrane with 5 wt% of TiO₂@CNTs, which was nearly twice as high as that of SPEEK membrane (0.052 S cm⁻¹).     

Preparation and investigation of acid–base composite membranes with modified graphitic carbon nanosheets for direct methanol fuel cells

The ethylenediamine-modified graphite oxide (EGO)-doped sulfonated poly (arylene ether ketone) (SPEEK) composite membranes have been prepared and developed for fuel cell applications in the present work. The base-modified EGO improves the dispersion of inorganic nanosheet in the polymer matrix and enhances proton conductivity by creating continuous conduction pathways. Furthermore, the methanol barrier property also be enhanced due to the nanosheet block the methanol-transport channels. EGO-filled membranes display improved dimensional stability, proton conductivity, and ethanol permeability than those using SPEEK control and graphite oxide (GO)-filled membranes. In the direct methanol fuel cells (DMFCs), the SPEEK/EGO-1.5 membrane displays the highest current density of 395.9 mA/cm² at 60°C, which is 1.6- and 1.4-fold higher than that of SPEEK (254.0 mA/cm²) and SPEEK/GO membrane (292.6 mA/cm²).     

高质子传导率及尺寸稳定性复合质子交换膜制备及性能研究

通过2?丙烯酰胺?2?甲基丙磺酸（AMPS）在1种具有多孔结构的金属有机骨架（MOF）UiO?66?NH₂中聚合,获得UiO?66?NH₂/PAMPS杂化填料后将其加入磺化聚醚醚酮（SPEEK）中制备纳米复合质子交换膜,并对纳米填料和膜性能进行了测试和表征。其中,UiO?66?NH₂/PAMPS中MOF组分的有序孔洞能够为质子提供较为快速的传输通道,同时PAMPS组分上的磺酸基团则为这些通道提供了额外的质子传输位点,从而促进了复合膜中的质子传导。结果表明,填料与基体之间的强静电相互作用使复合膜的溶胀率有所下降;当填料含量达到6 %（质量分数,下同）时,复合膜的质子电导率（σ）从0.040 S/cm 提升到0.057 S/cm,比纯SPEEK高42.5 %,而溶胀率由29 %下降到23 %。