燃料电池高温质子交换膜研究进展

高温质子交换膜燃料电池具有反应动力学快、CO耐受性高等特点,但磷酸掺杂的高温质子交换膜因磷酸的流失和聚合物的降解等原因导致燃料电池的输出功率发生衰减。本文通过介绍聚苯并咪唑衍生物的高温质子交换膜、聚苯并咪唑的复合型质子交换膜、新型芳基聚合物的高温质子交换膜,阐明聚合物的主链结构、官能团结构以及复合填料对高温质子交换膜性能的影响。在近期的研究报道中,提高膜性能的主要策略包括提升自由体积、建立交联结构、嵌段共聚、复合掺杂（ILs、MOFs、PIMs、MO_x）、阳离子官能团修饰等。文章指出,在未来的研究中应该加强对磷酸基高温质子交换膜质子传输通道结构的进一步理解,关注聚合物化学降解和物理性能衰败的原因,并开发更多的新型聚合物材料。     

A modified poly(aryle ether ketone sulfone) proton exchange membrane with in situ polymerized polypyrrole for the direct methanol fuel cells

Bone tissue interfacial scaffolds, which encourage cell growth, are critical determinants for clinical success after implant surgery. Over the years, a number of resorbable configurations have emerged for bone cell support and growth, but only a few have demonstrated clinical efficacy. Polymer coatings produced by electrospinning are regarded as very promising bone interfaces because of the ultrathin‐scaled dimensions of its physical structure. In this study, the morphology, composition, thermal properties, and cell growth viability of a number of polylactide‐based systems containing different binary and ternary formulations of this biomaterial with collagen and commercial hydroxyapatite nanoparticles were characterized. The best performance in terms of biocompatibility was obtained for the tricomponent system in which the submicron fibers were further subjected to uniaxial orientation process during formation. The in vitro proliferation of the cells, which harbored on these ultrathin‐structured mats, was examined by means of a metabolic activity indicator and ensured by means of scanning electron microscopy, and cell anchorage was checked by fluorescent optical microscopy. Finally, the optimum tricomponent material was successfully sterilized for the first time by gamma radiation without noticeable losses in cell‐seeding capacity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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。     

Preparation and characterization of poly(vinylidene fluoride)/sulfonated poly(phthalazinone ether sulfone ketone) blends for proton exchange membrane

Poly(vinylidene fluoride)/sulfonated poly(phthalazinone ether sulfone ketone) (PVdF/SPPESK) blend membranes are successfully prepared by solution blending method for novel proton exchange membrane (PEM). PVdF crystallinity, FTIR‐ATR spectroscopy, thermal stability, morphology, water uptake, dimension stability, and proton conductivity are investigated on PVdF/SPPESK blends with different PVdF contents. XRD and DSC analysis reveal that the PVdF crystallinity in the blends depends on PVdF content. The FTIR‐ATR spectra indicate that SPPESK remains proton‐conducting function in the blends due to the intactness of ? SO₃H group. Thermal analysis results show a very high thermal stability (T_d1 = 246–261°C) of the blends. PVdF crystallinity and morphology study demonstrate that with lower PVdF content, PVdF are very compatible with SPPESK. Also, with lower PVdF content, PVdF/SPPESK blends possess high water uptake, e.g., P/S 10/90 and P/S 15/85 have water uptake of 135 and 99% at 95°C, respectively. The blend membranes also have good dimension stability because the swelling ratios are at a fairly low level (e.g., 8–22%, 80°C). PVdF/SPPESK blends with low PVdF content exhibit very high proton conductivity, e.g., at 80°C, P/S 15/85 and P/S 10/90 reach 2.6 × 10^?2 and 3.6 × 10^?2 S cm^?1, respectively, which are close to or even higher than that (3.4 × 10^?2 S cm^?1) of Nafion115 under the same test condition. All above properties indicate that the PVdF/SPPESK blend membranes (particularly, with 10–20% of PVdF content) are very promising for use in PEM field. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Sulfonated (graphene oxide/poly(ether ketone ether sulfone) (S-GO/S-PEKES) composite proton exchange membrane with high proton conductivity for direct methanol fuel cell

ABSTRACT

Sulfonated poly(ether ketone ether sulfone) (S-PEKES) was successfully prepared to obtain the currently highest degree of sulfonation of 0.744. Sulfonated graphene oxide (S-GO) was incorporated into the S-PEKES matrix to increase sulfonic groups (SO₃H) which significantly improved the proton conductivity, methanol blocking, and mechanical stability. The proton conductivity of the S-GO/S-PEKES composite membrane was enhanced up to 5.93 × 10^?2 S.cm^?1, which was 7 times higher than the commercial Nafion 117. S-GO exhibited additional positive effects namely the blocking of methanol passing through the membrane, leading to lower methanol crossover than Nafion 117 by two orders of magnitude and high mechanical stability.     

直接甲醇燃料电池用三羧基丁烷膦酸锆/磺化杂萘联苯聚醚酮复合质子交换膜

用高磺化度的磺化杂萘联苯聚醚酮（SPPEK）制备DMFC质子交换膜时,膜的机械强度会因过度溶胀而下降。通过在SPPEK（DS=61%）中掺杂1,2,4-三羧基丁烷-2-膦酸锆(Zr(PBTC)),我们制备出 Zr(PBTC)/SPPEK复合质子交换膜。实验表明, Zr(PBTC)的掺杂能有效降低膜的吸水量（溶胀）,并能减小膜的甲醇透过系数。80℃时,30wt.%Zr(PBTC) /SPPEK复合膜的吸水量与SPPEK膜比降低了30％。室温下复合膜的甲醇透过系数在10－7 cm2.s-1数量级上,比Nafion 115膜低一个数量级以上。液体甲醇溶液进料的DMFC单电池测试表明,30wt.%Zr(PBTC) /SPPEK复合膜的电池性能优于SPPEK的电池性能。     

Sulfonated polyether ether ketone composite proton exchange membranes incorporated with a novel hierarchical-structure hybrid nanofiller consisting solid superacid zirconium phosphate and CNTs

How to simultaneously improved the proton conductivity and mechanical strength is a key problem facing currently used proton exchange membranes (PEMs). Herein, a solid inorganic superacid-zirconium phosphate (ZrP) with a two-dimensional layer structure was combined with one-dimensional carbon nanotubes (CNTs) to prepare hybrid nanofiller ZrP-CNTs by an in situ chemical deposition method. The new hybrid nanofiller was then applied to modify sulfonated polyether ether ketone (SPEEK), a widely used PEM matrix, to obtain a series of composite membranes. The structure and properties of the membranes were fully characterized by SEM, XRD, FTIR, TG, tensile properties, and proton conductivity. The results showed that the proton conductivities of the membranes were significantly improved due to the addition of super solid acid-ZrP that has abundant proton sources or proton sites. Moreover, the composite membranes exhibited better mechanical properties and thermal stability than those of pure SPEEK membrane, owing to the great interface interaction and good compatibility between ZrP-CNTs and SPEEK. The composite membrane (2 wt% ZrP-CNTs) demonstrated the optimal comprehensive performance. Its proton conductivity was 36.63 mS cm⁻¹ and its tensile strength was 37.56 MPa, which was 70% and 10%, respectively, higher than those of the pure SPEEK membrane under the same condition.     

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 compositemembrane indicated its promising application inDMFC operations at high temperature. __________ Translated from Acta Polymerica Sinica, 2007, (4): 337–342 [译自:高分子学报]     

Preparation and properties of bisphenol A‐based sulfonated poly(arylene ether sulfone) proton exchange membranes for direct methanol fuel cell

Novel bisphenol A‐based sulfonated poly(arylene ether sulfone) (bi A‐SPAES) copolymers were successfully synthesized via direct copolymerization of disodium 3,3′‐disulfonate‐4,4′‐dichlorodiphenylsulfone, 4,4′‐dichlorodiphenylsulfone, and bisphenol A. The copolymer structure was confirmed by Fourier transform infrared spectra and ¹H NMR analysis. The series of sulfonated copolymers based membranes were prepared and evaluated for proton exchange membranes (PEM). The membranes showed good thermal stability and mechanical property. Transmission electron microscopy was used to obtain the microstructures of the synthesized polymers. The membranes exhibit increased water uptake from 8% to 66%, ion exchange capacities from 0.41 to 2.18 meq/g and proton conductivities (25°C) from 0.012 to 0.102 S/cm with the degree of sulfonation increasing. The proton conductivities of bi A‐SPAES‐6 membrane (0.10–0.15 S/cm) with high‐sulfonated degree are higher than that of Nafion 117 membrane (0.095–0.117 S/cm) at all temperatures (20–100°C). Especially, the methanol diffusion coefficients of membranes (1.7 × 10^?8 cm²/s–8.5 × 10^?7 cm²/s) are much lower than that of Nafion 117 membrane (2.1 × 10^?6 cm²/s). The new synthesized copolymer was therefore proposed as a candidate of material for PEM in direct methanol fuel cell. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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 %。     

Sulfonation of poly(phthalazinone ether sulfone ketone) by heterogeneous method and its potential application on proton exchange membrane (PEM)

A series of sulfonated PPESK (SPPESKs) were synthesized through a heterogeneous sulfonation process with fuming sulfuric acid as sulfonating agent in a chloroform solvent. Membranes prepared from SPPESKs were investigated and proved to be candidates of proton exchange membrane in fuel cell operating at high temperature and low humidity. The heterogeneous sulfonation reaction is verified to first occur on the interface of the acid phase and the chloroform phase, then went on in the acid phase. SPPESKs with sulfonation degree (DS) up to 2.0 are obtained through a new reprecipitation method. Effects of reaction temperature, reaction time, acid/polymer ratio, and chloroform/polymer ratio on the sulfonation reaction are reported in details. An increase in sulfonation degree results in the increase of hydrophilicity, bringing about a substantial gain in proton conductivity. SPPESK membranes exhibit high water uptake of about 105.4% with DS of 1.01, almost two times higher than that of Nafion® with similar dimensional variation. Conductivity values at 35°C, 60% R.H. ranging from 10^?3 to 10^?2 S/cm were measured, which are comparable to or higher than that of Nafion® 112 (1.635 × 10^?2 S/cm) under the same test condition. Thermogravimetric analysis shows that SPPESK membranes are stable up to 290°C in N₂. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1002–1009, 2007     

三羧基丁烷膦酸锆/SPPEK复合膜在高温不同湿度下电导率

磺化杂萘联苯聚醚酮（SPPEK）膜在温度高于100℃时会因严重失水而导致电导率急剧下降。为此，合成出具有较高电导率的吸湿性质子导体1，2，4-三羧基丁烷-2-膦酸锆［Zr（PBTC）］，并将其掺杂到SPPEK中制备出Zr（PBTC）/SPPEK复合膜。实验表明，Zr（PBTC）的掺杂能有效提高复合膜在高温低湿情况下的吸水能力，从而提高其电导率。SPPEK膜在120℃、相对湿度为40％情况下电导率仅有约10^-4 S·cm^-1，而相同条件下30% Zr（PBTC）/SPPEK复合膜的电导率达到2×10^-3 S·cm^-1。而且相对湿度越小，复合膜电导率的提高幅度越大，在相对湿度小于20%时，复合膜的电导率大约比SPPEK膜高两个数量级。     

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。     

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.     

Synthesis and characterization of poly(arylene ether sulfone)-b-polybenzimidazole copolymers for high temperature low humidity proton exchange membrane fuel cells

Multiblock copolymers based on poly(arylene ether sulfone) and polybenzimidazole (PBI) with different block lengths were synthesized by coupling carboxyl functional aromatic poly(arylene ethers) with ortho diamino functional PBI oligomers in NMP, selectively doped with phosphoric acid, and evaluated as a high temperature proton exchange membrane (PEM). Transparent and ductile membranes were produced by solvent casting from DMAc. From dynamic mechanical analysis (DMA), the neat copolymer membranes showed two distinct glass transition temperatures which implies the existence of a nanostructured morphology in the membranes. These two nanophases became more distinct with increasing block length. The membranes were immersed in various concentrations of phosphoric acid solution to produce the proton conductivity. The doping level increased with increasing concentration of the acid solution and a maximum doping level of 12 was achieved when 14.6 M phosphoric acid solution was used. The acid doped membranes showed significantly reduced swelling behavior compared to a control conventional phosphoric acid doped PBI homopolymer system which appears to be related to the selective sorption into the PBI phase. The ionic conductivity of the doped samples at 200 °C afforded up to 47 mS/cm without external humidification. The protonic conductivity was found to increase with block length at a given doping level, reflecting the sharpness of the nanophase separation and the effect was even more prominent at a low doping level of 6-7. It is suggested that the phosphoric acid doped multiblock copolymer system would be a strong candidate for high temperature and low relative humidity PEM applications such as those required for stationary power.     

Fabrication and characterization of sulfonated polybenzimidazole/sulfonated imidized graphene oxide hybrid membranes for high temperature proton exchange membrane fuel cells

The sulfonated polybenzimidazole (sPBI)/sulfonated imidized graphene oxide (SIGO) was evaluated to be a potential candidate for high temperature proton exchange membranes fuel cells (HT-PEMFCs). Multifunctionalized covalently bonded SIGO is incorporated in sPBI matrix to resolve the drawbacks such as low proton conductivity, poor water uptake, and ion-exchange capacity (IEC) of sPBI polymer, synthesized by direct polycondensation in phosphoric acid for the application of proton exchange membranes. Strong hydrogen bonding among multifunctional groups established a neighborhood of interconnected hydrophobic graphene sheets and organic polymer chains. It provides hydrophobic–hydrophilic phase separation and facile proton hopping architecture. The optimized sPBI/SIGO (15 wt %) revealed 2.45 meq g⁻¹ IEC; 5.81 mS cm⁻¹ proton conductivity [120 °C and 10% relative humidity (RH)] and 2.45% bound water content. The maximum power density of the sPBI/SIGO-15 membrane was 0.40 W cm⁻² at 160 °C (5% RH) and ambient pressure with stoichiometric feed of H₂/air. This recommends that sPBI/SIGO composite membranes are compatible candidate for HT-PEMFCs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47892.     

Oxygen permeation studies on alternative proton exchange membranes designed for elevated temperature operation

Kinetic and mass transport properties were investigated for the oxygen reduction reaction in Nafion 117 and a sulfonated poly (arylene ether sulfone) membrane (SPES-40, 40% sulfonated groups/repeat unit) under 1 atm oxygen pressure, 100% relative humidity in a temperature range of 303-343 K using a solid-state electrochemical cell. Kinetic parameters were obtained using slow-sweep voltammetry while mass transport parameters, the diffusion coefficient (D) and solubility (C), were obtained using chronoamperometry at a Pt (microelectrode)/proton exchange membrane (PEM) interface. Oxygen reduction kinetics was found to be similar for both Nafion® 117 and SPES-40 membrane at the Pt microelectrode interface. The temperature dependence of O₂ permeation parameters showed same trends for both the membranes studied, there was an increase in D and a concomitant decrease in C. Despite lower equivalent weight and hence higher water content SPES-40 exhibited relatively close values of D with Nafion® 117. The results are discussed in the context of their different microstructures. Values of C showed a closer relationship to water content and the percent volume of aqueous phase in the respective membranes. The values of overall oxygen permeability were significantly higher in Nafion® 117, with a higher positive slope in its variation with temperature.     

AB-PBI分子量对高温膜燃料电池膜电极性能的影响

聚合物分子量是表征聚合物特征的基本参数之一,分子量不同,聚合物的性能差异很大,其对高温质子交换膜燃料电池膜电极的输出性能亦起着至关重要的作用。聚（2,5-苯并咪唑）(ABPBI)的结构简单, 合成方便,可由单一单体聚合而成, 而且其每一个苯并咪唑重复单元上的-N 基团都可与酸以氢键的方式结合, 因而呈现较好的质子电导率。合成了4种不同分子量的ABPBI,采用自制ABPBI膜作为电解质,Pt/C为催化剂,研究了不同分子量ABPBI配制的浆料组装的氢氧高温燃料电池的性能,通过极化曲线测试可以看出聚合物分子量越小膜电极(MEA)性能越好。进一步对膜电极交流阻抗性质进行了研究,经Zsimpwin软件拟合得出,分子量越大电荷转移电阻越大,与极化曲线测试结果相符,并且随着电流密度的增大,各部分电阻均成下降趋势。     

全钒液流电池用磺化聚芴醚酮质子交换膜的制备及性能

质子交换膜(PEM)作为全钒液流电池(VRFB)的核心组件之一,应当解决成本高昂、合成过程复杂等问题,并具备高质子传导率、低钒离子渗透率、高机械强度和优异化学稳定性等关键性能。本文基于四甲基双酚芴单体通过缩聚反应合成了一系列聚芴醚酮化合物PFEKs,再利用溴代反应将苯甲基功能化为溴甲基,接着通过4-羟基苯磺酸钠的SN₂亲核取代制得了一系列不同离子交换容量的磺化聚芴醚酮聚合物(SPFEKs)。通过溶液浇铸法成膜并酸化,得到一系列新型低成本PEMs。该合成路线的原料来源广泛,价格低廉,不涉及危险的磺化反应,易于工业放大。所得膜都具有良好的机械性能和氧化稳定性,其中SPFEK-40膜具有较高的质子传导率及离子选择性、较低的钒离子渗透率及面电阻,综合性能优异。以SPFEK-40膜组装的VRFB在电流密度为80 mA/cm₂^{时的能量效率}(EE)为88.2%,高于以Nafion 212膜组装的VRFB的84.8%。此外,以SPFEK-40膜组装的VRFB在30次循环后放电容量仅衰减至84.3%,远高于以Nafion 212膜组装的VRFB的66.1%。