有机-无机杂化材料制备质子交换膜的研究进展

综述了近年来采用有机-无机杂化材料制备质子交换膜的研究进展，重点介绍了由掺入了质子导电单元或经过磺化的有机-无机杂化材料制得的质子交换膜及由带磺酸基的有机硅通过溶胶-凝胶工艺制备的有机-无机杂化质子材料制得的交换膜，并从制备方法出发分析了每种质子交换膜的性能。     

交联质子交换膜研究进展

交联是近年来在质子交换膜改性中广泛使用的方法之一,交联可有效控制质子交换膜的水溶胀性,降低膜的甲醇渗透率.增加膜的耐久性,提高膜的力学性能等.作者对质子交换膜的交联方法进行了概述,重点分类讨论了共价交联,离子交联,矗子-共价交联和互穿结构交联,并对其研究进展进行了综述.     

A new synthesis approach for proton exchange membranes based on ultra-high-molecular-weight polyethylene

A new approach for gas-phase modification of ultra-high-molecular-weight polyethylene (UHMWPE) film for synthesis of proton exchange membranes (PEMs) has been successfully realized. First, the membrane precursors have been prepared by soaking the films in a monomers/AIBN solution followed by their modification with polystyrene (PS) in styrene vapor at 110°C. The developed method is characterized by high efficiency, simplicity, and ecological purity. The modified UHMWPE films containing up to 60 wt% of PS have been obtained. Then, PEMs were prepared by sulfonation of these precursors. According to energy-dispersive X-ray spectroscopy of the sulfonated samples, almost uniform distribution of PS through the film thickness was observed. The membranes with an ion exchange capacity up to 2.7 mmol/g and proton conductivity up to 60 mS/cm (water, 25°C) were obtained. Comparative tests of the obtained UHMWPE-sulfonated PS and commercial Nafion-115 membranes in a hydrogen–air fuel cell have been carried out. It has been shown that the cell with the synthesized membranes exhibits better performance than that with Nafion-115.     

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。     

Preparation of proton exchange membranes based on crosslinked polytetrafluoroethylene for fuel cell applications

We prepared proton exchange membranes by the γ-ray-induced post grafting of styrene into crosslinked polytetrafluoroethylene (PTFE) films and subsequent sulfonation. The degree of grafting was controlled in the range of 7-75% by the crosslinking density of the PTFE matrix as well as the grafting conditions. Under our preparation conditions, the films at the grafting yield of ≥30% were found to produce ion exchange membranes with a homogeneous distribution of sulfonic acid groups. The resulting membranes showed a large ion exchange capacity up to 2.9 meq g⁻¹, which exceeded the performance of commercially available perfluorosulfonic acid films such as Nafion; nevertheless, they appeared to be dimensionally stable in water. These should undoubtedly result from the use of the crosslinked PTFE films as graft substrates and make our ion exchange membranes promising for applications to polymer electrolyte fuel cells.     

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.     

高温质子交换膜研究进展

高温质子交换膜燃料电池（HT-PEMFCs）因其具有催化剂CO耐受性良好,能量转化率高,水热管理简单等优点,成为了能源领域重要的研究方向之一。高温质子交换膜（HTPEM）是它的主要部件之一,分别以水、磷酸分子和咪唑分子为质子传导载体分析了目前HTPEM的研究现状,比较后得出了以磷酸为质子载体的HTPEM性能最佳的结论,指出了研究中尚存的问题,并展望了未来HTPEM可能的研究方向。     

Electro-osmotic drag of methanol in proton exchange membranes

A good understanding of the fundamental transport phenomena of water and methanol in PSA (Perfluoro Sulfonic Acid) membranes is one of the keys in developing efficient direct methanol fuel cells (DMFCs). Electro-osmosis, being one of the most important water and methanol transport mechanisms in DMFCs, has been investigated with a number of different proton exchange membranes. Two aspects were of particular interest: firstly, the interdependencies between the electro-osmotic drag coefficient and methanol concentration and temperature, and secondly the interdependence between the electro-osmotic drag coefficient and current density. The results of these investigations are compared to published data.     

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.     

高温质子交换膜研究进展

高温质子交换膜燃料电池解决了传统质子交换膜燃料电池催化剂易受CO等杂质气体毒化、水热管理复杂等问题,成为当今燃料电池发展的主要方向。高温质子交换膜是实现高温操作的关键部分。本文结合质子传递机理,分析了以水作为质子溶剂、非水质子溶剂质子交换膜以及无机固态质子导体膜的研究现状,认为有机/无机复合膜和非水质子溶剂膜,尤其是其中的磷酸掺杂的PBI膜是高温质子交换膜的发展方向。     

Aligned electrospun sulfonated polyetheretherketone nanofiber based proton exchange membranes for fuel cell applications

In this study, electrospinning of sulfonated poly(ether ether ketone) (SPEEK) at different degrees of sulfonation (DS) was investigated. The polymer solution concentration of 22 wt% was obtained to collect smooth fiber in nanoscale range of 112 to 131 nm at various conditions. SEM observations of SPEEK nanofibers showed the decrease of diameter with increasing DS from 74% to 81%, mainly due to the increase of electrical conductivity of polymer solution at higher DS. The increase of collecting speed from 20 to 305 m/min decreased the diameter of nanofibers slightly and improved their alignment. The presence of SO₃H groups in collected nanofibers was demonstrated with FT‐IR analysis. WAXD patterns of SPEEK nanofibers indicated featureless amorphous peak with no crystalline regions that was broaden at higher DS and aligned nanofibers. The electrochemical impedance spectroscopy of SPEEK nanofibers showed the through‐plane proton conductivity of fully hydrated nanofibrous membranes measured at room temperature were improved with DS. The proton conductivity of randomly oriented and aligned nanofibers were measured from 0.0098 to 0.0722 S/cm and from 0.0592 to 0.0907 S/cm, respectively. Aligned nanofibers exhibited more proton conductivity than randomly collected nanofibers. POLYM. ENG. SCI., 57:789–796, 2017. © 2016 Society of Plastics Engineers     

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。     

Investigation on carbon nanotube oxide for anhydrous proton exchange membranes application

The widespread participation of polymers in the membrane preparation has been considering to be critical for the development of proton exchange membranes (PEMs). For the polymers without functional groups to conduct protons, the introduction of proton conduction carriers with the formation of composite membranes is an effective strategy to prepare PEMs with the outstanding proton conductivity. However, there remains a potential risk of the components leaking from composite membranes due to the lack of the interaction force. Here, the composite of carbon nanotube oxide (OCNT) assembling with cadmium telluride (CdTe) and 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF₆) was introduced into the system of phosphoric acid (PA) doping poly(vinylidene fluoride) (PVDF) with the formation of PVDF/OCNT-CdTe-bmimPF₆/85%PA membranes. PA molecules are anchored by the inorganics of OCNT-CdTe-bmimPF₆ and are stabilized in membranes. The high and stable proton conductivity values at the elevated temperature are obtained comparing the reported PVDF/bmimPF₆/PA membranes. Specifically, the proton conductivity value reached 1.28 × 10⁻¹ S/cm at 160 °C and the value is stable 1.70 × 10⁻² S/cm at 120 °C lasting for 350 h. The fine stability in components could make the membranes extricate from the predicament of proton conductivity decline exceeding 120 °C under anhydrous conditions in PVDF/bmimPF₆/PA membranes. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48833.     

Sulfonated polyimides bearing benzimidazole groups for proton exchange membranes

A series of sulfonated polyimides containing benzimidazole groups were synthesized using 4,4′-binaphthyl-1,1′,8,8′-tetracarboxylic dianhydride (BTDA), 4,4′-diaminodiphenyl ether-2,2′-disulfonic acid (ODADS) as the sulfonated diamine, and 2-(3′,5′-diaminophenyl)benzimidazole (a) or 6,4′-diamino-2-phenylbenzimidazole (b) as the nonsulfonated diamine. The electrolyte properties of the synthesized polyimides (Ia − x, Ib − x, x refers to molar percentage of the sulfonated diamine) were investigated and compared with those of polyimides (Ic − x) from BTDA, ODADS, and m-phenylenediamine (c). All synthesized polyimides possessed high molecular weights revealed by their high viscosity, and formation of tough and flexible membranes. Polyimides with benzimidazole groups exhibited much better swelling capacity than those without benzimidazole groups. This was attributed to the strong interchain interaction through basic benzimidazole functions and sulfonic acid groups. The sulfonated polyimides that are incorporated with 1,1′,8,8′-binaphthalimide exhibited better hydrolytic stability than that with 1,4,5,8-naphthalimide. Polyimide membranes with good water stability as well as high proton conductivity were developed. Polyimide membrane (Ia − 90), for example, did not lose mechanical properties after being soaked in boiling water for 1000 h, while its proton conductivity was still at a high level (compared to that of Nafion 117).     

Research on methanol permeation of proton exchange membranes with incorporating ionic liquids

Methanol permeation and conductivity of membrane materials are important factors to evaluate the feasibility of application as proton exchange membranes (PEMs) in direct methanol fuel cell (DMFC). The methanol permeation values of these composite membranes based on ionic liquids of trifluoroacetic propylamine (TFAPA) and the disubstituted imidazolium cations with different anions were summarized, and the methanol permeation behaviors were investigated in this work. Although these polymer/ionic liquid composite membranes displayed satisfactory conductivities, the relative selectivity values of conductivity to methanol permeability were lower than the value of Nafion^® membrane. Moreover, polymerized ionic liquids (PILs) membranes showed the strong ability to hinder methanol permeation with a value around 10^?11 cm²/s at 10 M methanol solution. The maximum relative selectivity value reached (2.23–1.76) × 10⁶ S·s/cm³ for PVC-MIMCl membrane, which was near two orders of magnitude higher than the reported 2.47 × 10⁴ S·s/cm³ for Nafion-117 membrane at 2 M methanol solution.

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An inorganic/organic self-humidifying composite membranes for proton exchange membrane fuel cell application

With an aim to operate the proton exchange membrane fuel cells (PEMFCs) with dry reactants, an inorganic/organic self-humidifying membrane based on sulfonated polyether ether ketone (SPEEK) hybrid with Cs_2.5H_0.5PW₁₂O₄₀ supported Pt catalyst (Pt-Cs2.5 catalyst) has been investigated. The Pt-Cs2.5 catalysts incorporated in the SPEEK matrix provide the site for catalytic recombination of permeable H₂ and O₂ to form water, and meanwhile avoid short circuit through the whole membrane due to the insulated property of Cs_2.5H_0.5PW₁₂O₄₀ support. Furthermore, the Pt-Cs2.5 catalyst can adsorb the water and transfer proton inside the membrane for its hygroscopic and proton-conductive properties. The structure of the SPEEK/Pt-Cs2.5 composite membrane was characterized by XRD, FT-IR, SEM and EDS. Comparison of the physicochemical and electrochemical properties, such as ion exchange capacity (IEC), water uptake and proton conductivity between the plain SPEEK and SPEEK/Pt-Cs2.5 composite membrane were investigated. Additive stability measurements indicated that the Pt-Cs2.5 catalyst showed improved stability in the SPEEK matrix compared to the PTA particle in the SPEEK matrix. Single cell tests employing the SPEEK/Pt-Cs2.5 self-humidifying membrane and the plain SPEEK membrane under wet or dry operation conditions and primary 100 h fuel cell stability measurement were also conducted in the present study.     

Methanol permeability and properties of DMFC membranes based on sulfonated PEEK/PVDF blends

Proton exchange membranes for a direct methanol fuel cell were prepared by blending poly(vinylidene fluoride) [PVDF] with sulfonated poly(etheretherketone) [SPEEK]. The effects of PVDF content on methanol permeability in the blend membranes were investigated by using a diffusion cell and gas chromatography technique. The thermal resistance and proton conductivity of the membranes were also determined by using a thermal gravimetric analysis (TGA) and an impedance analysis technique, respectively. It was found that methanol permeability in the blend membranes decreased with PVDF content at the expense of proton conductivity. The methanol permeability values of the blend membranes are much lower than that of Nafion 115, whereas proton conductivities of the membranes are comparable to that of Nafion. The thermal stability of these blend membranes are above 250°C which is sufficiently high for use in DMFC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5941–5947, 2006     

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%。     

Nafion®—titania nanocomposite proton exchange membranes

Proton exchange membranes consisting of Nafion^® and crystallized titania nanoparticles have been developed to improve water‐retention and proton conductivity at elevated temperature and low relative humidity. The anatase‐type titania nanoparticles were synthesized in situ in Nafion solution through sol–gel process and the size of the formed titiania nanoparticles is in the range of 3–6 nm. The formed nanoparticles are well‐dispersed in Nafion solution at the titania concentration of 5 wt %. The glass transition temperature of the formed Nafion‐titania composite membrane is about 20^oC higher than that of plain Nafion membrane. At elevated temperature (above 100°C), the Nafion‐titania nanocomposite membrane shows higher water uptake ability and improved proton conductivity compared to pure Nafion membrane. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011