聚合物燃料电池离子交换膜新进展

聚合物离子交换膜是聚合物电解质燃料电池的关键部件之一,根据聚合物携带反离子种类,可分为质子交换膜燃料电池（PEMFC）和碱性阴离子交换膜燃料电池（APEFC）。本文着重阐述近年来研究热点：高温低湿质子交换膜（HTPEM）和聚合物碱性阴离子交换膜（APE）的研究进展,指出燃料电池中聚合物离子交换膜（HTPEM和APE）面...     

燃料电池聚合物电解质膜的研究进展

本文根据聚合物电解质膜燃料电池操作温度、使用的电解质和燃料的不同,将其分为高温质子交换膜燃料电池、低温质子换膜燃料电池、直接甲醇燃料电池和阴离子交换膜燃料电池,综述了它们所用电解质膜的最新进展.第一部分简要介绍了这4种燃料电池的优点和不足.第二部分首先介绍了Nafion膜的结构模型,并对平行柱状纳米水通道模型在介观尺度上进行了修正;接着分别对应用于不同燃料电池的改性膜的改性思路作了分析;最后讨论了用于不同燃料电池的新型质子交换膜的研究,同时列举了性能突出的改性膜和新型质子交换膜.第三部分介绍了阴离子交换膜的研究现状.第四部分对未来聚合物电解质膜的研究作了展望.     

超高温(200-250 ℃)聚合物电解质膜燃料电池的机遇与挑战

低温质子交换膜燃料电池的商业化受到高纯度氢气制取、储存、运输及加注的制约。将燃料电池工作温度提高到200-250 ℃可显著提高电极动力学,提高对一氧化碳等杂质气体的耐受性,降低氢气制取成本,简化水和热管理,为燃料电池提供更多燃料选择,使得高温质子交换膜燃料电池有望实现原位甲醇重整制氢系统与燃料电池系统的无温差耦合,同时较高的运行温度为直接甲醇燃料电池和非贵金属催化剂替代铂基催化剂提供了有利条件。但超高温（200-250 ℃）聚合物电解质膜燃料电池的发展依然面临着艰巨的挑战,为促进超高温聚合物电解质膜燃料电池的发展,本文将系统总结近年的相关进展,探讨超高温聚合物电解质膜燃料电池面临的机遇与挑战。     

碱性固体燃料电池碱性聚合物电解质膜的最新研究进展

最近,碱性聚合物电解质膜燃料电池（APEMFC）因具有电极反应动力学快以及不依赖于贵金属铂催化剂等诸多优点而成为一个热门话题. 作为其中一个关键部件,碱性聚合物电解质膜直接影响燃料电池的性能和成本.然而,迄今为止,仍然没有令人满意的碱性电解质膜材料. 为此,大量研究被开展和报道. 本文综述了近三年内文献中关于燃料电池碱性聚合物电解质膜的最新研究进展：包括各种各样的合成策略,构效关系,水管理以及非原位或原位稳定性测试等等. 尤其是一些新的金属离子基阴离子交换膜和冠醚基阴离子交换膜首次被提及和评论.此外,还进一步预测了将来的发展趋势.     

碱性固体燃料电池碱性聚合物电解质膜的最新研究进展

最近,碱性聚合物电解质膜燃料电池（APEMFC）因具有电极反应动力学快以及不依赖于贵金属铂催化剂等诸多优点而成为一个热门话题. 作为其中一个关键部件,碱性聚合物电解质膜直接影响燃料电池的性能和成本.然而,迄今为止,仍然没有令人满意的碱性电解质膜材料. 为此,大量研究被开展和报道. 本文综述了近三年内文献中关于燃料电池碱性聚合物电解质膜的最新研究进展：包括各种各样的合成策略,构效关系,水管理以及非原位或原位稳定性测试等等. 尤其是一些新的金属离子基阴离子交换膜和冠醚基阴离子交换膜首次被提及和评论.此外,还进一步预测了将来的发展趋势.     

碱性固体燃料电池碱性聚合物电解质膜的最新研究进展

最近,碱性聚合物电解质膜燃料电池(APEMFC)因具有电极反应动力学快以及不依赖于贵金属铂催化剂等诸多优点而成为一个热门话题.作为其中一个关键部件,碱性聚合物电解质膜直接影响燃料电池的性能和成本.然而,迄今为止,仍然没有令人满意的碱性电解质膜材料.为此,大量研究被开展和报道.本文综述了近三年内文献中关于燃料电池碱性聚合物电解质膜的最新研究进展:包括各种各样的合成策略,构效关系,水管理以及非原位或原位稳定性测试等等.尤其是一些新的金属离子基阴离子交换膜和冠醚基阴离子交换膜首次被提及和评论.此外,还进一步预测了将来的发展趋势.     

碱性聚合物电解质膜的表面锥形阵列结构提升燃料电池性能

燃料电池作为一种清洁高效的能量转换装置,被认为是构建未来社会可再生能源结构的关键一环。不同于质子交换膜燃料电池(PEMFC),碱性聚合物电解质燃料电池(APEFC)的出现使非贵金属催化剂的使用成为可能,因而受到了日益广泛的关注和研究。APEFC的关键结构是膜电极,主要由聚合物电解质膜和阴阳极(含催化层、气体扩散层)组成,膜电极是电化学反应发生的场所,其优劣直接决定着电池性能的好坏。因此,基于现有的碱性聚合物电解质及催化剂体系,如何构筑更加优化的膜电极结构,使APEFC发挥出更高的电池性能是亟待开展的研究。本文首先通过模板法在碱性聚合物电解质膜的表面构建出有序的锥形阵列,再将具有阵列结构的一侧作为阴极来构筑膜电极,同时,作为对比,制备了由无阵列结构的聚合物电解质膜构筑而成的膜电极,最后对基于两种不同膜电极的APEFC的电化学性能进行了对比研究。实验结果表明,锥形阵列结构可以将APEFC的峰值功率密度由1.04 W·cm-2显著提高到1.48 W·cm-2,这主要归因于在APEFC的阴极侧具有锥形阵列结构的聚合物电解质膜的亲水性的提升和催化剂电化学活性面积的增加。本工作为碱性聚合物电解质燃...     

高温聚合物电解质膜燃料电池膜电极中磷酸分布及调控策略研究进展

高温聚合物电解质膜燃料电池(HT-PEMFC)由于其较高的运行温度(140–200°C)而具有较快的电极反应动力学和良好的抗CO等杂质气体毒化能力以及简化水热管理等优势,是PEMFC的重要发展方向之一。HT-PEMFC的核心部件为基于磷酸掺杂聚合物电解质膜(HT-PEM)组装的膜电极(MEA)。在高温膜电极(HT-MEA)中,一方面聚合物电解质膜和催化层中的离子传导极大地依赖于磷酸的含量;而另一方面磷酸分子填充在高分子链周围会引起聚合物膜力学性能的下降,迁移进催化层中的磷酸容易导致阴阳极催化层的"酸淹"以及在铂催化剂表面吸附而降低催化剂活性。因此,研究磷酸在高温聚合物电解质膜电极中的分布状态和迁移过程,对构建高性能和高稳定性的HT-PEMFC至关重要。基于此,本文对近年来HT-MEA中磷酸的分布、动态迁移过程的研究现状进行了梳理分析,对HT-MEA(包括高温聚合物电解质膜和催化层)中磷酸分布和迁移的调节与优化策略研究进展进行了较全面的综述,并对其未来发展趋势进行了评述和展望。     

最新电化学技术应用文献摘引

能量存储与转移氢氧聚合物电解质燃料电池孔填隙电解质膜的性能　HironobuNishimura ,TakeoYamaguchi,ElectrochemicalandSolid StateLetters,2 0 0 4 ,Vol 7( 1 1 ) ,A385 A388微管直接甲醇燃料电池的性能　MasayukiKunimatsu ,TatsuhiroOkada ,ElectrochemicalandSolid StateLetters,2 0 0 4 ,Vol 7( 1 1 ) ,A389～A390直接甲醇燃料电池表面修饰纳米孔玻璃膜电解质　TsutomuIoroi,KojiKuraoka ,KazuakiYa suda,TetsuoYazawa,andYoshinoriMiyazaki,ElectrochemicalandSolid StateLetters,2 0 0 4 ,Vol 7( 1 1 ) ,A394～A39…     

改性磺化聚醚醚酮用作直接甲醇燃料电池聚合物电解质膜

1引言 聚合物电解质膜燃料电池（Polymer electrolyte membrane fuel cell，PEMFC）是一种能直接将燃料和氧化剂中的化学能转化为电能的电化学装置，具有能量转换效率高、环境友好、比能量高（相对于电池）、操作温度低、启动快的特点，可广泛应用于汽车、电站、移动电源等领域。聚合物电解质膜则是PEMFC中的核心部件，起着分隔燃料和氧化剂、传导离子和绝缘电子的作用，一直以来都是燃料电池研究领域的热点。     

New sulfonated engineering polymers via the metalation route. II. Sulfinated/sulfonated poly(ether sulfone) PSU Udel and its crosslinking

New mixed sulfinated/sulfonated polysulfone PSU Udel has been produced by partial oxidation of sulfinated PSU with NaOCl. From the mixed sulfinated/sulfonated PSU, thin crosslinked polymer films have been produced by S-alkylation of the residual sulfinate groups with α,ω-diiodoalkanes having 4–10  (CH₂) units. The advantages of the partial oxidation process using NaOCl are as follows: (1) The desired oxidation degree can be adjusted finely. (2) No side reactions take place during oxidation. (3) The partially oxidized polymers is stable at ambient temperature. By variation of the oxidation degree of the sulfinated/sulfonated prepolymer and by variation of the chain length of the diiodo crosslinker, crosslinked membranes with a large range of properties in terms of ionic conductivity, swelling, and permselectivity have been produced. The partially oxidized polymers have been characterized by redox titration, ¹H-NMR, and FTIR. The crosslinked membranes have been characterized in terms of ionic conductivity (resistance), permselectivity, and swelling in dependence on ion-exchange capacity and oxidation degree of the prepolymers. In addition, the thermal stabilities of the membranes have been determined by TGA, and FTIR spectra have been recorded on the crosslinked films. Selected membranes show low ionic resistances, low swelling, and good temperature stability which makes them promising candidates for application in (electro)membrane processes. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1441–1448, 1998     

Development and characterization of crosslinked ionomer membranes based upon sulfinated and sulfonated PSU crosslinked PSU blend membranes by alkylation of sulfinate groups with dihalogenoalkanes

Crosslinked sulfonated PSU blend membranes have been produced via a new crosslinking process. The blends have been obtained from mixing of PSU Udel^tm Na-sulfonate and PSU Udel^tm Li-sulfinate in N-methyl pyrrolidone. The membranes have been crosslinked by S-alkylation of PSU sulfinate groups with dihalogenoalkanes The membranes produced via this process have been characterized in terms of ion-exchange capacity, electric resistance, swelling, ion-permselectivity. In addition, the thermal stability of the membranes has been determined by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), and FTIR-spectra of the prepolymers and of the crosslinked blend membranes have been recorded. The new crosslinking procedure shows following advantages: (i) the preparative effort for crosslinking is very low; (ii) the properties of the crosslinked membranes are reproducible; (iii) the crosslinking proceeds with a high yield when applying suitable dihalogenoalkanes or other crosslinkers which are capable to S-alkylate the sulfinate group. The properties of the crosslinked PSU blend membranes are: (i) low electrical resistance at high IEC's; (ii) low swelling rate in practical temperature ranges from 20–70°C; (iii) excellent hydrolysis stability; (iv) excellent thermal stability.     

Halogen‐Free Polyarylphosphonates and Polyelectrolyte Membranes for PEMFC by Nickel‐Catalyzed Phosphonylation with Silylated Phosphates

Summary: The nickel‐catalyzed arylphosphonylation with tris(trimethylsilyl) phosphite (TMSP) is applied to brominated high‐performance (HP) polymers in weakly coordinating high temperature solvents. At elevated temperatures, this affords halogen‐free, soluble, phosphonic acid‐functionalized polyelectrolytes and an unprecedented control of the degree of phosphonylation (ds_P). Brominated polysulfone (PSU) of various degrees of bromination (ds_Br) has been phosphonylated with TMSP in diphenyl ether at 200 °C in the presence of 1–10 mol‐% NiCl₂. Upon methanolysis, arylphosphonic PSU with ds_P up to 223 mol‐% is obtained in near quantitative bromine conversion. Catalyst residues are readily removed during methanolysis. This very versatile two‐step process affords soluble arylphosphonic polymers for casting tough membrane films. In contrast to sulfonated PSU, the arylphosphonic PSU membranes exhibit improved thermal and chemical stabilities, combined with far lower water swelling in accordance with the demands of polyelectrolyte membrane fuel cell (PEMFC) applications.

Mass swelling (sw_M) in water of sulfonated (A–C) and phosphonylated PSU (D).     

Permeation and separation characteristics for benzene/cyclohexane mixtures through tosylcellulose membranes in pervaporation

Tosylcelluloses (TosCells) with different degrees of tosylation were synthesized as membrane materials for the separation of benzene/cyclohexane (Bz/Chx) mixtures. TosCell membranes showed a high benzenepermselectivity for the Bz/Chx mixtures in pervaporation (PV). An increase in the benzene concentration in the feed mixtures increased permeation rate but decreased the benzenepermselectivity of the TosCell membranes. The increase in the permeation rate was attributed to the increase of the degree of swelling of the TosCell membranes by the feed mixtures and the decrease in the benzenepermselectivity was mainly caused by the decrease of sorption selectivity. With low benzene concentrations in the Bz/Chx mixtures, the permeation rate of a TosCell membrane with a higher degree of tosylation was greater than that with a lower degree of tosylation, but was vice versa with a high benzene concentration. The benzenepermselectivity of the former TosCell membrane was higher than that of the latter membrane. Differences of the permeation rate and benzenepermselectivity with changes in the benzene concentration in the feed mixture and degree of tosylation of the TosCell membrane were significantly influenced by the degree of swelling of the TosCell membrane and the benzene concentration sorbed into the TosCell membrane. Mechanism of separation for the Bz/Chx mixtures through the TosCell membranes is discussed by the solution–diffusion model.     

Preparation and characterizations of asymmetric sulfonated polysulfone membranes by wet phase inversion method

This paper presents an original approach to prepare the asymmetric sulfonated polysulfone membranes by using wet phase inversion method and their applications for dehydrating a water/ethanol mixture by pervaporation. The separation performances of sulfonated membranes were strongly affected by the degree of sulfonation and the degree of swelling of membranes. The substitution degree of sulfonic group enhanced the permselectivity of sulfonated polysulfone membranes by increasing the hydrophilicity of polymer backbone. Based on the observations of membrane morphology and light transmittance measurements, the degree of sulfonation of polysulfone presented less influence on the membrane formation pathway and the final structure of membrane in wet phase inversion process. It was also found that the sulfonated membranes showed well hydrophilic properties and facilitated water adsorption in the membranes. The sorption and permeation properties also showed that the permselectivity of asymmetric membrane was dominated by the permeate diffusion rather than the permeate sorption in the skin layer. The high separation performance of pervaporation membrane can be achieved by phase inverse method with sulfonated polysulfone.     

Electrochemical properties of hydrophilic weak-acid membranes from hydrolysed polyacrylonitrile—I. Effect of cross-linking and chemical composition

Gels cross-linked to various degrees and containing various amounts of nitrile, amide and carboxylic groups were prepared by polymerizing acrylonitrile at various concentrations in aqueous 70 per cent ZnCl₂ solution and by hydrolysis of polymers for various times in HCl vapours. Chemical characteristics of gels, concentration membrane potentials, membrane functions and permselectivities in KCl solutions were determined. It was proved that under the conditions used (pH close to 7, content of acrylic acid in the copolymer only 1·4–3·9 mole %). cross-linking is the decisive factor for permselectivity and ideality of the membrane functions. Cross-linking yielded almost 100 per cent permselectivity values and a slope of the membrane function of about 55 mV/decade. Further hydrolysis impairs the ideality of membranes, since the increase in swelling outweighs the effect of the increase in concentration of the active groups. Variability of the density of the ionizable groups is not sufficient to explain differences in the behaviour of the membranes under investigation.     

Preparation and basic characterization of heterogeneous weak acid cation exchange membrane

The goal of this article is focused on the preparation and the basic characterization of heterogeneous weak acid cation exchange membranes. The six weak cation exchange resins were chosen for the preparation of the membranes. The strong acid cation exchange membrane was prepared for the comparison of properties and preparation parameters. Heterogeneous membranes were prepared in the several steps. The last operations were the extrusion and hydraulic hot-pressing. The torque and pressure in the extrusion head were observed while the extrusion of heterogeneous membranes. According to the type of the ion exchange resin, parameters varied greatly. The strong acid cation exchange membrane and weak acid cation exchange membranes with carboxylic groups had the lowest values of the torque and pressure while the homogenization and extrusion. All membranes were characterized. Electrochemical (permselectivity, ion exchange capacity, resistance), physical (relative water content, swelling in the different solutions), and mechanical properties were measured. Properties varied distinctly according to the type of the ion exchange resins. Swelling dimensional changes of ion exchange membranes in sodium hydroxide and water were bigger than changes in hydrochloric acid. Ion exchange capacity of membranes related with ion exchange capacity of used ion exchange resins. Weak acid cation exchange membranes with carboxylic functional groups compared to the strong membrane had the best specific and areal resistance.     

高取代度氰乙基纤维素反渗透膜的研究

本文对高取代度氰乙基纤维素(HCEC)的制膜工艺进行了初步研究,并考察了膜的化学稳定性和渗透选择性。结果表明,HCEC膜除有优良的耐微生物分解性能外,在耐酸、碱水解和耐活性氯氧化性能上也远胜于醋酸纤维素膜,在对溶液的渗透选择性能方面,HCEC膜对荷负电溶质有较高的截留性能,并表现出类似于荷电型阳离子反渗透膜的某些特征。     

Microemulsion breakdown by pervaporation technique: effect of the alkyl chain length of n-alkanol, a cosurfactant of the microemulsion

Two sets of microemulsions, cyclohexane- and water-rich ones, were prepared with the following n-alkanols as cosurfactants: n-propanol, n-butanol, n-pentanol, and n-hexanol. The results showed the influence of the alkyl chain length of the n-alkanol on the permselectivity properties of the pervaporation technique in the breakdown of the microemulsions. The variations of the total flux rate J and the enrichment factor beta were in parallel with the effect of the cosurfactant on the swelling extent of the PDMS membrane.     

Preparation and properties of ionic cross‐linked sulfonated copolyimide membranes containing pyrimidine groups

A series of sulfonated copolyimides containing pyrimidine groups (SPIs) were synthesized by random copolymerization of 1,4,5,8‐naphthalenetetracarboxylic dianhydride (NTDA), 2‐(4‐aminophenyl)‐5‐aminopyrimidine (PAPRM), and 4,4′‐diaminodiphenyl ether‐2,2′‐disulfonic acid (ODADS). Proton exchange treatment in 1.0 M sulfuric acid solution resulted in ionic cross‐linking of the sulfonated copolymers due to the acid (sulfonic acid)‐base (pyrimidine group) interactions and the membrane with more basic PAPRM moiety could absorb sulfuric acid to favor the proton transfer. The effects of the structure of the diamines on the properties of SPI membranes were evaluated by studying the membrane parameters including water uptake, proton conductivity, water stability, and methanol permeability. The basic pyrimidine groups introduced in the main chains could effectively resist membrane swelling due to the strong interchain interactions through basic pyrimidine groups and sulfonic acid groups. Compared with the corresponding uncross‐linked copolyimides (NTDA/ODADS/ODA), the acid–base copolyimides displayed excellent water stability. The SPI membranes also exhibited improved mechanical properties and decreased methanol permeability. However, the cross‐linked membranes showed lowered proton conductivities than the uncross‐linked ones because a small part of the sulfonic acid groups had been consumed during the cross‐linking process. Copyright © 2010 John Wiley & Sons, Ltd.