燃料电池用质子交换膜的研究进展

介绍了三类质子交换膜,包括全氟磺酸膜、磺化聚芳烃系列膜和复合型质子交换膜,主要分析了每种膜的优缺点以及在质子交换膜燃料电池(PEMFC)中的应用前景.     

用于质子交换膜的高质子传导率聚合物研究进展

质子传导率超过Nafion膜的质子交换膜是近年来研究的焦点。质子交换膜的质子传导率与它们的IEC值和形态有关。形成离子通道是开发高质子传导率的质子交换膜的一种有效方法。形成离子通道主要有3种:1)用嵌段共聚物的微相分离;2)侧链和支链磺化的聚合物;3)局部区域的高密集磺化。此外,与无机纳米材料形成纳米复合材料的质子交换膜也能提高质子交换膜的质子传导率及质子交换膜的机械强度、尺寸稳定性、耐氧化稳定性等性能。综述了关于用于高质子传导率的燃料电池质子交换膜(PEM)的聚合物的研究进展。对高质子传导率的燃料电池膜聚合物的发展趋势进行了展望。     

质子交换膜燃料电池关键技术研究进展

简述了质子交换膜燃料电池(PEMFC)的工作原理及特点;综述了PEMFC关键技术的最新研究进展,包括质子交换膜合成、电催化剂制备、膜电极工艺及水管理和热控制;并简介了我国PEMFC的开发情况。     

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。     

直接甲醇燃料电池用质子交换膜的研究进展

综述了质子交换膜在直接甲醇燃料电池中的作用和要求,目前质子交换膜的研究进展,重点介绍了适用于直接甲醇燃料电池用质子交换膜的各种材料的改性方法。按照物理和化学两种方法对几类质子交换膜材料进行改性。同时对比了改性前和改性后各种聚合物膜的物性特点。     

质子交换膜燃料电池研究及应用现状

介绍了国内外质子交换膜燃料电池(PEMFC)研究的整体现状及水平,分别讨论了PEMFC的3个关键部件:质子交换膜的材料要求,电化学反应催化剂的特点,膜电极的组成、制备工艺和最新进展,重点讨论了全氟磺酸型质子交换膜的类型、优缺点和当前的研究方向。在此基础上,追述了近年来国内外以PEMFC作为电动汽车动力源的实际应用情况,并指出应用PEMFC存在的问题。可以看到,PEMFC具有广阔的应用前景,将会在电动汽车方面得到最早的商业化应用。     

氧化石墨烯在燃料电池质子交换膜中的应用

保护环境，开发环保型能源，对人类和社会具有重要意义。质子交换膜燃料电池由于其能量转化率高，可实现零排放，近年来引起了电池领域研究者们的兴趣。氧化石墨烯（GO）由于存在活性氧官能团，可以和离子型聚合物进行复合以制备复合质子交换膜。氧化石墨烯类的复合质子交换膜应用于燃料电池时可以提高膜在高温低湿度条件下的质子传导率，降低甲醇渗透率，提高电池的功率密度。本文首先介绍了氧化石墨烯的制备方法，然后从不同的离子型聚合物基质复合质子交换膜的类别出发，详细介绍了氧化石墨烯在Nafion、聚醚醚酮、聚苯并咪唑和壳聚糖等不同种类的离子型聚合物中的应用现状及作用机理，同时对其在质子交换膜的应用方面存在的问题及应用前景做了评论和展望。     

质子交换膜燃料电池技术的发展及应用

概述了质子交换膜燃料电池(PEMFC)的发展历史和现状,并对其应用前景进行了展望;对质子交换膜燃料电池的膜、膜电极、电催化剂和双极板等关键技术进行了简要介绍。     

燃料电池用质子交换膜

介绍了燃料电池用含氟质子交换膜的研究历程、应用、结构与性能的关系及当前针对性的改进,归纳了磺化碳氢聚合物、有机无机复合物、离子交联聚合物和无机固体酸等非氟质子交换膜的代表性研究,指出了各利非氟质子交换膜的优点和不足,对质子交换膜的发展做了相应的展望。     

聚砜类燃料电池质子交换膜研究进展

介绍了质子交换膜的分类，综述了主链型聚砜质子交换膜、侧链型聚砜质子交换膜、无机掺杂复合型聚砜质子交换膜等聚砜类燃料电池质子交换膜的最新研究进展，全面阐述了磺化聚砜的形貌、结构对材料物理化学性能的影响，并展望了聚砜类燃料电池质子交换膜的发展前景。     

5kW氢-空质子交换膜燃料电池堆的模型研究

采用机理模型和经验模型相结合的建模方法建立了一个5kw质子交换膜燃料电池堆实际装置的电化学模型。利用电池堆与单电池之间的内在关系,首先给出了单电池的数学描述,进而建立燃料电池堆的数学模型,其中包括热力学平衡电势、活化极化电势和欧姆极化电势等表达式,以及单电池内阻的经验公式。由于难以得到机理方程中的某些关键参数,因此采用实验设计,获得燃料电池堆的实验数据,运用线性回归的数学方法获得机理模型中活化极化电势方程中的相关参数,通过模拟研究和模型验证,所建立的模型可以较准确的描述燃料电池的极化曲线,预估出燃料电池的输出电压。     

Performance Analysis of a HT-PEMFC System with 6FPBI Membranes Doped with Cross-Linkable Polymeric Ionic Liquid

In this paper, a high-temperature proton-exchange membrane fuel cell (HT-PEMFC) system using fluorine-containing polybenzimidazole (6FPBI) composite membranes doped with cross-linkable polymer ionic liquid (cPIL) is developed and studied. The reliability of the model is verified by a comparison with the experimental data. The performance of the HT-PEMFC system using 6FPBI membranes with different levels of cPIL is analyzed. The results show that when the HT-PEMFC uses 6FPBI membranes with a cPIL content of 20 wt % (6FPBI-cPIL 20 membranes), the single cell power density is 4952.3 W·m−2. The excessive cPIL content will lead to HT-PEMFC performance degradation. The HT-PEMFC system using the 6FPBI-cPIL 20 membranes shows a higher performance, even at higher temperatures and pressures, than the systems using 6FPBI membranes. In addition, the parametric study results suggest that the HT-PEMFC system should be operated at a higher inlet temperature and hydrogen pressure to increase system output power and efficiency. The oxygen inlet pressure should be reduced to decrease the power consumption of the ancillary equipment and improve system efficiency. The proposed model can provide a prediction for the performance of HT-PEMFC systems with the application of phosphoric-acid-doped polybenzimidazole (PA-PBI) membranes.     

基于膜电极的质子交换膜微生物燃料电池

通过采用传统电化学燃料电池的技术和材料,以寻求提高微生物燃料电池的电流密度,制作基于膜电极的微生物燃料电池。通过构建温控压力机,制作了一系列膜电极(MEA),并对作为正极的多种碳材料进行了筛选。使用定制的玻璃微生物燃料电池来放置膜电极和培养Geobacter sulfurreducens,对产生的电流进行评价。细胞的生长以乙醇为唯一碳源,因而代表了一种新型的乙醇/氧气燃料电池。相比以前的设计,基于膜电极的微生物燃料电池的电极表面每个单位会多产生出100倍的电流,并且可以被长久使用。     

Preparation of a PVA/HAP composite polymer membrane for a direct ethanol fuel cell (DEFC)

A novel PVA/Hydroxyapatite (HAP) composite polymer membrane was prepared by the direct blend process and solution casting method. The characteristic properties of the PVA/HAP composite polymer membranes were investigated using thermal gravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), micro-Raman spectroscopy and the AC impedance method. An alkaline direct ethanol fuel cell, consisting of an air cathode with MnO₂ carbon inks based on Ni-foam, an anode with PtRu black on Ni-foam, and the PVA/HAP composite polymer membrane, was assembled and investigated. It was found that the alkaline direct ethanol fuel cell comprising of a novel cheap PVA/HAP composite polymer membrane showed an improved electrochemical performance in ambient temperature and air. As a result, the maximum power density of the alkaline DEFC, using a PtRu anode based on Ni-foam (10.74 mW cm⁻²), is higher than that of DEFC using an E-TEK PtRu anode based on carbon (7.56 mW cm⁻²) in an 8M KOH + 2M C₂H₅OH solution at ambient temperature and air. These PVA/HAP composite polymer membranes are a potential candidate for alkaline DEFC applications.     

Effects of a fuel cell test on the structure of irradiation grafted ion exchange membranes based on different fluoropolymers

The role of the fluoropolymer matrix in the stability of irradiation grafted proton conducting membranes under fuel cell conditions is investigated. The structure of a series of membranes with poly(vinylidene fluoride), poly(vinylidene fluoride-co-hexafluoropropylene), poly(tetrafluoroethylene-co-hexafluoropropylene), and poly(ethylene-alt-tetrafluoroethylene) matrices with poly(styrene sulfonic acid) side chains is studied before and after a fuel cell test using X-ray scattering techniques and confocal micro-Raman spectroscopy. All tested membranes suffer from a loss of poly(styrene sulfonic acid) leading to a decrease in conductivity. Changes in crystallinity, lamellar period, orientation and thickness of the membranes are reported and compared to corresponding properties of the initial polymer films and the pristine membranes. The membranes where most severe changes in the structure of the matrix polymer can be observed have the shortest lifetimes in the fuel cell.     

Alginic acid-imidazole composite material as anhydrous proton conducting membrane

Recently, membranes with high anhydrous proton conducting have been attracted remarkable interest for the application to the polymer electrolyte membrane fuel cell (PEFC). In this paper, we have investigated the anhydrous proton conductor consisting of alginic acid (AA), one of the acidic biopolymers, and imidazole (Im). This AA-Im composite material showed the proton conductivity of 2×10⁻³ S cm⁻¹ at 130 °C under anhydrous conditions. Additionally, these AA-Im composite materials have the highly mechanical property and thermal stability. Furthermore, the biological products, such as biopolymer, are cheap, non-hazardous, and environmentally benign. The proton conductive biopolymer composite material may have the potential for its superior ion conducting properties, in particular, under anhydrous (water-free) or extremely low humidity conditions.     

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。     

Simulation of membrane microreactor for fuel cell with methane feed

Microreactors are composed of channels with a dimension of 1–1000 μm in width and depth. Three types of membrane microreactors for production of electric power by fuel cells with methane feed, i.e. (1) Pd membrane microreactor (Pd-MMR) followed by polymer electrolyte fuel cell (PEFC), (2) oxide-ion conducting solid oxide fuel cell (SOFC) and (3) proton conducting solid oxide fuel cell (H⁺-SOFC) were simulated and compared.

The Pd-MMR followed by PEFC was the most effective system for electric power generation compared with the other two types of SOFC although the system was rather complex. However, the performances were dependent on the permeation properties of membranes (Pd, YSZ, perovskite) as well as kinetics of catalysts.     

Imidazolium functionalized poly(vinyl alcohol) membranes for direct methanol alkaline fuel cell applications

In this study, imidazolium functionalized poly(vinyl alcohol) (PVA) was synthesized by acetalization and direct quaternization reaction. Afterwards, composite anion exchange membranes based on imidazolium‐ and quaternary ammonium‐ functionalized PVA were used for direct methanol alkaline fuel cell applications. ¹H NMR and Fourier transform infrared spectroscopy data indicated that imidazole functionalized PVA was successfully synthesized. Inductively coupled plasma mass spectrometry data demonstrated that the imidazolium structure was efficiently obtained by direct quaternization of the imidazole group. Composite anion exchange membranes were fabricated by application of the functionalized PVA solution on the surface of porous polycarbonate (PC) membranes. Fuel cell related properties of all prepared membranes were investigated systematically. The imidazolium functionalized composite membrane (PVA‐Im/PC) exhibited higher ionic conductivity (7.8 mS cm^?1 at 30 °C) despite a lower water uptake and ion exchange capacity value compared to that of quaternary ammonium. In addition, PVA‐Im/PC showed the lowest methanol permeation rate and the highest membrane selectivity as well as high alkaline and oxidative stability. Dynamic mechanical analysis results reveal that both composite membranes were mechanically resistant up to 10⁷ Pa at 140 °C. The superior performance of imidazolium functionalized PVA composite membrane compared to quaternary ammonium functionalized membrane makes it a promising candidate for direct methanol alkaline fuel cell applications. © 2020 Society of Chemical Industry