Sulfonated aromatic hydrocarbon polymers as proton exchange membranes for fuel cells

This article reviews recent studies on proton exchange membrane (PEM) materials for polymer electrolyte fuel cells. In particular, it focuses on the development of novel sulfonated aromatic hydrocarbon polymers for PEMs as alternatives to conventional perfluorinated polymers. It is necessary to improve proton conductivity especially under low-humidity conditions at high operating temperatures to breakthrough the current aromatic PEM system. Capable strategies involve the formation of well-connected proton channels by microphase separation between hydrophilic and hydrophobic domains and the increase of the ion exchange capacity of PEMs while keeping water resistance. Herein, we introduce novel molecular designs of sulfonated aromatic hydrocarbon polymers and their performance as PEMs.     

质子交换膜燃料电池研究进展

由于质子交换膜燃料电池（PEMFC）具有能量转化效率高、寿命长、比功率和比能量高、以及对环境友好等优点,近年来得到迅速发展.笔者综述了PEMFC的特点,分析了PEMFC在国内外的最新研究进展,介绍了PEMFC的应用前景,并指出了PEMFC研究当前需要解决的技术问题及其发展趋势.     

Methods for modifying proton exchange membranes using the sol-gel process

Over the past 20 years, sol-gel processing has expanded into organic-inorganic hybrid materials. This expansion has benefited from the collaborations between the polymers community and the ceramics community, and the discovery that in many instances sol-gel processing and polymer processing are compatible. An active participant in this field has been Dr James E. Mark [Mark JE. Heterog Chem Rev 1996;3:307-320], and his accomplishments deserve this tribute. One example, which derives from his work in organically-modified silicates (ORMOSILS), is hybrid membranes for fuel cells. We present some recent progress in synthesis of hybrid membranes involving Nafion. These membranes have been prepared by infiltration and recasting, and contain silicates, phosphosilicates, zirconium phosphosilicates and titanosilicates.     

Diffusion in porous functional materials: Zeolite gas separation membranes, proton exchange membrane fuel cells, dye sensitized solar cells

The function of numerous technical apparatus and processes is diffusion controlled. In three cases studies, the diffusion of molecules, ions and electrons in gas separation membranes, fuel cell membranes and dye sensitized solar cells is discussed. In novel functional materials often an overlap of transport due to a concentration and/or a potential gradient takes place. The transport parameters measured in materials evaluation such as impedance spectroscopy can reflect a physical situation which is different from that of the working device. A detailed fundamental knowledge of various factors is necessary to fully understand the nature of transport as a basis to optimise the corresponding functional materials.     

Novel hydrophilic–hydrophobic multiblock copolyimides as proton exchange membranes: Enhancing the proton conductivity

A series of novel multiblock copolymers based on sulfonated copolyimides were developed and evaluated for use as proton exchange membranes (PEMs). In these multiblock copolyimides, the hydrophilic blocks were composed of the sulfonated dianhydride and the sulfonated diamine, with sulfonic acid groups on every aromatic ring (i.e., fully sulfonated). This molecular design was implemented to effectively enhance the proton conductivity. The properties of the multiblock copolyimides with varying IEC values or block lengths were investigated to obtain a better understanding of the relationship between molecular structure and properties of proton exchange membranes. The water uptake and proton conductivity were found to be highly dependent upon their structure. The block copolymers displayed significantly higher proton conductivities, especially at low relative humidity than the random copolymers with a similar IEC. The results indicated that the distribution of sulfonic acid and the length of the blocks play a key role on properties of proton exchange membranes.     

Ex situ hydrolytic degradation of sulfonated polyimide membranes for fuel cells

Ex situ hydrolytic stability of sulfonated polyimide (s-PI) membranes for fuel cells was studied depending on structural and external parameters including the ion exchange capacity, the block character, the temperature and the hydrogen peroxide concentration. Infrared spectroscopy was used to identify and quantify the chemical modifications such as the loss of imide functions and of ionic monomers. The decrease in ion exchange capacity due to the elution of sulfonated oligomers was confirmed by sulfur content analysis. A complete hydrolysis of some of the imide functions is observed leading to polymer chain scissions and to the loss of the mechanical properties. It is shown to be a thermo activated process and the activation energy (60 kJ/mol) is found in good agreement with the value determined from fuel cell lifetimes. The degradation in fuel cell conditions is similar but faster than in pure water. The same kinetic can be reproduced ex situ by addition 0.05% of hydrogen peroxide.     

Sulfonated hydrocarbon membranes for medium-temperature and low-humidity proton exchange membrane fuel cells (PEMFCs)

This review summarizes efforts in developing sulfonated hydrocarbon proton exchange membranes (PEMs) with excellent long-term electrochemical fuel cell performance in medium-temperature and/or low-humidity proton exchange membrane fuel cell (PEMFC) applications. Sulfonated hydrocarbon PEMs are alternatives to commercially available perfluorosulfonic acid ionomers (PFSA, e.g., Nafion^®) that inevitably lose proton conductivity when exposed to harsh operating conditions. Over the past few decades, a variety of approaches have been suggested to optimize polymer architectures and define post-synthesis treatments in order to further improve the properties of a specific material. Strategies for copolymer syntheses are summarized and future challenges are identified. Research pertaining to the sulfonation process, which is carried out in the initial hydrocarbon PEM fabrication stages, is first introduced. Recent synthetic approaches are then presented, focusing on the polymer design to enhance PEM performance, such as high proton conductivity even with a low ion exchange capacity (IEC) and high dimensional stability. Polymer chemistry methods for the physico-chemical tuning of sulfonated PEMs are also discussed within the framework of maximizing the electrochemical performance of copolymers in membrane-electrode assemblies (MEAs). The discussion will cover crosslinking, surface fluorination, thermal annealing, and organic–inorganic nanocomposite approaches.     

Membrane performance comparison in a proton exchange membrane fuel cell (PEMFC) stack

A 5-cell proton exchange membrane fuel cell (PEMFC) stack with different types of membrane electrode assemblies (MEAs) was tested to compare their performances and electrochemical characteristics. The experimental data were obtained with a stack of 5 cells and active area of 125 cm². The stack consisted of different Nafion^® and hydrocarbon membranes with the same types of electrocatalyst. The membranes were installed in different cells and in the same stack. Polarization and voltage measurement data were obtained to compare their performances at different temperatures and anode humidity conditions. Also, impedance spectroscopy data were obtained in similar manner to compare the differences in their resistance.     

Spreading of liquid droplets on proton exchange membrane of a direct alcohol fuel cell

Spreading of liquid droplets over solid surfaces is a fundamental process with a number of applications including electro-chemical reactions on catalyst surface in membrane electrode assembly of proton exchange membrane (PEM) fuel cell and direct alcohol fuel cell. The spreading process of droplet on the PEM porous substrate consists of two phenomena, e.g., spreading of droplet on PEM surface and imbibition of droplet into PEM porous substrate. The shrinkage of the droplet base occurs due to the suction of the liquid from the droplet into the PEM porous substrate. As a result of these two competing processes, the radius of the drop base goes through a maximum with time. The variation of droplet base and front diameter with time on the PEM porous substrate is monitored using microscope fitted with CCD camera and a PC. It is seen that the droplet base diameter goes through a maximum with time, whereas the front diameter increases continuously with time. Further, methanol droplet spreading and wetting front movement was faster than that for ethanol and deionized water. As the PEM porous substrate is wetted and imbibed well by the methanol compared to ethanol, it is expected that the cross over of methanol would be higher than that of ethanol in direct alcohol fuel cell. It should be noted that cross over of alcohol from anode side to cathode side through membrane is detrimental to the fuel cell operation. The experimental data on the variation of droplet base and wetting front diameter with time is predicted by the model available in the literature.     

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.     

直接甲醇燃料电池用有机-无机杂化质子交换膜研究进展

介绍了直接甲醇燃料电池用有机-无机杂化质子交换膜的研究目的和意义,综述了杂化膜的种类、制备方法、结构与性能和质子传输机理,展望了杂化膜的研究方向。     

直接甲醇燃料电池用阻醇质子交换膜研究进展

直接甲醇燃料电池是近十年兴起的新型燃料电池,并以其独特的优点引起了人们广泛的关注。作为其重要组成部分的质子交换膜的性质是影响电池性能的关键因素。本文在介绍近两年质子交换膜研究最新进展的基础上,综述了天然聚合物用作质子交换膜材料的研究情况,并分析了其优劣势及应用前景。     

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.     

Mesoscale modeling of the influence of morphology on the mechanical properties of proton exchange membranes

The nano-scale morphology of a proton exchange membrane (PEM) strongly influences its proton conductivity and mechanical performance. In this paper, a multi-scale modeling approach has been developed to obtain the morphologies of hydrated perfluorosulfonic acid (PFSA) membranes and then to predict their mechanical properties based on the simulated morphology. Two representative ionic domain morphologies were compared, spherical and cylindrical, to represent cast and extruded membranes. The calculated overall elastic Young’s moduli are very close for both morphologies and agree well with experiments. The nano-scale phase segregation in hydrated PFSA induces a non-uniform distribution of local stress. The peak stress is localized at the smeared water/PFSA interface. The cylindrical morphology develops much lower peak stress than the isotropic spherical morphology under the same level of strain. These results explain why the extruded membranes show more than 10 times longer life in durability tests than recast membranes, despite having similar bulk moduli.     

Non-isothermal effects of single or double serpentine proton exchange membrane fuel cells

Mathematical models on transport processes and reactions in proton exchange membrane (PEM) fuel cell generally assume an isothermal cell behavior for sake of simplicity. This work aims at exploring how a non-isothermal cell body affects the performance of PEM fuel cells with single and double serpentine cathode flow fields, considering the effects of flow channel cross-sectional areas. Low thermal conductivities of porous layers in the cell and low heat transfer coefficients at the surface of current collectors, as commonly adopted in cell design, increase the cell temperature. High cell temperature evaporates fast the liquid water, hence reducing the cathode flooding; however, the yielded low membrane water content reduces proton transport rate, thereby increasing ohmic resistance of membrane. An optimal cell temperature is presented to maximize the cell performance.     

质子交换膜燃料电池流场板研究进展

流场板是质子交换膜燃料电池的核心部件之一,其结构直接影响着反应气体的利用效率以及燃料电池的排水及散热性能。综述了近十余年来质子交换膜燃料电池流场板的设计与研究进展。研究者们基于平行流场、蛇形流场、交指流场、点状流场,从流道尺寸、流道截面、进口分配段、流道布置等方面开展结构设计和优化,不同程度提高了燃料电池水热管理以及电性能。此外,各种形式的组合流场可综合不同流场优点,多级分形仿生流场优化了反应物、压力与电流密度分布,三维精细化流场通过改善供气方式降低了浓差极化。     

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).     

High temperature proton exchange membrane fuel cell using a sulfonated membrane obtained via H2SO4 treatment of PEEK-WC

A method for the sulfonation of PEEK-WC, a glassy poly(ether ether ketone) with sulphuric acid is presented. Depending on the reaction time, polymers with ion exchange capacity (IEC) from 0.30 to 0.76 meq_H⁺/g are obtained, as determined by titration with NaOH solutions. The thermal properties of the polymers were studied by differential scanning calorimetry, showing that the glass transition temperature increases with increasing degree of sulfonation, from 224 °C for pure PEEK-WC to 246 °C for the polymer having an IEC of 0.76 meq_H⁺/g. The sulfonated polymers were used to prepare proton exchange membranes for possible application in fuel cells. Dense membranes were prepared by solvent evaporation, using DMA as the solvent. The transport properties of the membranes were determined in terms of water uptake and permeability for hydrogen and oxygen. Electrochemical characterization was performed by measuring cell voltage and power density curves as a function of current density at different working temperatures and the results were compared with those of a commercial Nafion membrane. A power density of 284 mW/cm² was obtained for S-PEEK-WC membrane at 120 °C in H₂/air fuel cell, slightly above the corresponding value found for Nafion.     

Synthesis of Pt nanocatalyst with micelle-encapsulated multi-walled carbon nanotubes as support for proton exchange membrane fuel cells

Micelle-encapsulated multi-walled carbon nanotubes (MWCNTs) with sodium dodecyl sulfate (SDS) were used as catalyst support to deposit platinum nanoparticles. High resolution transmission electron microscopy (HRTEM) images reveal the crystalline nature of Pt nanoparticles with a diameter of ∼4 nm on the surface of MWCNTs. A single proton exchange membrane fuel cell (PEMFC) with total catalyst loading of 0.2 mg Pt cm⁻² (anode 0.1 and cathode 0.1 mg Pt cm⁻², respectively) has been evaluated at 80 °C with H₂ and O₂ gases using Nafion-212 electrolyte. Pt/MWCNTs synthesized by using modified SDS-MWCNTs with high temperature treatment (250 °C) showed a peak power density of 950 mW cm⁻². Accelerated durability evaluation was carried out by conducting 1500 potential cycles between 0.1 and 1.2 V with 50 mV s⁻¹ scan rate, H₂/N₂ at 80 °C. The membrane electrode assembly (MEA) with Pt/MWCNTs showed superior performance stability with a power density degradation of only ∼30% compared to commercial Pt/C (70%) after potential cycles.