空气抽吸式甲醇燃料电池传热与传质特性

空气抽吸式直接甲醇燃料电池不仅具有被动式燃料电池的优点,同时又便于将其串联成电堆提高输出电压。建立以阴极为管道抽吸式结构的直接甲醇燃料电池的三维、两相、非等温稳态数值模型,研究了质子交换膜性能、供给甲醇浓度以及电堆规模对电池性能及燃料利用率的影响。对于保温较好的大电堆,采用低甲醇穿透的改性质子交换膜能同时提升燃料利用率和比功率;此类电堆若采用穿透率低的改性膜,则2 mol/L的甲醇浓度就能保证电池在较大的电流密度区间内维持较高的功率与效率。作为影响电池运行温度的重要因素,电堆规模的大小将直接影响质子交换膜种类与甲醇浓度等关键参数的设计与选择。     

Enhancement in proton conductivity and methanol cross-over resistance by sulfonated boron nitride composite sulfonated poly (ether ether ketone) proton exchange membrane

Fuel cells are the promising new non-conventional power source for vehicles as well as portable devices. Direct methanol fuel cell (DMFC) is especially attractive since it uses low cost liquid methanol as a fuel. Proton exchange membrane is one of the most crucial part of DMFC. Herein, we synthesized the sulfonated boron nitride (SBN) based SPEEK composite membranes for the DMFC application. SBN was synthesized by covalent functionalization of hydroxylated BN by using 3-mercaptopropyl trimethoxysilane and sulfonated by subsequent oxidation of mercapto group. Sulfonated poly (ether ether ketone) is used as a polymer matrix for SBN. With well controlled content of SBN into SPEEK matrix exhibit high proton conductivity, IEC and water content along with excellent mechanical strength. Composite membranes show low methanol cross over and high selectivity, which makes them attractive candidate for proton exchange membrane for direct methanol fuel cells.     

Sulfonic acid functionalized graphene oxide paper sandwiched in sulfonated poly(ether ether ketone): A proton exchange membrane with high performance for semi-passive direct methanol fuel cells

Sulfonated poly(ether ether ketone) (SPEEK) membranes have been deposited on the both sides of a sulfonic acid functionalized graphene oxide (SGO) paper to form a proton exchange membrane (PEM) with a sandwiched structure. The obtained SPEEK/SGO/SPEEK membrane could exhibit proton conductivity close to Nafion^® 112 and lower methanol permeability. The use of this SPEEK/SGO/SPEEK membrane greatly improves the performance of the semi-passive direct methanol fuel cell (DMFC). The semi-passive DMFC with the SPEEK/SGO/SPEEK membrane is found to be capable of delivering the peak power density 60% higher than that with the commercial Nafion^® 112. This, along with its comparable durability to Nafion^® 112, strongly suggests the great promise of using the SPEEK/SGO/SPEEK membrane as the PEM.     

New membranes for direct methanol fuel cells

The performance of direct methanol fuel cells (DMFC) is limited by the cross-over of methanol through the electrolyte. Electrolyte membranes prepared by blending of sulfonated arylene main-chain polymers like sulfonated PEEK Victrex (sPEEK) or sulfonated PSU Udel (sPSU) with basic polymers like poly(4-vinylpyridine) (P4VP) or polybenzimidazole (PBI) show excellent chemical and thermal stability, good proton-conductivity, and good performance in H₂ PEM fuel cells. Furthermore, these materials have potentially lower methanol cross-over when compared to standard Nafion-type membranes.In this work, membrane electrode assemblies (MEAs) have been prepared from such membranes according to the thin-film method. The catalyst layer was spray-coated directly on the heated membrane using an ink consisting of an aqueous suspension of catalyst powder and Nafion solution. Unsupported catalysts were used for anode and cathode. A rather high catalyst loading was chosen in order to minimize the effects of limited catalyst utilization due to flooding conditions at both electrodes.     

40SiO2–40P2O5–20ZrO2 sol-gel infiltrated sSEBS membranes with improved methanol crossover and cell performance for direct methanol fuel cell applications

Membranes commonly used in direct methanol fuel cell (DMFC) are expensive and show a great permeability to methanol which reduces fuel utilization and leads to mixed potential at the cathode. In this work, sulfonated styrene-ethylene-butylene-styrene (sSEBS) modified membranes with zirconia silica phosphate sol-gel phase are developed and studied in order to evaluate their potential use in DMFC applications. The synthesized hybrid membranes and sSEBS are subjected to an exhaustive physicochemical characterization by liquid uptake, ion exchange capacity, atomic force microscopy, X-ray photoelectron spectroscopy and dynamic mechanical and thermogravimetric analyses. Likewise, the potential use of the prepared membranes in DMFC is evaluated by means of electrochemical characterizations in single cell, determining the limiting methanol crossover current densities, proton conductivities and DMFC performances. The hybrid membranes show lower water and methanol uptakes, higher stiffness, water retention capability, upper power density and lower methanol crossover than sSEBS and Nafion 112.     

Evaluation of composite membranes for direct methanol fuel cells

The performance of direct methanol fuel cells (DMFCs) can be significantly affected by the transport of methanol through the membrane, depolarising the cathode. In this paper, the literature on composite membranes that have been developed for reduction of methanol crossover in DMFCs is reviewed. While such membranes can be effective in reducing methanol permeability, this is usually combined with a reduction in proton conductivity. Measurements of methanol permeability and proton conductivity are relatively straightforward, and these parameters (or a membrane ‘selectivity’ based on the ratio between them) are often used to characterize DMFC membranes. However, we have carried out one-dimensional simulations of DMFC performance for a wide range of membrane properties, and the results indicate that DMFC performance is normally either limited by methanol permeability or proton conductivity. Thus use of a ‘selectivity’ is not appropriate for comparison of membrane materials, and results from the model can be used to compare different membranes. The results also show that Nafion^® 117 has an optimum thickness, where DMFC performance is equally limited by both methanol permeability and proton conductivity. The model also indicates that new composite membranes based on Nafion^® can only offer significant improvement in DMFC performance by enabling operation with increased methanol concentration in the fuel. A number of composite membrane materials that have been reported in the literature are shown to deliver significant reduction in DMFC performance due to reduced proton conductivity, although improved performance at high methanol concentration may be possible.     

Active direct methanol fuel cell: An overview

Direct methanol fuel cells (DMFC) are attractive for portable applications such as phone chargers, LEDs, sensors, etc. This study will present an overview of an active system of DMFC. An active system of DMFC is suitable for portable applications due to its high power output. A complete active system of DMFC consists of internal and external components. However, most of the research work only focused on the fundamental issues of internal components such as membranes and catalysts. Very few works have presented on a complete active system of DMFC. This study presents a review of both external and internal components used in active systems, including the fuel and product management utilized in active DMFC. The performance of a DMFC tested in an active system is also included. Finally, this paper summarizes the challenges and future advances in the design of active system DMFC.     

Modeling and simulation of a direct methanol fuel cell anode

A mathematical model for the anode of a direct methanol fuel cell (DMFC) is presented. This model considers the mass transport in the whole anode compartment and the proton exchange membrane (PEM), together with the kinetic and ohmic resistance effects through the catalyst layer. The influence of key parameters on methanol crossover and anode performance is investigated. Our results indicate that, at low current density and high methanol concentration, the methanol crossover poses a serious problem for a DMFC. The anodic overpotential and reaction-rate distributions throughout the catalyst layer are more sensitive to the protonic conductivity than to the diffusion coefficient of methanol. Increasing the protonic conductivity can effectively enhance the performance of a DMFC.     

Progress in poly(phenylene oxide) based cation exchange membranes for fuel cells and redox flow batteries applications

In fuel cell technologies, low-temperature proton exchange membrane fuel cells (LT-PEMFC), high-temperature proton exchange membrane fuel cells (HT- PEMFC), and direct methanol fuel cells (DMFC) are gained significant attention as a promising energy system for practical applications. The developments of cost-effective membrane materials with excellent physicochemical properties are indispensable for replacing the high cost of commercial membranes and achieving the higher performance of fuel cell systems. This review focuses on the developments and modifications of cost-effective poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) as a cation exchange membrane for LT-PEMFC, HT- PEMFC and DMFC. Notably, this review bridges the understanding of PPO based membranes, current advancements, structure, physicochemical properties and fuel cell performances. Progressive developments and a systematic overview of PPO-based membrane developments are explained in detail in terms of functionalization, blend, composite, acid-base, cross-linking, copolymerization, coated and reinforcement. Moreover, the changes in physicochemical properties and fuel cell performances in the membrane are deeply reviewed. Additionally, the utilization of PPO based membranes in different kinds of redox flow battery systems are reviewed. Overall, this review provides an exclusive vision and perspectives to develop the PPO based advanced, cost-effective, and high-performance membranes for fuel cell technologies and redox flow battery systems.     

White graphene based composite proton exchange membrane: Improved durability and proton conductivity

Boron nitride, which is also known as “white graphene” may be an attractive filler for composite proton exchange membrane. Application of polymer electrolyte membranes in fuel cell as an electrolyte is gaining attention due to the requirement of clean energy. However, despite its attractive features it requires more consideration for complete commercialization. Herein we demonstrate the preparation of novel functionalized WHITE GRAPHENE (hexagonal boron nitride) and sulfonated poly ether sulfone (SPES) based polymer electrolyte membranes (PEM). Composite membranes have been characterized through thermal, mechanical, structural analysis. Membranes have been subjected to measure methanol permeability and proton conductivity at different temperatures for its use in DMFC. Composite membranes exhibit good physicochemical properties as well as high methanol crossover resistance. 0.5 wt % of FBN (SP-FBN-05) membrane is found to be adequate to get the better performance in DMFC.     

Proton electrolyte membrane properties and direct methanol fuel cell performance: I. Characterization of hybrid sulfonated poly(ether ether ketone)/zirconium oxide membranes

This paper presents an evaluation of the zirconium oxide effects in sulfonated poly(ether ether ketone) (sPEEK) with sulfonation degree (SD) of 87%. A series of inorganic–organic hybrid membranes were prepared with a systematic variation of the zirconium oxide content via in situ zirconia formation (2.5, 5.0, 7.5, 10, 12.5 wt.%). This procedure enabled the preparation of proton electrolyte membranes (PEM) with a wide range of properties, which can be useful for evaluating the relationship between the PEM properties and the direct methanol fuel cell (DMFC) performance. The investigated properties are the proton conductivity, proton transport resistance, water uptake, water, methanol, oxygen, carbon dioxide and nitrogen permeability coefficients, morphology and elemental analysis. The results obtained show that the inorganic oxide network decreases the proton conductivity and water swelling. It is found that it leads also to a decrease of the water, methanol, carbon dioxide and oxygen permeability coefficients, an increase of the water/methanol selectivity and a decrease of the carbon dioxide/nitrogen and oxygen/nitrogen selectivities. In terms of morphology, it is found that in situ zirconium alkoxide hydrolysis enables the preparation of homogeneous membranes that present a good adhesion between inorganic domains and the polymer matrix.     

Electrodeposited platinum with various morphologies on carbon paper as efficient and durable self-supporting electrode for methanol and ammonia oxidation reactions

Direct methanol fuel cell (DMFC) and direct ammonia fuel cell (DAFC) have attracted wide attention due to high energy density, environment friendliness, easy availability and transportation of liquid fuel. However, the high cost and low durability of platinum (Pt) impede the large-scale application. Herein, we report a simple and effective approach to develop self-supporting electrodes (SSEs) using the square-wave potential (SWP) electrodeposition method. Compare with conventional electrode, this approach enables the absence of binder, in-situ growth of Pt catalyst on carbon paper, and easily controlled Pt morphologies. Consequently, prepared SSEs exhibit superior catalytic activity and durability toward methanol and ammonia oxidation reactions than the conventional electrode with Pt black as the catalyst. In particular, the SSE with cauliflower-like Pt catalyst exhibits the best catalytic activity and durability. This study suggests that SSE has a great potential in accelerating the practical application of direct liquid fuel cell (DMFC and DAFC).     

A DMFC stack operating with hydrocarbon blend membranes and Pt–Ru–Sn–Ce/C and Pd–Co/C electrocatalysts

Direct methanol fuel cell (DMFC) stacks consisting of 5 cells and 20 cells were assembled with low-cost hydrocarbon blend membranes and new electrocatalysts with better methanol tolerance and stability. The hydrocarbon blend membranes consisting of an acidic polymer (sulfonated poly (ether ether ketone), SPEEK) and a basic polymer (polysulfone-2-amide-benzimidazole, PSf-ABIm) exhibited low methanol crossover, high conductivity, and good mechanical stability. The Pt–Ru–Sn–Ce/C anode catalyst exhibited better stability than the commercial PtRu/C catalyst, while the cathode catalyst Pd–Co/C showed better methanol tolerance than the commercial Pt/C catalyst. A maximum power of around 20 W was achieved with a DMFC stack consisting of 20 membrane-electrode assemblies (MEAs) fabricated with the above membranes and electrocatalysts. The results demonstrate the feasibility of utilizing these acid-base blend membranes and novel catalysts for DMFC applications.     

A high-performance chitosan-based double layer proton exchange membrane with reduced methanol crossover

A novel double layer proton exchange membrane (PEM) comprising a layer of structurally modified chitosan, as a methanol barrier layer, coated on Nafion^®112 was prepared and assessed for direct methanol fuel cell (DMFC) applications. Scanning electron microscope (SEM) micrographs of the designed membrane revealed a tight adherence between layers, which indicate the high affinity of opposite charged polyelectrolyte layers. Proton conductivity and methanol permeability measurements showed improved transport properties of the designed membrane compared to Nafion^®117. Moreover, DMFC performance tests revealed a higher open circuit voltage and power density, as well as overall fuel cell efficiency for the double layer membrane in comparison with Nafion^®117, especially at elevated methanol solution feed. The obtained results indicate the designed double layer membrane as a promising PEM for high-performance DMFC applications.     

Stresses and their impacts on proton exchange membrane fuel cells: A review

The Proton Exchange Membrane (PEM) fuel cell is a promising substitute for combustion engines owing to its low level of output pollutants and high efficiency. Great efforts have been done toward the commercialization of PEM fuel cell. A number of review papers that investigate the electrochemical aspects of the fuel cell have already been published. However, the literature on the mechanical aspects is relatively limited. The durability of a PEM fuel cell is one of the significant factors that influence the industrialization of this technology. The PEM fuel cell is subjected to several mechanical stresses due to the different assembly procedures, operational and environmental aggressive conditions. Avoiding the high stress points is necessary for long term PEM fuel cell durability. The behavior of these generated stresses and how they affect each other is not well understood, including the compressive clamping stress, hygrothermal stress, freeze-thaw stress, and the stress due to vibration conditions. This paper reviews the developed stresses within the PEM fuel cell under different conditions. In addition, the various failure and damage mechanisms in the MEA, GDL, gas flow channel and bipolar plate due to these stresses are reviewed. The aforementioned stresses are discussed separately in the literature. The review shows that the combination of these stresses could be a key reason for the performance degradation and structural damage. This review suggests an effective tool to explore the correlation between the addressed stresses and to find out how they contribute to mechanical damage of PEM fuel cell systems and recommendations that can be implemented for improving the cell durability.     

Current status of cross-linking and blending approaches for durability improvement of hydrocarbon-based fuel cell membranes

Due to the demand for developing reliable and economical fuel cells, many researchers have focused on durability improvement of hydrocarbon-based proton exchange membranes (PEMs), without compromising performance. Among various techniques, cross-linking and blending show promising potentials by introducing physical and/or chemical bonds between polymer chains and creating a 3D network within their structure. Cross-linking is accomplished through thermal, solvothermal, radiation-assisted, and cross-linker assisted methods, whereas blending is categorized based upon the existing interactions between polymers, namely acid-acid, acid-base, and charge transfer network. This review article discusses the recent achievements of cross-linked and blend hydrocarbon-based PEMs in long-term stability tests and durability studies. Additionally, their salient dimensional, thermo-chemical, and transport properties are highlighted, including the in-situ fuel cell performance and electrochemical diagnostics. Accordingly, cross-linked and blend membranes have shown over 4000 h durability in hydrogen fuel cells and more than 100 times lower methanol cross-over compared to conventional fluorinated membranes, implying significant potential for commercialization.     

Low methanol crossover and high performance of DMFCs achieved with a pore-filling polymer electrolyte membrane

We compared the performance of the membrane electrode assembly for direct methanol fuel cells (DMFCs) composed of a pore-filling polymer electrolyte membrane (PF membrane) with that composed of a commercial Nafion-117 membrane. In DMFC tests, the methanol crossover flux was 23% lower in the PF membrane than in the Nafion-117 membrane even though the thickness of the PF membrane was 43% that of Nafion-117. This led to a higher DMFC performance and the lower overpotential of the cathode of the PF membrane. Feeding an aqueous 10 M methanol solution at 50 °C produced a low cathode overpotential, as low as 0.40 V at 0.2 A in the PF membrane, whereas the potential was 0.65 V at 0.2 A in the Nafion-117 membrane. In contrast, the ohmic loss and anode overpotential were almost the same in the two membranes. We confirmed that a reduction in methanol crossover using the PF membrane results in lower cathode overpotential and higher DMFC performance. In addition, the electro-osmotic coefficient was estimated as 1.3 in the PF membrane and 2.6 in Nafion-117, based on a water mass-balance model and values showing that the PF membrane prevents the flooding of the cathode at a low gas flow rate using. A highly concentrated methanol solution can be applied as a fuel without decreasing DMFC performance using PF membranes.     

Direct methanol fuel cell performance of sulfonated polyimide membranes

Sulfonated polyimides (SPIs) derived from 1,4,5,8-naphthalene tetracarboxylic dianhydride, 4,4′-bis(4-aminophenoxy) biphenyl-3,3′-disulfonic acid and hydrophobic aromatic diamines showed the much lower methanol permeability and the lower proton conductivity than Nafion 112. The performance and the water and methanol crossover for direct methanol fuel cells (DMFCs) with the SPI membranes were investigated in comparison with Nafion membranes. The methanol and water fluxes increased significantly with increasing load current density for Nafion membranes but not for the SPI membranes, indicating that they were controlled by both the electro-osmotic drag and the molecular diffusion for the former but by only the molecular diffusion for the latter. These resulted in the much better DMFC performance for the SPIs than Nafion membranes especially at high methanol feed concentrations. The Faraday's efficiency and overall DMFC efficiency at 60 °C and 200 mA cm⁻² for SPI membrane with IEC of 1.51 meq g⁻¹ were 75% and 21%, respectively, at 5 wt.% methanol feed concentration, and 36% and 9.5%, respectively, at 20 wt.% methanol concentration. They were about two times and three times higher at 5 wt.% and 20 wt.% methanol concentrations, respectively, than those for Nafion 112. The short-term durability test for 300 h at 60 °C revealed no deterioration in the DMFC performance. The SPI membranes have high potential for DMFC applications at mediate temperatures (40–80 °C).     

Sulfonated PEEK-based polymers in PEMFC and DMFC applications: A review

Nowadays, polymer electrolyte membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs) are devices known for using proton conducting membranes. From a conceptual point of view, DMFC and PEMFC systems are very similar, except for being supplied by different fuels such as methanol and hydrogen, respectively. Commonly, PEMFCs are performed at temperature lower than 100 °C owing to the failure of the electrochemical performances of Nafion. Nevertheless, taking into account the poisoning effect of CO on the fuel cell catalyst (conventionally based on Pt), the ideal working temperature of the PEMFCs should be above 100 °C, where CO poisoning could be drastically reduced or avoided. Today, Nafion is recognized as the most used proton exchange membrane in the market, useful for both PEMFC and DMFC applications. It is based on a perfluorinated polymer and shows good thermal stability and high proton conductivity as main benefits. On the contrary, Nafion is an expensive material and suffers high fuel crossover (particularly, methanol crossover in DMFC applications) besides the proton conductivity loss above 100 °C. Therefore, in the last decades many scientists paid special attention on the development of new materials based on non-fluorinated polymers as an alternative to Nafion. One of the most promising class of is represented by the polyetheretherketone (PEEK). According to the specialized literature, interesting performances in terms of proton conductivity and thermo-chemical properties as well as low fuel crossover and costs are noticeable for sulfonated PEEK-based polymers. Indeed, many scientific applications are devoted to modify PEEK polymer for manufacturing membranes alternative to Nafion for both PEMFC and DMFC applications. Among them, important methods are exploited for preparing electrolyte membranes from PEEK such as: a) PEEK electrophilic sulfonation (S-PEEK); b) S-PEEK and non-functional polymers blending; c) S-PEEK, heteropolycompounds and poly-ether-imide doping with inorganic acids, etc.