Characteristics and performance of membrane electrode assemblies with operating conditions in polymer electrolyte membrane fuel cell

The degradation behavior of a membrane-electrode assembly (MEA) was investigated in accelerated degradation tests under constant voltage (0.8 V and 0.7 V) and load cycling (from open circuit voltage to 0.35 V) conditions. Changes in the structural and electrochemical characteristics of MEA after the durability tests give information as to the degradation mechanism of MEAs. The results of cyclic voltammogram and postmortem analysis by X-ray diffraction and high resolution-transmission electron microscopy indicate that the cathode catalyst layers of the MEAs showed no extreme degradation under constant voltage mode, whereas MEAs under repetition of load cycling mode showed very severe degradation after 280 h. However, the single cell performance of the MEA under repetition of load cycling mode was higher than under constant voltage mode. In addition, although the Pt band in the membrane of the MEA under repetition of load cycling mode was observed by field emission scanning electron microscopy, it did not affect the ohmic resistance.     

Fuel cell performance of polymer electrolyte membrane based on hexafluorinated sulfonated poly(ether sulfone)

The potential-current fuel cell characteristics of membrane electrode assemblies (MEAs) using hexafluorinated sulfonated poly(ether sulfone) copolymer are compared to those of Nafion^® based MEAs in the case of proton exchange membrane fuel cell (PEMFC) and direct methanol fuel cell (DMFC). The hexafluorinated copolymer with 60 mol% of monosulfonated comonomer based acid form membrane is chosen for this study due to its high proton conductivity, high thermal stability, low methanol permeability, and its insolubility in boiling water. The catalyst powder is directly coated on the membrane and the catalyst coated membrane is used to fabricate MEAs for both fuel cells. A current density of 530 mA cm^?2 at 0.6 V is obtained at 70 °C with H₂/air as the fuel and oxidant. The peak power density of 110 mW cm^?2 is obtained at 80 °C under specific DMFC operating conditions. Other electrochemical characteristics such as electrochemical impedance spectroscopy, cyclic voltammetry, and linear sweep voltammetry are also studied.     

Performance improvement of electrode for polymer electrolyte membrane fuel cell

The very high power density output available from polymer electrolyte membrane fuel cells combined with low cost has high potential for commercialization. Such high power densities are attained via better utilization of Pt crystallites in the reaction layer. This enhanced performance can be achieved by making a thin catalyst layer on the membrane surface. The robustness in the front surface catalysts is essential to minimize the coagulation of Pt particles when the fuel cells are subjected to long-term operation. This robustness of the catalyst structure depends on the manufacturing processes and also the organic solvents used to make the slurry. In this work, five different electrodes were fabricated by using different fabrication procedures, and the poison effect of CO was investigated at the anode interface.     

Characteristics of membrane humidifiers for polymer electrolyte membrane fuel cells

Water management plays an important role in obtaining high performance from a polymer electrolyte membrane fuel cell (PEMFC). To reduce the volume and energy consumption of widely-used bubble humidifiers, membrane humidifiers were fabricated by using an ultrafiltration (UF) membrane and Nafion membranes. The performance of the membrane humidifiers was examined as a function of gas flow rate and operating temperature. A single cell was operated using the UF membrane humidifiers exhibiting almost the same performance with that employing bubble humidifiers.     

Enhanced performance and improved interfacial properties of polymer electrolyte membrane fuel cells fabricated using sputter-deposited Pt thin layers

For this study, catalyst layers for polymer electrolyte membrane fuel cells (PEMFC) were prepared by spraying and sputtering to deposit Pt amount of 0.1 and 0.01 mg cm⁻², respectively. These Pt layers were then assembled to fabricate membrane electrode assemblies (MEA) having either single- or double-layered catalysts. The PEM fuel cell with double layers showed a current density of 777 mA cm⁻² at a cell voltage of 0.6 V, which is a higher current density than state-of-the-art fuel cells at 643 mA cm⁻². These results indicate that Pt loading in state-of-the-art PEMFCs could be reduced by approximately 50% with no performance loss by using both spraying and sputtering method in the MEA fabrication process.     

Tungsten oxide in polymer electrolyte fuel cell electrodes—A thin-film model electrode study

Thin films of WO_x and Pt on WO_x were evaporated onto the microporous layer of a gas diffusion layer (GDL) and served as model electrodes in the polymer electrolyte fuel cell (PEFC) as well as in liquid electrolyte measurements. In order to study the effects of introducing WO_x in PEFC electrodes, precise amounts of WO_x (films ranging from 0 to 40 nm) with or without a top layer of Pt (3 nm) were prepared. The structure of the thin-film model electrodes was characterized by scanning electron microscopy and X-ray photoelectron spectroscopy prior to the electrochemical investigations. The electrodes were analyzed by cyclic voltammetry and the electrocatalytic activity for hydrogen oxidation reaction (HOR) and CO oxidation was examined. The impact of Nafion in the electrode structure was examined by comparing samples with and without Nafion solution sprayed onto the electrode. Fuel cell measurements showed an increased amount of hydrogen tungsten bronzes formed for increasing WO_x thicknesses and that Pt affected the intercalation/deintercalation process, but not the total amount of bronzes. The oxidation of pre-adsorbed CO was shifted to lower potentials for WO_x containing electrodes, suggesting that Pt-WO_x is a more CO-tolerant catalyst than Pt. For the HOR, Pt on thicker films of WO_x showed an increased limiting current, most likely originating from the increased electrochemically active surface area due to proton conductivity and hydrogen permeability in the WO_x film. From measurements in liquid electrolyte it was seen that the system behaved very differently compared to the fuel cell measurements. This exemplifies the large differences between the liquid electrolyte and fuel cell systems. The thin-film model electrodes are shown to be a very useful tool to study the effects of introducing new materials in the PEFC catalysts. The fact that a variety of different measurements can be performed with the same electrode structure is a particular strength.     

Effects of MEA fabrication method on durability of polymer electrolyte membrane fuel cells

To study the effects of fabrication methods on the durability of polymer electrolyte membrane fuel cells (PEMFCs), membrane-electrode assemblies (MEAs) were fabricated using a conventional method, a catalyst-coated membrane (CCM) method, and a CCM-hot pressed method. Single cells assembled with the prepared MEAs were operated galvanostatically at 600 mA cm⁻² for 1000 h for the conventional MEA and the CCM MEA and for 500 h for the CCM-hot pressed MEA. During operation, i-V curves, impedance spectra, and cyclic voltammograms were measured roughly every 100 h. Before and after long-term operation, the physical and chemical characteristics of the MEAs were analyzed using mercury porosimetry, X-ray diffraction (XRD), scanning electron microscopy (SEM), electron probe microanalysis (EPMA), and Fourier transformation infrared spectroscopy (FTIR). Under the operating conditions, the CCM MEA exhibited the lowest degradation rate as well as the highest initial performance.     

Basic examination of membrane electrode assembly of proton exchange membrane fuel cell considering heat deterioration

The purpose of this research is to develop a standard preparation method for membrane electrode assemblies (MEAs). Therefore, the preparation method for multilayered MEAs with gas diffusion layers (GDLs) and the degree to which polymer membranes deteriorate by heating were studied. As a result, improvement of power density by making multi catalyst layers provides a solution to some problems found in thin polymer membranes. In addition, it was found that improving the diffusion of gas through two-layer GDLs in cathode (duct side: carbon paper, catalyst layer side: carbon cross) results in a cross leak reduction. Moreover, a making condition of MEAs was optimized by varying the temperatures used for the multi catalyst layers and two-layer GDLs. The analysis of heat deterioration of the Nafion membrane using X-ray photoelectron spectroscopy (XPS) indicates that the optimal hot press temperature is 130 °C.     

DMFC electrode preparation,performance and proton conductivity measurements

A method that involves stenciling electrodes using dry powders for fuel cells is described and compared to anodes and cathodes prepared by the traditional spraying method using catalyst inks. Methods to determine the proton conductivity of the DMFC anode layer are also discussed. The stenciling method allows for the preparation of highly reproducible membrane electrode assemblies (MEAs) utilizing little waste material. MEAs can be prepared in a controlled manner using the stenciling technique. The resulting morphology of the as-prepared electrodes is observed to be dependent on the preparation method, while the thickness of the once hot-pressed catalyst layers appears to be independent of the preparation method. Stenciled anodes of the same catalyst loading were found to show a lower proton resistance (R_p) than sprayed anodes. However, the lower R_p value was not sufficient to result in a measurable increase in the performance of a direct methanol fuel cell (DMFC); as in fact, the average steady-state DMFC performance was found to be the same using sprayed or stenciled electrodes. The DMFC performance was found to be strongly dependent on the Nafion content and large increases in the Nafion content were needed to increase the DMFC performance measurably. Even though thick electrodes were prepared in this work, the R_p values of the stenciled anodes were found to be comparable to results reported in the literature for much thinner electrodes made using high metal catalyst loadings on carbon. This observation is most probably due to the higher Nafion content used in this work.     

On a new degradation mode for high-temperature polymer electrolyte fuel cells: How bipolar plate degradation affects cell performance

The contribution of the bipolar plate material to the overall degradation of a high temperature membrane electrode assembly (HT MEA) for polymer electrolyte fuel cells (PEFCs) is studied in terms of performance decrease, phosphoric acid uptake in the bipolar plates and change of surface morphology of the bipolar plates. Two different high temperature graphite composites, a surface treated graphite and a gold coated stainless steel flowfield and the respective MEAs are compared after operation at 180 °C. Both graphite surface treatment and gold coating lead to negligible uptake of the electrolyte and ensure low degradation rates, whereas the composite plates exhibit high uptake of acid from the MEA into the surface near bulk. Apparent MEA degradation caused by acid redistribution from the MEA to the increasingly porous plates is observed in terms of increased ohmic cell resistances and reduction of catalyst utilization as consequence of acid loss from the catalyst layers.     

Simulation of a polymer electrolyte fuel cell electrode

A detailed one dimensional dynamic model of a gas diffusion electrode as part of a complete fuel cell model is presented. Various effects of parameter changes are considered. Comparison of experimental results and simulation is performed and a new approach to simulation of a complete current voltage curve is discussed.     

Realising a reference electrode in a polymer electrolyte fuel cell by laser ablation

This work presents a new concept for realising a reference electrode configuration in a PEM fuel cell by means of laser ablation. The laser beam is used to evaporate a small part of the electrode of a catalyst-coated membrane (CCM) to isolate the reference electrode from the active catalyst layer. This method enables the simultaneous ablation of the electrodes on both sides of the CCM because the membrane is transparent for the laser beam. Therefore, a smooth electrode edge without electrode misalignment can be realised. A test fuel cell was constructed which together with the ablated CCM enables the separation of the total cell losses during operation into the cathode, anode and membrane overpotentials in PEFC as well as in DMFC mode. The methanol tolerance of a selenium-modified ruthenium-based catalyst (RuSe _x ) was investigated under real fuel cell conditions by measuring polarisation curves, electrochemical impedance spectroscopy (EIS) and current interrupt measurements (CI).     

A polymer electrolyte membrane for high temperature fuel cells to fit vehicle applications

Poly(tetrafluoroethylene) PTFE/PBI composite membranes doped with H₃PO₄ were fabricated to improve the performance of high temperature polymer electrolyte membrane fuel cells (HT-PEMFC). The composite membranes were fabricated by immobilising polybenzimidazole (PBI) solution into a hydrophobic porous PTFE membrane. The mechanical strength of the membrane was good exhibiting a maximum load of 35.19 MPa. After doping with the phosphoric acid, the composite membrane had a larger proton conductivity than that of PBI doped with phosphoric acid. The PTFE/PBI membrane conductivity was greater than 0.3 S cm⁻¹ at a relative humidity 8.4% and temperature of 180 °C with a 300% H₃PO₄ doping level. Use of the membrane in a fuel cell with oxygen, at 1 bar overpressure gave a peak power density of 1.2 W cm⁻² at cell voltages >0.4 V and current densities of 3.0 A cm⁻². The PTFE/PBI/H₃PO₄ composite membrane did not exhibit significant degradation after 50 h of intermittent operation at 150 °C. These results indicate that the composite membrane is a promising material for vehicles driven by high temperature PEMFCs.     

Optimum condition of membrane electrode assembly fabrication for PEM fuel cells

The aim of this research was to study the effect of fabrication factors on the performance of MEA of a PEM fuel cell. The MEA was prepared by using 5 cm² of porous electrodes with Pt loading 1 mg/cm² and Nafion 115 membrane from Electrochem Co. Ltd. The studied factors were temperature, pressure and time of compression in the range of 130–150 ‡C, 50–100 kg/cm² and 1–5 minutes, respectively. A 2^k factorial design was conducted in this study. The results showed that interaction between pressure and temperature and interaction between temperature and time of compression have significant effects on the performance of the MEA. With low pressure, but high temperature and long compression time, current density is increased. The results showed that the optimum condition was 65 kg/cm², 137 ‡C and 5.5 min of compression time. It was also found that the force of 69 kg-cm for assembling the single cell gave the best performance.     

Effects of heat and water transport on the performance of polymer electrolyte membrane fuel cell under high current density operation

Key challenges to the acceptance of polymer electrolyte membrane fuel cells (PEMFCs) for automobiles are the cost reduction and improvement in its power density for compactness. In order to get the solution, the further improvement in a fuel cell performance is required. In particular, under higher current density operation, water and heat transport in PEMFCs has considerable effects on the cell performance. In this study, the impact of heat and water transport on the cell performance under high current density was investigated by experimental evaluation of liquid water distribution and numerical validation. Liquid water distribution in MEA between rib and channel area is evaluated by neutron radiography. In order to neglect the effect of liquid water in gas channels and reactant species concentration distribution in the flow direction, the differential cell was used in this study. Experimental results suggested that liquid water under the channel was dramatically changed with rib/channel width. From the numerical study, it is found that the change of liquid water distribution was significantly affected by temperature distribution in MEA between rib and channel area. In addition, not only heat transport but also water transport through the membrane also significantly affected the cell performance under high current density operation.     

AB-PBI分子量对高温膜燃料电池膜电极性能的影响

聚合物分子量是表征聚合物特征的基本参数之一,分子量不同,聚合物的性能差异很大,其对高温质子交换膜燃料电池膜电极的输出性能亦起着至关重要的作用。聚（2,5-苯并咪唑）(ABPBI)的结构简单, 合成方便,可由单一单体聚合而成, 而且其每一个苯并咪唑重复单元上的-N 基团都可与酸以氢键的方式结合, 因而呈现较好的质子电导率。合成了4种不同分子量的ABPBI,采用自制ABPBI膜作为电解质,Pt/C为催化剂,研究了不同分子量ABPBI配制的浆料组装的氢氧高温燃料电池的性能,通过极化曲线测试可以看出聚合物分子量越小膜电极(MEA)性能越好。进一步对膜电极交流阻抗性质进行了研究,经Zsimpwin软件拟合得出,分子量越大电荷转移电阻越大,与极化曲线测试结果相符,并且随着电流密度的增大,各部分电阻均成下降趋势。     

Effect of ambient conditions on performance and current distribution of a polymer electrolyte membrane fuel cell

The performance and current distribution of a free-breathing polymer electrolyte membrane fuel cell (PEMFC) was studied experimentally in a climate chamber, in which temperature and relative humidity were controlled. The performance was studied by simulating ambient conditions in the temperature range 10 to 40 °C. The current distribution was measured with a segmented current collector. The results indicated that the operating conditions have a significant effect on the performance of the fuel cell. It was observed that a temperature gradient between the fuel cell and air is needed to achieve efficient oxygen transport to the electrode. Furthermore, varying the air humidity resulted in major changes in the mass diffusion overpotential at higher temperatures.     

Electrochemical performance and stability of thin film electrodes with metal oxides in polymer electrolyte fuel cells

Thin film electrodes are prepared by thermal evaporation of nanometer thick layers of metal oxide and platinum on a gas diffusion layer (GDL), in order to evaluate different metal oxides’ impact on the activity and stability of the platinum cathode catalyst in the polymer electrolyte fuel cell. Platinum deposited on tin, tantalum, titanium, tungsten and zirconium oxide is investigated and the morphology and chemistry of the catalysts are examined with scanning electron microscopy and X-ray photoelectron spectroscopy. Cyclic sweeps in oxygen and nitrogen are performed prior and after potential cycling degradation tests. Platinum seems to disperse better on the metal oxides than on the GDL and increased electrochemically active surface area (ECSA) of platinum is observed on tin, titanium and tungsten oxide. A thicker layer metal oxide results in a higher ECSA. Platinum deposited on tungsten performs better than sole platinum in the polarisation curves and displays higher Tafel slopes at higher current densities than all other samples. The stability does also seem to be improved by the addition of tungsten oxide, electrodes with 3 nm platinum on 3, 10 and 20 nm tungsten oxide, performs better than all other electrodes after the accelerated degradation tests.     

燃料电池自增湿膜电极的研究进展

使用自增湿膜电极可以减去燃料电池复杂的增湿系统,并使得膜电极的水热管理变得容易和简单,对于燃料电池的大规模商业化具有重要意义。本文主要从自增湿复合膜、自增湿催化层以及自增气体扩散层等几个方面介绍了近年来自增湿膜电极的一些重要研究进展和发展趋势。首先介绍了基于掺杂和复合机构的自增湿复合膜的发展状况,指出自增湿复合膜是最直接有效的自增湿方式;其次介绍了基于物理或化学方法构筑的自增湿催化层的研究现状,认为构筑自增湿催化层能够促进阴极侧电化学反应生成的水向阳极侧的反扩散,从而提高膜电极的低湿度性能;最后综述了自增湿气体扩散层,对这类电极的发展趋势及应用前景进行了展望。     

Performance and durability of sulfonated poly(arylene ether sulfone) membrane-based membrane electrode assemblies fabricated by decal method for polymer electrolyte fuel cells

The combination of Nafion-based electrode and hydrocarbon-based membrane is an ideal choice for researcher in making membrane electrode assemblies (MEAs) containing alternative membranes replacing Nafion for polymer electrolyte fuel cells (PEFCs) due to their intrinsic properties. This advantage, however, is limited by the incompatibility between the membrane and the electrode, which results in MEA performance decay and low durability. In this study, we propose fabrication of MEA made of sulfonated poly(aryl ether sulfone) (SPES) membrane and Nafion-based electrode using the decal process. The decal process was found to be very effective in forming good interface between SPES and the electrode, although hot pressing temperature was relatively low (140 °C). The SPES-MEA revealed comparable performance to conventional Nafion-MEA at high humidity, indicating negligible contact resistance in the SPES–electrode interface. Open circuit voltage (OCV) drop of SPES-MEA during OCV holding at 40% RH for 200 h was from 0.975 V to 0.8 V, implying slight chemical degradation of SPES leading to increased hydrogen crossover in the membrane. However, it seems that the interfacial damage between the SPES and Nafion electrode in the SPES-MEA is negligible during the OCV test. Nonetheless, further investigation is necessary to confirm the long-term stability of the SPES-MEA fabricated by the decal process under harsher conditions such as dry/wet and freeze/thaw cycling.