Electrochemical durability of gas diffusion layer under simulated proton exchange membrane fuel cell conditions

An effective ex-situ method for characterizing electrochemical durability of a gas diffusion layer (GDL) under simulated polymer electrolyte membrane fuel cell (PEMFC) conditions is reported in this article. Electrochemical oxidation of the GDLs are studied following potentiostatic treatments up to 96 h holding at potentials from 1.0 to 1.4 V (vs.SCE) in 0.5 mol L⁻¹ H₂SO₄. From the analysis of morphology, resistance, gas permeability and contact angle, the characteristics of the fresh GDL and the oxidized GDLs are compared. It is found that the maximum power densities of the fuel cells with the oxidized GDLs hold at 1.2 and 1.4 V (vs.SCE) for 96 h decreased 178 and 486 mW cm⁻², respectively. The electrochemical impedance spectra measured at 1500 mA cm⁻² are also presented and they reveal that the ohmic resistance, charge-transfer and mass-transfer resistances of the fuel cell changed significantly due to corrosion at high potential.     

Degradation mitigation effects of pressure swing in proton exchange membrane fuel cells with dead-ended anode

High cost remains to be one of the primary obstacles for the commercialization of proton exchange membrane fuel cells (PEMFCs). To simplify the fuel cell system and reduce cost, dead-ended anode (DEA) is widely used. However, water and nitrogen can accumulate in the dead-ended anode, resulting in cell performance decrease and severe cell degradation. Anode pressure swing supply is a new technology which has been shown to be effective in reducing local water and nitrogen accumulation in the anode channel. In this work, the effects of pressure swing supply on fuel cell degradation have been experimentally studied. Two sets of experiments on the same fuel cell are conducted, one under conventional constant pressure operation and the other under pressure swing operation. Polarization curves show that pressure swing supply can significantly mitigate cell degradation during DEA operations. Electrochemical characterizations are performed to study the mechanisms of mitigations in cell degradation. The cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) results show that pressure swing supply can significantly reduce electrolyte membrane degradation, but has no significant mitigation effect on the cathode catalyst degradation during DEA operation. Further examinations of the membrane-electrode-assembly (MEA) by scanning electron microscope (SEM) confirm the significant difference in membrane degradations since there is a very large difference in average thickness of the membranes after the degradation tests.     

Different flow fields,operation modes and designs for proton exchange membrane fuel cells with dead-ended anode

Water and nitrogen can accumulate in the anode channel in proton exchange membrane fuel cells (PEMFCs) with dead-ended anode (DEA) and can affect cell performance significantly. In this paper, the cell performance characteristics in DEA PEMFCs with three different anode flow fields under two operating modes are studied through measuring the cell voltages and local current densities. The effect of the anode exit reservoir is also studied for the three different anode flow fields. The experimental results show that the interdigitated flow field has the most stable cell performance under both constant pressure and pressure swing supply modes. Parallel and serpentine flow fields lead to very non-uniform local current distributions under constant pressure supply mode and experience severe fluctuations and spikes in local current densities under pressure swing supply mode. The results also show that anode pressure swing supply mode can achieve more stable cell performance than anode constant pressure supply mode for parallel and serpentine anode flow fields. The anode exit reservoir can significantly improve cell performance stability for parallel and serpentine flow fields, but has no significant effect on interdigitated flow fields. Besides, the results further show that PEMFCs with DEA can maintain very stable operation with anode serpentine flow field and an anode exit reservoir under pressure swing operation.     

Analysis of the spatially distributed performance degradation of a polymer electrolyte membrane fuel cell stack

Herein we report the spatially uneven degradation of a polymer electrolyte membrane fuel cell (PEMFC) stack operated under load variation. Fifteen sub-membrane electrode assemblies (sub-MEAs) at various cell positions and various points within each cell were obtained from the original MEAs employed in the fuel cell stack. Polarization curves and the voltammetric charge of these MEAs were measured in order to correlate localized performances with the redistributed electrochemically active surface on Pt using the polarization technique and cyclic voltammetry. Several ex situ characterizations including electron probe microanalysis, environmental scanning electron microscopy, and X-ray diffraction were also performed to find evidence, supporting the inhomogeneous degradation of the fuel cell stack. Possible routes and processes for the non-uniform stack degradation during the PEMFC stack operation will also be discussed.     

Experimental study on carbon corrosion of the gas diffusion layer in polymer electrolyte membrane fuel cells

Generally, the GDL of a PEM fuel cell experiences three external attacks: dissolution of water, erosion of gas flow, and corrosion of electric potential. Of these degradation factors, this study focuses on the carbon corrosion of electric potential and investigates its impact through the accelerated carbon corrosion test. This study confirms that carbon corrosion occurs at the GDL, which decreases the operating fuel cell’s performance. To discover the effects of carbon corrosion, the GDL property changes are measured through various devices, including a scanning electron microscopy, a thermo gravimetric analyzer, and a tensile stress test. Carbon corrosion causes not only loss of weight and thickness but also degradation of mechanical strength in the GDL. In addition, the GDL shows serious damage in its center.     

Effects of anode air bleeding on the performance of CO-poisoned proton-exchange membrane fuel cells

In the present work, the dynamic behavior of a PEM fuel cell under CO-poisoning and the effects of air bleeding on the recovery ratio are reported. Pt-Ru catalyst is used as the anode in a single cell and the hydrogen is pre-mixed with 53 ppm of CO as the fuel. The result indicates that even using a CO-tolerant catalyst, CO-poisoning cannot be avoided with the operating conditions in our study. About 80% of the output current is lost within 20 min. Upon anode air bleeding with 5% air, 90% of the current is recovered within 1 min. Higher air bleeding ratio only results in minor improvement of the cell performance. We have developed a transient model to estimate the current reduction due to CO-poisoning and to evaluate the amount of air bleeding needed for a given recovery ratio. A long-term durability test has also been conducted using simulated reformatted gas, in which 1% O₂ is injected into the fuel stream. After more than 3000 h, the cell voltage degradation is less than 3%.     

Effect of anode iridium oxide content on the electrochemical performance and resistance to cell reversal potential of polymer electrolyte membrane fuel cells

An ideal polymer electrolyte membrane fuel cell (PEMFC) is one that continuously generates electricity as long as hydrogen and oxygen (or air) are supplied to its anode and cathode, respectively. However, internal and/or external conditions could bring about the degradation of its electrodes, which are composed of nanoparticle catalysts. Particularly, when the hydrogen supply to the anode is disrupted, a reverse voltage is generated. This phenomenon, which seriously degrades the anode catalyst, is referred to as cell reversal. To prevent its occurrence, iridium oxide (IrO₂) particles were added to the anode in the membrane-electrode assembly of the PEMFC single-cells. After 100 cell reversal cycles, the single-cell voltage profiles of the anode with Pt/C only and the anodes with Pt/C and various IrO₂ contents were obtained. Additionally, the cell reversal-induced degradation phenomenon was also confirmed electrochemically and physically, and the use of anodes with various IrO₂ contents was also discussed.     

Challenges and future developments in proton exchange membrane fuel cells

Fuel cell system is an advanced power system for the future that is sustainable, clean and environmental friendly. The importance of fuel cell as the future power system is discussed in the light of future fossil fuel depletion, impending international law on green house gases control and the national renewable energy policy. The modern development of the proton exchange membrane fuel cell (PEMFC) for the last 20 years is then briefly reviewed and the current status of international and national research and development of this type of are established. The review also discuss the remaining research and development issues that still need to be resolved before these fuel cells are available for commercial application. The main thrust in PEMFC research and development is to lower the cost of the fuel cell by reduction in membrane and electrocatalyst costs. Although Europe, USA, Canada and Japan are leading fuel cell research and development as commercialization, it is not too late for Malaysia to master this technology and to apply it to niche markets in the future.     

Hydrocarbon-based electrode ionomer for proton exchange membrane fuel cells

The electrode ionomer is a key factor that significantly affects the catalyst layer morphology and fuel cell performance. Herein, sulfonated poly(arylene ether sulfone)-based electrode ionomers with polymers of various molecular weights and alcohol/water mixtures were prepared, and those comprising the alcohol/water mixture showed a higher performance than the ones prepared using higher boiling solvents, such as dimethylacetamide; this is owing to the formation of the uniformly dispersed ionomer catalyst layer. The relation between ionomer molecular weight for the same polymer structure and the sulfonation degree was investigated. Because the chain length of polymer varies with molecular weight and chain entanglement degree, its molecular weight affects the electrode morphology. As the ionomer covered the catalyst, the agglomerates formed were of different morphologies according to their molecular weight, which could be deduced indirectly through dynamic light scattering and scanning electron microscopy. Additionally, the fuel cell performance was confirmed in the current-voltage curve.     

Nanowire-based three-dimensional hierarchical core/shell heterostructured electrodes for high performance proton exchange membrane fuel cells

In order to effectively utilize expensive Pt in fuel cell electrocatalyst and improve the durability of PEM fuel cells, new catalyst supports with three-dimensional (3D) open structure are highly desirable. Here, we report the fabrication of a 3D core/shell heterostructure consisting tin nanowire core and carbon nanotube shell (SnC) grown directly onto fuel cell backing (here carbon paper) as Pt catalyst support for PEM fuel cells. Compared with the conventional Pt/C membrane electrode assembly (MEA), SnC nanowire-based MEA shows significantly higher oxygen reaction performance and better CO tolerance as well as excellent stability in PEM fuel cells. The results demonstrate that the core/shell nanowire-based composites are very promising supports in making cost effective and electrocatalysts for fuel cell applications.     

Direct ethanol fuel cells using an anion exchange membrane

Direct ethanol fuel cells (DEFCs) with a PtRu anode and a Pt cathode were prepared using an anion exchange membrane (AEM) as an electrolyte instead of a cation exchange membrane (CEM), as in conventional polymer electrolyte fuel cells. The maximum power density of DEFCs significantly increased from 6 mW cm⁻² to 58 mW cm⁻² at room temperature and atmospheric pressure when the electrolyte membrane was changed from CEM to AEM. The anode and cathode polarization curves showed a decrease in the anode potential and an increase in the cathode potential for AEM-type DEFCs compared to CEM-type. This suggests that AEM-type DEFCs have superior catalytic activity toward both ethanol oxidation and oxygen reduction in alkaline medium than in acidic medium. The product species from the exhausted liquid from DEFCs operated at a constant current density were identified by enzymatic analysis. The main product was confirmed to be acetic acid in AEM-type, while both acetaldehyde and acetic acid were detected in 1:1 ratio in CEM-type. The anodic reaction of AEM-type DEFCs can be estimated to be the oxidation of ethanol to acetic acid via a four-electron process under these experimental conditions.     

Electrochemical carbon corrosion in high temperature proton exchange membrane fuel cells

Electrochemical carbon corrosion occurring in a high temperature proton exchange membrane fuel cell (HT-PEMFC) operating under non-humidification conditions was investigated by measuring CO₂ generation using on-line mass spectrometry and comparing the results with a low-temperature proton exchange membrane fuel cell (LT-PEMFC) operated under fully humidified conditions. The experimental results showed that more CO₂ was measured for the HT-PEMFC, indicating that more electrochemical carbon corrosion occurs in HT-PEMFCs. This observation is attributed to the enhanced kinetics of electrochemical carbon corrosion due to the elevated operating temperature in HT-PEMFCs. Additionally, electrochemical carbon corrosion in HT-PEMFCs showed a strong dependence on water content. Therefore, it is critical to remove the water content in the supply gases to reduce electrochemical carbon corrosion.     

Micro fluidic structure selection of metal mesh combinations in proton exchange membrane fuel cells for air supply enhancement

One of the most significant factors affecting the performance of a proton exchange membrane fuel cell is the flow path for the passage of air and water, which is responsible for oxygen dispersion. A three-dimensional fine mesh, with optimized flow paths, exhibits the best performance in commercialized fuel cell electric vehicles, but the manufacturing cost is significantly high. To achieve high performance at a lower cost, the possibility of using a combination of commercially available screen meshes was investigated. The overlapped screen meshes should provide improved mass transport similar to a 3-D fine mesh. By using an optimized combination of screen meshes (200 and 100 mesh) and gasket thickness (150 μm thinner than the mesh flow field), an improvement in oxygen mass transport was achieved. The suggested combination shows a lower oxygen gain (0.030 V) than a single mesh (0.050 V) and a conventional single serpentine flow field (0.150 V).     

Study on the processes of start-up and shutdown in proton exchange membrane fuel cells

Several different start-up and shutdown processes of a fuel cell were investigated in this paper by measuring cathode, anode and membrane potentials respectively versus reference hydrogen electrode (RHE). The membrane potential was measured by using thin copper wire sandwiched between two membranes. During the formation of hydrogen/air boundary at the anode caused by unprotected start-up and shutdown, the in-plane potential difference between membrane inlet and outlet was measured to be as high as 0.8 V, and the interfacial potential difference between cathode and membrane outlet increased to about 1.6 V, which in turn would cause carbon corrosion. Appropriate start-up and shutdown processes were suggested to avoid the formation of hydrogen/air boundary.     

Thickness effects of anode catalyst layer on reversal tolerant performance in proton exchange membrane fuel cell

Real-world driving conditions will likely cause hydrogen starvation at the anode chambers of stacks to trigger voltage reversal events, posing a tremendous challenge to the durability of proton exchange membrane fuel cells (PEMFCs). The reversal-tolerant anode (RTA), a material-based solution, that inclusion of oxygen evolution reaction (OER) catalyst into the anode is usually employed to cope with the voltage reversal issue. In this work, we investigate the impact of anode catalyst layer thickness on the voltage reversal performance of the membrane-electrode assemblies (MEAs) with conventional anodes (Pt/C catalyst) and RTAs doped with IrO₂ catalyst, a representative OER catalyst. We find that regardless of how thick the anode catalyst layer is, the conventional MEAs exhibit almost similar voltage reversal behaviors and times, only about 1 min to reach the shutdown voltage (?2.5 V). As for the RTA MEAs, a surprising thickness effect that the thinner RTA with the same IrO₂ loading shows superior voltage reversal tolerance. Notably, an ultra-thin RTA (~2 μm) exhibits the reversal tolerance time of 310 min, which is five times higher reversal tolerance time than most of the reported RTAs. We conclude that this thickness effect mainly results from the ionomer distribution on the OER catalyst. Besides, we observe that the RTA with a higher ionomer content shows the better reversal tolerance performance. Our work highlights the importance of the OER Triple-Phase-Boundary (TPB) and the need for improved electrode designs for robust RTAs.     

Effects of chlorides on the performance of proton exchange membrane fuel cells

This paper investigates the effects of cathode gases containing chloride ions on the proton exchange membrane fuel cell (PEMFC) performance. Chloride solutions are vaporized using an ultrasonic oscillator and mixed with oxygen/air. The salt concentration of the mixed gas in the cathode is set by varying the concentration of the chloride solution. Five-hour tests show that an increase in the concentration of sodium chloride did not significantly affect the cell performance of the PEMFC. It is found that variations in the concentration of chloride do not show significant influence on the cell performance at low current density operating condition. However, for high current density operating conditions and high calcium chloride concentrations, the chloride ion appears to have a considerable effect on cell performance. Experimental results of 108-h tests indicate that the fuel cell operating with air containing calcium chloride has a performance decay rate of 3.446 mV h⁻¹ under the operating condition of current density at 1 A/cm². From the measurements of the I-V polarization curves, it appears that the presence of calcium chloride in the cathode fuel gas affects the cell performance more than sodium chloride does.     

Effect of operating conditions on carbon corrosion in polymer electrolyte membrane fuel cells

The influence of humidity, cell temperature and gas-phase O₂ on the electrochemical corrosion of carbon in polymer electrolyte membrane fuel cells is investigated by measuring CO₂ emission at a constant potential of 1.4 V for 30 min using on-line mass spectrometry. Carbon corrosion shows a strong positive correlation with humidity and cell temperature. The presence of water is indispensable for electrochemical carbon corrosion. By contrast, the presence of gas-phase O₂ has little effect on electrochemical carbon corrosion. With increased carbon corrosion, changes in fuel cell electrochemical characteristics become more prominent and thereby indicate that such corrosion significantly affects fuel cell durability.     

Effect of chloride impurities on the performance and durability of polybenzimidazole-based high temperature proton exchange membrane fuel cells

The effect of chloride as an air impurity and as a catalyst contaminant on the performance and durability of polybenzimidazole (PBI)-based high temperature proton exchange membrane fuel cell (HT-PEMFC) was studied. The ion chromatographic analysis reveals the existence of chloride contaminations in the Pt/C catalysts. Linear sweep voltammetry was employed to study the redox behavior of platinum in 85% phosphoric acid containing chloride ions, showing increase in oxidation and decrease in reduction current densities during the potential scans at room temperature. The potential scans at high temperatures in 85% phosphoric acid containing chloride ions showed both increase in oxidation and reduction current densities. The fuel cell performance, i.e. the current density at a constant voltage of 0.4 V and 0.5 V was found to be degraded as soon as HCl was introduced in the air humidifier. The performance loss was recovered when switching from the HCl solution back to pure water in the air humidifier. Under an accelerated aging performance test conducted through potential cycling between 0.9 V and 1.2 V, the PBI-based fuel cell initially containing 0.5 NaCl mg cm⁻² on the cathode catalyst layer exhibited a drastic degradation in the performance as compared to the chloride free MEAs. The mechanisms of the chloride effect on the fuel cell performance and durability were further discussed.     

Carbon monoxide poisoning of proton exchange membrane fuel cells

Proton exchange membrane fuel cell (PEMFC) performance degrades when carbon monoxide (CO) is present in the fuel gas; this is referred to as CO poisoning. This paper investigates CO poisoning of PEMFCs by reviewing work on the electrochemistry of CO and hydrogen, the experimental performance of PEMFCs exhibiting CO poisoning, methods to mitigate CO poisoning and theoretical models of CO poisoning. It is found that CO poisons the anode reaction through preferentially adsorbing to the platinum surface and blocking active sites, and that the CO poisoning effect is slow and reversible. There exist three methods to mitigate the effect of CO poisoning: (i) the use of a platinum alloy catalyst, (ii) higher cell operating temperature and (iii) introduction of oxygen into the fuel gas flow. Of these three methods, the third is the most practical. There are several models available in the literature for the effect of CO poisoning on a PEMFC and from the modeling efforts, it is clear that small CO oxidation rates can result in much increased performance of the anode. However, none of the existing models have considered the effect of transport phenomena in a cell, nor the effect of oxygen crossover from the cathode, which may be a significant contributor to CO tolerance in a PEMFC. In addition, there is a lack of data for CO oxidation and adsorption at low temperatures, which is needed for detailed modeling of CO poisoning in PEMFCs. Copyright © 2001 John Wiley & Sons, Ltd.     

Parametric analysis of the proton exchange membrane fuel cell performance using design of experiments

Proton exchange membrane fuel cell (PEMFC) performance depends on different fuel cell operating temperatures, humidification temperatures, operating pressures, flow rates, and various combinations of these parameters. This study employed the method of the design of experiments (DOE) to obtain the optimal combination of the six primary operating parameters (fuel cell operating temperatures, operating pressures, anode and cathode humidification temperatures, anode and cathode stoichiometric flow ratios). In the first stage, this study adopted a 2^k−2 fractional factorial design of the DOE to determine whether these factors have significant effects on a response and the interactions between various parameters. Second, the L₂₇(3¹³) orthogonal array of the Taguchi method is utilized to determine the optimal combination of factors for a fuel cell. Based on this study, the operating pressure, the operating temperature, and the interactions between operating temperature and operating pressure have a significant effect on the fuel cell performance. Among them, the operating pressure is the most important contributor. When the operating pressure increases, it should simultaneously lower the effects of other factors. While both the operating temperature and pressure increase simultaneously with that, the other factors are at appropriate conditions, it is possible to improve the fuel cell performance.