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.     

Degradation phenomena in PEM fuel cell with dead-ended anode

To improve the performance and durability of a dead-ended anode (DEA) fuel cell, it is important to understand and characterize the degradation associated with the DEA operation. To this end, the multiple degradation phenomena in DEA operation were investigated via systematic experiments. Three lifetime degradation tests were conducted with different cell temperatures and cathode relative humidities, during which the temporal evolutions of cell voltage and high frequency resistance (HFR) were recorded. When the cathode supply was fully humidified and the cell temperature was mild, the cathode carbon corrosion was the predominant degradation observed from scanning electronic microscopy (SEM) of postmortem samples. The catalyst layer and membrane thickness were measured at multiple locations across the cell active area in order to map the degradation patterns. These observations confirm a strong correlation between the cathode carbon corrosion and the anode fuel starvation occurring near the cell outlet. When the cathode supply RH reduced to 50%, membrane pin-hole failures terminated the degradation test. Postmortem analysis showed membrane cracks and delamination in the inlet region where membrane water content was the lowest.     

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.     

Improved PEM fuel cell performance with hydrophobic catalyst layers

Flooding of catalyst layers is one of the major issues, which effects performance of low temperature proton exchange membrane fuel cells (PEMFC). Rendering catalyst layers hydrophobic one may improve the performance of PEMFC depending on Pt percentage in the catalyst and Polytetrafluoroethylene (PTFE) loading on the electrode. In this study, effect of hydrophobicity in catalyst layers on performance has been investigated by comparing performances of membrane electrode assemblies prepared with 48% Pt/C. Ultrasonic coating technique was used to manufacture highly efficient electrodes. Power density at 0.45 V increased by the addition of PTFE, from 0.95 to 1.01 W/cm² with H₂/O₂ feed; while it slightly increased from 0.52 W/cm² to 0.53 W/cm² with H₂/Air feed. Addition of PTFE to catalyst layers while keeping Pt loading constant, enhanced performance providing improved water management. Kinetic activity increased by decreasing Nafion loading from 0.37 mg/cm² to 0.25 mg/cm² while introducing PTFE (0.12 mg/cm²) to the electrode. Electrochemical impedance spectroscopy (EIS) results proved that charge transfer resistance decreased with hydrophobic catalyst layers for H₂/O₂ feed. This is attributed to enhanced water management due to PTFE presence.     

A novel self-humidifying membrane electrode assembly with water transfer region for proton exchange membrane fuel cells

A novel self-humidifying membrane electrode assembly (MEA) with the active electrode region surrounded by a unactive “water transfer region (WTR)” was proposed to achieve effective water management and high performance for proton exchange membrane fuel cells (PEMFCs). By this configuration, excess water in the cathode was transferred to anode through Nafion membrane to humidify hydrogen. Polarization curves and power curves of conventional and the self-humidifying MEAs were compared. The self-humidifying MEA showed power density of 85 mW cm⁻² at 0.5 V, which is two times higher than that of a conventional MEA with cathode open. The effects of anode hydrogen flow rates on the performance of the self-humidifying MEA were investigated and its best performance was obtained at a flow rate of 40 ml min⁻¹. Its performance was the best when the environmental temperature was 40 °C. The performance of the self-humidifying MEA was slightly affected by environmental humidity. The area of WTR was optimized, and feasible area ratio of the self-humidifying MEA was 28%.     

Enhancement of proton exchange membrane fuel cell performance by titanium-coated anode gas diffusion layer

Titanium was coated onto an anode gas diffusion layer (GDL) by direct current sputtering to improve the performance and durability of a proton exchange membrane fuel cell (PEMFC). Scanning electron microscopy (SEM) images showed that the GDLs were thoroughly coated with titanium, which showed angular protrusion. Single-cell performance of the PEMFCs with titanium-coated GDLs as anodes was investigated at operating temperatures of 25 °C, 45 °C, and 65 °C. Cell performances of all membrane electrode assemblies (MEAs) with titanium-coated GDLs were superior to that of the MEA without titanium coating. The MEA with titanium-coated GDL, with 10 min sputtering time, demonstrated the best performance at 25 °C, 45 °C, and 65 °C with corresponding power densities 58.26%, 32.10%, and 37.45% higher than that of MEA without titanium coating.     

Effect of water distribution in gas diffusion layer on proton exchange membrane fuel cell performance

Water management of proton exchange membrane fuel cells remains a prominent issue in research concerning fuel cells. In this study, the gas diffusion layer (GDL) of a fuel cell is partially treated with a hydrophobic agent, and the effect of GDL hydrophobicity on the water distribution in the fuel cell is examined. First, the effect of the position of the cathode GDL hydrophobic area relative to the channel on the fuel cell performance is investigated. Then, the water distribution in the fuel cell cathode GDL is observed using X-ray imaging. The experimental results indicate that when the hybrid GDL's hydrophobic area lies on the channel, water tends to accumulate under the rib, and the water content in the channel is low; this improves the fuel cell performance. When the hydrophobic area is under the rib, the water distribution is more uniform, but the performance deteriorates.     

Numerical modeling of a non-flooding hybrid polymer electrolyte fuel cell

Experimental results were recently reported regarding a novel “non-flooding” hybrid fuel cell consisting of proton exchange membrane (PEM) and anion exchange membrane (AEM) half-cells on opposite sides of a water-filled, porous intermediate layer. Product water formed in the porous layer, where it could permeate to the exterior of the cell, rather than at the electrodes. Although electrode flooding was mitigated, the reported power output was low. To investigate the potential for increased power output, a physicochemical charge transport model of the porous electrolyte layer is reported here. Traditional electrochemical modeling was generalized in a novel way to consider both ion transport and reaction in the aqueous phase and electronic conduction in the graphitic scaffold using a unified Poisson–Nernst–Planck framework. Though the model used no arbitrary or fitting parameters, the ionic resistance calculated for the porous layer agreed well with the highly non-Ohmic experimental values previously reported for the entire fuel cell. Interestingly, electronic charge carriers in the scaffold were found to obviate the need for counterion presence in this unique electrolyte structure. Still, the thickness- and temperature-dependent model results offer limited prospects for improving the power output.     

Engineering model of a passive planar air breathing fuel cell cathode

The behavior of an air breathing fuel cell (ABFC) operated on dry-hydrogen in dead-ended mode is studied using theoretical analysis. A one-dimensional, non-isothermal, combined heat and mass transport model is developed that captures the coupling between water generation, oxygen consumption, self-heating and natural convection at the air breathing cathode. The model is validated against planar ABFC experimental measurements over a range of ambient temperatures. The model confirms the strong effect of self-heating on the water balance within passive ABFCs. Model analysis provides several conclusions: (1) thermal runaway caused by inadequate heat rejection predominantly limits ABFC performance. (2) The natural convection boundary layer represents a significant barrier to cathode mass and heat transfer. (3) Because the mass and heat transport numbers associated with natural convection are small, even slight forced convection dramatically affects cell behavior. (4) Performance optimization requires maximizing heat rejection while minimizing flooding. Decoupling the latter two phenomena is challenging due to the exponential relationship between water vapor saturation and temperature.     

Development of a polymer electrolyte fuel cell dead-ended anode purge strategy for use with a nitrogen-containing hydrogen gas supply

The effect of nitrogen content within the hydrogen fuel supplied to a polymer electrolyte fuel cell (PEFC) operating in dead-ended anode mode is examined, with a view to using an ammonia decomposition product gas mix (containing 75H₂:25N₂) as the hydrogen-containing fuel. The impact of this impure hydrogen stream, supplied to the anode, was evaluated in terms of mean cell voltage and in relation to actual operating conditions (purge interval, dead-ended interval and fuel cell load). Design of Experiments (DoE) methodology, using multi-linear models, assessed hydrogen utilisation in terms of stack efficiency and identified an effective and viable dead-ended anode purge strategy for this nitrogen-containing hydrogen fuel.     

Influence of cathode flow pulsation on performance of proton-exchange membrane fuel cell

The effect of cathode flow pulsation on the performance of a 10-cell proton-exchange membrane fuel cell is investigated. An acoustic woofer generates a pulsating flow, which is added to a unidirectional flow supplied from a compressed air tank. By adding the flow pulsation, the fuel cell power output and the limit current dramatically increase while the fuel cell efficiency slightly decreases. As the pulsation amplitude increases, the improvement in fuel cell performance is more pronounced. The performance enhancement shows no obvious dependency on a pulsation frequency change from 10 to 30 Hz. The cathode flow pulsation effect is more distinct at low cathode flow rates.     

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.     

Poly(ethylene glycol) modified activated carbon for high performance proton exchange membrane fuel cells

A high water retention membrane is developed by co-assembling poly(ethylene glycol) (PEG) grafted activated carbon (AC-PEG) with Nafion. The AC-PEG is prepared via a sol–gel process. The use of PEG as a transporting medium in AC-PEG shows a largely improved water retention ability, a higher proton conductivity and a reduced swelling ratio, making it well suited for proton exchange membrane fuel cells (PEMFCs). Further, the composite membranes show improved mechanical properties at high temperature, thus ensuring the structural stability of membranes during the fuel cell operation. Compositional optimized AC-PEG/Nafion composite membrane (15 wt% compared to Nafion) demonstrates a better performance than the commercially available counterpart, Nafion 212, in fuel cell measurements. To identify the key factor of the improved performance, current interrupt technique is used to quantitatively verify the changes of resistance under different relative humidity environment.     

Liquid water flooding process in proton exchange membrane fuel cell cathode with straight parallel channels and porous layer

Liquid water management plays a significant role in proton exchange membrane fuel cell (PEMFC) performance, especially when the PEMFC is operating with high current density. Therefore, understanding of liquid water behavior and flooding process is a critical challenge that must be addressed. To overcome PEMFC durability problems, a liquid water flooding process is studied in the cathode side of a PEMFC with straight parallel channels and a porous layer using FLUENT^® v6.3.26 software with a volume-of-fluid (VOF) algorithm and user-defined-function (UDF). The general process of liquid water flooding within this type of PEMFC cathode is investigated by analyzing the behavior of liquid water in porous layer and gas flow channels. Two important phenomena, the “first channel phenomenon” and the “last channel phenomenon”, and their effects on the flow distribution along different parallel channels are discussed.     

Influence of properties of gas diffusion layers on the performance of polymer electrolyte-based unitized reversible fuel cells

Polymer electrolyte-based unitized reversible fuel cells (URFCs) combine the functionality of a fuel cell and an electrolyzer in a single device. In a URFC, titanium (Ti)-felt is used as a gas diffusion layer (GDL) of the oxygen electrode, whereas typical carbon paper is used as a GDL of the hydrogen electrode. Different samples of Ti-felt with different structural properties (porosity and fiber diameter) and PTFE content were prepared for use as GDLs of the oxygen electrode, and the relation between the properties of the GDL and the fuel cell performance was examined for both fuel cell and electrolysis operation modes. Experimental results showed that the cell with a Ti-felt GDL of 80 μm fiber diameter had the highest round-trip efficiency due to excellent fuel cell operation under relatively high-humidity conditions despite degradation in performance in the electrolysis mode.     

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.     

Improved molten carbonate fuel cell performance via reinforced thin anode

The effects of anode thickness on electrochemical performance and cell voltage stability of molten carbonate fuel cell (MCFC) were examined using single cell test. It was found that supported thin nickel-aluminum (Ni–Al) anode with small pore size enhanced cell performance by reducing its mass transfer resistance and crossover. The stability of cell voltage was also observed. This was achieved after 0.25 mm thick anode was reinforced with Ni 60 mesh. Unsupported 0.3 mm thick anode yielded poor performance due to deformation and cracks after a long thermal exposure. The performance was improved significantly after all the anodes were reinforced with Ni mesh.     

A theoretical study of inlet relative humidity control in PEM fuel cell

In this paper, the individual roles of inlet anode and cathode humidification, and their influences on PEM fuel cell’s electrical performance are discussed systematically by using a pseudo two-dimensional, two-phase PEM fuel cell model. It follows that the maximum power density point of a PEM fuel cell is strongly dependent on the combination of the inlet anode and cathode humidification conditions. Their influences, however, are predicted to be highly asymmetrical, with the anode and cathode humidification mainly affecting ohmic and concentration overpotential, respectively. The physical explanation to this asymmetry is given with the aid of a detailed set of simulation results. Finally, the developed understanding of their influences are employed to formulate two examples on the use of inlet relative humidity control as a simple and effective method for maximizing the volumetric power density and operating range of PEM fuel cell, respectively.     

Monodimensional modeling and experimental study of the dynamic behavior of proton exchange membrane fuel cell stack operating in dead-end mode

The dynamic behavior of a five cells proton exchange membrane fuel cell (PEMFC) stack operating in dead-end mode has been studied at room temperature, both experimentally and by simulation. Its performances in “fresh” and “aged” state have been compared. The cells exhibited two different response times: the first one at about 40 ms, corresponding to the time needed to charge the double-layer capacitance, and the second one at about 15–20 s. The first time response was not affected by the ageing process, despite the decrease of the performances, while the second one was. Our simulations indicated that a high amount of liquid water was present in the stack, even in “fresh” state. This liquid water is at the origin of the performances decrease with ageing, due to its effect on decreasing the actual GDL porosity that in turn cause the starving of the active layer with oxygen. As a consequence, it appears that water management issue in a fuel cell operating in dead-end mode at room temperature mainly consists in avoiding pore flooding instead of providing enough water to maintain membrane conductivity.     

Enhanced low-humidity performance of proton exchange membrane fuel cell by incorporating phosphoric acid-loaded covalent organic framework in anode catalyst layer

Developing self-humidifying membrane electrode assembly (MEA) is of great significance for the practical use of proton exchange membrane fuel cell (PEMFC). In this work, a phosphoric acid (PA)-loaded Schiff base networks (SNW)-type covalent organic framework (COF) is proposed as the anode catalyst layer (CL) additive to enhance the PEMFC performance under low humidity conditions. The unique polymer structure and immobilized PA endow the proposed COF network with not only excellent water retention capacity but also proton transfer ability, thus leading to the superior low humidity performance of the PEMFC. The optimization of the additive content, the effect of relative humidity (RH) and PEMFC operating temperature are investigated by means of electrochemical characterization and single cell test. At a normal operation temperature of 60 °C and 38% RH, the MEA with optimized COF content (10 wt%) showes the maximum power density of 582 mW cm^?2, which is almost 7 times higher than that of the routine MEA (85 mW cm^?2). Furthermore, a preliminary durability test demonstrates the potential of the proposed PEMFC for practice operation under low humidity environment.