A review of polymer electrolyte membrane fuel cell durability test protocols

Durability is one of the major barriers to polymer electrolyte membrane fuel cells (PEMFCs) being accepted as a commercially viable product. It is therefore important to understand their degradation phenomena and analyze degradation mechanisms from the component level to the cell and stack level so that novel component materials can be developed and novel designs for cells/stacks can be achieved to mitigate insufficient fuel cell durability. It is generally impractical and costly to operate a fuel cell under its normal conditions for several thousand hours, so accelerated test methods are preferred to facilitate rapid learning about key durability issues. Based on the US Department of Energy (DOE) and US Fuel Cell Council (USFCC) accelerated test protocols, as well as degradation tests performed by researchers and published in the literature, we review degradation test protocols at both component and cell/stack levels (driving cycles), aiming to gather the available information on accelerated test methods and degradation test protocols for PEMFCs, and thereby provide practitioners with a useful toolbox to study durability issues. These protocols help prevent the prolonged test periods and high costs associated with real lifetime tests, assess the performance and durability of PEMFC components, and ensure that the generated data can be compared.     

Analysis and control of a hybrid fuel delivery system for a polymer electrolyte membrane fuel cell

A polymer electrolyte membrane fuel cell (PEM FC) system as a power source used in mobile applications should be able to produce electric power continuously and dynamically to meet the demand of the driver by consuming the fuel, hydrogen. The hydrogen stored in the tank is supplied to the anode of the stack by a fuel delivery system (FDS) that is comprised of supply and recirculation lines controlled by different actuators. Design of such a system and its operation should take into account several aspects, particularly efficient fuel usage and safe operation of the stack.     

Effect of contaminants on polymer electrolyte membrane fuel cells

Increasing demand for energy, energy security and the need to minimize the impact on the environment related to energy are the major drivers for the research and development of alternative energy technologies. Polymer electrolyte membrane (PEM) fuel cells are a promising alternative technology. However, their performance, in other words efficiency, can be hindered severely by the presence of contaminants. Impurities in the oxidant and fuel feeds act as barriers to the oxygen reduction and hydrogen oxidation. These impurities arise from the use of atmospheric air as the oxidant and hydrogen from reformate as the fuel. The electrolyte membrane can be attacked by ions originating from the cell components. These ions decrease the mechanical and chemical stability of the membrane resulting in the decrease of proton conductivity and reactant crossover. Due to the severity of these poisoning phenomena, much work has been dedicated to understanding their chemical kinetics, their effects and mitigation methods. This paper provides a comprehensive review of the experimental, analytical and numerical work devoted to understanding the contamination of the cathode, electrolyte membrane and anode. A summary of future directions and research topics is also given.     

Externally cooled high temperature polymer electrolyte membrane fuel cell stack

One key issue in high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) stack development is heat removal at the operating temperature of 140–180 °C. Conventionally, this process is done using coolants such as thermooil, steam or pressurized water. In this contribution, external liquid cooling designs are described, which are avoiding two constraints. First, in the cell active area, no liquid coolant is present avoiding any sealing problems with respect to the electrode. Secondly, the external positioning allows high temperature gradients between the heat removal zone and the active area resulting in a good adjustability of appropriate reformate conversion temperatures (e.g. 160 °C) and a more compact cell design. Different design concepts were investigated using modeling techniques and a selection of them has also been investigated experimentally. The experiments proved the feasibility of the external cooling design and showed that the temperature gradients within the active area are below 15 K under typical operating conditions.     

Polymer electrolyte membrane fuel cell contamination: Testing and diagnosis of toluene-induced cathode degradation

The effects of toluene contamination on the performance of polymer electrolyte membrane (PEM) fuel cells were investigated, using various levels of toluene concentration in the air streams, under different operational conditions and with different catalyst loadings. Constant-current polarization and electrochemical impedance spectroscopy (EIS) were conducted to analyze the poisoning behaviour of toluene. The severity of the contamination effect increased with an increase in both the current density and the toluene concentration, but decreased with an increase in both the relative humidity (RH) and the cathode-side Pt loading. The toluene-poisoned fuel cell could not be fully recovered by replacing toluene-contaminated air with pure air. EIS measurements revealed that both kinetic resistance and mass transfer resistance increased as a result of toluene contamination, while membrane resistance remained unchanged. However, the increase in kinetic resistance was a major contributor to cell performance degradation.     

Analysis and control of a fuel delivery system considering a two-phase anode model of the polymer electrolyte membrane fuel cell stack

The fuel delivery system using both an ejector and a blower for a PEM fuel cell stack is introduced as a fuel efficiency configuration because of the possibility of hydrogen recirculation dependent upon load states.A high pressure difference between the cathode and anode could potentially damage the thin polymer electrolyte membrane. Therefore, the hydrogen pressure imposed to the stack should follow any change of the cathode pressure. In addition, stoichiometric ratio of the hydrogen should be maintained at a constant to prevent a fuel starvation at abrupt load changes.Furthermore, liquid water in the anode gas flow channels should be purged out in time to prevent flooding in the channels and other layers. The purging control also reduces the impurities concentration in cells to improve the cell performance.We developed a set of control oriented dynamic models that include a anode model considering the two-phase phenomenon and system components The model is used to design and optimize a state feedback controller along with an observer that controls the fuel pressure and stoichiometric ratio, whereby purging processes are also considered. Finally, included is static and dynamic analysis with respect to tracking and rejection performance of the proposed control.     

Detailed thermodynamic analysis of polymer electrolyte membrane fuel cell efficiency

It is common knowledge that efficiency of fuel cells is highest when no electric current is produced while when the fuel cell is really working, the efficiency is reduced by dissipation. In this paper the relation between efficiency and dissipation inside the fuel cell is formulated within the framework of classical irreversible thermodynamics of mixtures. It is shown that not only dissipation influences the efficiency but that there are also some other terms which become important if there are steep temperature gradients inside the fuel cell. Indeed, we show that the new terms are negligible in polymer-electrolyte membrane fuel cells while they become important in solid oxide fuel cells. In summary, this paper presents a formulation of non-equilibrium thermodynamics of fuel cells and provides analysis of efficiency in terms of processes inside the fuel cells, revealing some new terms affecting the efficiency.     

Current distribution in polymer electrolyte membrane fuel cell with active water management

Air delivery is typically the greatest parasitic power loss in polymer electrolyte membrane fuel cell (PEMFC) systems. We here present a detailed study of an active water management system for PEMFCs, which uses a hydrophilic, porous cathode flow field, and an electroosmotic (EO) pump for water removal. This active pumping of liquid water allows for stable operation with relatively low air flow rates and low air pressure and parallel cathode channel architectures. We characterize in-plane transport issues and power distributions using a three by three segmented PEMFC design. Our transient and steady state data provide insight into the dynamics and spatial distribution of flooding and flood-recovery processes. Segment-specific polarization curves reveal that the combination of a wick and an EO pump can effect a steady state, uniform current distribution for a parallel channel cathode flow field, even at low air stoichiometries (α_air = 1.5). The segmented cell measurements also reveal the mechanisms and dynamics associated with EO pump based recovery from catastrophic flooding. For most operating regimes, the EO pump requires less than 1% of the fuel cell power to recover from near-catastrophic flooding, prevent flooding, and extend the current density operation range.     

Meliorated oxygen reduction reaction of polymer electrolyte membrane fuel cell in the presence of cerium-zirconium oxide

Oxygen Reduction Reaction (ORR) kinetics is known to be one of the major bottle necks in PEM Fuel Cell performance. Several attempts are being made to enhance the ORR. Inspite of several attempts Pt in the vicinity of high surface area oxide catalysts seems to be the best choice although some alloy catalyst have shown good performance in half cell studies and single cell studies. We are investigating methods to improve the performance of PEM fuel cell especially in low air flow conditions which is the condition that will arise in surge power requirements. We have found that oxygen reduction reaction (ORR) performance of Pt/C can be increased in the presence of cerium-zirconium oxides especially Ce_0.8Zr_0.2O₂ (CZO) in the cathode catalyst layer. Ce_0.8Zr_0.2O₂ was prepared by co-precipitation method and the formation is confirmed by the XRD results. An XPS study of Ce 3d emission spectra dominated by atomic multiplet effects in core level spectroscopy of Ce_0.8Zr_0.2O₂-Pt/C are studied from which the possible oxidation states of Ce on Ce_0.8Zr_0.2O₂-Pt/C surface are examined. The ORR improvement in the CZO added electrodes have been studied using chronoammperometry and fuel cell testing.     

An experimental investigation of electro-osmotic drag coefficients in a polymer electrolyte membrane fuel cell

Through the use of a water balance experiment, the electro-osmotic drag coefficients of Nafion 115 were obtained under several conditions (as a function of water content and thermodynamics conditions). For the cases when the anode was fully hydrated (corresponding to water content λ ≈ 14 in the adjacent membrane) and the cathode suffered from drying when dry air was supplied (λ ≈ 2), the electro-osmotic drag coefficients varied from 0.82 (±0.06) to 0.50 (±0.03) H₂O/H⁺ when the current density varied from 0.4 to 1.0 A cm⁻² (95% confidence level). When the current density increased, the electro-osmotic drag coefficient decreased. When the water content at the anode increased from λ ≈ 5 to λ ≈ 14, the cathode was supplied with dry air (λ ≈ 2), and the fuel cell discharged constant current density at 0.6 A cm⁻², the electro-osmotic drag coefficient increased from 0.44 (±0.06) to 0.68 (±0.06) H₂O/H⁺ (95% confidence level). Higher relative humidity gas leads to a higher electro-osmotic drag coefficient at constant current density.     

Modeling the phenomena of dehydration and flooding of a polymer electrolyte membrane fuel cell

A one-dimensional, two-phase, transient PEM fuel cell model including gas diffusion layer, cathode catalyst layer and membrane is developed. The electrode is assumed to consist of a network of dispersed Pt/C forming spherically shaped agglomerated zones that are filled with electrolyte. Water is modeled in all three phases: vapor, liquid and dissolved in the ionomer to capture the effect of dehydration of the ionomer as well as flooding of the porous media. The anode is modeled as a sophisticated spatially reduced interface. Motivated by environmental scanning electron microscope (ESEM) images of contact angles for microscopic water droplets on fibers of the gas diffusion layer, we introduce the feature of immobile saturation. A step change of the saturation between the catalyst layer and the gas diffusion layer is modeled based on the assumption of a continuous capillary pressure at the interface. The model is validated against voltammetry experiments under various humidification conditions which all show hysteresis effects in the mass transport limited region. The transient saturation profiles clearly show that insufficient liquid water removal causes pore flooding, which is responsible for the oxygen mass transport limitation at high current density values. The simulated and measured current responses from chronoamperometry experiments are compared and analyzed.     

Passive water management at the cathode of a planar air-breathing proton exchange membrane fuel cell

Water management is a significant challenge in portable polymer electrolyte membrane (PEM) fuel cells and particularly in proton exchange membrane (PEM) fuel cells with air-breathing cathodes. Liquid water condensation and accumulation at the cathode surface is unavoidable in a passive design operated over a wide range of ambient and load conditions. Excessive flooding or dry out of the open cathode can lead to a dramatic reduction of fuel cell power. We report a water management design based on a hydrophilic and electrically conductive wick. A prototype air-breathing fuel cell with the proposed water management design successfully operated under severe flooding conditions, ambient temperature 10 °C and relative humidity of 80%, for up to 6 h with no observable cathode flooding or loss of performance.     

Design strategy for a polymer electrolyte membrane fuel cell flow-field capable of switching between parallel and interdigitated configurations

Novel water management strategies are important to the development of next generation polymer electrolyte membrane fuel cell systems (PEMFCs). Parallel and interdigitated flow fields are two common types of PEMFC designs that have benefits and draw backs depending upon operating conditions. Parallel flow fields rely predominately on diffusion to deliver reactants and remove byproduct water. Interdigitated flow fields induce convective transport, known as cross flow, through the porous gas diffusion layer (GDL) and therefore are superior at water removal beneath land areas which can lead to higher cell performance. Unfortunately, forcing flow through the GDL results in higher pumping losses as the inlet pressure for interdigitated flow fields can be up to an order of magnitude greater than that for a parallel flow field. In this study a flow field capable of switching between parallel and interdigitated configurations was designed and tested. Results show, taking into account pumping losses, that using constant stoichiometry the parallel flow field results in a higher system power under low current density operation compared to the interdigitated configuration. The interdigitated flow-field configuration was observed to have lower overvoltage at elevated current densities resulting in a higher maximum power and a higher limiting current density. An optimal system power curve was produced by switching from parallel to interdigitated configuration based on which produces a higher system power at a given current density. This design method can be easily implemented with current PEMFC technology and requires minimal hardware. Some of the consequences this design has on system components are discussed.     

3D neutron tomography of a polymer electrolyte membrane fuel cell under sub-zero conditions

In this article, we implement both 2D and 3D based neutron imaging techniques on a polymer electrolyte membrane (PEFC) fuel cell under sub-zero conditions. A cell was run at steady state power, purged for 60 s, and then brought down to −5 °C inside an environmental chamber situated in front of a neutron beam. A series of 2D radiographs were taken as the cell dropped in temperature capturing the condensation and redistribution of flow field and gas diffusion layer (GDL) water. Immediately after this, 3D tomography was conducted while the cell remained at −5 °C. The image data was reconstructed into a 3D model in order to highlight regions where water/ice formations occur. The tomography results show where ice forms within the flow field and which regions are subject to blockages. Ice is observed predominately under channel areas due to water rejection by the GDL. The cathode side channel exit region displays higher ice content which correlates with elevated saturation levels from reaction water production during operation. Larger ice formations reside in the lower region of the flow field due to gravity. These blockages may pose significant issues to cold start of the cell as well as highlight potential drawbacks to shorter purge durations.     

Performance equations for a polymer electrolyte membrane fuel cell with unsaturated cathode feed

A mathematical formulation for the cathode of a membrane electrode assembly of a polymer electrolyte membrane fuel cell is proposed, in which the effect of unsaturated vapor feed in the cathode is considered. This mechanistic model formulates the water saturation front within the gas diffusion layer with an explicit analytical expression as a function of operating conditions. The multi-phase flows of gaseous species and liquid water are correlated with the established capillary pressure equilibrium in the medium. In addition, less than fully hydrated water contents in the polymer electrolyte and catalyst layers are considered, and are integrated with the relevant liquid and vapor transfers in the gas diffusion layer. The developed performance equations take into account the influences of all pertinent material properties on cell performance using first principles. The mathematical approach is logical and concise in terms of revealing the underlying physical significance in comparison with many other empirical data fitting models.     

Characterization of flooding and two-phase flow in polymer electrolyte membrane fuel cell stacks

A partially flooded gas diffusion layer (GDL) model is proposed and solved simultaneously with a stack flow network model to estimate the operating conditions under which water flooding could be initiated in a polymer electrolyte membrane (PEM) fuel cell stack. The models were applied to the cathode side of a stack, which is more sensitive to the inception of GDL flooding and/or flow channel two-phase flow. The model can predict the stack performance in terms of pressure, species concentrations, GDL flooding and quality distributions in the flow fields as well as the geometrical specifications of the PEM fuel cell stack. The simulation results have revealed that under certain operating conditions, the GDL is fully flooded and the quality is lower than one for parts of the stack flow fields. Effects of current density, operating pressure, and level of inlet humidity on flooding are investigated.     

Transport phenomena within the porous cathode for a proton exchange membrane fuel cell

A two-phase, one-dimensional steady model is developed to analyze the coupled phenomena of cathode flooding and mass-transport limiting for the porous cathode electrode of a proton exchange membrane fuel cell. In the model, the catalyst layer is treated not as an interface between the membrane and gas diffusion layer, but as a separate computational domain with finite thickness and pseudo-homogenous structure. Furthermore, the liquid water transport across the porous electrode is driven by the capillary force based on Darcy's law. And the gas transport is driven by the concentration gradient based on Fick's law. Additionally, through Tafel kinetics, the transport processes of gas and liquid water are coupled. From the numerical results, it is found that although the catalyst layer is thin, it is very crucial to better understand and more correctly predict the concurrent phenomena inside the electrode, particularly, the flooding phenomena. More importantly, the saturation jump at the interface of the gas diffusion layer and catalyst layers is captured, when the continuity of the capillary pressure is imposed on the interface. Elsewise, the results show further that the flooding phenomenon in the CL is much more serious than that in the GDL, which has a significant influence on the mass transport of the reactants. Moreover, the saturation level inside the cathode is determined, to a great extent, by the surface overpotential, the absolute permeability of the porous electrode, and the boundary value of saturation at the gas diffusion layer-gas channel interface. In order to prevent effectively flooding, it should remove firstly the liquid water accumulating inside the CL and keep the boundary value of liquid saturation as low as possible.     

A model-based parametric analysis of a direct ethanol polymer electrolyte membrane fuel cell performance

In the present work, a model-based parametric analysis of the performance of a direct ethanol polymer electrolyte membrane fuel cell (DE-PEMFC) is conducted with the purpose to investigate the effect of several parameters on the cell's operation. The analysis is based on a previously validated one-dimensional mathematical model that describes the operation of a DE-PEMFC in steady state. More precisely, the effect of several operational and structural parameters on (i) the ethanol crossover rate from the anode to the cathode side of the cell, (ii) the parasitic current generation (mixed potential formation) and (iii) the total cell performance is investigated. According to the model predictions it was found that the increase of the ethanol feed concentration leads to higher ethanol crossover rates, higher parasitic currents and higher mixed potential values resulting in the decrease of the cell's power density. However there is an optimum ethanol feed concentration (approximately 1.0 mol L⁻¹) for which the cell power density reaches its highest value. The platinum (Pt) loading of the anode and the cathode catalytic layers affects strongly the cell performance. Higher values of Pt loading of the catalytic layers increase the specific reaction surface area resulting in higher cell power densities. An increase of the anode catalyst loading compared to an equal one of the cathode catalyst loading has greater impact on the cell's power density. Another interesting finding is that increasing the diffusion layers’ porosity up to a certain extent, improves the cell power density despite the fact that the parasitic current increases. This is explained by the fact that the reactants’ concentrations over the catalysts are increased, leading to lower activation overpotential values, which are the main source of the total cell overpotentials. Moreover, the use of a thicker membrane leads to lower ethanol crossover rate, lower parasitic current and lower mixed potential values in comparison to the use of a thinner one. Finally, according to the model predictions when the cell operates at low current densities the use of a thick membrane is necessary to reduce the negative effect of the ethanol crossover. However, in the case where the cell operates at higher current densities (lower ethanol crossover rates) a thinner membrane reduces the ohmic overpotential leading to higher power density values.