A review of PEM fuel cell durability: Degradation mechanisms and mitigation strategies

This paper reviews publications in the literature on performance degradation of and mitigation strategies for polymer electrolyte membrane (PEM) fuel cells. Durability is one of the characteristics most necessary for PEM fuel cells to be accepted as a viable product. In this paper, a literature-based analysis has been carried out in an attempt to achieve a unified definition of PEM fuel cell lifetime for cells operated either at a steady state or at various accelerated conditions. Additionally, the dependence of PEM fuel cell durability on different operating conditions is analyzed. Durability studies of the individual components of a PEM fuel cell are introduced, and various degradation mechanisms are examined. Following this analysis, the emphasis of this review shifts to applicable strategies for alleviating the degradation rate of each component. The lifetime of a PEM fuel cell as a function of operating conditions, component materials, and degradation mechanisms is then established. Lastly, this paper summarizes accelerated stress testing methods and protocols for various components, in an attempt to prevent the prolonged test periods and high costs associated with real lifetime tests.     

PEM fuel cell performance with solar air preheating

Proton Exchange Membrane Fuel Cells (PEMFC) have proven to be a promising energy conversion technology in various power applications and since it was developed, it has been a potential alternative over fossil fuel-based engines and power plants, all of which produce harmful by-products. The inlet air coolant and reactants have an important effect on the performance degradation of the PEMFC and certain power outputs. In this work, a theoretical model of a PEM fuel cell with solar air heating system for the preheating hydrogen of PEM fuel cell to mitigate the performance degradation when the fuel cell operates in cold environment, is proposed and evaluated by using energy analysis. Considering these heating and energy losses of heat generation by hydrogen fuel cells, the idea of using transpired solar collectors (TSC) for air preheating to increase the inlet air temperature of the low-temperature fuel cell could be a potential development. The aim of the current article is applying solar air preheating for the hydrogen fuel cells system by applying TSC and analyzing system performance. Results aim to attention fellow scholars as well as industrial engineers in the deployment of solar air heating together with hydrogen fuel cell systems that could be useful for coping with fossil fuel-based power supply systems.     

A general model for air-side proton exchange membrane fuel cell contamination

This paper presents a general model for air-side feed stream contamination that has the capability of simulating both transient and steady-state performance of a PEM fuel cell in the presence of air-side feed stream impurities. The model is developed based on the oxygen reduction reaction mechanism, contaminant surface adsorption/desorption, and electrochemical reaction kinetics. The model is then applied to the study of air-side toluene contamination. Experimental data for toluene contamination at four current densities (0.2, 0.5, 0.75 and 1.0 A cm⁻²) and three contamination levels (1, 5 and 10 ppm) were used to validate the model. In addition, it is expected that, with parameter adjustment, this model can also be used to predict performance degradation caused by other air impurities such as nitrogen oxides (NO_x) and sulfur oxides (SO_x).     

Optimization of hydrogen feeding procedure in PEM fuel cell systems for transportation

The hydrogen feeding sub-system is one of balance of plant (BOP) components necessary for the correct operation of a fuel cell system (FCS). In this paper the performance of a 6 kW PEM (Proton Exchange Membrane) FCS, able to work with two fuel feeding procedures (dead-end or flow-through), was experimentally evaluated with the aim to highlight the effect of the anode operation mode on stack efficiency and durability. The FCS operated at low reactant pressure (<50 kPa) and temperature (<330 K), without external humidification. The experiments were performed in both steady state and dynamic conditions. The performance of some cells in dead-end mode worsened during transient phases, while a more stable working was observed with fuel recirculation. This behavior evidenced the positive role of the flow-through procedure in controlling flooding phenomena, with the additional advantage to simplify the management issues related to hydrogen purge and air stoichiometric ratio. The flow-through modality resulted a useful way to optimize the stack efficiency and to reduce the risks of fast degradation due to reactant starvation during transient operative phases.     

Operating line analysis of fuel processors for PEM fuel cell systems

At least three different definitions of fuel processor efficiency are in widespread use in the fuel cell industry. In some instances the different definitions are qualitatively the same and differ only in their quantitative values. However, in certain limiting cases, the different efficiency definitions exhibit qualitatively different trends as system parameters are varied. In one limiting case that will be presented, the use of the wrong efficiency definition can lead a process engineer to believe that a theoretical maximum in fuel processor efficiency exists at a particular operating condition, when in fact no such efficiency optimum exists. For these reasons, the objectives of this paper are to: (1) quantitatively compare and contrast these different definitions, (2) highlight the advantages and disadvantages of each definition and (3) recommend the correct definition of fuel processor efficiency.     

Methanol fuel processor and PEM fuel cell modeling for mobile application

The use of hydrocarbon fed fuel cell systems including a fuel processor can be an entry market for this emerging technology avoiding the problem of hydrogen infrastructure. This article presents a 1 kW low temperature PEM fuel cell system with fuel processor, the system is fueled by a mixture of methanol and water that is converted into hydrogen rich gas using a steam reformer. A complete system model including a fluidic fuel processor model containing evaporation, steam reformer, hydrogen filter, combustion, as well as a multi-domain fuel cell model is introduced. Experiments are performed with an IDATECH FCS1200™ fuel cell system. The results of modeling and experimentation show good results, namely with regard to fuel cell current and voltage as well as hydrogen production and pressure. The system is auto sufficient and shows an efficiency of 25.12%. The presented work is a step towards a complete system model, needed to develop a well adapted system control assuring optimized system efficiency.     

Modeling of PEM fuel cell Pt/C catalyst degradation

Pt/C catalyst degradation remains as one of the primary limitations for practical applications of proton exchange membrane (PEM) fuel cells. Pt catalyst degradation mechanisms with the typically observed Pt nanoparticle growth behaviors have not been completely understood and predicted. In this work, a physics-based Pt/C catalyst degradation model is proposed with a simplified bi-modal particle size distribution. The following catalyst degradation processes were considered: (1) dissolution of Pt and subsequent electrochemical deposition on Pt nanoparticles in cathode; (2) diffusion of Pt ions in the membrane electrode assembly (MEA); and (3) Pt ion chemical reduction in membrane by hydrogen permeating through the membrane from the negative electrode. Catalyst coarsening with Pt nanoparticle growth was clearly demonstrated by Pt mass exchange between small and large particles through Pt dissolution and Pt ion deposition. However, the model is not adequate to predict well the catalyst degradation rates including Pt nanoparticle growth, catalyst surface area loss and cathode Pt mass loss. Additional catalyst degradation processes such as new Pt cluster formation on carbon support and neighboring Pt clusters coarsening was proposed for further simulative investigation.     

A systematic approach for matching simulated and experimental polarization curves for a PEM fuel cell

Matching simulated and experimental polarization curves is an essential step in the modelling of polymer electrolyte membrane (PEM) fuel cells, but the numerical values of many input parameters like exchange current densities, charge transfer coefficients, protonic conduction coefficient and water removal coefficient are hard to be found experimentally. In this paper, the influence of these input parameters on the performance of PEM fuel cells has been investigated using the ANSYS PEM Fuel Cell Module. The simulation results show how the exchange current densities and charge transfer coefficients influence the activation losses; membrane resistance and contact resistance between the different components of a fuel cell contribute to the ohmic losses; and the coefficient of liquid water removal affects the concentration losses. A systematic procedure to match a simulated polarization curve with an experimental curve is presented and illustrated by application to an experimental PEM fuel cell with 5 cm² active area.     

Platinum-plated nanoporous gold: An efficient,low Pt loading electrocatalyst for PEM fuel cells

Platinum-plated nanoporous gold leaf (Pt-NPGL) is made by coating a conformal, atomically thin skin of platinum over the high surface area pores of a thin membrane of nanoporous gold. Because Pt loading in Pt-NPGL can be controlled down to 0.01 mg cm⁻² using only simple benchtop chemistry, the material holds promise as a low Pt loading, carbon-free electrocatalyst. Here, we report successful use of Pt-NPGL as a catalyst in proton exchange membrane (PEM) fuel cells. Stable and high performance Pt-NPGL/Nafion membrane electrode assemblies (MEAs) were made using a stamping technique. The performance of Pt-NPGL MEAs is comparable to conventional carbon-supported nanoparticles-based MEAs with much higher loading, generating an output power density of up to 4.5 kW g⁻¹ Pt in our non-optimized test configuration. Correlations between the performance of Pt-NPGL MEAs, the electrochemically accessible surface area, and material microstructure are discussed. Our success in using Pt-NPGL as a fuel cell catalyst suggests that creating precious metals skins over nanoporous metal supports is a viable strategy for designing new catalysts for PEM fuel cells. This promising approach allows tailoring catalytic activity by engineering precious metal/substrate interactions, employs materials with dual functionality acting both as current collector and catalyst, and may avoid the sintering problems plaguing conventional nanoparticle-based catalysts.     

Optimization of PEM fuel cell flow channel dimensions—Mathematic modeling analysis and experimental verification

The objective of this work is to optimize the dimensions of gas flow channels and walls/ribs in a proton-exchange membrane (PEM) fuel cell. To achieve this goal conveniently, a relatively easy-to-approach mathematical model for PEM fuel cells has been developed. The model was used for the design optimization of fuel cells, which were fabricated and experimentally tested to compare the performance and examine these optimization effects. The model analyzes the average mass transfer and species' concentrations in flow channels, which allows the determination of an average concentration polarization, the humidity in anode and cathode gas channels, the proton conductivity of membranes, as well as the activation polarization. An electrical circuit for the current and ion conduction is applied to analyze the ohmic losses from anode current collector to cathode current collector. This model needs relatively less amount of computational time to find the V–I curve of the fuel cell, and thus it can be applied to compute a large amount of cases with different flow channel dimensions and operating parameters for optimization. Experimental tests of several PEM fuel cells agreed with the modeling results satisfactorily. Both simulation and experimental results showed that relatively small widths of flow channels and ribs, together with a small ratio of the rib's width versus channel's width, are preferred for obtaining high power densities. To further demonstrate the advantage of optimized fuel cell designs, two four-cell stacks, one with optimized channel/rib designs and the other without, were compared experimentally and a much better performance of the one with the optimized design was confirmed.     

Modelling CO poisoning and O2 bleeding in a PEM fuel cell anode

Fuel gas containing carbon monoxide severely degrades the performance of a polymer electrolyte membrane (PEM) fuel cell. However, CO poisoning can be mitigated by introducing oxygen into the fuel (oxygen bleeding). A mathematical PEM fuel cell model is developed that simulates both CO poisoning and oxygen bleeding, and obtains excellent agreement with published, experimental data. Modelling efforts indicate that CO adsorption and desorption follow a Temkin model. Increasing operating pressure or temperature mitigates CO poisoning, while use of reformate fuel increases the severity of the poisoning effect. Although oxygen bleeding mitigates CO poisoning, an unrecoverable performance loss exists at high current densities due to competition for reaction sites between hydrogen adsorption and the heterogeneous catalysis of CO. Copyright © 2003 John Wiley & Sons, Ltd.     

Modeling efficiency and water balance in PEM fuel cell systems with liquid fuel processing and hydrogen membranes

Integrating PEM fuel cells effectively with liquid hydrocarbon reforming requires careful system analysis to assess trade-offs associated with H₂ production, purification, and overall water balance. To this end, a model of a PEM fuel cell system integrated with an autothermal reformer for liquid hydrocarbon fuels (modeled as C₁₂H₂₃) and with H₂ purification in a water–gas-shift/membrane reactor is developed to do iterative calculations for mass, species, and energy balances at a component and system level. The model evaluates system efficiency with parasitic loads (from compressors, pumps, and cooling fans), system water balance, and component operating temperatures/pressures. Model results for a 5-kW fuel cell generator show that with state-of-the-art PEM fuel cell polarization curves, thermal efficiencies >30% can be achieved when power densities are low enough for operating voltages >0.72 V per cell. Efficiency can be increased by operating the reformer at steam-to-carbon ratios as high as constraints related to stable reactor temperatures allow. Decreasing ambient temperature improves system water balance and increases efficiency through parasitic load reduction. The baseline configuration studied herein sustained water balance for ambient temperatures ≤35 °C at full power and ≤44 °C at half power with efficiencies approaching ∼27 and ∼30%, respectively.     

Carbon monoxide clean-up of the reformate gas for PEM fuel cell applications: A conceptual review

The removal of CO from hydrocarbon- and methanol-derived hydrogen can be performed by a series of methods to achieve the 10 ppm CO limit required for proton exchange membrane fuel cell (PEMFC) applications. The fuel processing includes reforming of the feed followed by water-gas shift (WGS) and a final CO removal with the latter decreasing the CO concentration below the desirable level. Pressure swing adsorption (PSA), membrane separation, selective methanation (SMET) and preferntial oxidation (PROX) are the applicable techniques as the final clean-up step. The appropriate method depends on the scale but for small scale portable fuel processors, catalytic processes are more appropriate due to the operating conditions close to that of PEMFC. The PROX appears to be the best due to rapid reaction rate and mild operation conditions which renders intensification of the processes possible. Extensive research and development efforts are underway to increase catalyst activity and improve the temperature window of the reaction.     

Experimental validation of a lumped model of single droplet deformation,oscillation and detachment on the GDL surface of a PEM fuel cell

Proton Exchange Membrane Fuel Cell (PEMFC) performance significantly depends on electrodes water content. Liquid water emerging from the Gas Diffusion Layer (GDL) micro-channels can form droplets, films or slugs in the Gas Flow Channel (GFC). In the regime of droplets formation, the interaction with the gas flow leads to an oscillating mechanisms that is fundamental to study the detachment from the GDL surface. In this work, a numerical model of a droplet growing on the GDL surface is developed to describe the interaction between droplet and gas flow. Therefore, a lumped force balance is enforced to determine the center of mass motion law. Oscillation frequencies during growth and at detachment are found as a function of droplet size. The model is also exploited to find the relationship between droplet critical detachment size and gas velocity. The numerical results are compared with the experimental data previously published by the authors as well as with other experimental results available in the literature. The matching between the numerical and experimental data is very good. The low computational burden and the conciseness of the proposed approach make the model suitable for applications such as control and optimization strategies development to enhance PEMFC performance. Additionally, the model can be exploited to implement monitoring and diagnostic algorithm as well.     

Economics of hydrogen production and utilization strategies for the optimal operation of a grid-parallel PEM fuel cell power plant

This paper integrates the hydrogen production and utilization strategies with an economic model of a PEM fuel cell power plant (FCPP). The model includes the operational cost, thermal recovery, power trade with the local grid, and hydrogen management strategies. The model is used to determine the optimal operational strategy, which yields the minimum operating cost. The optimal operational strategy is achieved through estimation of the following: hourly generated power, thermal power recovered from the FCPP, power trade with the local grid, and hydrogen production. An evolutionary programming-based technique is used to solve for the optimal operational strategy. The model is tested using different seasonal load demands. The results illustrate the impact of hydrogen management strategies on the operational cost of the FCPP when subjected to seasonal load variation. Results are encouraging and indicate viability of the proposed model.     

Computational model of a PEM fuel cell with serpentine gas flow channels

A three-dimensional computational fluid dynamics model of a PEM fuel cell with serpentine flow field channels is presented in this paper. This comprehensive model accounts for the major transport phenomena in a PEM fuel cell: convective and diffusive heat and mass transfer, electrode kinetics, and potential fields. A unique feature of the model is the implementation of a voltage-to-current (VTC) algorithm that solves for the potential fields and allows for the computation of the local activation overpotential. The coupling of the local activation overpotential distribution and reactant concentration makes it possible to predict the local current density distribution more accurately. The simulation results reveal current distribution patterns that are significantly different from those obtained in studies assuming constant surface overpotential. Whereas the predicted distributions at high load show current density maxima under the gas channel area, low load simulations exhibit local current maxima under the collector plate land areas.     

A 5 kWt catalytic burner for PEM fuel cells: Effect of fuel type,fuel content and fuel loads on the capacity of the catalytic burner

For proton exchange membrane fuel cell systems (PEMFC) integrated with fuel processors, the calorific value of reformate gases produced during the start-up phase must be recovered. An appropriate exhaust after treatment system has crucial importance for PEMFC systems. Catalytic combustion is a promising alternative regarding its total oxidation capability of low calorific value gases at low temperatures, thereby reducing environmentally hazardous emissions. The aim of the study is to develop an after treatment system using a catalytic burner with a nominal capacity of 5 kW_t, which is also adaptive to partial loads of PEM fuel cell capacity. Fuel type, fuel composition and fuel loads are important parameters determining the operating window of the catalytic burner. Precious metal based catalysts, as proved to be the most active catalysts for the oxidation of hydrocarbons, can withstand temperatures of about 1073 K without exhibiting a rapid deactivation. This is the main barrier dictating the operating window and thereby determining the capacity of the burner. In this work, 1.5% natural gas (NG) alone was found to be the upper limit to control the catalyst bed temperature below 1073 K. In the case of catalytic combustion of hydrogen–NG mixture, 7% of hydrogen with NG up to 0.6% could be totally oxidized below 1073 K. Within the experimented ranges of fuel loads, between 2.5 kW_t and 5.5 kW_t, the temperature of the catalyst bed was seen to increase with increasing the fuel load at constant fuel percentages. It has been observed that fuel type was another parameter affecting the exhaust gas temperature.     

Water balance for the design of a PEM fuel cell system

The design of a proton exchange membrane (PEM) fuel cell system is important for the optimization of the function of supporting parameters in the fuel cell. The water balance in a PEM fuel cell is investigated based on the water transport phenomena. In this investigation, the diffusion of water from the cathode side to the anode side of the cell is observed to not occur at 20% relative humidity at the cathode (RHC) and 58% relative humidity at the anode (RHA). The minimum concentration of condensed water at the cathode side is observed at a cathode gas inlet relative humidity of 40% RHC–92% RHC and at temperatures between 343 K and 363 K. RHC operating conditions that are greater than 90% and at a temperature of 363 K increased the concentration of condensed water and occurred quickly, which result in a water balance that became difficult to control. On the anode side, the condensation of water is observed at operating temperatures of 353 K and 363 K.     

Corrosion of metal bipolar plates for PEM fuel cells: A review

PEM fuel cells are of prime interest in transportation applications due to their relatively high efficiency and low pollutant emissions. Bipolar plates are the key components of these devices as they account for significant fractions of their weight and cost. Metallic materials have advantages over graphite-based ones because of their higher mechanical strength and better electrical conductivity. However, corrosion resistance is a major concern that remains to be solved as metals may develop oxide layers that increase electrical resistivity, thus lowering the fuel cell efficiency. This paper aims to present the main results found in recent literature about the corrosion performance of metallic bipolar plates.     

30,000 h operation of a 70 kW stationary PEM fuel cell system using hydrogen from a chlorine factory

A pilot PEM Power Plant is described utilizing by-product hydrogen from the electrolysis of brine in the Akzo Nobel chlor-alkali plant at Delfzijl, the Netherlands. The performance of this 70 kW fuel cell unit is reported for a period of five and a half years, starting in April 2007. Results of measurements of cell voltages on PEM fuel cells with different types of Membrane Electrode Assemblies are reported for an operational period of 30,000 h. Stack performance is highly dependent on the MEA it contains, leading to a wide variety in reversible and irreversible voltage decay rates. Best performing MEAs enable stack operation of more than 16,000 h of power generation, with an average voltage decay rate of 2.5 μV/h. The reversible decay is linked to contaminants, primarily at the anode.