A review of polymer electrolyte membrane fuel cell stack testing

This paper presents an overview of polymer electrolyte membrane fuel cell (PEMFC) stack testing. Stack testing is critical for evaluating and demonstrating the viability and durability required for commercial applications. Single cell performance cannot be employed alone to fully derive the expected performance of PEMFC stacks, due to the non-uniformity in potential, temperature, and reactant and product flow distributions observed in stacks. In this paper, we provide a comprehensive review of the state-of-the art in PEMFC testing. We discuss the main topics of investigation, including single cell vs. stack-level performance, cell voltage uniformity, influence of operating conditions, durability and degradation, dynamic operation, and stack demonstrations. We also present opportunities for future work, including the need to verify the impact of stack size and cell voltage uniformity on performance, determine operating conditions for achieving a balance between electrical efficiency and flooding/dry-out, meet lifetime requirements through endurance testing, and develop a stronger understanding of degradation.     

Water transport in polymer electrolyte membrane fuel cells

Polymer electrolyte membrane fuel cell (PEMFC) has been recognized as a promising zero-emission power source for portable, mobile and stationary applications. To simultaneously ensure high membrane proton conductivity and sufficient reactant delivery to reaction sites, water management has become one of the most important issues for PEMFC commercialization, and proper water management requires good understanding of water transport in different components of PEMFC. In this paper, previous researches related to water transport in PEMFC are comprehensively reviewed. The state and transport mechanism of water in different components are elaborated in detail. Based on the literature review, it is found that experimental techniques have been developed to predict distributions of water, gas species, temperature and other parameters in PEMFC. However, difficulties still remain for simultaneous measurements of multiple parameters, and the cell and system design modifications required by measurements need to be minimized. Previous modeling work on water transport in PEMFC involves developing rule-based and first-principle-based models, and first-principle-based models involve multi-scale methods from atomistic to full cell levels. Different models have been adopted for different purposes and they all together can provide a comprehensive view of water transport in PEMFC. With the development of computational power, application of lower length scale methods to higher length scales for more accurate and comprehensive results is feasible in the future. Researches related to cold start (startup from subzero temperatures) and high temperature PEMFC (HT-PEMFC) (operating at the temperatures higher than 100 °C) are also reviewed. Ice formation that hinders reactant delivery and damages cell materials is the major issue for PEMFC cold start, and enhancing water absorption by membrane electrolyte and external heating have been identified as the most effective ways to reduce ice formation and accelerate temperature increment. HT-PEMFC that can operate without liquid water formation and membrane hydration greatly simplifies water management strategy, and promising performance of HT-PEMFC has been demonstrated.     

Static and dynamic modeling of a diesel fuel processing unit for polymer electrolyte fuel cell supply

This article introduces the energetic macroscopic representation (EMR) as approach for the dynamic modeling of a diesel fuel processing unit. The EMR is the first step toward model-based control structure development. The autothermal fuel processing system containing: heat exchanger, reformer, desulfurization, water gas shift, preferential oxidation and condensation is divided into a multitude simple subblocks. Each subblock describes an elementary step of the fuel conversion, several of these blocks may occur in a single module. Calculations are carried out using two basic principles: mass and energy balances. For model-based control development, it is imperative that the model represents dynamic behavior, therefore temperature and pressure dynamics are taken into account in the model. It is shown that the model is capable to predict the stationary behavior of the entire fuel processing unit correctly by comparison with given data. Predictions regarding reformer heat up, temperature and pressure dynamics are also provided.     

Parametric study on geometric and material properties of polymer electrolyte membrane fuel cell with free vibration analysis

The mechanical aspect of understanding the dynamic behaviour is very important in stack assembly of fuel cell configuration. Designing such configuration would be very useful to tune the system accordingly to avoid catastrophic failure due to resonance. The dynamic analysis of a polymer electrolyte membrane fuel cell (PEMFC) is performed to understand its response during complex loading nature. The stack assembly of bipolar plate, gas diffusion electrolyte (GDE) and membrane are modelled and analysed using Mindilin plate element with finite element method (FEM). The parametric study on thickness, density and young's modulus and its influence on dominant modes of natural frequencies are analysed with a 5%–20% range of variations. It is observed that the bipolar plate's thickness plays a vital role in the vibration behaviour of the PEMFC.     

Quantitative visualization of temporal water evolution in an operating polymer electrolyte fuel cell

Synchrotron X-ray radiography is employed to visualize the temporal evolution of water inside the gas diffusion layer (GDL) of an operating (in situ) polymer electrolyte fuel cell (PEFC). A single-cell PEFC test kit is specially designed for the convenient capture of X-ray images. X-ray images of water in the PEFC components, such as the polymer membrane, GDL, and end plate, are captured consecutively. The synchrotron X-ray radiography of high-spatial and high-temporal resolution is suitable for observing the transport of a liquid layer and for visualizing water distribution inside the PEFC. As a result, the spatial distribution of water in the PEFC components is clearly and quantitatively visualized. The temporal evolution of water in the anode GDL due to back diffusion effect is clearly observed by adopting the image normalization method. The water-saturation characteristics at the cathode GDL, including saturation time and speed, are quite different from those at the anode GDL.     

The catalytic properties of the sputtered iron on carbon nanotubes for polymer electrolyte membrane fuel cells

Pure iron metal target was sputtered onto carbon nanotube grown on carbon paper to fabricate iron-based catalysts for the oxygen reduction reaction (ORR). The carbon nanotube-supported Fe-based catalysts have active sites which are believed to include iron cations coordinated by pyridinic nitrogen functionalities between the graphitic sheets. A Fe-based electrocatalyst treated at 950 °C displayed the highest mass activity. The treated sample at lower temperature could not form the Fe/N/CNT sufficiently. On the other hand, the formed Fe/N/CNTs were degraded thermally at higher temperature. Cyclic voltammetry of the Fe-based electrocatalysts showed similar trends with mass activity which is the largest value at 950 °C. Even though the catalytic activity is not comparable with that of Pt/C catalysts yet, sputtered Fe-based electrocatalysts are promising to explore the non-precious metal electrocatalysts.     

Simultaneous visualization of oxygen distribution and water blockages in an operating triple-serpentine polymer electrolyte fuel cell

Visualization inside polymer electrolyte fuel cells (PEFCs) is important for elucidating reaction distributions to improve the performance and durability of the cells. An O₂-sensitive porphyrin luminescent dye film was used to visualize oxygen partial pressures and water blockages simultaneously in triple-serpentine gas flow channels in an operating PEFC. Water droplets formed near the exit of a gas-flow channel lowered the oxygen partial pressure noticeably over the channel by blocking air flow near the entrance. Meanwhile, air was continuously supplied from the other channels through the gas diffusion layer, thus allowing power to be generated in the blocked channel. With water blockages, however, the catalyst layer under the channel became flooded by the water produced during the reaction, and the flooded state continued to exist in the catalyst and/or porous layers, even after blowing the water droplet out, so that the power generation was lowered along the channel.     

Development of porous carbon foam polymer electrolyte membrane fuel cell

In order to prove the feasibility of using porous carbon foam material in a polymer electrolyte membrane fuel cell (PEMFC), a single PEMFC is constructed with a piece of 80PPI (pores per linear inch) Reticulated Vitreous Carbon (RVC) foam at a thickness of 3.5 mm employed in the cathode flow-field. The cell performance of such design is compared with that of a conventional fuel cell with serpentine channel design in the cathode and anode flow-fields. Experimental results show that the RVC foam fuel cell not only produces comparative power density to, but also offers interesting benefits over the conventional fuel cell. A 250 h long term test conducted on a RVC foam fuel cell shows that the durability and performance stability of the material is deemed to be acceptable. Furthermore, a parametric study is conducted on single RVC foam fuel cells. Effect of geometrical and material parameters of the RVC foam such as PPI and thickness and operating conditions such as pressure, temperature, and stoichiometric ratio of the reactant gases on the cell performance is experimentally investigated in detail. The single cell with the 80PPI RVC foam exhibits the best performance, especially if the thinnest foam (3.5 mm) is used. The cell performance improves with increasing the operating gauge pressure from 0 kPa to 80 kPa and the operating temperature from 40 °C to 60 °C, but deteriorates as it further increases to 80 °C. The cell performance improves as the stoichiometric ratio of air increases from 1.5 to 4.5; however, the improvement becomes marginal when it is raised above 3.0. On the other hand, changing the stoichiometric ratio of hydrogen does not have a significant impact on the cell performance.     

The effect of diffusioosmosis on water transport in polymer electrolyte fuel cells

An analytical study of the effect of diffusioosmosis caused by the concentration gradient of hydrogen ions on the isothermal transport of water in a fully hydrated membrane of a polymer electrolyte fuel cell (PEFC) is presented. A capillary tube or slit with a negatively charged wall is chosen to model the nanopores of the membrane. The electric double layer adjacent to the capillary wall may have an arbitrary thickness relative to the capillary radius and its electrostatic potential distribution is determined as the solution of the Poisson–Boltzmann equation. Solving a modified Navier–Stokes equation, the fluid velocity in the axial direction of the capillary induced by the macroscopic electric field and protonic concentration gradient is obtained as a function of the radial position in closed forms. The results for the local and averaged electrokinetic velocities in the capillary show that the effect of diffusioosmosis on the water transport in the membrane of a PEFC can be significant in comparison with that of electroosmosis under low-potential-difference operations.     

Impact of defective single cell on the operation of polymer electrolyte membrane fuel cell stack

Potential inversion of a single cell in a PEMFC stack reduces its performance and can lead to severe damage in the MEAs. Numerous causes of potential inversion can be considered, from MEA degradation to insufficient feed of reacting gases. The first part of the paper deals with experiments carried out to investigate whether the potential inversion could be suppressed by increasing the inlet gas flow. Then, the defective cell resistances were measured and compared to those exhibited by the other cells in the 23-cell stack. We also studied the influence of this cell on the whole stack resistances. Finally, the defective cell was dismantled and analysed, in order to explain where the defect comes from and whether it has affected each part of the cell.     

Adaptive operation strategy of a polymer electrolyte membrane fuel cell air system based on model predictive control

The present article investigates a model predictive control-based operation strategy of an automotive fuel cell air system. For this purpose, a nonlinear model of a fuel cell system is derived, which is linearized and discretized around the current operation point during each time sample. This model is combined with a cost function taking into account power reference tracking and hydrogen minimization. Additional system constraints ensure a safe and robust operation. Subsequently, the adaptive and efficiency-optimal behavior of the model predictive controller is demonstrated based on a simulation study of different scenarios with varying power profiles. Furthermore, the thermal derating behavior of this control is studied using an exemplary situation with critical thermal conditions. Finally, the model predictive control approach is compared with a validated map-based operation strategy highlighting the potential of reducing the hydrogen consumption by 3% while decreasing the risk of harmful operation conditions.     

A lumped parameter model of the polymer electrolyte fuel cell

A model of a polymer electrolyte fuel cell (PEFC) is developed that captures dynamic behaviour for control purposes. The model is mathematically simple, but accounts for the essential phenomena that define PEFC performance. In particular, performance depends principally on humidity, temperature and gas pressure in the fuel cell system. To simulate accurately PEFC operation, the effects of water transport, hydration in the membrane, temperature, and mass transport in the fuel cells system are simultaneously coupled in the model. The PEFC model address three physically distinctive fuel cell components, namely, the anode channel, the cathode channel, and the membrane electrode assembly (MEA). The laws of mass and energy conservation are applied to describe each physical component as a control volume. In addition, the MEA model includes a steady-state electrochemical model, which consists of membrane hydration and the stack voltage models.     

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.     

Diagnosis of contamination introduced by ammonia at the cathode in a polymer electrolyte membrane fuel cell

Contamination introduced by impurities from feed streams can impact polymer electrolyte membrane fuel cell performance dramatically. The presence of unwanted trace species, such as CO, H₂S, and NH₃, can adversely affect the function of a fuel cell. It has been reported that the major impact of CO and H₂S contamination on fuel cell performance is kinetic, while the effect of NH₃ contamination is speculated to be mainly membrane conductivity reduction. In this paper, the effect of NH₃ contamination from the cathode side was investigated. The mechanisms of NH₃ contamination were diagnosed based on degradation tests using electrochemical impedance spectroscopy and cyclic voltammetry. The contamination factors investigated included ammonia concentration, operating current, temperature, and relative humidity. The results show that the severity of the adverse effect caused by ammonia contamination was enhanced by increased ammonia concentration, decreased operating temperature, and decreased relative humidity. The performance decay induced by ammonia is attributable to reduced membrane/ionomer conductivity and ammonia adsorption on the catalyst surface, which blocks the active sites and hinders mass transfer.     

Numerical modeling of an automotive derivative polymer electrolyte membrane fuel cell cogeneration system with selective membranes

Cogeneration power plants based on fuel cells are a promising technology to produce electric and thermal energy with reduced costs and environmental impact. The most mature fuel cell technology for this kind of applications are polymer electrolyte membrane fuel cells, which require high-purity hydrogen.The most common and least expensive way to produce hydrogen within today's energy infrastructure is steam reforming of natural gas. Such a process produces a syngas rich in hydrogen that has to be purified to be properly used in low temperature fuel cells. However, the hydrogen production and purification processes strongly affect the performance, the cost, and the complexity of the energy system.Purification is usually performed through pressure swing adsorption, which is a semi-batch process that increases the plant complexity and incorporates a substantial efficiency penalty. A promising alternative option for hydrogen purification is the use of selective metal membranes that can be integrated in the reactors of the fuel processing plant. Such a membrane separation may improve the thermo-chemical performance of the energy system, while reducing the power plant complexity, and potentially its cost. Herein, we perform a technical analysis, through thermo-chemical models, to evaluate the integration of Pd-based H₂-selective membranes in different sections of the fuel processing plant: (i) steam reforming reactor, (ii) water gas shift reactor, (iii) at the outlet of the fuel processor as a separator device. The results show that a drastic fuel processing plant simplification is achievable by integrating the Pd-membranes in the water gas shift and reforming reactors. Moreover, the natural gas reforming membrane reactor yields significant efficiency improvements.     

A dynamic model of air-breathing polymer electrolyte fuel cell (PEFC): A parametric study

A dynamic model for an air-breathing PEFC has been built to investigate the transient response of the fuel cell to load changes. The sensitivities of the dynamic response, as well as the steady state performance, to: the ambient temperature and relative humidity; the thickness and the thermal conductivity of the cathode GDL; and the fuel utilisation, have been studied. A previously-developed steady-state model of the fuel cell was linked to the dynamic model to feed the latter with the data of the cell temperature as it changes with the current density. It was found that, when there are sudden changes to high loads, there exist optimum values for the ambient temperature and GDL thickness at which the overshoots are mitigated and the steady state performance is improved. Further, the transient and steady state performance were found to improve with increasing the ambient relative humidity and GDL thermal conductivity. Finally, the fuel utilisation was found to have no impact on the dynamic response of the fuel cell. All the above findings have been presented and discussed in the paper.     

Fabrication of polymer electrolyte membrane fuel cell MEAs utilizing inkjet print technology

Utilizing drop-on-demand technology, we have successfully fabricated hydrogen–air polymer electrolyte membrane fuel cells (PEMFC), demonstrated some of the processing advantages of this technology and have demonstrated that the performance is comparable to conventionally fabricated membrane electrode assemblies (MEAs). Commercial desktop inkjet printers were used to deposit the active catalyst electrode layer directly from print cartridges onto Nafion^® polymer membranes in the hydrogen form. The layers were well-adhered and withstood simple tape peel, bending and abrasion tests and did so without any post-deposition hot press step. The elimination of this processing step suggests that inkjet-based fabrication or similar processing technologies may provide a route to less expensive large-scale fabrication of PEMFCs. When tested in our experimental apparatus, open circuit voltages up to 0.87 V and power densities of up to 155 mW cm⁻² were obtained with a catalyst loading of 0.20 mg Pt cm⁻². A commercially available membrane under identical, albeit not optimized test conditions, showed about 7% greater power density. The objective of this work was to demonstrate some of the processing advantages of drop-on-demand technology for fabrication of MEAs. It remains to be determined if inkjet fabrication offers performance advantages or leads to more efficient utilization of expensive catalyst materials.     

Modeling of two-phase transport in the diffusion media of polymer electrolyte fuel cells

A three-dimensional model of polymer electrolyte fuel cells (PEFCs) is developed to investigate multiphase flows, species transport, and electrochemical processes in fuel cells and their interactions. This two-phase model consists of conservation principles of mass, momentum, species concentration and charges, and elucidates the key physicochemical mechanisms in the constituent components of PEFCs that govern cell performance. Efforts are made to formulate two-phase transport in the anode diffusion media and its coupling with cathode flooding as well as the interaction between single- and two-phase flows. Numerical simulations are carried out to investigate multiphase flow, electrochemical activity, and transport phenomena and the intrinsic couplings of these processes inside a fuel cell at low humidity. The results indicate that multiphase flows may exist in both anode and cathode diffusion media at low-humidity operation, and two-phase flow emerges near the outlet for co-flow configuration while is present in the middle of the fuel cell for counter-flow one. The validated numerical tools can be applied to investigate vital issues related to anode performance and degradation arising from flooding for PEFCs.     

Free vibration analysis of a polymer electrolyte membrane fuel cell

A free vibration analysis of a polymer electrolyte membrane fuel cell (PEMFC) is performed by modelling the PEMFC as a 20 cm × 20 cm composite plate structure. The membrane, gas diffusion electrodes, and bi-polar plates are modelled as composite material plies. Energy equations are derived based on Mindlin's plate theory, and natural frequencies and mode shapes of the PEMFC are calculated using finite element modelling. A parametric study is conducted to investigate how the natural frequency varies as a function of thickness, Young's modulus, and density for each component layer. It is observed that increasing the thickness of the bi-polar plates has the most significant effect on the lowest natural frequency, with a 25% increase in thickness resulting in a 17% increase in the natural frequency. The mode shapes of the PEMFC provide insight into the maximum displacement exhibited as well as the stresses experienced by the single cell under vibration conditions that should be considered for transportation and stationary applications. This work provides insight into how the natural frequencies of the PEMFC should be tuned to avoid high amplitude oscillations by modifying the material and geometric properties of individual components.