Gas selectivity measurements as a diagnostic tool for fuel cells

In this study, gas permeability and selectivity measurements are used to identify when membrane thinning or integrity failures have occurred in a fuel cell membrane electrode assembly and hence be used as a tool to identify when chemical or mechanical degradation is the dominant mode of failure. A fuel cell was operated at open circuit voltage conditions and the permeability of five different gasses (H₂, He, N₂, O₂, Ar) were measured periodically. The results showed that through a fresh MEA the gasses permeated via a solution diffusion type mechanism though after 150 h of degradation the permeation behaviour changed to Knudsen diffusion mechanism. This was interpreted to indicate that an integrity failure had occurred in the ionomer membrane. Voltage data also shows an increase in voltage degradation rate after 150 h and a drop in polarization performance. Furthermore, there was an increase in fluoride emission rate. Analysis of the de-catalyzed membrane after degradation revealed rips and tears in the ionomer membrane and no significant thickness changes.     

Investigation of degradation behavior of membrane electrode assembly with polytetrafluoroethylene/Nafion composite membrane

The main purpose of this study is to investigate the accelerated degradation of the PTFE/Nafion membrane electrode assembly through open circuit voltage and relative humidity cycling. The state of a PTFE/Nafion membrane electrode assembly is evaluated in a fuel cell by monitoring the polarization curve, AC impedance, cyclic voltammetry, and linear sweep voltammetry data over time. The experimental results are then fitted to equations of an equivalent circuit. The results of the first 160 experimental cycles show that catalyst degradation is the main cause for the decay of the membrane electrode assembly. During the 160-520th cycles, the membrane electrode assembly experiences creep deformation, which is due to relative humidity cycling. During the 640-840th cycles, the degradation causes a gradual transition from minor to major membrane cracking; after which the combustion reaction dramatically accelerates membrane electrode assembly degradation.     

Effect of assembly error of bipolar plate on the contact pressure distribution and stress failure of membrane electrode assembly in proton exchange membrane fuel cell

In practice, the assembly error of the bipolar plate (BPP) in a PEM fuel cell stack is unavoidable based on the current assembly process. However its effect on the performance of the PEM fuel cell stack is not reported yet. In this study, a methodology based on FEA model, “least squares-support vector machine (LS-SVM)” simulation and statistical analysis is developed to investigate the effect of the assembly error of the BPP on the pressure distribution and stress failure of membrane electrode assembly (MEA). At first, a parameterized FEA model of a metallic BPP/MEA assembly is established. Then, the LS-SVM simulation process is conducted based on the FEA model, and datasets for the pressure distribution and Von Mises stress of MEA are obtained, respectively for each assembly error. At last, the effect of the assembly error is obtained by applying the statistical analysis to the LS-SVM results. A regression equation between the stress failure and the assembly error is also built, and the allowed maximum assembly error is calculated based on the equation. The methodology in this study is beneficial to understand the mechanism of the assembly error and can be applied to guide the assembly process for the PEM fuel cell stack.     

Silicon carbide fiber-reinforced composite membrane for high-temperature and low-humidity polymer exchange membrane fuel cells

Currently, efforts are being made to commercialize a fuel cell system through research on fuel cell material enhancements. In particular, improvements in the membrane-electrode assembly, a key component of polymer electrolyte membrane (PEM) fuel cells, are essential to increase the performance of a fuel cell, in addition to accelerating its commercialization. Therefore, in this study, we used silicon carbide (SiC) fibers (web type) by electrospinning, which possess superior material, thermal, and chemical properties, as a structural material for the composite electrolyte membrane in the membrane-electrode assembly by impregnating it with the polymer electrolyte ionomer of short-side chain (SSC). In addition, we enhanced the ion-exchange capability of functionalized SiC fibers by introducing the hydroxyl (OH) group and phosphoric acid. The resulting functionalized composite electrolyte membrane exhibited a 70% better ion-exchange capability than the conventional cast electrolyte membrane and SiC webs composite electrolyte membranes was observed to excellent mechanical strength. We characterized and illustrative modeled the functionalized silicon carbide fibers, on the basis of which we further developed composite membrane. We then fabricated a unit cell of PEMFC based on this composite electrolyte membrane, and evaluated its single-cell performance, electrochemical properties, and accelerated voltage life-time durability test of operating 35 h according to the electro- and physic-chemical characteristics of the MEA under high-temperature and low humidity (120 °C/RH 40%).     

The effects of excess phosphoric acid in a Polybenzimidazole-based high temperature proton exchange membrane fuel cell

A series of experiments are conducted in order to investigate the performance of a proton exchange membrane (PEM) fuel cell using a commercially available polybenzimidazole (PBI)-based high temperature membrane. During the study a drastic degradation in performance is observed over time and a significant amount of solid material built-up is found in the flow field plate and the membrane-electrode assembly (MEA). The built-up material is examined by the use of a Scanning Electron Microscope (SEM). Further elemental analysis using Energy Dispersive X-ray Spectroscopy (EDS) finds that the built-up material contains large amount of phosphorus, thus relating it with the excess phosphoric acid found in the MEA. Additional experimental studies show that the built-up material is caused by the excess acid solution in the MEA, and when the excess phosphoric acid is removed from the MEA the fuel cell performance improves significantly and becomes very stable.     

Gas diffusion layer deformation and its effect on the transport characteristics and performance of proton exchange membrane fuel cell

Cell/stack assembly force can strongly affect the transport characteristics and performance of a proton exchange membrane fuel cell (PEMFC) through causing the structural deformation. In this study, a mathematical model has been developed to investigate the effect of the assembly force for different gas diffusion layers (GDL) and membranes. The results indicate that the predominant deformation of the cell structure occurs in the porous GDL due to its weak mechanical strength. Thicker GDLs result into lower water content in the GDL structure, and can sustain a larger assembly force without the risk of “electrode flooding”; while thinner GDLs have higher water content, can maintain the hydration required for the membrane, and yield a better cell performance with less sensitivity to the variations in the assembly force. Thinner membranes yield better cell performance, but the cell performance is more sensitive to the changes in the assembly force. A combination of thin GDL and membrane is beneficial for better cell performance with reasonable sensitivity to the assembly force. For thinner GDLs, an optimal assembly force exists beyond which the cell performance is reduced; and practical cell assembly force will limit the GDL thickness.     

Diagnosis of membrane electrode assembly degradation with drive cycle test technique

One of important factors determining the lifetime of proton exchange membrane fuel cells (PEMFCs) is degradation and failure of membrane electrode assembly (MEA). The lack of effective mitigation methods is largely due to the currently limited understanding of the degradation mechanisms for fuel cell MEAs. This study adopted the accelerating degradation technique to analyze durability of MEA using drive cycle test protocol developed by Chinese NERC Fuel Cell & Hydrogen Technology to assess the long-term durability of fuel cells for vehicular application. During 900 h durability test of the MEA, the polarization curve, cyclic voltammetry (CV), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) were performed as diagnostics during and on completion the test. The experimental results show that the performance degradation rate of the cell is about 70 μV h⁻¹ at the operating current density of 500 mA cm⁻², failure of the proton exchange membrane is the decisive factor leading to the failure of the MEA. And the damage of the micro-structural of catalytic layer, crucial for electrochemical reaction, is the decisive factor for the performance degradation.     

Novel technique for measuring oxygen crossover through the membrane in polymer electrolyte membrane fuel cells

In this study, the exact amount of oxygen crossover that reacts with hydrogen has been investigated using a mass spectrometer system. By measuring the amount of oxygen crossover that reacts with hydrogen, the exact amount of oxygen crossover that affects membrane degradation and/or water generation can be calculated under the fuel cell operating conditions. The amount of oxygen crossover that reacts with hydrogen is expressed as an effective oxygen crossover ratio, which is in a range between 0.927 and 0.933 under the fuel cell operating temperature conditions. This means that approximately 93% of the entire oxygen crossover through the membrane can affect membrane degradation and/or water generation at the anode catalyst layer. Thus, the effective oxygen crossover ratio should be considered as a novel index of oxygen crossover because it represents the exact amount of oxygen crossover that reacts with hydrogen.     

Structure failure of the sealing in the assembly process for proton exchange membrane fuel cells

Sealing stability in proton exchange membrane fuel cell (PEMFC) is critical to the performance and safety of stacks. However, sealing structure failure (SSF), which leads to the leakage of reactant gases, often occurs in the assembly process or start-up operation for PEMFCs. This study aims to investigate the effects of geometrical structure and material parameters of sealing components on the sealing structure failure. Slippage angle and slippage distance are adopted to evaluate the risk of SSF. Finite element (FE) simulations are conducted with consideration of the assembly process and start-up operation. Experiments are carried out to validate the accuracy of the FE model. Influences of parameters of gasket, membrane electrode assembly (MEA) frame, sealing groove shape of bipolar plate (BPP), and gas pressure are discussed in detail. Meanwhile, the risks of SSF for the stack by using metallic and graphite BPPs are compared. It is demonstrated that material properties and geometrical parameters of sealing components in PEMFC have great effects on SSF. The methodology developed is beneficial to the understanding of the SSF, and it can also be applied to guide the design of PEMFC stack assembly process to keep a good sealing reliability.     

Robust design of assembly parameters on membrane electrode assembly pressure distribution

The membrane electrode assembly (MEA) pressure distribution is an important factor that affects the performance of polymer membrane electrolyte fuel cell (PEMFC) stack. However, the general rules for assembly parameters that affect the MEA pressure distribution are hardly reported. In this study, a robust design analysis based on response surface methodology (RSM) was performed on a simplified fuel cell stack in order to identify the effect of assembly parameters on the MEA pressure distribution. The assembly pressure and bolt position were considered as randomly varying parameters with given probabilistic property and acted as the design variables. The max normal stress and normal stress uniformity of the MEA were determined in terms of the probabilistic design variables. The reliability of the robust design has been verified by comparing the robust solution with the optimal solution and an arbitrary solution.     

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.     

Effects of open-circuit operation on membrane and catalyst layer degradation in proton exchange membrane fuel cells

Durability issues have been attracting a great deal of attention in hydrogen/air proton exchange membrane (PEM) fuel cell research. In the present work, membrane electrode assembly (MEA) degradation under open circuit (OC) conditions was carried out for more than 250 h. By means of several on-line electrochemical measurements, the performance of the fuel cell was analysed at different times during the degradation process. The results indicate that structural changes in the PEM and catalyst layers (CLs) are the main reasons for the decline in performance during OC operation. The results also show that degradation due to platinum oxidation or catalyst contamination can be partially recovered by a subsequent potential cycling process, whereas the same cycling process cannot recover the membrane degradation.     

Recycling of membrane electrode assembly of PEMFC by acid processing

A simple, high efficient and environmentally friendly approach was investigated to recycle the key materials of membrane electrode assembly (MEA) applied in proton exchange membrane fuel cell (PEMFC). The catalyst coated membranes (CCMs) was dipped into sulfuric acid until the formation of transparent solution composed of Pt and perfluorosulfonic acid resin. Wherein, the membrane was dissolved, and the amorphous carbon nanoparticles as catalyst supports in catalyst layers were oxidized. Subsequently, both metal Pt and perfluorosulfonic acid resin were separated by centrifugal separation. Then the resin was recast into a membrane and the single fuel cell performance was tested. As a result, the solution to recycle the key materials of MEAs is promising for recycling MEA materials used in PEMFC.     

Quantifying water transport in anion exchange membrane fuel cells

Sufficient water transport through the membrane is necessary for a well-performing anion exchange membrane fuel cell (AEMFC). In this study, the water flux through a membrane electrode assembly (MEA), using a Tokuyama A201 membrane, is quantified using humidity sensors at the in- and outlet on both sides of the MEA. Experiments performed in humidified inert gas at both sides of the MEA or with liquid water at one side shows that the aggregation state of water has a large impact on the transport properties. The water fluxes are shown to be approximately three times larger for a membrane in contact with liquid water compared to vaporous. Further, the flux during fuel cell operation is investigated and shows that the transport rate of water in the membrane is affected by an applied current. The water vapor content increases on both the anode and cathode side of the AEMFC for all investigated current densities. Through modeling, an apparent water drag coefficient is determined to −0.64, indicating that the current-induced transport of water occurs in the opposite direction to the transport of hydroxide ions. These results implicate that flooding, on one or both electrodes, is a larger concern than dry-out in an AEMFC.     

In situ measurements of water transfer due to different mechanisms in a proton exchange membrane fuel cell

Water management is of critical importance in a proton exchange membrane (PEM) fuel cell, in particular, those based on a sulfonic acid polymer, which requires water to conduct protons. Yet there are limited in situ studies of water transfer through the membrane and no data are available for water transfer due to individual mechanisms through the membrane in an operational fuel cell. Thus it is the objective of this study to measure water transfer through the membrane due to each individual mechanism in an operational PEM fuel cell. The three different mechanisms of water transfer, i.e., electro-osmotic drag, diffusion and hydraulic permeation are isolated by specially imposed boundary conditions. Therefore water transfer through the membrane due to each mechanism is measured separately. In this study, all the data is collected in an actual assembled operational fuel cell. The experimental results show that water transfer due to hydraulic permeation, i.e. the pressure difference between the anode and cathode is at least an order of magnitude lower than those due to the other two mechanisms. The data for water transfer due to diffusion through the membrane are in good agreement with some of the ex situ data in the literature. The data for electro-osmosis show that the number of water molecules dragged per proton increases not only with temperature but also with current density, which is different from existing data in the literature. The methodology used in this study is simple and can be easily adopted for in situ water transfer measurement due to different mechanisms in other PEM fuel cells without any cell modifications.     

Mechanical degradation of proton exchange membrane during assembly and running processes in proton exchange membrane fuel cells with metallic bipolar plates

The mechanical degradation of the proton exchange membrane (PEM) is one of the main aspects affecting the lifetime of proton exchange membrane fuel cells (PEMFCs). It was observed in our previous study that the stress/strain distribution in the PEM of fuel cells with metallic bipolar plates (BPPs) is more complex, owing to manufacturing and assembly errors of the BPPs. The present study further concentrates on the stress/strain evolution in the membrane of fuel cells throughout the assembly and running processes by a finite element model. In membranes at the joint area between the gasket and gas diffusion layers, a serious stress concentration aggravated as the misalignment displacement increases. As for the membrane in reaction area, the plastic strain reaches highest level at the center of the groove after hygrothermal loading. The maximum stress is mainly relevant to the temperature and humidity and has little concern with the misalignment. The model and results of this study offer guidance regarding the design of PEMFC. Owing to the stress concentration, an additional protection should be set in the joint area, and the assembly error should be limited within 0.05 mm.     

Durability and characterization studies of polymer electrolyte membrane fuel cell’s coated aluminum bipolar plates and membrane electrode assembly

Coated aluminum bipolar plates demonstrate better mechanical strength, ease of manufacturability, and lower interfacial contact resistance (ICR) than graphite composite plates in polymer electrolyte membrane (PEM) fuel cell applications. In this study, coated aluminum and graphite composite bipolar plates were installed in separate single PEM fuel cells and tested under normal operating conditions and cyclic loading. After 1000 h of operation, samples of both the bipolar plates and the membrane electrode assembly (MEA) were collected from both the cathode and the anode sides of the cell and characterized to examine the stability and integrity of the plate coating and evaluate possible changes of the ionic conductivity of the membrane due any electrochemical reaction with the coating material. Scanning electron microscope (SEM) and energy dispersive X-ray (EDX) analysis were performed on the land and valley surfaces of the reactant flow fields at both the anode and the cathode sides of the bipolar plates. The measurements were superimposed on the reference to identify possible zones of anomalies for the purpose of conducting focused studies in these locations. The X-ray diffraction (XRD) analysis of samples scraped from the anode and cathode electrodes of the MEA showed the tendency for catalyst growth that could result in power degradation. Samples of the by-product water produced during the single fuel cell operation were also collected and tested for the existence of chromium, nickel, carbon, iron, sulfur and aluminum using mass spectroscopy techniques. The EDX measurements indicated the possibility of dissociation and dissolution of nickel chrome that was used as the binder for the carbide-based corrosion-resistant coating with the aluminum substrate.     

Numerical study of assembly pressure effect on the performance of proton exchange membrane fuel cell

The performance of the fuel cell is affected by many parameters. One of these parameters is assembly pressure that changes the mechanical properties and dimensions of the fuel cell components. Its first duty, however, is to prevent gas or liquid leakage from the cell and it is important for the contact behaviors of fuel cell components. Some leakage and contact problems can occur on the low assembly pressures whereas at high pressures, components of the fuel cell, such as bipolar plates (BPP), gas diffusion layers (GDL), catalyst layers, and membranes, can be damaged. A finite element analysis (FEA) model is developed to predict the deformation effect of assembly pressure on the single channel PEM fuel cell in this study. Deformed fuel cell single channel model is imported to three-dimensional, computational fluid dynamics (CFD) model which is developed for simulating proton exchange membrane (PEM) fuel cells. Using this model, the effect of assembly pressure on fuel cell performance can be calculated. It is found that, when the assembly pressure increases, contact resistance, porosity and thickness of the gas diffusion layer (GDL) decreases. Too much assembly pressure causes GDL to destroy; therefore, the optimal assembly pressure is significant to obtain the highest performance from fuel cell. By using the results of this study, optimum fuel cell design and operating condition parameters can be predicted accordingly.     

Nafion degradation mechanisms in proton exchange membrane fuel cell (PEMFC) system: A review

Nafion is one of the polymer materials used as polymer electrode membrane (PEM) for fuel cells. However, the electrochemical reaction and water management processes that occur at the catalyst layer affect the performance and degradation of the membrane in the fuel cell resulting in various degradation mechanisms. Understanding the degradation mechanisms of the Nafion membrane in operation, the anhydrous and electrochemical conditions in the fuel cell is highly a necessity as outlined in this review. This review further recommends that further improvement in the Nafion membrane can be made by fabrication and coating the Nafion membrane with materials that can withstand the electrochemical environment in the fuel cell.     

Proton exchange membrane fuel cell degradation under close to open-circuit conditions: Part I: In situ diagnosis

Durability of polymer exchange membrane (PEM) fuel cells under a wide range of operational conditions has been generally identified as one of the top technical gaps that need to be overcome for the acceptance of this fuel cell technology as a commercially viable power source, especially for automotive and portable applications. In this study, a 1200 h lifetime test was conducted with a six-cell PEM fuel cell stack under close to open-circuit conditions. In situ measurements of the hydrogen crossover rate through the membrane, high frequency resistance and electrochemically active surface area of each single cell, in combination with cell polarization curves, were used to investigate the degradation mechanisms. Direct gas mass spectrometry of the cathode exhaust gas indicated the formation of HF, H₂O₂ and CO₂ during the durability testing. The overall cell degradation rate under this accelerated stress testing is approximately 0.128 mV h⁻¹. The cell degradation rate for the first 800 h is much lower than that after 800 h, which may result from the dominance of different degradation mechanisms. For the first period, the degradation of fuel cell performance was mainly attributed to catalyst decay, while the subsequent dramatic degradation is likely caused by membrane failure.