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.     

Relative humidity control in polymer electrolyte membrane fuel cells without extra humidification

The performance of polymer electrolyte membrane fuel cells is highly influenced by the water content in the membrane. To prevent the membrane from drying, several researchers have proposed extra humidification on the input reactants. But in some applications, the extra size and weight of the humidifier should be avoided. In this research a control technique, which maintains the relative humidity on saturated conditions, is implemented by adjusting the air stoichiometry; the effects of drying of membrane and flooding of electrodes are considered, as well. For initial analysis, a mathematical model reveals the relationship among variables that can be difficult to monitor in a real machine. Also prediction can be tested optimizing time and resources. For instance, the effects of temperature and humidity can be analyzed separately. For experimental validation, tests in a fault tolerant fuel cell are conducted.     

Hybrid electrode effects on polymer electrolyte membrane fuel cells

Research on membrane electrode assemblies (MEA) is focused on reducing cost and increasing durability in polymer electrolyte membrane fuel cells (PEMFC). Development of the electrode structure and reduction of platinum (Pt) contents are studied to improve the efficiency of Pt catalysts. We studied the combined effects of improved electrode structure and reduced Pt loading. To enhance the performance of an MEA, a commercial Pt/C catalyst with micro graphite (MG) was used. The 40 wt% Pt/C catalyst content was reduced about 5, 15, 30 and 60 wt% at the cathode. MG was added as a reduced weight percent of Pt/C. Cell performance was significantly dependent on the content of MG. The MEA with 15 wt% of MG was seen to best performance compare with other MEA. These results showed that the catalyst with mixed MG improved both performance and cost savings with reduced Pt content of PEMFC.     

Degradation of polymer electrolyte membrane fuel cells repetitively exposed to reverse current condition under different temperature

Effects of operating temperature on performance degradation of polymer electrolyte membrane fuel cells (PEMFCs) were investigated under the repetitive startup/shutdown cycling operation that induced the so-called ‘reverse current condition’. With repeating the startup/shutdown cycle, polarization curves, electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), linear sweep voltammetry (LSV) were measured to examine in situ electrochemical degradation of the MEAs. To investigate physicochemical degradation of the MEAs, scanning electron microscopy (SEM), electron probe micro analysis (EPMA), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FT-IR) were employed before and after the startup/shutdown cycling operation. With increasing operating temperature from 40 to 65 and 80 °C under the repetitive reverse-current condition, the cell performance decayed faster since corrosion of the carbon support and dissolution/migration/agglomeration of Pt catalyst were accelerated resulting in increases in ohmic and charge transfer resistance and loss of EAS.     

Effect of operating conditions on carbon corrosion in polymer electrolyte membrane fuel cells

The influence of humidity, cell temperature and gas-phase O₂ on the electrochemical corrosion of carbon in polymer electrolyte membrane fuel cells is investigated by measuring CO₂ emission at a constant potential of 1.4 V for 30 min using on-line mass spectrometry. Carbon corrosion shows a strong positive correlation with humidity and cell temperature. The presence of water is indispensable for electrochemical carbon corrosion. By contrast, the presence of gas-phase O₂ has little effect on electrochemical carbon corrosion. With increased carbon corrosion, changes in fuel cell electrochemical characteristics become more prominent and thereby indicate that such corrosion significantly affects fuel cell durability.     

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.     

New materials for polymer electrolyte membrane fuel cell current collectors

Polymer Electrolyte Membrane Fuel cells for automotive applications need to have high power density, and be inexpensive and robust to compete effectively with the internal combustion engine. Development of membranes and new electrodes and catalysts have increased power significantly, but further improvements may be achieved by the use of new materials and construction techniques in the manufacture of the bipolar plates. To show this, a variety of materials have been fabricated into flow field plates, both metallic and graphitic, and single fuel cell tests were conducted to determine the performance of each material. Maximum power was obtained with materials which had lowest contact resistance and good electrical conductivity. The performance of the best material was characterised as a function of cell compression and flow field geometry.     

Porosity-graded micro-porous layers for polymer electrolyte membrane fuel cells

In this paper, the effect of porosity-graded micro-porous layer (GMPL) on the performance of polymer electrolyte membrane fuel cells (PEMFCs) was studied in detail. The GMPL was prepared by printing micro-porous layers (MPL) with different content of NH₄Cl pore-former and the porosity of the GMPL decreased from the inner layer of the MPLs at the membrane/MPL interface to the outer layer of the MPLs at the gas diffusion electrode/MPL interface. The morphology and porosity of the GMPLs were characterized and the performance of the cell with GMPLs was compared with those having conventional homogeneous MPLs. The result demonstrates that the fuel cells consisting of GMPL have better performance than those consisting of conventional homogeneous MPLs, especially at high current densities. Micro-porous layer with graded porosity is beneficial for the electrode process of fuel cell reaction probably by facilitating the liquid water transportation through large pores and gas diffusion via small pores in the GMPLs.     

Performance of membrane electrode assemblies using PdPt alloy as anode catalysts in polymer electrolyte membrane fuel cell

Pd-based nanoparticles, such as 40 wt.% carbon-supported Pd₅₀Pt₅₀, Pd₇₅Pt₂₅, Pd₉₀Pt₁₀ and Pd₉₅Pt₅, for anode electrocatalyst on polymer electrolyte membrane fuel cells (PEMFCs) were synthesized by the borohydride reduction method. PdPt metal particles with a narrow size distribution were dispersed uniformly on a carbon support. The membrane electrode assembly (MEA) with Pd₉₅Pt₅/C as the anode catalyst exhibited comparable single-cell performance to that of commercial Pt/C at 0.7 V. Although the Pt loading of the anode with Pd₉₅Pt₅/C was as low as 0.02 mg cm⁻², the specific power (power to mass of Pt in the MEA) of Pd₉₅Pt₅/C was higher than that of Pt/C at 0.7 V. Furthermore, the single-cell performance with Pd₅₀Pt₅₀/C and Pd₇₅Pt₂₅/C as the anode catalyst at 0.4 V was approximately 95% that of the MEA with the Pt/C catalyst. This indicated that a Pd-based catalyst that has an extremely small amount of Pt (only 5 or 50 at.%) can be replaced as an anode electrocatalyst in PEMFC.     

Effect of mechanical vibrations on damage propagation in polymer electrolyte membrane fuel cells

Vibrations and impact loads are common sources of mechanical damage in transportation applications; however, their impacts on polymer electrolyte membrane fuel cells (PEMFCs) have yet to be fully investigated. In this work, the damage propagation in the membrane electrode assembly (MEA) is investigated under vibration conditions with a focus placed on the interface between the membrane and catalyst layer at the cathode. A numerical model based on the cohesive element approach is developed, and a parametric study is performed to investigate the effects of amplitude and frequency of applied vibrations as well as initial delamination length on damage propagation. Non-linear relationships were found between the damage propagation and these parameters, with the frequency of vibration having the dominant effect on damage propagation at larger amplitudes. This work provides insight into the importance of considering mechanical damage to the MEA under vibration conditions in transportation applications.     

Analysis of the spatially distributed performance degradation of a polymer electrolyte membrane fuel cell stack

Herein we report the spatially uneven degradation of a polymer electrolyte membrane fuel cell (PEMFC) stack operated under load variation. Fifteen sub-membrane electrode assemblies (sub-MEAs) at various cell positions and various points within each cell were obtained from the original MEAs employed in the fuel cell stack. Polarization curves and the voltammetric charge of these MEAs were measured in order to correlate localized performances with the redistributed electrochemically active surface on Pt using the polarization technique and cyclic voltammetry. Several ex situ characterizations including electron probe microanalysis, environmental scanning electron microscopy, and X-ray diffraction were also performed to find evidence, supporting the inhomogeneous degradation of the fuel cell stack. Possible routes and processes for the non-uniform stack degradation during the PEMFC stack operation will also be discussed.     

Comparative studies of polymer electrolyte membrane fuel cell stack and single cell

The polymer electrolyte membrane fuel cell (PEMFC) was investigated comparatively as a single cell and a 30-cell stack. Various types of Nafion membranes, such as Nafion 117, 115, 112 and 105, were tested as electrolyte within the single cell and at different temperatures, among which Nafion 112 gave the optimal result. The 30-cell stack was evaluated at different humidities and temperatures. The potential–current and power–current curves, both for single cell and the stack, were analyzed by computer simulation, whereby the kinetic and mass-transfer parameters were calculated. The long-term performance of the stack and the water production during long-term operation were also measured.     

Nitrogen plasma-implanted titanium as bipolar plates in polymer electrolyte membrane fuel cells

Nitrogen plasma immersion ion implantation (PIII), a non-line-of-sight surface treatment technique suitable for bipolar plates in polymer electrolyte membrane fuel cells, is conducted at low and high temperature to improve the corrosion resistance and conductivity of titanium sheets. X-ray photoelectron spectroscopy (XPS) shows that high-temperature (HT) nitrogen PIII produces a thick oxy-nitride layer on the titanium surface. This layer which provides good corrosion resistance and high electrical conductivity as verified by electrochemical tests, inductively coupled plasma optical emission spectroscopy, and interfacial contact resistance (ICR) measurements renders the materials suitable for polymer electrolyte membrane fuel cells. In comparison, the low-temperature (LT) PIII titanium sample exhibits poorer corrosion resistance and electrical conductivity than the untreated titanium control.     

Performance enhancement of air-cooled open cathode polymer electrolyte membrane fuel cell with inserting metal foam in the cathode side

In this study, a novel way to improve performance of the air-cooled open cathode polymer electrolyte membrane fuel cell is introduced. We suggest using a metal foam in the cathode side of the planar unit fuel cell for the solution to conventional problems of the open cathode fuel cell such as excessive water evaporation from the membrane and poor transportation of air. We conduct experiment and the maximum power density of the fuel cell with metal foam increases by 25.1% compared with the conventional fuel cell without metal foam. The open cathode fuel cell with metal foam has smaller ohmic losses and concentration losses. In addition, we prove that the open cathode fuel cell with metal foam prevents excessive water evaporation and membrane drying out phenomena with numerical approach. Finally, we apply the metal foam to the air-cooled open cathode fuel cell stack as well as the planar unit cell.     

Dynamic water management of polymer electrolyte membrane fuel cells using intermittent RH control

A novel method of water management of polymer electrolyte membrane (PEM) fuel cells using intermittent humidification is presented in this study. The goal is to maintain the membrane close to full humidification, while eliminating channel flooding. The entire cycle is divided into four stages: saturation and de-saturation of the gas diffusion layer followed by de-hydration and hydration of membrane. By controlling the duration of dry and humid flows, it is shown that the cell voltage can be maintained within a narrow band. The technique is applied on experimental test cells using both plain and hydrophobic materials for the gas diffusion layer and an improvement in performance as compared to steady humidification is demonstrated. Duration of dry and humid flows is determined experimentally for several operating conditions.     

A poly (ethylene oxide)/graphene oxide electrolyte membrane for low temperature polymer fuel cells

A novel method to prepare poly (ethylene oxide)/graphene oxide (PEO/GO) composite membrane aimed for the low temperature polymer electrolyte membrane fuel cells without any chemical modification is presented in this work. The membrane thickness is 80 μm with a GO content of 0.5 wt%. And SEM images show the PEO/GO membrane is condensed composite material without structure defects. Small angle XRD results for the membrane samples show that the d-spacing reflection (0 0 1) of GO in PEO matrix is shifted from 2θ = 11° to 4.5° as the PEO molecules intercalated into the GO layers during the membrane preparation process. FTIR tests show the typical -COOH vibration near 1700 cm⁻¹. Tensile tests show the resultant PEO/GO membrane tensile strength of 52.22 MPa and Young's modulus 3.21 GPa, and the fractured elongation was about 5%. The ionic conductivity of this PEO/GO membrane increases from 0.086 to 0.134 S cm⁻¹ when the operation temperature increases from 25 to 60 °C with 100% relative humidity. And further tests show the DC electronic resistance of this membrane is higher than 20 MΩ at room temperature with 100% relative humidity. Polarization curves in a single cell with this membrane give a maximum power density of 53 mW cm⁻² at the operation temperature around 60 °C, without optimizing the catalyst layer composition.     

Modification of hydrocarbon structure for polymer electrolyte membrane fuel cell binder application

The development of novel hydrocarbon polymer membranes needs to be accompanied by catalyst layer hydrocarbon binder research so that the resultant membrane electrode assembly (MEA) can be durable. Hydrocarbon polymers which show high performance levels as membranes, however, are inadequate as catalyst layer binders as they are designed for low fuel penetration. Modification to the hydrocarbon polymer structure of high performing hydrocarbon polymers such as Sulfonated poly(arylene ether sulfone) (SPAES) can take advantage of its high conductivity while increasing gas permeability and maintaining interfacial compatibility with the membrane. The incorporation of a biphenyl fluorene group into the polymer backbone of SPAES successfully increased d-spacing which led to an increase in gas crossover. In the catalyst layer, the modified polymer ionomer showed higher penetration into primary pore volume thus increasing ESA. Higher catalyst utilization due to easier fuel access and ionomer coverage led to higher fuel cell performance. Durability tests revealed that structural modification did not hinder interfacial compatibility as well as performance.     

Performance enhancement of membrane electrode assemblies with plasma etched polymer electrolyte membrane in PEM fuel cell

In this work, a surface modified Nafion 212 membrane was fabricated by plasma etching in order to enhance the performance of a membrane electrode assembly (MEA) in a polymer electrolyte membrane fuel cell. Single-cell performance of MEA at 0.7 V was increased by about 19% with membrane that was etched for 10 min compared to that with untreated Nafion 212 membrane. The MEA with membrane etched for 20 min exhibited a current density of 1700 mA cm⁻² at 0.35 V, which was 8% higher than that of MEA with untreated membrane (1580 mA cm⁻²). The performances of MEAs containing etched membranes were affected by complex factors such as the thickness and surface morphology of the membrane related to etching time. The structural changes and electrochemical properties of the MEAs with etched membranes were characterized by field emission scanning electron microscopy, Fourier transform-infrared spectrometry, electrochemical impedance spectroscopy, and cyclic voltammetry.     

Nitride films as protective layers for metallic bipolar plates of polymer electrolyte membrane fuel cell stacks

The idea of using nitride films coated by sputtering Nb and Cr, using N₂ as a reaction gas, as protective layers for metallic bipolar plates (BP) of polymer electrolyte membrane fuel cell (PEMFC) stacks, was explored by experiments. Specimens were fabricated from austenite 304 stainless steels, which are frequently used as bipolar plate materials for fuel cells due to their good corrosion resistance and high strength at elevated temperature. The results of XRD analysis and Gaussian function analysis of the coated films suggest that NbN or NbN/NbCrN films were induced depending on the process parameters. The NbN/NbCrN multiphase films were induced at high Cr target powers and low gas ratios among the process parameters selected in this investigation. The result of ICR measurement of the films suggests that the effect of the Cr target power, i.e. the effect of the Cr amount in the film, on the ICR of the films is not significant, while the effect of the gas ratio on the ICR of the films is noticeable. For the films deposited at different gas ratios, the ICR of the film generally decreases as the gas ratio increases. In general, all the 304 SS specimens coated by the NbN single phase or NbN/NbCrN multiphase films at the given process parameters showed significantly improved corrosion resistance in comparison with the bare 304 SS. Among NbN single phase and NbN/NbCrN multiphase films, the performance of NbN/NbCrN multiphase films was more stable. Depending on the process parameters, the polarization curves of the specimens coated with NbN films showed rapid increase of the current density due to the pitting. Therefore, as corrosion resistance coating for metallic BP of PEMFC stacks, NbN/NbCrN multiphase film may be preferred to NbN single phase films.