Carbon support oxidation in PEM fuel cell cathodes

Oxidation of the cathode carbon catalyst support in polymer electrolyte fuel cells (PEMFC) has been examined. For this purpose platinum supported electrodes and pure carbon electrodes were fabricated and tested in membrane-electrode-assemblies (MEAs) in air and nitrogen atmosphere. The in situ experiments account for the fuel cell environment characterized by the presence of a solid electrolyte and water in the gas and liquid phases. Cell potential transients occurring during automotive fuel cell operation were simulated by dynamic measurements. Corrosion rates were calculated from CO₂ and CO concentrations in the cathode exhaust measured by non-dispersive infrared spectroscopy (NDIR). Results from these potentiodynamic measurements indicate that different potential regimes relevant for carbon oxidation can be distinguished. Carbon corrosion rates were found to be higher under dynamic operation and to strongly depend on electrode history. These characteristics make it difficult to predict corrosion rates accurately in an automotive drive cycle.     

Mathematical modeling and experimental study of the performance of PEM water electrolysis cell with different loadings of platinum metals in electrocatalytic layers

This paper describes a numerical and experimental analysis of the optimum loadings of noble metals (Pt, Ir) in electrocatalytic layers of the polymer electrolyte membrane (PEM) water electrolysis cells. Based on the obtained results, the Pt loading of ca. 0.4 mg/cm² (or 1 mg/cm² of Pt/C with 40 wt. % of Pt) and ca. 2.5 mg/cm² of IrO₂ loading could be recommended. The developed mathematical model has shown that these optimum values are derived from the interference of activation and ohmic losses in the electrocatalytic layers. The membrane-electrode assembly (MEA) with these noble metal contents does not exhibit significant catalytic layer degradation within 4000 h of operation.     

Experimental investigation of PEM fuel cells for a m-CHP system with membrane reformer

An innovative small-scale cogeneration system based on membrane reformer and PEM fuel cells is under development within the FluidCELL project. An experimental campaign has been carried out to characterize the PEM fuel cell and to define the operative conditions when integrated within the system. The hydrogen feeding the PEM is produced by a membrane reactor which in principle can separate pure hydrogen; however, in general, hydrogen purity is around 99.9%–99.99%. The focus of this work is the assessment of the PEM performance under different hydrogen purities featuring actual membrane selectivity and gases build-up by anode off-gas recirculation. Their effects on the cells voltage and local current distribution are measured at different conditions (pressure, humidity, stoichiometry, with and without air bleeding, in flow-through and dead-end operation). In flow-through mode, the cell voltage is relatively insensitive to the presence of inert gases (e.g. ?20 mV with inerts/H₂ from 0 to 20·10^?2 at 0.3 A/cm²), and resistant also to CO (e.g. ?35 mV with inerts/H₂ = 20·10^?2 and CO/H₂ from 0 to 20·10^?6 at 0.3 A/cm²), thanks to the Ru presence in the anode catalyst. Looking at the current density distribution on the cell surface, the most critical areas are the cathode inlet, likely due to insufficient air humidification, and the anode outlet, because of low hydrogen concentration and CO poisoning of the catalyst. Dead-end operation is also investigated using humid or impure hydrogen. In this case relatively small amount of impurities in the hydrogen feed rapidly reduces the cell voltage, requiring frequent purges (e.g. every 30 s with inerts/H₂ = 0.5·10^?2 at 0.3 A/cm²). These experiments set the basis for the management of the PEMFC stack integrated into the m-CHP system based on the FluidCELL concept.     

Effect of anode iridium oxide content on the electrochemical performance and resistance to cell reversal potential of polymer electrolyte membrane fuel cells

An ideal polymer electrolyte membrane fuel cell (PEMFC) is one that continuously generates electricity as long as hydrogen and oxygen (or air) are supplied to its anode and cathode, respectively. However, internal and/or external conditions could bring about the degradation of its electrodes, which are composed of nanoparticle catalysts. Particularly, when the hydrogen supply to the anode is disrupted, a reverse voltage is generated. This phenomenon, which seriously degrades the anode catalyst, is referred to as cell reversal. To prevent its occurrence, iridium oxide (IrO₂) particles were added to the anode in the membrane-electrode assembly of the PEMFC single-cells. After 100 cell reversal cycles, the single-cell voltage profiles of the anode with Pt/C only and the anodes with Pt/C and various IrO₂ contents were obtained. Additionally, the cell reversal-induced degradation phenomenon was also confirmed electrochemically and physically, and the use of anodes with various IrO₂ contents was also discussed.     

Along‐channel flooding prediction of polymer electrolyte membrane fuel cells

Non‐uniform current distribution in polymer electrolyte membrane (PEM) fuel cells results in local over‐heating, accelerated ageing, and lower power output than expected. This issue is quite critical when a fuel cell experiences water flooding. In this study, the performance of a PEM fuel cell is investigated under cathode flooding conditions. A two‐dimensional approach is proposed for a single PEM fuel cell based on conservation laws and electrochemical equations to provide useful insight into water transport mechanisms and their effect on the cell performance. The model results show that inlet stoichiometry and humidification, and cell operating pressure are important factors affecting cell performance and two‐phase transport characteristics. Numerical simulations have revealed that the liquid saturation in the cathode gas distribution layer (GDL) could be as high as 20%. The presence of liquid water in the GDL decreases oxygen transport and surface coverage of active catalyst, which in turn degrades the cell performance. The thermodynamic quality in the cathode flow channel is found to be greater than 99.7%, indicating that liquid water in the cathode gas channel exists in very small amounts and does not interfere with the gas phase transport. A detailed analysis of the operating conditions shows that cell performance should be optimized based on the maximum average current density achieved and the magnitude of its dispersion from its mean value. Copyright © 2010 John Wiley & Sons, Ltd.     

Solid-phase temperature measurements in a HTPEM fuel cell

Segmented temperature measurements were performed to better understand the thermal behaviour and thermal interactions between the fluid-(gas)-phase and solid-phase temperature within a working high temperature polymer electrolyte membrane (HTPEM) fuel cell. Three types of flow-fields were studied, and the influence of temperature for no-load and load operating conditions was investigated. Tests were performed under various operating conditions, and the results demonstrate the utility of segmented temperature measurements. A significant difference in the temperature distribution was observed when the HTPEM fuel cell was operated with pure hydrogen and with hydrogen containing carbon monoxide. The findings may lead to improved HTPEM fuel cells and future middle temperature polymer electrolyte membrane (MTPEM) fuel cell designs.     

Nano mineral fiber enhanced catalyst coated membranes for improving polymer electrolyte membrane fuel cell durability

In order to protect the perfluorosulfonic acid (PFSA) ionomer from an attack of contaminant metal ions as well as to enhance the mechanical stability of catalyst layers, palygorskite (PGS) is introduced into the catalyst layer of polymer electrolyte membrane fuel cells. PGS is a widely used natural nano-sized silicate mineral fiber with unique nano-sized channel structure, has a strong absorption capacity for heavy metal ions. We identify a negative influence of Fe²⁺ on PFSA membranes to make a comparative study. Subsequently catalyst coated membranes (CCMs) prepared with a PGS-Pt/C composite catalyst show a great effect in reducing Fe²⁺ ion crossover. Results display that PGS absorbs Fe²⁺ in nano-structure channels, and effectively protect PFSA ionomer in both the catalyst layer and membrane from hydroxyl radicals (OH) attack. Thus, the chemical stability of PFSA ionomer in both the catalyst layer and membrane is greatly improved. Furthermore, the enhancement of the mechanical performance of catalyst layers is discussed.     

Influence of local porosity and local permeability on the performances of a polymer electrolyte membrane fuel cell

In the literature, many models and studies focused on the steady-state aspect of fuel cell systems while their dynamic transient behavior is still a wide area of research. In the present paper, we study the effects of mechanical solicitations on the performance of a proton exchange membrane fuel cell as well as the coupling between the physico-chemical phenomena and the mechanical behavior. We first develop a finite element method to analyze the local porosity distribution and the local permeability distribution inside the gas diffusion layer induced by different pressures applied on deformable graphite or steel bipolar plates. Then, a multi-physical approach is carried out, taking into account the chemical phenomena and the effects of the mechanical compression of the fuel cell, more precisely the deformation of the gas diffusion layer, the changes in the physical properties and the mass transfer in the gas diffusion layer. The effects of this varying porosity and permeability fields on the polarization and on the power density curves are reported, and the local current density is also investigated. Unlike other studies, our model accounts for a porosity field that varies locally in order to correctly simulate the effect of an inhomogeneous compression in the cell.     

Direct liquid-feed fuel cells: Thermodynamic and environmental concerns

The present paper briefly reviews the different direct liquid-feed fuel cells that have been regarded through the open literature. It especially focuses on thermodynamic-energetic data and toxicological–ecological hazards of the chemicals used as liquid fuels. The analysis of those two databases shows that borohydride, ethanol and 2-propanol would be the most adequate liquid fuels for the polymer electrolyte membrane fuel cell-type systems, even if they are inferior to hydrogen. All the fuels and also all the by-products stem from their decomposition are more or less harmful towards health and environment. More particularly, hydrazine should be avoided because it and its by-product are very dangerous. It is to note that the present paper does not intend to review and to compare the performances of those fuel cells because of great differences in the efforts devoted to each of them.     

Measurement and modelling of carbon monoxide poisoning distribution within a polymer electrolyte fuel cell

The distribution of carbon monoxide (CO) across the anode of a polymer electrolyte fuel cell with a single channel flow-field is modelled and compared with experimental results obtained using localised stripping voltammetry. Good agreement is observed between experiment and model over a wide range of CO carrier gas flow rates. The model is used to predict the effect of CO transient poisoning, expected to occur during system start-up, when high CO slippage is likely to occur from the fuel processor and the fuel cell is not electrically loaded.     

Numerical studies of a separator for stack temperature control in a molten carbonate fuel cell

The use of a separator to control stack temperature in a molten carbonate fuel cell was studied by numerical simulation using a computational fluid dynamics code. The stack model assumed steady-state and constant-load operation of a co-flow stack with an external reformer at atmospheric pressure. Representing a conventional cell type, separators with two flow paths, one each for the anode and cathode gas, were simulated under conditions in which the cathode gas was composed of either air and carbon dioxide (case I) or oxygen and carbon dioxide (case II). The results showed that the average cell potential in case II was higher than that in case I due to the higher partial pressures of oxygen and carbon dioxide in the cathode gas. This result indicates that the amount of heat released during the electrochemical reactions was less for case II than for case I under the same load. However, simulated results showed that the maximum stack temperature in case I was lower than that in case II due to a reduction in the total flow rate of the cathode gas. To control the stack temperature and retain a high cell potential, we proposed the use of a separator with three flow paths (case III); two flow paths for the electrodes and a path in the center of the separator for the flow of nitrogen for cooling. The simulated results for case III showed that the average cell potential was similar to that in case II, indicating that the amount of heat released in the stack was similar to that in case II, and that the maximum stack temperature was the lowest of the three cases due to the nitrogen gas flow in the center of the separator. In summary, the simulated results showed that the use of a separator with three flow paths enabled temperature control in a co-flow stack with an external reformer at atmospheric pressure.     

Effect of platinum amount in carbon supported platinum catalyst on performance of polymer electrolyte membrane fuel cell

The performance of polymer electrolyte membrane fuel cells fabricated with different catalyst loadings (20, 40 and 60 wt.% on a carbon support) was examined. The membrane electrode assembly (MEA) of the catalyst coated membrane (CCM) type was fabricated without a hot-pressing process using a spray coating method with a Pt loading of 0.2 mg cm⁻². The surface was examined using scanning electron microscopy. The catalysts with different loadings were characterized by X-ray diffraction and cyclic voltammetry. The single cell performance with the fabricated MEAs was evaluated and electrochemical impedance spectroscopy was used to characterize the fuel cell. The best performance of 742 mA cm⁻² at a cell voltage of 0.6 V was obtained using 40 wt.% Pt/C in both the anode and cathode.     

Transient phenomena in a PEMFC during the start-up of gas feeding observed with a 97-fold segmented cell

To measure local phenomena in a PEMFC during a transitional state induced by changing of the feeding gas, a segmented cell was fabricated and the local current and local potential distribution were measured under open-circuit conditions. The anode or cathode was divided into 97 segments of 1.5 mm each. A change in the anode gas from nitrogen or oxygen to hydrogen induced momentary internal currents among the segments. The potential distribution in the electrolyte was observed simultaneously using three quasi-reference electrodes located locally. The results supported the reverse-current decay mechanism, which is known to be a mechanism of cathode degradation. Furthermore, internal currents were observed when the cathode gas was changed from nitrogen to oxygen. While the cathode was not subjected to a harmful potential, a large potential distribution was induced in the anode.     

Numerical studies of liquid water behaviors in PEM fuel cell cathode considering transport across different porous layers

In this paper, a two-phase two-dimensional PEM fuel cell model, which is capable of handling liquid water transport across different porous materials, is employed for parametric studies of liquid water transport and distribution in the cathode of a PEM fuel cell. Attention is paid particularly to the coupled effects of two-phase flow and heat transfer phenomena. The effects of key operation parameters, including the outside cell boundary temperature, the cathode gas humidification condition, and the cell operation current, on the liquid water behaviors and cell performance have been examined in detail. Numerical results elucidate that increasing the fuel cell temperature would not only enhance liquid water evaporation and thus decrease the liquid saturation inside the PEM fuel cell cathode, but also change the location where liquid water is condensed or evaporated. At a cell boundary temperature of 80 °C, liquid water inside the catalyst layer and gas diffusion media under the current-collecting land would flow laterally towards the gas channel and become evaporated along an interface separating the land and channel. As the cell boundary temperature increases, the maximum current density inside the membrane would shift laterally towards the current-collecting land, a phenomenon dictated by membrane hydration. Increasing the gas humidification condition in the cathode gas channel and/or increasing the operating current of the fuel cell could offset the temperature effect on liquid water transport and distribution.     

Temperature-dependent performance of the polymer electrolyte membrane fuel cell using short-side-chain perfluorosulfonic acid ionomer

We report on polymer electrolyte membrane fuel cells (PEMFCs) that function at high temperature and low humidity conditions based on short-side-chain perfluorosulfonic acid ionomer (SSC-PFSA). The PEMFCs fabricated with both SSC-PFSA membrane and ionomer exhibit higher performances than those with long-side-chain (LSC) PFSA at temperatures higher than 100 °C. The SSC-PFSA cell delivers 2.43 times higher current density (0.524 A cm⁻¹) at a potential of 0.6 V than LSC-PFSA cell at 140 °C and 20% relative humidity (RH). Such a higher performance at the elevated temperature is confirmed from the better membrane properties that are effective for an operation of high temperature fuel cell. From the characterization technique of TGA, XRD, FT-IR, water uptake and tensile test, we found that the SSC-PFSA membrane shows thermal stability by higher crystallinity, and chemical/mechanical stability than the LSC-PFSA membrane at high temperature. These fine properties are found to be the factor for applying Aquivion™ E87-05S membrane rather than Nafion^® 212 membrane for a high temperature fuel cell.     

Optimizing the relative humidity to improve the stability of a proton exchange membrane by segmented fuel cell technology

The segmented fuel cell technology was applied to investigate the effects of the humidification conditions on the internal locally resolved performance and the stability of the fuel cell system. It was found at certain operating conditions, the time-dependent oscillation of current at potentio-static state appeared. The appearance of positive spikes of current indicated a temporary improved performance, while the negative current spikes indicated a temporary decreased performance. The periodic build-up and removal of liquid water in the cell caused unstable cell performance. Through the analyses of the evolution of the locally resolved current density distributions, the reasons for the positive or the negative spikes of current peaks with respect to a stationary value were found, which might be due to the drying-out of the membrane or the flooding of the membrane. The contour of the current density mapping differed to each other at the period of current peaks up or down, which might be due to different effect of the drying-out or flooding on the membrane. Through optimizing the relative humidity of anode (RHa) or cathode (RHc) of the fuel cell, the oscillation of the current disappeared and the performance of the cell became stable. RHc affects the performance of fuel cell much more obviously than RHa. The stability of the fuel cell system is also dependent on the imposed voltage. With the cell voltage decreased, the amplitude and the frequency of positive spikes of current increased.     

Current mapping of a proton exchange membrane fuel cell with a segmented current collector during the gas starvation and shutdown processes

Current distribution during the gas starvation and shutdown processes is investigated in a proton exchange membrane fuel cell with an active area of 184 cm². The cell features a segmented cathode current collector. The response characteristics of the segmented single cell under different degrees of hydrogen and air starvation are explored. The current responses of the segment cells at different positions under a dummy load in the shutdown process are reported for various operating conditions, such as different dummy loads, cell temperatures, and gas humidities under no back pressure. The results show that applying a dummy load during the cell shutdown process can quickly reduce the cell potential and thereby avoid the performance degradation caused by high potentials. The currents of all the segment cells decrease with time, but the rate of decrease varies with the segment cell positions. The rate for the segment cells near the gas outlet is much higher than that of the segment cells near the gas inlet. The current of the segment cells decreases much more quickly at a lower gas humidity and high temperature. This study provides insights in the development of mitigation strategies for the degradation caused by starvation and shutdown process.