Measurement and modeling of liquid film thickness evolution in stratified two-phase microchannel flows

Polymer electrolyte membrane (PEM) fuel cells incorporating microchannels (D < 500 μm) can benefit from improved fuel delivery and convective cooling. However, this requires a better understanding of two-phase microchannel transport phenomena, particularly liquid–gas interactions and liquid clogging in cathode air-delivery channels. This paper develops optical fluorescence imaging of water films in hydrophilic channels with varying air velocity and water injection rate. Micromachined silicon test structures with optical access and distributed water injection simulate the cathode channels of a PEM fuel cell. Film thickness data vary strongly with air velocity and are consistent with stratified flow modeling. This work facilitates the study of regime transitions in two-phase microchannel flows and the effects of flow regimes on heat and mass transfer and axial pressure gradients.     

Transient behavior of a PEMFC

The transient behavior of a proton exchange membrane fuel cell (PEMFC) with porosity is investigated in this study using a two-phase, half-cell model. The thin film agglomerate approach is used to model the catalyst layer. Both vapor transport and liquid water transport in the PEMFC are examined in this study. Proton transport is much faster than the gaseous and liquid water transport. The ionic potential reaches a steady state level in ∼10⁻¹ s but liquid water transport takes ∼10 s. The variation of the ionic potential loss reaches a critical value, decreasing to a steady state, and is not monotonic. The gas diffusion layer (GDL) and the catalyst layer (CL) porosity, which can affect cell performance, have been carefully investigated. The current density rises rapidly within 10⁻² s, then remaining constant. After 1 s, this is affected by the cell voltage, GDL porosity, and CL porosity, and if the GDL porosity is below 0.4, the current density drops. For the gas diffusion layer porosity, the current density increases between ɛ_GDL = 0.2 and ɛ_GDL = 0.5, with increased GDL porosity. For the catalyst layer porosity, the optimum value appears between ɛ_CL = 0.06 and ɛ_CL = 0.1.     

Optimization of water and air management systems for a passive direct methanol fuel cell

A multi-phase, multi-component, thermal and transient model is applied to simulate the operation of a passive direct methanol fuel cell and optimize the design. The model takes into consideration the thermal effects and the variation of methanol concentration at the feeding reservoir above the fuel cell. Polarization and constant current cases are numerically simulated and compared with experiments for liquid feed concentration, membrane thickness, water management and air management systems. Parameters considered when determining an optimal design include power density, fuel utilization and energy efficiencies and water balance coefficients. An optimal liquid feed concentration is determined to be 2.0 mol kg^?1, which achieved a maximum power density of 21 mW cm^?2 and a fuel utilization efficiency of 63.0%. An optimal design of a cell uses a thick membrane (Nafion 117) to reduce methanol crossover and two additional cathode GDLs to improve the water balance coefficient and efficiency of the cell. This combination results in a power density of 23.8 mW cm^?2 and a water balance coefficient of ?1.71. An air filter may also be added to improve the efficiency and water balance coefficient of the cell, however, a small loss in power density will also occur. Using an Oil Sorbents air filter the water balance coefficient is increased to ?0.85, the fuel utilization efficiency is improved by 27.35% and the maximum power density decreased to 21.6 mW cm^?2.     

Transient analysis for the cathode gas diffusion layer of PEM fuel cells

A one-dimensional, non-isothermal, two-phase transient model has been developed to study the transient behaviour of water transport in the cathode gas diffusion layer of PEM fuel cells. The effects of four parameters, namely the liquid water saturation at the interface of the gas diffusion layer and flow channels, the proportion of liquid water to all of the water at the interface of the cathode catalyst layer and the gas diffusion layer, the current density, and the contact or wetting angle, on the transient distribution of liquid water saturation in the cathode gas diffusion layer are investigated. Especially, the time needed for liquid water saturation to reach steady state and the liquid water saturation at the interface of the cathode catalyst layer and gas diffusion layer are plotted as functions of the above four parameters. The ranges of water vapour condensation and liquid water evaporation are identified across the thickness of the gas diffusion layer. In addition, the effects of the above four parameters on the steady state distributions of gas phase pressure, water vapour concentration, oxygen concentration and temperature are also presented. It is found that increasing any one of the first three parameters will increase the water saturation at the interface of the catalyst layer and gas diffusion layer, but decrease the time needed for the liquid water saturation to reach steady state. When the liquid water saturation at the interface of the gas diffusion layer and flow channels is high enough (≥0.1), the liquid water saturation at steady state is almost uniformly distributed across the thickness of the gas diffusion layer. It is also found that, under the given initial and boundary conditions in this paper, evaporation takes place within the gas diffusion layer close to the channel side and is the major process for water phase change at low current density (<2000 A m⁻²); condensation occurs close to the catalyst layer side within the gas diffusion layer and dominates the phase change at high current density (>5000 A m⁻²). For hydrophilic gas diffusion layers, both the time needed for liquid water saturation to reach steady state and the water saturation at the interface of the catalyst layer and gas diffusion layer will increase when the contact angle increases; but for hydrophobic gas diffusion layers, both of them decrease when the contact angle increases.     

The role of ambient conditions on the performance of a planar,air-breathing hydrogen PEM fuel cell

This paper presents experimental data on the effects of varying ambient temperature (10–40 °C) and relative humidity (20–80%) on the operation of a free-breathing fuel cell operated on dry-hydrogen in dead ended mode. We visualize the natural convection plume around the cathode using shadowgraphy, measure the gas diffusion layer (GDL) surface temperature and accumulation of water at the cathode, as well as obtain polarization curves and impedance spectra. The average free-convection air speed was 9.1 cm s⁻¹ and 11.2 cm s⁻¹ in horizontal and vertical cell orientations, respectively. We identified three regions of operation characterized by increasing current density: partial membrane hydration, full membrane hydration with GDL flooding, and membrane dry-out. The membrane transitions from the fully hydrated state to a dry out regime at a GDL temperature of approximately 60 °C, irrespective of the ambient temperature and humidity conditions. The cell exhibits strong hysteresis and the dry membrane regime cannot be captured by a sweeping polarization scan without complete removal of accumulated water after each measurement point. Maximum power density of 356 mW cm⁻² was measured at an ambient temperature of 20 °C and relative humidity of 40%.     

Passive direct methanol fuel cells fed with methanol vapor

A vapor fed passive direct methanol fuel cell (DMFC) is proposed to achieve a high energy density by using pure methanol for mobile applications. Vapor is provided from a methanol reservoir to the membrane electrode assembly (MEA) through a vaporizer, barrier and buffer layer. With a composite membrane of lower methanol cross-over and diffusion layers of hydrophilic nanomaterials, the humidity of the MEA was enhanced by water back diffusion from the cathode to the anode through the membrane in these passive DMFCs. The humidity in the MEA due to water back diffusion results in the supply of water for an anodic electrochemical reaction with a low membrane resistance. The vapor fed passive DMFC with humidified MEA maintained 20–25 mW cm⁻² power density for 360 h and performed with a 70% higher fuel efficiency and 1.5 times higher energy density when compared with a liquid fed passive DMFC.     

Improvement in high temperature proton exchange membrane fuel cells cathode performance with ammonium carbonate

Proton exchange membrane (PEM) fuel cells with optimized cathode structures can provide high performance at higher temperature (120 °C). A “pore-forming” material, ammonium carbonate, applied in the unsupported Pt cathode catalyst layer of a high temperature membrane electrode assembly enhanced the catalyst activity and minimized the mass-transport limitations. The ammonium carbonate amount and Nafion^® loading in the cathode were optimized for performance at two conditions: 80 °C cell temperature with 100% anode/75% cathode R.H. and 120 °C cell temperature with 35% anode/35% cathode R.H., both under ambient pressure. A cell with 20 wt.% ammonium carbonate and 20 wt.% Nafion^® operating at 80 °C and 120 °C presented the maximum cell performance. Hydrogen/air cell voltages at a current density of 400 mA cm⁻² using the Ionomem/UConn membrane as the electrolyte with a cathode platinum loading of 0.5 mg cm⁻² were 0.70 V and 0.57 V at the two conditions, respectively. This was a 19% cell voltage increase over a cathode without the “pore-forming” ammonium carbonate at the 120 °C operating condition.     

A new direct methanol fuel cell with a zigzag-folded membrane electrode assembly

We propose a new direct methanol fuel cell with a zigzag-folded membrane electrode assembly. This fuel cell is formed by a membrane, which is made up of anode and cathode electrodes on a zigzag-folded sheet, separated by insulation film and current collectors. Individual anodes, cathodes and membranes form a unit cell, which is connected to the adjacent unit cell. The fuel cell can achieve high output voltage through easy in-series connection. Since it is not necessary to connect electrodes, as in the manner of conventional bipolar plates, there is no increase in fabrication cost and no degradation in reliability. The fuel feeds for the anode and cathode are achieved through methanol and air feeds on each electrode, which do not require electricity to run a pump or blower. The experimental cells were formed with an active area of 16 cm × 2 cm on membrane-folded cells. Filter papers with slits were inserted between anodes to improve their methanol supply. A power density of 3 mW cm⁻² was obtained at a methanol concentration of 2 M at ambient temperature. The cell power was affected by the slit area on cathode.     

Water flooding and two-phase flow in cathode channels of proton exchange membrane fuel cells

The water flooding and two-phase flow of reactants and products in cathode flow channels (0.8 mm in width, 1.0 mm in depth) were studied by means of transparent proton exchange membrane fuel cells. Three transparent proton exchange membrane fuel cells with different flow fields including parallel flow field, interdigitated flow field and cascade flow field were used. The effects of flow field, cell temperature, cathode gas flow rate and operation time on water build-up and cell performance were studied, respectively. Experimental results indicate that the liquid water columns accumulating in the cathode flow channels can reduce the effective electrochemical reaction area; it makes mass transfer limitation resulting in the cell performance loss. The water in flow channels at high temperature is much less than that at low temperature. When the water flooding appears, increasing cathode flow rate can remove excess water and lead to good cell performance. The water and gas transfer can be enhanced and the water removal is easier in the interdigitated channels and cascade channels than in the parallel channels. The cell performances of the fuel cells that installed interdigitated flow field or cascade flow field are better than that installed with parallel flow field. The images of liquid water in the cathode channels at different operating time were recorded. The evolution of liquid water removing out of channels was also recorded by high-speed video.     

Sulfonated poly(ether sulfone) for universal polymer electrolyte fuel cell operations

The performances of the proton exchange membrane fuel cell (PEMFC), direct formic acid fuel cell (DFAFC) and direct methanol fuel cell (DMFC) with sulfonated poly(ether sulfone) membrane are reported. Pt/C was coated on the membrane directly to fabricate a MEA for PEMFC operation. A single cell test was carried out using H₂/air as the fuel and oxidant. A current density of 730 mA cm⁻² at 0.60 V was obtained at 70 °C. Pt–Ru (anode) and Pt (cathode) were coated on the membrane for DMFC operations. It produced 83 mW cm⁻² maximum power density. The sulfonated poly(ether sulfone) membrane was also used for DFAFC operation under several different conditions. It showed good cell performances for several different kinds of polymer electrolyte fuel cell applications.     

Construction of fuel reformer using proton conducting oxides electrolyte and hydrogen-permeable metal membrane cathode

We constructed a reformer of methane based on an electrochemical principle. This apparatus consists of the proton conducting ceramics electrolyte and the hydrogen-permeable metal membrane cathode. For methane reforming, a mixture of methane and oxygen gas is supplied to the porous Ag cathode. The hydrogen ions, which formed by the anode reaction: CH₄ + O₂ → CO₂ + 4H⁺ + 4e⁻, are transported through the proton conducting ceramics to the cathode. Then, the hydrogen is formed at the cathode by the reaction: 4H⁺ + 4e⁻ → 2H₂. The hydrogen, which permeates through the metal membrane cathode, is 100% purity.The hydrogen separation ability of the reformer was investigated at 400–650 °C by measuring the electric current through the proton conducting oxide electrolyte. Since the ionic transport number of the proton conducting oxide is nearly unity, the current through the electrolyte corresponds to the proton flux through the electrolyte.The current measurements showed that the extracted proton flux through the electrolyte increased with increasing the applied voltage as well as temperature as we expected. However, the current measurements under the low voltage revealed that the extracted current was lesser than the expected value from Ohm's law. The decrease of the current is possibly caused for the reduction of the effective voltage by the anode polarization. In order to separate the hydrogen with higher efficiency, the applied voltage must be as low as possible using the thinner electrolyte and the improved anode.     

SOFC modeling considering electrochemical reactions at the active three phase boundaries

It is expected that fuel cells will play a significant role in a future sustainable energy system, due to their high energy efficiency and the possibility to use renewable fuels. A fully coupled CFD model (COMSOL Multiphysics) is developed to describe an intermediate temperature SOFC single cell, including governing equations for heat, mass, momentum and charge transport as well as kinetics considering the internal reforming and the electrochemical reactions. The influences of the ion and electron transport resistance within the electrodes, as well as the impact of the operating temperature and the cooling effect by the surplus of air flow, are investigated. As revealed for the standard case in this study, 90% of the electrochemical reactions occur within 2.4 μm in the cathode and 6.2 μm in the anode away from the electrode/electrolyte interface. In spite of the thin electrochemical active zone, the difference to earlier models with the reactions defined at the electrode–electrolyte interfaces is significant. It is also found that 60% of the polarizations occur in the anode, 10% in the electrolyte and 30% in the cathode. It is predicted that the cell current density increases if the ionic transfer tortuosity in the electrodes is decreased, the air flow rate is decreased or the cell operating temperature is increased.     

Operation of PEM fuel cells at 120–150 °C to improve CO tolerance

Sulfonic acid modified perfluorocarbon polymer proton exchange membrane (PEM) fuel cells operated at elevated temperatures (120–150 °C) can greatly alleviate CO poisoning on anode catalysts. However, fuel cells with these PEMs operated at elevated temperature and atmospheric pressure typically experience low relative humidity (RH) and thus have increased membrane and electrode resistance. To operate PEM fuel cells at elevated temperature and high RH, work is needed to pressurize the anode and cathode reactant gases, thereby decreasing the efficiency of the PEM fuel cell system. A liquid-fed hydrocarbon-fuel processor can produce reformed gas at high pressure and high relative humidity without gas compression. If the anode is fed with this high-pressure, high-relative humidity stream, the water in the anode compartment will transport through the membrane and into the ambient pressure cathode structure, decreasing the cell resistance. This work studied the effect of anode pressurization on the cell resistance and performance using an ambient pressure cathode. The results show that high RH from anode pressurization at both 120 and 150 °C can decrease the membrane resistance and therefore increase the cell voltage. A cell running at 150 °C obtains a cell voltage of 0.43 V at 400 mA cm⁻² even with 1% CO in H₂. The results presented here provide a concept for the application of a coupled steam reformer and PEM fuel cell system that can operate at 150 °C with reformate and an atmospheric air cathode.     

Performance of an air-breathing direct methanol fuel cell

An air-breathing direct methanol fuel cell (DMFC) is attractive for portable-power applications. There are, however, several barriers that must be overcome before DMFCs reach commercially viability. This study shows that the cell power density is strongly affected by the fabrication conditions of the membrane electrode assembly (MEA) and by the technique used for assembly of the cell components. The results indicate that reducing the pressure and the thickness of catalyst layer in the MEA fabrication process can significantly improve power density. The production of water at the cathode, especially at a high power density, is shown to have a strong impact on the operation of an air-breathing DMFC since water blocks the feeding of air to the cathode. The power density (≧20 mW cm⁻²) of an air-breathing DMFC is found to drop to nearly half of its initial value after 30–40 min of operation in a short-term stability test. This appears to be one of the major limitations for potable electronic applications. Despite the many practical difficulties associated with an air-breathing DMFC, an attempt is also made to highlight the importance of the component assembly technique using a small cell pack with four integrated unit cells.     

Transient phenomenon of step switching for current or voltage in PEMFC

The transient phenomenon of fuel cell with 5 cm² active area is investigated in this study by current density step increase and switching voltage under different conditions. It is found that there is an undershoot when the current density step increase is at the loading of 60% RH anode cathode, 3 stoic., 70 °C, 15 psi for automobile applications. The voltage is almost zero under 0.2 step increase to 1.0 A/cm² due to the H⁺ transport in membrane or H₂/O₂ in catalyst layer is almost used up. The undershoot phenomenon is more serious under gases stoichiometries of 3.0/3.0 when H₂ is fully humidified due to low gas concentration or flooding on the electrode. This phenomenon would induce the degradation of fuel cell components.     

Diagnostic tool to detect liquid water removal in the cathode channels of proton exchange membrane fuel cells

A transparent PEMFC with a single straight channel was designed to study liquid water transport in the cathode channel. The pressure-drop between the inlet and outlet of the channel was measured and used as a diagnostic signal to monitor liquid water accumulation and removal. This method was non-destructive for the fuel cell, and is capable of monitoring the water droplet buildup and removal in the channel on-line directly, and giving real-time liquid water buildup information. The proper velocity for liquid water removal can be determined according to the pressure-drop curve, which was very helpful to design a flow field and to optimize fuel cell operation. Under the study conditions, and to ensure liquid water discharge, the gas velocity should not lower than 2, 3 and 5 m s⁻¹ for 600, 1000 and 1200 mA cm⁻², respectively. The results were further verified by visualization in a transparent PEMFC.     

Parametric studies of a double-cell stack of PEMFC using Grafoil™ flow-field plates

A parametric study of a double-cell stack of a proton exchange membrane fuel cell (PEMFC) using Grafoil™ flow-field plates is performed. A self-made membrane–electrode assembly (MEA) is used to integrate the PEMFC. Emphasis is placed on the effect of the transport parameters such as cell temperature, pressure and humidity of the reaction side, and flow-field geometry on the performance of the stack. Potential–current and power–current curves are presented. At a fixed dew point of the incoming reactants, say T_dp=30 °C, increasing the cell operating temperature past a threshold value of about 50 °C reduces the cell performance due to membrane dehydration. At a fixed cell operating temperature, a high flow back-pressure increases the cell performance through enhancing the reaction on both electrodes of the fuel cell. Moreover, the cell performance for the pressurised cathode side is better than that for the pressurised anode side due to the favourable back-diffusion of water in the membrane. Finally, empirical correlations are developed to describe the electrode process of the PEMFC stack under various operating conditions.     

Performance and efficiency of a DMFC using non-fluorinated composite membranes operating at low/medium temperatures

In order to increase the chemical/thermal stability of the sulfonated poly(ether ether ketone) (sPEEK) polymer for direct methanol fuel cell (DMFC) applications at medium temperatures (up to 130 °C), novel inorganic–organic composite membranes were prepared using sPEEK polymer as organic matrix (sulfonation degree, SD, of 42 and 68%) modified with zirconium phosphate (ZrPh) pretreated with n-propylamine and polybenzimidazole (PBI). The final compositions obtained were: 10.0 wt.% ZrPh and 5.6 wt.% PBI; 20.0 wt.% ZrPh and 11.2 wt.% PBI. These composite membranes were tested in DMFC at several temperatures by evaluating the current–voltage polarization curve, open circuit voltage (OCV) and constant voltage current (CV, 35 mV). The fuel cell ohmic resistance (null phase angle impedance, NPAI) and CO₂ concentration in the cathode outlet were also measured. A method is also proposed to evaluate the fuel cell Faraday and global efficiency considering the CH₃OH, CO₂, H₂O, O₂ and N₂ permeation through the proton exchange membrane (PEM) and parasitic oxidation of the crossover methanol in the cathode. In order to improve the analysis of the composite membrane properties, selected characterization results presented in [V.S. Silva, B. Ruffmann, S. Vetter, A. Mendes, L.M. Madeira, S.P. Nunes, Catal. Today, in press] were also used in the present study. The unmodified sPEEK membrane with SD = 42% (S42) was used as the reference material. In the present study, the composite membrane prepared with sPEEK SD = 68% and inorganic composition of 20.0 wt.% ZrPh and 11.2 wt.% PBI proved to have a good relationship between proton conductivity, aqueous methanol swelling and permeability. DMFC tests results for this membrane showed similar current density output and higher open circuit voltage compared to that of sPEEK with SD = 42%, but with much lower CO₂ concentration in the cathode outlet (thus higher global efficiency) and higher thermal/chemical stability. This membrane was also tested at 130 °C with pure oxygen (cathode inlet) and achieved a maximum power density of 50.1 mW cm⁻² at 250 mA cm⁻².     

Dependence of high-temperature PEM fuel cell performance on Nafion® content

Operating a proton exchange membrane (PEM) fuel cell at elevated temperatures (above 100 °C) has significant advantages, such as reduced CO poisoning, increased reaction rates, faster heat rejection, easier and more efficient water management and more useful waste heat. Catalyst materials and membrane electrode assembly (MEA) structure must be considered to improve PEM fuel cell performance. As one of the most important electrode design parameters, Nafion^® content was optimized in the high-temperature electrodes in order to achieve high performance. The effect of Nafion^® content on the electrode performance in H₂/air or H₂/O₂ operation was studied under three different operation conditions (cell temperature (°C)/anode (%RH)/cathode (%RH)): 80/100/75, 100/70/70 and 120/35/35, all at atmospheric pressure. Different Nafion^® contents in the cathode catalyst layers, 15–40 wt%, were evaluated. For electrodes with 0.5 mg cm⁻² Pt loading, cell voltages of 0.70, 0.68 and 0.60 V at a current density of 400 mA cm⁻² were obtained at 35 wt% Nafion^® ionomer loading, when the cells were operated at the three test conditions, respectively. Cyclic voltammetry was conducted to evaluate the electrochemical surface area. The experimental polarization curves were analyzed by Tafel slope, catalyst activity and diffusion capability to determine the influence of the Nafion^® loading, mainly associated with the cathode.     

New borohydride fuel cell with multiwalled carbon nanotubes as anode: A step towards increasing the power output

A borohydride fuel cell has been constructed using a platinized multiwalled carbon nanotube (MWCNT) anode and an air cathode having an anionic exchange membrane separating the anode and cathode. The MWCNT was functionalized with carboxylic acid under nitric acid reflux. Platinum metal was subsequently incorporated into it by galvanostatic deposition. The platinized functionalized MWCNT was characterized by thermogravimetric analysis, Fourier transform infrared spectrum, scanning electron microscope and X-ray diffraction. The fuel cell produced a voltage of 0.95 V at low currents and a maximum power density of 44 mW cm⁻² at room temperature in 10% sodium borohydride in a 4 M sodium hydroxide medium. Another borohydride fuel cell under identical conditions using carbon as the anode produced a cell voltage of 0.90 V and power density of about 20 mW cm⁻². The improved performance of the MWCNT is attributed to the higher effective surface area and catalytic activity.