CF4 plasma treatment for preparing gas diffusion layers in membrane electrode assemblies

The hydrophobic properties of carbon fibers improved by a CF₄ plasma treatment were used to fabricate gas diffusion layers (GDLs) for use in proton exchange membrane fuel cells. The water contact angle of the CF₄ plasma treated GDL was measured as 132.8 ± 0.2° at 45 °C and very few surface gas diffusion pores were either sealed or blocked by the excessive hydrophobic material residuals. Polarization measurements verified that the CF₄ plasma treated modules can indeed enhance fuel cell performance, compared to the membrane electrode assemblies (MEAs) with a non-wet-proofed GDL, 10 wt% PTFE dip-coated GDL, and commercially available GDL (10 wt% PTFE).     

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.     

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%.     

Study of sintered stainless steel fiber felt as gas diffusion backing in air-breathing DMFC

Adoption of a sintered stainless steel fiber felt was evaluated as gas diffusion backing in air-breathing direct methanol fuel cell (DMFC). By using a sintered stainless steel fiber felt as an anodic gas diffusion backing, the peak power density of an air-breathing DMFC is 24 mW cm⁻², which is better than that of common carbon paper. A 30-h-life test indicates that the degraded performance of the air-breathing DMFC is primarily due to the water flooding of the cathode. Twelve unit cells with each has 6 cm² of active area are connected in series to supply the power to a mobile phone assisted by a constant voltage diode. The maximum power density of 26 mW cm⁻² was achieved in the stack, which is higher than that in single cell. The results show that the sintered stainless steel felt is a promising solution to gas diffusion backing in the air-breathing DMFC, especially in the anodic side because of its high electronical conductivity and hydrophilicity.     

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.     

Surface modified Nafion® membrane by ion beam bombardment for fuel cell applications

The interfacial structure between an electrolyte membrane and an electrode catalyst layer plays an important role in determining performance of proton exchange membrane fuel cell (PEMFC) since the electrochemical reactions produce electricity occur on the interfaces that are in contact with hydrogen or oxygen gas, so-called three phase boundaries. To improve performance of the PEMFC by enlarging effective area of the interfaces, surface of Nafion^® 115 membrane was roughened by Ar⁺ ion beam bombardment before being coated with a catalyst ink to form the electrode layer. With increasing ion dose density from 0 to 1 × 10¹⁷ ions cm⁻², roughness and hydrophobicity of the membrane surface increased, which could be favored for a high-performance PEMFC. In fuel cell tests, the single cell using Nafion^® membrane bombarded at an ion dose density of 10¹⁶ ions cm⁻² exhibited maximum power density of 0.62 W cm⁻², which was two times higher than that of the single cell employing untreated Nafion^® 115 membrane, i.e. 0.30 W cm⁻².     

Advanced air-breathing direct methanol fuel cells for portable applications

A novel MEA is fabricated to improve the performance of air-breathing direct methanol fuel cells. A diffusion barrier on the anode side is designed to control methanol transport to the anode catalyst layer and thus suppressing the methanol crossover. A catalyst coated membrane with a hydrophobic gas diffusion layer on the cathode side is employed to improve the oxygen mass transport. It is observed that the maximum power density of the advanced DMFC with 2 M methanol solution achieves 65 mW cm⁻² at 60 °C. The value is nearly two times more than that of a commercial MEA. At 40 °C, the power densities operating with 1 and 2 M methanol solutions are over 20 mW cm⁻² with a cell potential at 0.3 V.     

Effects of sputtering parameters on the performance of electrodes fabricated for proton exchange membrane fuel cells

One way to alleviate the emission of air pollutants and CO₂ due to burning fossil fuels is the use of fuel cells. Sputter deposition techniques are good candidates for the fabrication of electrodes used for proton exchange membrane fuel cells (PEMFCs). Input power and sputtering-gas pressure are two important parameters in a sputtering process. However, little is known about the effects of these sputtering parameters on the performance of PEMFC electrodes. Therefore, this study applied a radio frequency (RF) magnetron sputter deposition process to prepare PEMFC electrodes and investigated the effects of RF power and sputtering-gas pressure in electrode fabrication on electrode/cell performance. At a Pt loading of 0.1 mg cm⁻², the electrode fabricated at 100 W, 10⁻³ Torr was found to exhibit the best performance mainly due to its lowest kinetic (activation) resistance (dominating the cell performance) in comparison to those fabricated by 50 and 150 W at 10⁻³ Torr, as well as by 10⁻⁴ and 10⁻² Torr at 100 W. In the tested ranges, the control of sputtering-gas pressure seems to be more critical than that of RF power for the activation loss. In addition to electrochemically active surface area, electrode microstructure should also be responsible for electrode/cell polarization, particularly the activation polarization.     

Effect of cathode separator structure on performance characteristics of free-breathing PEMFCs

The performance of free-breathing polymer electrolyte membrane fuel cells (PEMFCs) was studied experimentally and the effect of the cathode separator structure on the cell performance was investigated. Two types of cathode separators were used for a cell with an 18 cm² active area: an open type with parallel rectangular open-slits and a channel type with straight vertical channels with open ends. The polarization curves, cell impedance, and contact pressure distribution of the separators were measured with each type of cathode structure. The result showed that it is difficult to realize a uniform contact pressure across the cell layers for the open type separator, and this results in higher contact resistance and poorer cell performance than the channel type separator. The channel type separator can maintain a low contact resistance, and the cell performance is strongly affected by the natural convection inside the channel. Optimization of the channel design of the channel type separator achieves good performance and this type of separator is superior for a free-breathing PEMFC. A computational three-dimensional analysis for the free-breathing channel type PEMFC with the different channel depths was performed, and it identified the influence of natural convection.     

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.     

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.     

Enhancement of proton exchange membrane fuel cell performance by titanium-coated anode gas diffusion layer

Titanium was coated onto an anode gas diffusion layer (GDL) by direct current sputtering to improve the performance and durability of a proton exchange membrane fuel cell (PEMFC). Scanning electron microscopy (SEM) images showed that the GDLs were thoroughly coated with titanium, which showed angular protrusion. Single-cell performance of the PEMFCs with titanium-coated GDLs as anodes was investigated at operating temperatures of 25 °C, 45 °C, and 65 °C. Cell performances of all membrane electrode assemblies (MEAs) with titanium-coated GDLs were superior to that of the MEA without titanium coating. The MEA with titanium-coated GDL, with 10 min sputtering time, demonstrated the best performance at 25 °C, 45 °C, and 65 °C with corresponding power densities 58.26%, 32.10%, and 37.45% higher than that of MEA without titanium coating.     

Effects of platinum loading on performance of proton-exchange membrane fuel cells using surface-modified Nafion® membranes

The interface between the electrolyte and electrode catalyst plays an important role in determining the performance of proton-exchange membrane fuel cells (PEMFCs) since the electrochemical reactions take place at the interface in contact with the reactant gases. To enhance catalyst activity by enlarging the interfacial area, the surface of a Nafion^® membrane is roughened by Ar⁺ ion beam bombardment that does not change the chemical structure of the membrane, as confirmed by FT-IR spectra. Among the membranes treated with ion dose densities of 0, 10¹⁵, 10¹⁶, 5 × 10¹⁶ and 10¹⁷ ions cm⁻² at ion energy of 1 keV, the membrane treated at ion dose density of 5 × 10¹⁶ ions cm⁻² exhibits the highest performance. Using the untreated and the treated membrane with 5 × 10¹⁶ ions cm⁻², the effects of platinum loading on cell performance are examined with Pt loadings of 01, 0.2, 0.3, 0.4 and 0.55 mg cm⁻². Except for a Pt loading of 0.55 mg cm⁻² where mass transport limits the cell performance, the single cell using a treated membrane gives a higher performance than that using an untreated membrane. This implies that the cell performance can be improved and the Pt loading can be reduced by ion beam bombardment.     

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.     

Ferritic stainless steels as bipolar plate material for polymer electrolyte membrane fuel cells

Both interfacial contact resistance (ICR) measurements and electrochemical corrosion techniques were applied to ferritic stainless steels in a solution simulating the environment of a bipolar plate in a polymer electrolyte membrane fuel cell (PEMFC). Stainless steel samples of AISI434, AISI436, AISI441, AISI444, and AISI446 were studied, and the results suggest that AISI446 could be considered as a candidate bipolar plate material. In both polymer electrolyte membrane fuel cell anode and cathode environments, AISI446 steel underwent passivation and the passive films were very stable. An increase in the ICR between the steel and the carbon backing material due to the passive film formation was noted. The thickness of the passive film on AISI446 was estimated to be 2.6 nm for the film formed at −0.1 V in the simulated PEMFC anode environment and 3.0 nm for the film formed at 0.6 V in the simulated PEMFC cathode environment. Further improvement in the ICR will require some modification of the passive film, which is dominated by chromium oxide.     

A study of Ni + 8YSZ/8YSZ/La0.6Sr0.4CoO3−δ ITSOFC fabricated by atmospheric plasma spraying

An intermediate temperature solid oxide fuel cell (ITSOFC) based on 8YSZ electrolyte, La_0.6Sr_0.4CoO_3−δ (LSCo) cathode, and Ni − 8YSZ anode coatings were consecutively deposited onto a porous Ni-plate substrate by atmospheric plasma spraying (APS). The spray parameters including current, argon and hydrogen flow rate, and powder feed rate were investigated by an orthogonal experiment to fabricate a thin gas-tight 8YSZ electrolyte coating (80 μm). By proper selection of the spray parameters to decrease the particles velocity and temperature, the sprayed NiO + 8YSZ coating after reducing with hydrogen shows a good electrocatalytic activity for H₂ oxidation. With the same treatment, 100–170 μm dimensions LSCo particle could keep phase structure after spraying. And the deposited LSCo cathode shows a good cathode performance and chemical compatibility with 8YSZ electrolyte after operating at 800 °C for 50 h. Output power density of the sprayed cell achieved 410 mW cm⁻² at 850 °C and 260 mW cm⁻² at 800 °C. Electrochemical characterization indicated that IR drop of 8YSZ electrolyte, cathodic polarization, and the contact resistance at LSCo/8YSZ interface were the main factors restricting the cell performance. The results suggested that the use of APS cell allowed the reduction of the operating temperature of the SOFC to below 850 °C with lower production costs.     

Adhesive copper films for an air-breathing polymer electrolyte fuel cell

A design for an air-breathing and passive polymer electrolyte fuel cell is presented. Such a type of fuel cell is in general promising for portable electronics. In the present design, the anode current collector is made of a thin copper foil. The foil is provided with an adhesive and conductive coating, which firstly tightens the hydrogen compartment without mask or clamping pressure, and secondly secures a good electronic contact between the anode backing and the current collector. The cathode comprises a backing, a gold-plated stainless steel mesh and a current collector cut out from a printed circuit board. Three geometries for the cathode current collector were evaluated. Single cells with an active area of 2 cm² yielded a peak power of 250–300 mW cm⁻² with air and pure H₂ in a complete passive mode except for the controlled flow of H₂. The cells’ response was investigated in steady state and transient modes.     

Effect of hydrophobic gas diffusion layers on the performance of the polymer exchange membrane fuel cell

This study uses fuel cell gas diffusion layers (GDLs) fabricated in the laboratory from carbon fiber cloth with different concentrations of hydrophobic agents in proton exchange membrane fuel cells (PEMFCs), and investigates the relationship between the hydrophobic agent content of the carbon fiber cloth and fuel cell performance.The paper examines the effect of hydrophobic agent content on GDL thickness, contact angle, air permeability, and surface and through-plane resistivity. Carbon fiber cloth is impregnated with hydrophobic agent concentrations of 0, 3, 5, 10, 30, and 50 wt%, and the resulting GDLs are subjected to performance tests. When the test piece area is 25 cm², the test temperature 80 °C, the gasket thickness 0.36 mm, and the hydrophobic agent content 5 wt%, a fuel cell using the GDL has a current density of 1430 mA cm⁻² at 0.3 V.     

Durability of (Pr0.7Sr0.3)MnO3±δ/8YSZ composite cathodes for solid oxide fuel cells

Half cell SOFCs with (Pr_0.7Sr_0.3)MnO_3±δ/8YSZ composite cathodes on 8YSZ electrolytes were aged up to 1000 h at 1000 °C in air with/without 0.318 A cm⁻² cathodic polarization. During the aging, the performance of the half cell SOFCs was measured using electrochemical impedance spectroscopy (EIS). After aging, the surface of the composite cathode and the interface between the composite cathode and the electrolyte was investigated with scanning electron microscopy (SEM). Chemical element analysis was performed with energy dispersive X-ray spectroscopy (EDS). The performance of the half cell SOFCs degraded after aging with/without polarization compared to the initial state. The SOFCs had a larger polarization resistance after 1000 h of aging. The cathodic current was shown to have an impact on the performance by slowing down the rate of decrease of polarization resistance of the SOFCs. After aging, the microstructural properties—mean pore size increased and cumulative pore volume decreased, and growth of grains was found on the (Pr_0.7Sr_0.3)MnO_3±δ phases.     

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.