Degradation behaviour of Al–Fe coatings in wet-seal area of molten carbonate fuel cells

The corrosion resistance of Al–Fe coatings increases as a protective LiAlO₂ layer forms. If, however, the Al–Fe coatings lack sufficient aluminium for maintaining this protective layer, the corrosion resistance of the coating is degraded by the growth of non-protective scales, such as LiFeO₂. In this study, the degradation behaviour of Al–Fe coatings is investigated in the wet-seal environment of molten carbonate fuel cells (MCFC). Al–Fe coated specimens with various amounts of aluminium in the range 8–70 at.% and bulk specimens of Fe–23.9 Al (at.%) are prepared. A corrosion test is performed in Li/K carbonate systems at 650 °C with a single-cell and an immersion test. Test results reveal that aluminium contents in the coatings should be higher than 25 at.% in order to form and maintain a protective LiAlO₂ layer. In addition to aluminium content, the influence of microstructural features on the degradation behaviour of Al–Fe coatings is discussed.     

An investigation into the effects of a nano-thick gold interlayer on polypyrrole coatings on 316L stainless steel for the bipolar plates of PEM fuel cells

Polypyrrole is one of the most important conductive polymers because it is easily oxidized, water soluble and commercially available. Also, polypyrrole coatings have potential applications in batteries, fuel cells, electrochemical sensors, anti-corrosion coatings and drug delivery systems. In this study, a very thin gold layer was first coated on SS316L, and then a polypyrrole coating was laid on top. The nucleation and growth mechanisms of polypyrrole on the gold-coated SS316L were studied by electrochemical nucleation and growth techniques. SEM was used to characterize the polypyrrole coating morphology. Potentiodynamic tests were performed to determine the corrosion parameters of the polypyrrole coatings. Potentiostatic tests of the coated SS316L were conducted in simulated anode and cathode environments of a PEM fuel cell. The simulated anode environment was at a potential of about −0.1 V versus SCE purged with H₂ and the simulated cathode environment was at a potential of about 0.6 V versus SCE purged with O₂. After coating with Au and polypyrrole, the polarization resistance of SS316L is increased about six times, and the corrosion current density is decreased about seven times, compared to the base SS316L. Also, our calculations show that the metal ion concentration in solution for the polypyrrole/Au/SS316L had met the target of 10 ppm after 5000 h fuel cell operation.     

Investigation of hydrogen production from boron compounds for pem fuel cells

This paper presents a comprehensive study of hydrogen production from sodium borohydride (NaBH₄), which is synthesized from sodium tetraborate (Na₂B₄O₇) decomposition, for proton exchange membrane (PEM) fuel cells. For this purpose, Na₂B₄O₇ decomposition reaction at 450–500 °C under hydrogen atmosphere and NaBH₄ decomposition reaction at 25–40 °C under atmospheric pressure are selected as a common temperature range in practice, and the inlet molar quantities of Na₂B₄O₇ are chosen from 1 to 6 mol with 0.5 mol interval as well. In order to form NaBH₄ solution with 7.5 wt.% NaBH₄, 1 wt.% NaOH, 91.5 wt.% H₂O, the molar quantities of NaBH₄ are determined. For a PEM fuel cell operation, the required hydrogen production rates are estimated depending on 60, 65, 70 and 75 g of catalyst used in the NaBH₄ solution at 25, 32.5 and 40 °C, respectively. It is concluded that the highest rate of hydrogen production per unit area from NaBH₄ solution at 40 °C is found to be 3.834 × 10⁻⁵ g H₂ s⁻¹ cm⁻² for 75 g catalyst. Utilizing 80% of this hydrogen production, the maximum amounts of power generation from a PEM fuel cell per unit area at 80 °C under 5 atm are estimated as 1.121 W cm⁻² for 0.016 cm by utilizing hydrogen from 75 g catalyst assisted NaBH₄ solution at 40 °C.     

New lightweight bipolar plate system for polymer electrolyte membrane fuel cells

The use of metal based bipolar plates in polymer electrolyte membrane (PEM) fuel cells, with an active coating on titanium to reduce voltage losses due to the formation of passive layers has been demonstrated. Lifetime data in excess of 8000 h has been achieved and power densities in excess of 1.8 kW dm⁻³ and 1 kW kg⁻¹ are predicted.     

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.     

Direct formic acid fuel cells

The performance of formic acid fuel oxidation on a solid PEM fuel cell at 60 °C is reported. We find that formic acid is an excellent fuel for a fuel cell. A model cell, using a proprietary anode catalyst produced currents up to 134 mA/cm² and power outputs up to 48.8 mW/cm². Open circuit potentials (OCPs) are about 0.72 V. The fuel cell runs successfully over formic acid concentrations between 5 and 20 M with little crossover or degradation in performance. The anodic polarization potential of formic acid is approximately 0.1 V lower than that for methanol on a standard Pt/Ru catalyst. These results show that formic acid fuel cells are attractive alternatives for small portable fuel cell applications.     

Development and demonstration of a higher temperature PEM fuel cell stack

Research and development was conducted on a proton exchange membrane (PEM) fuel cell stack to demonstrate the capabilities of Ionomem Corporation's composite membrane to operate at 120 °C and ambient pressure for on-site electrical power generation with useful waste heat. The membrane was a composite of polytetrafluoroethylene (PTFE), Nafion^®, and phosphotungstic acid. Studies were first performed on the membrane, cathode catalyst layer, and gas diffusion layer to improve performance in 25 cm², subscale cells. This technology was then scaled-up to a commercial 300 cm² size and evaluated in multi-cell stacks. The resulting stack obtained a performance near that of the subscale cells, 0.60 V at 400 mA cm⁻² at near 120 °C and ambient pressure with hydrogen and air reactants containing water at 35% relative humidity. The water used for cooling the stack resulted in available waste heat at 116 °C. The performance of the stack was verified. This was the first successful test of a higher-temperature, PEM, fuel-cell stack that did not use phosphoric acid electrolyte.     

Polymeric composite bipolar plates for vehicle applications

At present membrane electrode assembly performance levels and stack operating conditions of PEM fuel cells, a plate area specific resistance of less than approximately 20 mΩ cm² and a plate thickness of less than 2 mm are required to meet the vehicular volumetric power density target (>2 kW l⁻¹). It is, however, difficult to meet these aggressive requirements, and simultaneously obtain good mechanical properties when using polymeric plate materials. Polymers become brittle and break frequently at the high conductive filler loadings (e.g., >50 v/o graphite) required for high conductivity. This study investigates a potential approach for obtaining high plate conductivity at low conductive filler loadings, thus enabling high volumes of thin and ductile plates to be manufactured at low scrap rates.     

Effect of heat-treatment temperature on carbon corrosion in polymer electrolyte membrane fuel cells

This study examines the effect of heat-treatment temperature on the electrochemical corrosion of carbon nanofibers (CNFs) in polymer electrolyte membrane (PEM) fuel cells. Corrosion is investigated by monitoring the generation of CO₂ using an on-line mass spectrometer at a constant potential of 1.4 V for 30 min. The experimental results show that the generation of CO₂ decreases with increasing heat-treatment temperature, indicating that less electrochemical carbon corrosion occurs. In particular, when the heat-treatment temperature is 2400 °C, the change intensifies. X-ray photoelectron spectroscopic analysis shows that oxygen functional groups on the carbon surface decrease with increasing heat-treatment temperature. A reduction in oxygen functional groups increases the hydrophobic nature of the carbon surface, which is responsible for the increased corrosion resistance of CNFs.     

Development of a miniaturized polymer electrolyte membrane fuel cell with silicon separators

The fabrication process and electrochemical characterization of a miniaturized PEM fuel cell with silicon separators were investigated. Silicon separators were fabricated with silicon fabrication technologies such as by photolithography, anisotropic wet etching, anodic bonding and physical vapor deposition (PVD). A 400 μm × 230 μm flow channel was made with KOH wet etching on the front side of a silicon separator, and then a 550 nm gold current collector and 350 nm TiN_x thin film heater were respectively formed on the front side and the opposite side by PVD. Two separators were assembled with the membrane electrode assembly (MEA) having a 4 cm² active area for the single cell. With pure hydrogen and oxygen under atmospheric pressure without humidification, the performance of the single fuel cell was measured. A single cell operation led to generation of 203 mW cm⁻² at 0.6 V at room temperature, which corresponded to 360 mW cm⁻³ in terms of volumetric fuel cell power density, with 20 ccm of gas flow rate of hydrogen and oxygen at the inlet.     

Control of miniature proton exchange membrane fuel cells based on fuzzy logic

A control strategy is presented in this paper which is suitable for miniature hydrogen/air proton-exchange membrane (PEM) fuel cells. The control approach is based on process modelling using fuzzy logic and tested using a PEM stack consisting of 15 cells with parallel channels on the cathode side and a meander-shaped flow-field on the anode side. The active area per cell is 8 cm². Commercially available materials are used for the bipolar plates, gas diffusion layers and the membrane-electrode assembly (MEA). It is concluded from a simple water balance model that water management at different temperatures can be achieved by controlling the air stoichiometry. This is achieved by varying the fan voltage for the air supply of the PEM stack. A control strategy of the Takagi Sugeno Kang (TSK) type, based on fuzzy logic, is presented. The TSK-type controller offers the advantage that the system output can be computed in an efficient way: the rule consequents of the controller combine the system variables in linear equations. It is shown experimentally that drying out of the membrane at high temperatures can be monitored by measuring the ac impedance of the fuel cell stack at a frequency of 1 kHz. Flooding of single cells leads to an abrupt drop of the corresponding single-cell voltage. Therefore, the fuzzy rule base consists of the ac impedance at 1 kHz and all single-cell voltages. The parameters of the fuzzy rule base are determined by plotting characteristic diagrams of the fuel cell stack at constant temperatures. The fuel cell stack can be controlled at T=60 °C up to a power level of 7.5 W. The fuel cell stack is controlled successfully even when the external electric load changes. At T=65 °C, a maximum power level of 8 W is found. A decrease of the maximum power level is observed for higher temperatures.     

Hydrogen photosynthesis by Rhodobacter capsulatus and its coupling to a PEM fuel cell

Four different mutant strains of Rhodobacter capsulatus (IR1, IR3, IR4 and JP91), a photosynthetic purple non-sulfur bacterium, were tested for their ability to produce hydrogen in a 3 L volume photobioreactor coupled to a small PEM fuel cell. The four mutants, together with the wild-type strain, B10, were grown at 30 °C under illumination with 30 mmol L⁻¹ dl-lactate and 5 mmol L⁻¹ l-glutamate as carbon and nitrogen source, respectively. Bacterial growth was measured by monitoring the increase in absorbance at 660 nm, and hydrogen yield, and substrate conversion efficiency were measured under the same conditions. The hydrogen production capability of the five strains was then compared and shown to be in the order: IR3 > JP91 > IR4 > B10 > IR1. The most preferment strain, IR3, showed a substrate conversion efficiency of 84.8% and a hydrogen yield of 3.9 L L⁻¹ of culture. The biogas produced by these photobioreactor cultures was successfully used as feed for a small PEM fuel cell system, with the mutant IR3 showing the most sustained hydrogen and current production. The maximum current was similar to that obtained using pure hydrogen produced by a small electrolysis cell (High-Tec Inc.).     

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.     

Technical cost analysis for PEM fuel cells

The present cost of fuel cells estimated at about $200 kW⁻¹ is a major barrier for commercialization and use in automotive applications. In the United States the target costs for fuel cell systems for the year 2004 as formulated by PNGV are $50 kW⁻¹. Lomax et al. have estimated the costs of polymer electrolyte membrane (PEM) fuel cells to be as low as $20 kW⁻¹. These estimates are based on careful consideration of high volume manufacturing processes. Recently, Arthur D. Little (ADL) has estimated the cost of a fuel cell system for transportation at $294 kW⁻¹. This estimate considers a fuel processor and directly related balance of plant components. The difference of the cost estimates results from the vastly different design assumptions. Both of these estimates are based on considering a single high volume of production, 500,000 fuel cells per year. This work builds on these earlier estimates by employing the methods of technical cost modeling and thereby including explicit consideration of design specifications, exogenous factor cost and processing and operational details. The bipolar plate is analyzed as a case study. The sensitivity of the costs to uncertainty in process conditions are explored following the ADL design. It is shown that the PNGV targets can only be achieved with design changes that reduce the quantity of material used. This might necessitate a reduction in efficiency from the assumed 80 mpg.     

Electrophoretic deposition of polypyrrole/Vulcan XC-72 corrosion protection coatings on SS-304 bipolar plates by asymmetric alternating current for PEM fuel cells

In this study, corrosion protection composite films composed of polypyrrole (formed from the electropolymerization of pyrrol monomer) and Vulcan XC-72, labeled as PPy-C, were deposited on SS-304 substrates by EPD using an asymmetric AC signal (AAC) in acetone and acetone:methanol solutions. Prior to deposition, Vulcan powders were functionalized in order to create functional groups that develop a negative surface charge. Under the applied electric field, both pyrrole monomer and carbon colloidal particles migrated simultaneously toward the SS anode surface to create the corrosion protection PPy-C coatings. The effect of applied voltages (50, 70, 90 and 120 V) and deposition time (2, 6, 10 and 15 min) on the film characteristics was evaluated. The coatings were analyzed by SEM and the results showed improved characteristics of the films deposited by AAC, in terms of homogeneity and porosity, compared to samples prepared by a continuous DC process. Polarization curves were conducted in order to evaluate the corrosion characteristics of the bipolar plates in 0.1 M H₂SO₄ at room temperature. The experimental results indicated that the PPy-C composites significantly enhanced the corrosion resistance of the SS substrates. For example, the T1 sample increased the corrosion potential by about 541 mV and decreased the corrosion current density by two orders of magnitude, compared to uncoated SS. FTIR studies confirmed the formation of PPy after electropolymerization of the pyrrole monomer under the EPD process. Even though this characterization has been carried out in a half cell, it has been proposed that the PPy-C-coated SS bipolar plates may find application in the acidic atmosphere of PEMFCs.     

Performance of a poly(2,5-benzimidazole) membrane based high temperature PEM fuel cell in the presence of carbon monoxide

The performance of a poly(2,5-benzimidazole) (ABPBI) membrane based high temperature PEM fuel cell in presence of carbon monoxide, at various temperatures is reported here. The ABPBI was synthesized by polymerization of 3,4-diaminobenzoic acid in a polymerization medium containing methanesulfonic acid (CH₃SO₃H) and phosphorous pentoxide (P₂O₅). The ABPBI membranes were characterized by fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). A maximum conductivity of 0.026 S cm⁻¹ at 180 °C was obtained for the membrane doped with 1.2 molecules of phosphoric acid (H₃PO₄) per polymer repeat unit. Fuel cell performance was evaluated using dry hydrogen/oxygen gases and was comparable with that reported in the literature. Performance of a single cell at different temperatures was studied with 0.48 and 1.0 vol.% of CO in the hydrogen fuel. The studies lead to the conclusion that CO poisoning is not a serious problem above 170 °C. Performance of the fuel cell operating at 210 °C is not at all affected by 1.0 vol.% of CO in the hydrogen feed.     

Improved photographic production of Pt nano-particles for fuel cell electrodes

An improved photographic Pt printing process has been developed, which is called the print-out process (POP). No developer is required in this process and the deposition efficiency was significantly improved by more than 6 times on carbon paper (CP) and 22 times on carbon-black-coated carbon paper (CB/CP) over the previously reported develop-out process (DOP) [1]. The Pt particle size can be easily controlled by varying the moisture content in the substrate and was reduced to 5 nm on blank CP by adding a stabilizing agent, ethylene glycol (EG), to the photo-emulsion. Due to the hydrophobic nature of CB/CP, both Nafion ionomer solution and ethylene glycol (EG) were mixed with the emulsion during the printing. SEM revealed that on this substrate Pt was distributed as ∼25 nm clusters consisting of 5 nm particles on the carbon-black. The mass specific catalytic activity for methanol oxidation of Pt printed on CB/CP by POP was increased five times compared to that of Pt printed by the previous DOP. The performance of the POP Pt in a H₂ PEM single fuel cell (5 cm²) was also evaluated. A peak power density of 288 mW cm⁻² was achieved with an anode POP Pt catalyst loading of 0.16 mg cm⁻² at 70 °C and 0.9 mg cm⁻² JM Pt at the cathode. Compared to the DOP Pt catalyst at about the same loading, peak power density was improved more than four times by using the POP Pt.     

Development of micro direct methanol fuel cells for high power applications

A micro direct methanol fuel cell (μDMFC) with active area of 1.625 cm² has been developed for high power portable applications and its electrochemical characterization carried out in this study. The fragility of the silicon wafer makes it difficult to compress the cell for good sealing and hence to reduce contact resistance in the Si-based μDMFC. We have instead used very thin stainless steel plates as bipolar plates with the flow field machined by photochemical etching technology. For both anode and cathode flow fields, widths of both the channel and rib were 750 μm, with a channel depth of 500 μm. A gold layer was deposited on the stainless steel plate to prevent corrosion. This study used an advanced MEA developed in-house featuring a modified anode backing structure with a compact microporous layer. Maximum power density of the micro DMFC reached 62.5 mW cm⁻² at 40 °C, and 100 mW cm⁻² at 60 °C at atmospheric pressure, which almost doubled the performance of our previous Si-based μDMFC.     

Unusually active palladium-based catalysts for the electrooxidation of formic acid

Formic acid fuel cells offer exciting prospects for powering portable electronic and MEMS devices. Pd-based catalysts further improve the performance of direct formic acid fuel cells while reducing catalyst costs over Pt-based catalysts. This study investigates several Pd-based catalysts, both unsupported and carbon-supported, and compares the electrochemical results with results obtained in an operating fuel cell. Power densities of up to 260 mW cm⁻² were achieved in a fuel cell at 750 mA operating at 30 °C. Carbon-supported catalysts and addition of other metals, such as gold, show potential in further improving the performance of Pd-based catalysts.     

A sharp peak in the performance of sputtered platinum fuel cells at ultra-low platinum loading

Proton exchange membrane fuel cells were fabricated by direct sputter deposition of platinum on the surface of Nafion 117 membranes. A sharp spike in the performance of these sputtered platinum fuel cells was observed at ultra-low platinum thickness values of 5–10 nm. Within this narrow thickness range, the power output capability of sputtered platinum fuel cells is several orders of magnitude better than the performance produced by thinner or thicker coatings. The spike in performance is explained by rapid changes in the sputtered film microstructure at the nanometer thickness level. When the membrane surface is deliberately modified by abrasion prior to sputtering, this sharp peak is not seen. Instead, a broad plateau is observed, where the performance is insensitive to the amount of sputtered platinum. This behavior stems from how surface roughening affects the sputtered catalyst layer continuity. The performance of a sputter-deposited membrane with a platinum loading level of 0.04 mg/cm² is compared to a commercial membrane electrode assembly (MEA) with a platinum loading of 0.4 mg/cm². The maximum power output of the sputtered cell is three-fifths that of the commercial MEA, but uses one-tenth the platinum.