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.     

Development of 10 kW-scale hydrogen generator using chemical hydride

We have developed a hydrogen generator that generates high purity hydrogen gas from the aqueous solution of sodium borohydride, NaBH₄. This paper discussed the performance testing of the hydrogen generator using a Pt-LiCoO₂-coated honeycomb monolith. The NaBH₄ solution hydrolyzed to generate H₂ and sodium metaborate when it contacted the monolith. The gravimetric and the volumetric H₂ densities of the system were 2 wt.% and 1.5 kg H₂/100 l, respectively. The volumetric density was similar to that of the compressed H₂ at 25 MPa. The hydrogen generator successfully provided a maximum H₂ generation rate of 120 nl/min. Assuming a standard PEM (polymer electrolyte fuel cell, PEFC) fuel cell operated at 0.7 V, generating 120 nl/min was equivalent to12 kW.     

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.     

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.     

Ammonia fuel cell using doped barium cerate proton conducting solid electrolytes

Proton-conducting solid electrolytes composed of gadolinium-doped barium cerate (BCG) or gadolinium and praseodymium-doped barium cerate (BCGP) were tested in an intermediate-temperature fuel cell in which hydrogen or ammonia was directly fed. At 700 °C, BCG electrolytes with porous platinum electrodes showed essentially no loss in performance in pure hydrogen. Under direct ammonia at 700 °C, power densities were only slightly lower compared to pure hydrogen feed, yielding an optimal value of 25 mW cm⁻² at a current density of 50 mA cm⁻². This marginal difference can be attributed to a lower partial pressure of hydrogen caused by the production of nitrogen when ammonia is decomposed at the anode.A comparative test using BCGP electrolyte showed that the doubly doped barium cerate electrolyte performed better than BCG electrolyte. Overall fuel cell performance characteristics were enhanced by approximately 40% under either hydrogen or ammonia fuels using BCGP electrolyte. At 700 °C using direct ammonia feed, power density reached 35 mW cm⁻² at a current density of approximately 75 mA cm⁻². Minimal loss of performance was noted over approximately 100 h on-stream in alternating hydrogen/ammonia fuels.     

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.     

Operation of ceria-electrolyte solid oxide fuel cells on iso-octane–air fuel mixtures

Reduced-temperature solid oxide fuel cells (SOFCs) – with thin Ce_0.85Sm_0.15O_1.925 (SDC) electrolytes, thick Ni–SDC anode supports, and composite cathodes containing La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) and SDC – were fabricated and tested with iso-octane/air fuel mixtures. An additional supported catalyst layer, placed between the fuel stream and the anode, was needed to obtain a stable output power density (e.g. 0.6 W cm⁻² at 590 °C) without anode coking. The Ru-CeO₂ catalyst produced CO₂ and H₂ at temperatures <350 °C, while H₂ and CO became predominant above 500 °C. Power densities were substantially less than for the same cells with H₂ fuel (e.g. 1.0 W cm⁻² at 600 °C), due to the dilute (≈20%) hydrogen in the fuel mixture produced by iso-octane partial oxidation. Electrochemical impedance analysis showed a main arc that represented ≈60% of the total resistance, and that increased substantially upon switching from hydrogen to iso-octane/air.     

Screen-printed thin YSZ films used as electrolytes for solid oxide fuel cells

A thin yttria-stabilized zirconia (8 mol% YSZ) film was successfully fabricated on a NiO-YSZ anode substrate by a screen-printing technique. The scanning electron microscope (SEM) results suggested that the YSZ film thickness was about 31 μm after sintering at 1400 °C for 4 h in air. A 60 wt% La_0.7Sr_0.3MnO₃ + 40 wt% YSZ was screen-printed onto the YSZ film surface as cathode. A single cell was tested from 650 to 850 °C using hydrogen as fuel and ambient air as oxidant, which showed an open circuit voltage (OCV) of 1.02 V and a maximum power density of 1.30 W cm⁻² at 850 °C. The OCV was higher than 1.0 V, which suggested that the YSZ film was quite dense and that the fuel gas leakage through the YSZ film was negligible. Screen-printing can be a promising method for manufacturing YSZ films for solid oxide fuel cells (SOFCs).     

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.     

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.     

Study of electrodeposited polypyrrole coatings for the corrosion protection of stainless steel bipolar plates for the PEM fuel cell

Polypyrrole coatings were prepared on stainless steel SS304 in order to study the corrosion protection provided by the conductive polymer in a simulated PEM fuel cell environment. The polypyrrole was deposited by electrochemical polymerization with 0.04, 0.07 and 0.14 g cm⁻² onto SS304 electrodes. Polarization curves, taken after immersion for 1, 3 or 24 h in 0.1 M sulphuric acid at either room temperature or 60 °C were used as an accelerated test. For short immersion times, it was found that corrosion current densities (at free corrosion potentials), diminished up to 2 orders of magnitude for samples tested at room temperature and up to 4 orders of magnitude for samples tested at 60 °C. Furthermore, at potentials in the range of the PEM fuel cell anode potential, corrosion rates also decreased up to several orders of magnitude. However, these protective properties were lost at longer times of immersion. The addition of DBSA to the polypyrrole coatings did lead to improved corrosion current densities at the free corrosion potential, however due to the loss of passivity of these samples, the corrosion rates in the potential range applicable to PEM fuel cells were either similar to or larger than bare metal. SEM was used to determine the morphology of the coatings and showed that the most homogeneous coating was obtained for 0.07 g cm⁻² polypyrrole, without the incorporation of DBSA.     

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.).     

Preparation and properties of ceramic interconnecting materials,La0.7Ca0.3CrO3−δ doped with GDC for IT-SOFCs

One of the challenges for improving the performance and cost-effectiveness of solid oxide fuel cells (SOFCs) is the development of effective interconnect materials. A widely used interconnect ceramic for SOFCs is doped lanthanum chromite. In this paper, we report a doped lanthanum chromite, La_0.7Ca_0.3CrO_3−δ (LCC) + x wt.% Gd_0.2Ce_0.8O_1.9 (GDC) (x = 0–10), with improved electrical conductivity and sintering capability. In this composite material system, LCC + GDC were prepared by an auto-ignition process and the electrical conductivity was characterized in air and in H₂. The LCC powders exhibited a better sintering ability and could reach a 94.7% relative density at 1400 °C for 4 h in air and with the increase of GDC content the relative density increased, reached 98.5% when the GDC content was up to 10 wt.%. The electrical conductivity of the samples dramatically increased with GDC addition until a maximum of 134.48 S cm⁻¹ in air at 900 °C when the materials contained 3 wt.% GDC. This is 5.5 times higher than pure LCC (24.63 S cm⁻¹). For the sample with a 1 wt.% GDC content, the conductivity in pure H₂ at 900 °C was a maximum 5.45 S cm⁻¹, which is also higher than that of pure LCC ceramics (4.72 S cm⁻¹). The average thermal expansion coefficient (TEC) increased with the increase of GDC content, ranging from 11.12 to 14.32 × 10⁻⁶ K⁻¹, the majority of which unfortunately did not match that of 8YSZ. The oxygen permeation measurement presented a negligible oxygen ionic conduction, indicating that it is still an electronically conducting ceramic. Therefore, it is a very promising interconnect material for higher performance and cost-effectiveness for SOFCs.     

A 28-W portable direct borohydride–hydrogen peroxide fuel-cell stack

A 28-W direct borohydride–hydrogen peroxide fuel-cell stack operating at 25 °C is reported for contemporary portable applications. The fuel cell operates with the peak power-density of ca. 50 mW cm⁻² at 1 V. This performance is superior to the anticipated power-density of 9 mW cm⁻² for a methanol–hydrogen peroxide fuel cell. Taking the fuel efficiency of the sodium borohydride–hydrogen peroxide fuel cell as 24.5%, its specific energy is ca. 2 kWh kg⁻¹. High power-densities can be achieved in the sodium borohydride system because of its ability to provide a high concentration of reactants to the fuel cell.     

Solid oxide fuel cells operated by internal partial oxidation reforming of iso-octane

Two types of solid oxide fuel cells (SOFCs), with thin Ce_0.85Sm_0.15O_1.925 (SDC) or 8 mol% Y₂O₃-stabilized ZrO₂ (YSZ) electrolytes, were fabricated and tested with iso-octane/air fuel mixtures. An additional Ru–CeO₂ catalyst layer, placed between the fuel stream and the anode, was needed to obtain a stable output power density without anode coking. Thermodynamic analysis and catalysis experiments showed that H₂ and CO were primary reaction products at ≈750 °C, but that these decreased and H₂O and CO₂ increased as the operating temperature dropped below ≈600 °C. Power densities for YSZ cells were 0.7 W cm⁻² at 0.7 V and 790 °C, and for SDC cells were 0.6 W cm⁻² at 0.6 V and 590 °C. Limiting current behavior was observed due to the relatively low (≈20%) H₂ content in the reformed fuel.     

Production of NaBH4 and hydrogen release with catalyst

The purpose of this study was to investigate the production of NaBH₄ as hydrogen storage material and testing its hydrogen storage capacity in presence of catalyst. Synthesis of NaBH₄ was investigated with NaH and trimethyl borate which was also produced in previous studies. Different reaction temperatures, times and reactant ratios constitute the three parameters of the production process. The best combination determined by FT-IR, XRF and XRD analyses, was found to be 1.413 (mol/mol) TMB over NaH at 250 °C for 90 min. In order to increase the NaBH₄ purity ethylene diamine was used as solvent at 75 °C. After 4 extraction and crystallization processes 85.17% NaBH₄ purity was obtained. Moreover, hydrogen content of the product NaBH₄ was measured in a system with different catalysts since catalyst efficiency is important in decreasing the water dependence of dehydrogenation. CoCl₂ catalyst proved best by taking out more hydrogen, both from the NaBH₄ structure and from water.     

Electrocatalysis of oxygen reduction on carbon supported Ru-based catalysts in a polymer electrolyte fuel cell

Powder of nanosized particles of Ru-based (Ru_x, Ru_xSe_y and Ru_xFe_ySe_z) clusters were prepared as catalysts for oxygen reduction in 0.5 M H₂SO₄ and for fuel cells prepared by pyrolysis in organic solvent. These electrocatalysts show a high uniformity of agglomerated nanometric particles. The reaction kinetics were studied using rotating disk electrodes and an enhanced catalytic activity for the powders containing selenium and iron was observed. The Ru-based electrocatalysts were used as the cathode in a single prototype PEM fuel cell, which was prepared by spray deposition of the catalyst on the surface of Nafion^® 117 membranes. The electrochemical performance of each single fuel cell was compared to that of a platinum/platinum conventional membrane electrode assembly (MEA), using hydrogen and oxygen feed streams. A maximum power density of 140 mW cm⁻², at 80 °C with 460 mA cm⁻² was obtained for the Ru_xFe_ySe_z catalysts; approximately 55% lower power density than that obtained with platinum.     

Increasing the operation temperature of polymer electrolyte membranes for fuel cells: From nanocomposites to hybrids

Among the possible systems investigated for energy production with low environmental impact, polymeric electrolyte membrane fuel cells (PEMFCs) are very promising as electrochemical power sources for application in portable technology and electric vehicles. For practical applications, operating FCs at temperatures above 100 °C is desired, both for hydrogen and methanol fuelled cells. When hydrogen is used as fuel, an increase of the cell temperature produces enhanced CO tolerance, faster reaction kinetics, easier water management and reduced heat exchanger requirement. The use of methanol instead of hydrogen as a fuel for vehicles has several practical benefits such as easy transport and storage, but the slow oxidation kinetics of methanol needs operating direct methanol fuel cells (DMFCs) at intermediate temperatures. For this reason, new membranes are required. Our strategy to achieve the goal of operating at temperatures above 120 °C is to develop organic/inorganic hybrid membranes. The first approach was the use of nanocomposite class I hybrids where nanocrystalline ceramic oxides were added to Nafion. Nanocomposite membranes showed enhanced characteristics, hence allowing their operation up to 130 °C when the cell was fuelled with hydrogen and up to 145 °C in DMFCs, reaching power densities of 350 mW cm⁻². The second approach was to prepare Class II hybrids via the formation of covalent bonds between totally aromatic polymers and inorganic clusters. The properties of such covalent hybrids can be modulated by modifying the ratio between organic and inorganic groups and the nature of the chemical components allowing to reach high and stable conductivity values up to 6.4 × 10⁻² S cm⁻¹ at 120 °C.     

Solid-state Li/LiFePO4 polymer electrolyte batteries incorporating an ionic liquid cycled at 40 °C

The cycle behaviour and rate performance of solid-state Li/LiFePO₄ polymer electrolyte batteries incorporating the N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR₁₃TFSI) room temperature ionic liquid (IL) into the P(EO)₂₀LiTFSI electrolyte and the cathode have been investigated at 40 °C. The ionic conductivity of the P(EO)₂₀LiTFSI + PYR₁₃TFSI polymer electrolyte was about 6 × 10⁻⁴ S cm⁻¹ at 40 °C for a PYR₁₃⁺/Li⁺ mole ratio of 1.73. Li/LiFePO₄ batteries retained about 86% of their initial discharge capacity (127 mAh g⁻¹) after 240 continuous cycles and showed excellent reversible cyclability with a capacity fade lower than 0.06% per cycle over about 500 cycles at various current densities. In addition, the Li/LiFePO₄ batteries exhibited some discharge capability at high currents up to 1.52 mA cm⁻² (2 C) at 40 °C which is very significant for a lithium metal-polymer electrolyte (solvent-free) battery systems. The addition of the IL to lithium metal-polymer electrolyte batteries has resulted in a very promising improvement in performance at moderate temperatures.     

Dynamic behaviour of SOFC short stacks

Electrical output behaviour obtained on solid oxide fuel cell stacks, based on planar anode supported cells (50 or 100 cm² active area) and metallic interconnects, is reported. Stacks (1–12 cells) have been operated with cathode air and anode hydrogen flows between 750 and 800 °C operating temperature. At first polarisation, an activation phase (increase in power density) is typically observed, ascribed to the cathode but not clarified. Activation may extend over days or weeks. The materials are fairly resistant to thermal cycling. A 1-cell stack cycled five times in 4 days at heating/cooling rates of 100–300 K h⁻¹, showed no accelerated degradation. In a 5-cell stack, open circuit voltage (OCV) of all cells remained constant after three full cycles (800–25 °C). Power output is little affected by air flow but markedly influenced by small fuel flow variation. Fuel utilisation reached 88% in one 5-cell stack test. Performance homogeneity between cells lay at ±4–8% for three different 5- or 6-cell stacks, but was poor for a 12-cell stack with respect to the border cells. Degradation of a 1-cell stack operated for 5500 h showed clear dependence on operating conditions (cell voltage, fuel conversion), believed to be related to anode reoxidation (Ni). A 6-cell stack (50 cm² cells) delivering 100 W_el at 790 °C (1 kW_el L⁻¹ or 0.34 W cm⁻²) went through a fuel supply interruption and a thermal cycle, with one out of the six cells slightly underperforming after these events. This cell was eventually responsible (hot spot) for stack failure.