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.     

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.     

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.     

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%.     

Proton-conducting polymer membrane comprised of a copolymer of 2-acrylamido-2-methylpropanesulfonic acid and 2-hydroxyethyl methacrylate

In order to identify a proton-conducting polymer membrane suitable for replacing Nafion^® 117 in direct methanol fuel cells (DMFC), we prepared a cross-linked copolymer of hydrophilic 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and 2-hydroxyethyl methacrylate (HEMA). Fumed silicas were also added in an attempt to increase the amount of water adsorbed by the membrane and to enhance water retention. Hydrated copolymer membranes adsorbed significantly more water than Nafion^® 117, but were no better at retaining water during drying under ambient conditions. Films composed of 4% AMPS—96% HEMA had a room temperature proton conductivity of 0.029 S cm⁻¹, which increased to 0.06 S cm⁻¹ at 80 °C.     

Electrochemical oxidation of 1-methoxy-2-propanol in direct liquid fuel cells

Some interesting features have been observed when 1-methoxy-2-propanol was studied in direct liquid fuel cells. Air flow rate ranging from 180 to 920 ml/min had no effect on performance, but the performance increased largely when the cell temperature was increased from 40, to 60, and then to 80 °C. The open circuit voltage of the cell was around 0.70 V, which was 0.08–0.33 V higher than that when methanol was used. At low air flow rates, 1-methoxy-2-propanol performed much better than methanol in the entire current density region at 60 and 80 °C. At high air flow rates, methanol performed better than 1-methoxy-2-propanol at current densities higher than 100 mA/cm², but the latter performed better than the former at current densities less than ca. 50 mA/cm². The crossover current density of 1.0 M 1-methoxy-2-propanol through a Nafion^® 112 membrane was estimated electrochemically, and it was 25.6, 60.8 and 96.0 mA/cm² at cell temperatures of 40, 60, and 80 °C, respectively, measured at 0.90 V. These numbers were much smaller than those of methanol that, e.g. had a crossover current density of 232 mA/cm² at 0.9 V and 60 °C. One problem with using 1-methoxy-2-propanol as a fuel was that the cell anode seemed to be seriously poisoned by the oxidation intermediates at anode overpotentials lower than ca. 0.2 V.     

Sulfonic-functionalized heteropolyacid–silica nanoparticles for high temperature operation of a direct methanol fuel cell

Sulfonic-functionalized heteropolyacid–SiO₂ nanoparticles were synthesized by grafting and oxidizing of a thiol-silane compound onto the heteropolyacid–SiO₂ nanoparticle surface. The surface functionalization was confirmed by solid-state NMR spectroscopy. The composite membrane containing the sulfonic-functionalized heteropolyacid–SiO₂ nanoparticles was prepared by blending with Nafion^® ionomer. TG–DTA analysis showed that the composite membrane was thermally stable up to 290 °C. The DMFC performance of the composite membrane increased the operating temperature from 80 to 200 °C. The function of the sulfonic-functionalized heteropolyacid–SiO₂ nanoparticles was to provide a proton carrier and act as a water reservoir in the composite membrane at elevated temperature. The power density was 33 mW cm⁻² at 80 °C, 39 mW cm⁻² at 160 °C and 44 mW cm⁻² at 200 °C, respectively.     

Thin yttria-stabilized zirconia electrolyte and transition layers fabricated by particle suspension spray

In order to develop high performance intermediate temperature (<800 °C) solid oxide fuel cells (SOFCs) with a lower fabrication cost, a pressurized spray process of ceramic suspensions has been established to prepare both dense yttria-stabilized zirconia (YSZ) electrolyte membranes and transition anode layers on NiO + YSZ anode supports. A single cell with 10 μm thick YSZ electrolyte on a porous anode support and ∼20 μm thick cathode layer showed peak power densities of only 212 mW cm⁻² at 700 °C and 407 mW cm⁻² for 800 °C. While a cell with 10 μm thick YSZ electrolyte and a transition layer on the porous anode support using a ultra-fine NiO + YSZ powder showed peak power densities of 346 and 837 mW cm⁻² at 700 and 800 °C, respectively. The dramatic improvement of cell performance was attributed to the much improved anode microstructure that was confirmed by both scanning electron microscopes (SEM) observation and impedance spectroscopy. The results have demonstrated that a pressurized spray coating is a suitable technique to fabricate high performance SOFCs and at lower cost.     

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.     

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.     

Performance of direct methanol fuel cell using carbon nanotube-supported Pt–Ru anode catalyst with controlled composition

The performance of a single-cell direct methanol fuel cell (DMFC) using carbon nanotube-supported Pt–Ru (Pt–Ru/CNT) as an anode catalyst has been investigated. In this study, the Pt–Ru/CNT electrocatalyst was successfully synthesized using a modified polyol approach with a controlled composition very close to 20 wt.%Pt–10 wt.%Ru, and the anode was prepared by coating Pt–Ru/CNT electrocatalyst on a wet-proof carbon cloth substrate with a metal loading of about 4 mg cm⁻². A commercial gas diffusion electrode (GDE) with a platinum black loading of 4 mg cm⁻² obtained from E-TEK was employed as the cathode. The membrane electrode assembly (MEA) was fabricated using Nafion^® 117 membrane and the single-cell DMFC was assembled with graphite endplates as current collectors. Experiments were carried out at moderate low temperatures using 1 M CH₃OH aqueous solution and pure oxygen as reactants. Excellent cell performance was observed. The tested cell significantly outperformed a comparison cell using a commercial anode coated with carbon-supported Pt–Ru (Pt–Ru/C) electrocatalyst of similar composition and loading. High conductivity of carbon nanotube, good catalyst morphology and suitable catalyst composition of the prepared Pt–Ru/CNT electrocatalyst are considered to be some of the key factors leading to enhanced cell performance.     

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.     

High power-density single-chamber fuel cells operated on methane

Single-chamber solid oxide fuel cells (SC-SOFCs) incorporating thin-film Sm_0.15Ce_0.85O_1.925 (SDC) as the electrolyte, thick Ni + SDC as the (supporting) anode and SDC + BSCF (Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ) as the cathode were operated in a mixture of methane, oxygen and helium at furnace temperatures of 500–650 °C. Because of the exothermic nature of the oxidation reactions that occur at the anode, the cell temperature was as much as 150 °C greater than the furnace temperature. Overall, the open circuit voltage was only slightly sensitive to temperature and gas composition, varying from ∼0.70 to ∼0.78 V over the range of conditions explored. In contrast, the power density strongly increased with temperature and broadly peaked at a methane to oxygen ratio of ∼1:1. At a furnace temperature of 650 °C (cell temperature ∼790 °C), a peak power density of 760 mW cm⁻² was attained using a mixed gas with methane, oxygen and helium flow rates of 87, 80 and 320 mL min⁻¹ [STP], respectively. This level of power output is the highest reported in the literature for single chamber fuel cells and reflects the exceptionally high activity of the BSCF cathode for oxygen electro-reduction and its low activity for methane oxidation.     

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.     

High temperature and pressure alkaline electrolysis

This paper describes experimental work involving the direct-current electrolysis of highly concentrated potassium hydroxide solutions at high temperatures (up to 400 °C) and under various pressures. A high-temperature alkaline electrolysis cell resistant to chemical attack from the highly corrosive electrolyte solution and capable of high-pressure operation was designed and tested. The cell was constructed with a Monel^® alloy housing and cathode, while various anode materials were compared. The anode materials tested included nickel, Monel alloy, lithiated nickel, and cobalt-plated nickel. The advantages of operating an alkaline electrolysis cell at high temperatures include increasing the ionic conductivity of the electrolyte and enhancing the rates of electrochemical reactions at the electrode surfaces. Cell operation with increasing steam partial pressure over the solution is also shown to enhance cell performance. The prudent selection of anode material also impacts the required terminal potential for a given current density, and consequently the cell's electric power efficiency. The best cell performance was achieved using a cobalt-plated nickel anode at a temperature of 400 °C and a steam partial pressure of 8.7 MPa.     

Tantalum oxide–ruthenium oxide hybrid(R) capacitors

A hybrid capacitor consisting of porous tantalum oxide anode electrode and ruthenium oxide cathode electrode was examined and characterized. The capacitor has a capacitance of 35 mF and an internal resistance of 45 mΩ. It was found that the capacitance was insensitive to current density up to 110 mA/cm², and temperature ranging from −70 to 50 °C. During dc charge and discharge cycles, the potential of the cathode electrode was within the electrochemical stability window. However, a sudden voltage-jump as high as 7.5 V could occur at the cathode electrode during a short circuit discharge. A simple model was established to describe the transient behavior of cathode and anode electrodes. It was found that the voltage-jump was proportional to the ratio of the internal resistance of the cathode electrode to the total resistance of the capacitor. The resistance distribution inside the capacitor was also determined to be 47, 28, and 25% from the cathode, anode, and electrolyte, respectively.     

Progress in the development of a high-power,direct ethylene glycol fuel cell (DEGFC)

We recently reported on a high-power nanoporous proton-conducting membrane (NP-PCM)-based direct methanol fuel cell (DMFC) operated with triflic acid. However, accompanying the advantages of methanol as a fuel, such as low cost and ease of handling and storage, are several pronounced disadvantages: toxicity, high flammability, low boiling point (65 °C) and the strong tendency to pass through the polymer-exchange membrane (high crossover). The focus of this work is the development of a high-power direct ethylene glycol fuel cell (DEGFC) based on the NP-PCM. Ethylene glycol (EG) has a theoretical capacity 17% higher than that of methanol in terms of Ah ml⁻¹ (4.8 and 4, respectively); this is especially important for portable electronic devices. It is also a safer (bp 198 °C) fuel for direct-oxidation fuel cell (DOFC) applications. Maximum power densities of 320 mW cm⁻² (at 0.32 V) at 130 °C have been achieved in the DEGFC fed with 0.72 M ethylene glycol in 1.7 M triflic acid at 3 atm at the anode and with dry air at 3.7 atm at the cathode. The cell platinum loading was 4 mg Pt cm⁻² on each electrode. The overpotentials at the cathodes and at the anodes of the DEGFC and DMFC were measured, compared and discussed.     

Sulfated zirconia–Nafion composite membranes for higher temperature direct methanol fuel cells

A sulfated zirconia/Nafion^®115 nanocomposite membrane is prepared by ion-exchange of zirconium ions into the Nafion followed by precipitation of sulphated ZrO₂ by treatment in 5 M H₂SO₄ at 80 °C. The incorporation of sulfated zirconia increases water uptake by the Nafion membrane, and importantly, more water is absorbed than by an unmodified membrane at high temperatures. The proton conductivity of the composite membrane is evaluated and compared with that of an unmodified Nafion^®115 membrane. The nanocomposite membrane experiences a smaller decrease in proton conductivity than the Nafion^®115 membrane at high temperatures.     

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.     

Fabrication and characterization of micro tubular SOFCs for operation in the intermediate temperature

Tubular SOFC systems appear to be well-suited to accommodate repeated cycling under rapid changes in electrical load and in cell operating temperatures. Our goal is to develop innovative processing method to fabricate new micro tubular SOFCs with sub-millimeter diameter and its stack module which enable to generate high volumetric power density. In this study, micro tubular SOFCs under 1 mm diameter have been successfully fabricated and tested in the intermediate temperature region (550 °C or under). The cell consists of NiO–Gd doped ceria (GDC) as an anode (support tube), GDC as an electrolyte and (La, Sr)(Fe, Co)O₃ (LSCF)–GDC as a cathode. The single tubular cell with 0.8 mm diameter and 12 mm length generated over 70 mW at 550 °C with H₂ fuel, which indicates that the cell generated over 0.3 W cm⁻² at 550 °C.