Development of a PEM stack and performance analysis including the effects of water content in the membrane and cooling method

For the use of proton exchange membrane (PEM) fuel cell systems to become widespread, the components required to build one should be minimized. Because a PEM fuel cell has a limited operating temperature range, it requires some kind of cooling method. In this study, different cooling methods were investigated experimentally. A PEM fuel cell stack with an active area of 100 cm² and 8 cells in series was developed and used in this research. When 50% relative humidity inlet gases were supplied (at 15 A of current discharge and 70 °C), cell temperatures at the center increased from around 60 °C to 85 °C, and cell voltage dropped from 4.8 V to 3.2 V because of membrane drying (insufficient cooling). When fully hydrated inlet gases (100% relative humidity) were supplied to the PEM stack at the same test conditions, the cell temperature remained around 65 °C, and stack voltage remained around 5.7 V at 15 A of current discharge. Fully hydrated inlet gases play a positive role both for water transport (when the proton moves from the anode to the cathode) and to maintain the fuel cell stack temperature to prevent stack drying.     

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 of high performance carbon composite catalyst for oxygen reduction reaction in PEM Proton Exchange Membrane fuel cells

Highly active and stable carbon composite catalysts for oxygen reduction in PEM fuel cells were developed through the high-temperature pyrolysis of Co–Fe–N chelate complex, followed by the chemical post-treatment. A metal-free carbon catalyst was used as the support. The carbon composite catalyst showed an onset potential for oxygen reduction as high as 0.87 V (NHE) in H₂SO₄ solution, and generated less than 1% H₂O₂. The PEM fuel cell exhibited a current density as high as 0.27 A cm⁻² at 0.6 V and 2.3 A cm⁻² at 0.2 V for a catalyst loading of 6.0 mg cm⁻². No significant performance degradation was observed over 480 h of continuous fuel cell operation with 2 mg cm⁻² catalyst under a load of 200 mA cm⁻² as evidenced by a resulting cell voltage of 0.32 V with a voltage decay rate of 80 μV h⁻¹. Materials characterization studies indicated that the metal–nitrogen chelate complexes decompose at high pyrolysis temperatures above 800 °C, resulting in the formation of the metallic species. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface doped with nitrogen groups is catalytically active for oxygen reduction.     

Ageing of anode-supported solid oxide fuel cell stacks including thermal cycling,and expansion behaviour of MgO–NiO anodes

This paper reports on medium term tests of anode-supported five-cell short stacks, as well as on some separate anode development. Two stacks were operated under steady-state conditions: one with unprotected metal interconnects, H₂ fuel and 0.35 A cm⁻² (40% fuel utilisation) polarisation current showed an average cell voltage degradation of 56 mV per 1000 h for 2750 h; one with coated metal interconnects, synthetic reformate fuel and 0.5 A cm⁻² (60% fuel utilisation) polarisation current showed an averaged cell voltage degradation slope of 6.6 mV per 1000 h for 800 h before a power cut prematurely interrupted the test. A third stack was subjected to 13 complete thermal cycles over 1000 h, average cell voltage degradation was evaluated to −2 mV per cycle for operation at 0.3 A cm⁻², open circuit voltage (OCV) remained stable, whereas area specific resistance (ASR) increase amounted on average to 0.008 Ω cm² per cycle.     

Performance of laboratory polymer electrolyte membrane hydrogen generator with sputtered iridium oxide anode

The continuous improvement of the anode materials constitutes a major challenge for the future commercial use of polymer electrolyte membranes (PEM) electrolyzers for hydrogen production. In accordance to this direction, iridium/titanium films deposited directly on carbon substrates via magnetron sputtering are operated as electrodes for the oxygen evolution reaction interfaced with Nafion 115 electrolyte in a laboratory single cell PEM hydrogen generator. The anode with 0.2 mg cm⁻² Ir catalyst loading was electrochemically activated by cycling its potential value between 0 and 1.2 V (vs. RHE). The water electrolysis cell was operated at 90 °C with current density 1 A cm⁻² at 1.51 V without the ohmic contribution. The corresponding current density per mgr of Ir catalyst is 5 A mg⁻¹. The achieved high efficiency is combined with sufficient electrode stability since the oxidation of the carbon substrate during the anodic polarization is almost negligible.     

Hydrogen production by advanced proton exchange membrane (PEM) water electrolysers—Reduced energy consumption by improved electrocatalysis

Proton exchange membrane (PEM) water electrolysis systems offers several advantages over traditional technologies including greater energy efficiency, higher production rates, and more compact design. Normally in these systems, the anode has the largest overpotential at typical operating current densities. By development of the electrocatalytic material used for the oxygen evolving electrode, great improvements in efficiency can be made. We find that using cyclic voltammetry and steady state polarisation analysis, enables us to separate the effects of true specific electrocatalytic activity and active surface area. Understanding these two factors is critical in developing better electrocatalytic materials in order to further improve the performance of PEM water electrolysis cells. The high current performance of a PEM water electrolysis cell using these oxides as the anode electrocatalyst has also been examined by steady state polarisation measurements and electrochemical impedance spectroscopy. Overall the best cell voltage obtained is 1.567 V at 1 A cm⁻² and 80 °C was achieved when using Nafion 115 as the electrolyte membrane.     

Preparation and performance characterization of the Fe–Ni/ScSZ cermet anode for oxidation of ethanol fuel in SOFCs

An anodic cermet of Fe–Ni alloy and scandia stabilized zirconia (ScSZ) has been investigated for a solid oxide fuel cell (SOFC) running on ethanol fuel. Composite anodes having alloy compositions of 0, 12.5, 25, 37.5, 50 and 100 wt.% Ni were exposed to ethanol stream at 700 °C for 12 h to demonstrate that carbon formation is greatly suppressed on the Fe–Ni alloys compared to that of pure Ni. Then the short-term stability for the cells with the Ni/ScSZ and Fe_0.5Ni_0.5/ScSZ anodes in ethanol stream at 700 °C was checked over a relative long period of operation. Open circuit voltages (OCVs) increased from 1.03 to 1.1 V, and power densities increased from 120 to 460 mW cm² as the operating temperature of a SOFC with Fe_0.5Ni_0.5/ScSZ anode was increased from 700 to 850 °C in ethanol stream. Electrochemical impedance spectra (EIS) illustrated that the cell with Ni/ScSZ anode exhibits slightly less total impedance than that observed for the cell with Fe_0.5Ni_0.5/ScSZ anode. The performance of a fuel cell made with the Ni/ScSZ and Fe_0.5Ni_0.5/ScSZ anodes was tested in ethanol stream for 48 h and showed a significant decrease in polarization resistance with time. Impedance spectra of similar fuel cells suggest that small carbon deposits are formed with time and that the decrease in polarization resistance is due to enhanced electronic conductivity in the anode.     

Effects of anode air bleeding on the performance of CO-poisoned proton-exchange membrane fuel cells

In the present work, the dynamic behavior of a PEM fuel cell under CO-poisoning and the effects of air bleeding on the recovery ratio are reported. Pt-Ru catalyst is used as the anode in a single cell and the hydrogen is pre-mixed with 53 ppm of CO as the fuel. The result indicates that even using a CO-tolerant catalyst, CO-poisoning cannot be avoided with the operating conditions in our study. About 80% of the output current is lost within 20 min. Upon anode air bleeding with 5% air, 90% of the current is recovered within 1 min. Higher air bleeding ratio only results in minor improvement of the cell performance. We have developed a transient model to estimate the current reduction due to CO-poisoning and to evaluate the amount of air bleeding needed for a given recovery ratio. A long-term durability test has also been conducted using simulated reformatted gas, in which 1% O₂ is injected into the fuel stream. After more than 3000 h, the cell voltage degradation is less than 3%.     

3D modeling of anode-supported planar SOFC with internal reforming of methane

Deposition of carbon on conventional anode catalysts and formation of large temperature gradients along the cell are the main barriers for implementing internal reforming in solid oxide fuel cell (SOFC) systems. Mathematical modeling is an essential tool to evaluate the effectiveness of the strategies to overcome these problems. In the present work, a three-dimensional model for a planar internal reforming SOFC is developed. A co-flow system with no pre-reforming, methane fuel utilization of 75%, voltage of 0.7 V and current density of 0.65 A cm⁻² was used as the base case. The distributions of both temperature and gas composition through the gas channels and PEN (positive electrode/electrolyte/negative electrode) structure were studied using the developed model. The results identified the most susceptible areas for carbon formation and thermal stress according to the methane to steam ratio and temperature gradients, respectively. The effects of changing the inlet gas composition through recycling were also investigated. Recycling of the anode exhaust gas, at an optimum level of 60% for the conditions studied, has the potential to significantly decrease the temperature gradients and reduce the carbon formation at the anode, while maintaining a high current density.     

Experimental study of commercial size proton exchange membrane fuel cell performance

Commercial sized (16 × 16 cm² active surface area) proton exchange membrane (PEM) fuel cells with serpentine flow chambers are fabricated. The GORE-TEX® PRIMEA 5621 was used with a 35-μm-thick PEM with an anode catalyst layer with 0.45 mg cm⁻² Pt and cathode catalyst layer with 0.6 mg cm⁻² Pt and Ru or GORE-TEX® PRIMEA 57 was used with an 18-μm-thick PEM with an anode catalyst layer at 0.2 mg cm⁻² Pt and cathode catalyst layer at 0.4 mg cm⁻² of Pt and Ru. At the specified cell and humidification temperatures, the thin PRIMEA 57 membrane yields better cell performance than the thick PRIMEA 5621 membrane, since hydration of the former is more easily maintained with the limited amount of produced water. Sufficient humidification at both the cathode and anode sides is essential to achieve high cell performance with a thick membrane, like the PRIMEA 5621. The optimal cell temperature to produce the best cell performance with PRIMEA 5621 is close to the humidification temperature. For PRIMEA 57, however, optimal cell temperature exceeds the humidification temperature.     

An investigation into TiN-coated 316L stainless steel as a bipolar plate material for PEM fuel cells

In order to reduce the cost, weight and volume of the bipolar plates, considerable attention is being paid to developing metallic bipolar plates to replace the non-porous graphite bipolar plates that are in current use. However, metals are prone to corrosion in the proton exchange membrane (PEM) fuel cell environments, which decreases the ionic conductivity of the membrane and lowers the overall performance of the fuel cells. In this study, TiN was coated on SS316L using a physical vapor deposition (PVD) technology (plasma enhanced reactive evaporation) to increase the corrosion resistance of the base SS316L. X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical methods were used to characterize the TiN-coated SS316L. XRD showed that the TiN coating had a face-centered-cubic (fcc) structure. Potentiodynamic tests and electrochemical impedance tests showed that the corrosion resistance of SS316L was significantly increased in 0.5 M H₂SO₄ at 70 °C by coating with TiN. In order to investigate the suitability of these coated materials as cathodes and anodes in a PEMFC, potentiostatic tests were conducted under both simulated cathode and anode conditions. The simulated anode environment was −0.1 V versus SCE purged with H₂ and the simulated cathode environment was 0.6 V versus SCE purged with O₂. In the simulated anode conditions, the corrosion current of TiN-coated SS316L is −4 × 10⁻⁵ A cm⁻², which is lower than that of the uncoated SS316L (about −1 × 10⁻⁶ A cm⁻²). In the simulated cathode conditions, the corrosion current of TiN-coated SS316L is increased to 2.5 × 10⁻⁵ A cm⁻², which is higher than that of the uncoated SS316L (about 5 × 10⁻⁶ A cm⁻²). This is because pitting corrosion had taken place on the TiN-coated specimen.     

Microstructure and electrochemical characterization of solid oxide fuel cells fabricated by co-tape casting

A co-tape casting technique was applied to fabricate electrolyte/anode for solid oxide fuel cells. YSZ and NiO-YSZ powders are raw materials for electrolyte and anode, respectively. Through adjusting the Polyvinyl Butyral (PVB) amount in slurry, the co-sintering temperature for electrolyte/anode could be dropped. After being co-sintered at 1400 °C for 5 h, the half-cells with dense electrolytes and large three phase boundaries were obtained. The improved unit cell exhibited a maximum power density of 589 mW cm⁻² at 800 °C. At the voltage of 0.7 V, the current densities of the cell reached 667 mA cm⁻². When the electrolyte and the anode were cast within one step and sintered together at 1250 °C for 5 h and the thickness of electrolyte was controlled exactly at 20 μm, the open-circuit voltage (OCV) of the cell could reach 1.11 V at 800 °C and the maximum power densities were 739, 950 and 1222 mW cm⁻² at 750, 800 and 850 °C, respectively, with H₂ as the fuel under a flow rate of 50 sccm and the cathode exposed to the stationary air. Under the voltage of 0.7 V, the current densities of cell were 875, 1126 and 1501 mA cm⁻², respectively. These are attributed to the large anode three phase boundaries and uniform electrolyte obtained under the lower sintering temperature. The electrochemical characteristics of the cells were investigated and discussed.     

Y-doped SrTiO3 based sulfur tolerant anode for solid oxide fuel cells

A solid oxide fuel cell (SOFC) anode with high sulfur tolerance was developed starting from a Y-doped SrTiO₃ (SYTO)-yttria stabilized zirconia (YSZ) porous electrode backbone, and infiltrated with nano-sized catalytic ceria and Ru. The size of the infiltrated particles on the SYTO-YSZ pore walls was 30–200 nm, and both infiltrated materials improved the performance of the SYTO-YSZ anode significantly. The infiltrated ceria covered most of the surface of the SYTO-YSZ pore walls, while Ru was dispersed as individual nano-particles. The performance and sulfur tolerance of a cathode supported cell with ceria- and Ru-infiltrated SYTO-YSZ anode was examined in humidified H₂ mixed with H₂S. The anode showed high sulfur tolerance in 10–40 ppm H₂S, and the cell exhibited a constant maximum power density 470 mW cm⁻² at 10 ppm H₂S, at 1073 K. At an applied current density 0.5 A cm⁻², the addition of 10 ppm H₂S to the H₂ fuel dropped the cell voltage slightly, from 0.79 to 0.78 V, but completely recovered quickly after the H₂S was stopped. The ceria- and Ru-infiltrated SYTO-YSZ anode showed much higher sulfur tolerance than conventional Ni-YSZ anodes.     

Evaluating the impact of enhanced anode CO tolerance on performance of proton-exchange-membrane fuel cell systems fueled by liquid hydrocarbons

Recent advances in anode electrocatalysts for low-temperature PEM fuel cells are increasing tolerance for CO in the H₂-rich anode stream. This study explores the impact of potential improvements in CO-tolerant electrocatalysts on the system efficiency of low-temperature Nafion-based PEM fuel cell systems operating in conjunction with a hydrocarbon autothermal reformer and a preferential CO oxidation (PROx) reactor for CO clean-up. The incomplete H₂ clean-up by PROx reactors with partial CO removal can present conditions where CO-tolerant anode electrocatalysts significantly improve overall system efficiency. Empirical fuel cell performance models were based upon voltage-current characteristics from single-cell MEA tests at varying CO concentrations with new Pt-Mo alloy reformate-tolerant electrocatalysts tested in conjunction with this study. A system-level model for a liquid-fueled PEM fuel cell system with a 5 kW full power output is used to study the trade-offs between the improved performance with decreased CO concentration and the increased penalties from the air supply to the PROx reactor and associated reduction in H₂ partial pressures to the anode. As CO tolerance is increased over current state-of-the-art Pt alloy catalysts, system efficiencies improve due primarily to higher fuel cell voltages and to a lesser extent to reductions in parasitic loads. Furthermore, increasing CO tolerance of anode electrocatalysts allows for the potential for reduced system costs with minimal efficiency penalty by reducing PROx reactor size through reduced CO conversion requirements.     

Scale-up of a high temperature polymer electrolyte membrane fuel cell based on polybenzimidazole

A high temperature PEM fuel cell stack with a total active area 150 cm² has been studied. The PEM technology is based on a polybenzimidazole (PBI) membrane. Cast from a PBI polymer synthesised in our lab, the performance of a three-cell stack was analysed in static and dynamic modes. In static mode, operating at high constant oxygen flow rate (QO₂>1105 ml O₂/min) produces a small decrease on the stack performance. High constant oxygen stoichiometry (λO₂>3) does not produce a decrease on the performance of the stack. There are not differences between operating at constant flow rate of oxygen and constant stoichiometry of oxygen in the stack performance. The effect of operating at high temperature with a pressurization system and operating at higher temperatures are beneficial since the performance of the fuel cell is enhanced. A large shut-down stage produces important performance losses due to the loss of catalyst activity and the loss of membrane conductivity. After 150 h of operation at 0.2 A cm⁻², it is observed a very high voltage drop. The phosphoric acid leached from the stack was also evaluated and did not exceed 2% (w/w). This fact suggests that the main degradation mechanism of a fuel cell stack based on polybenzimidazole is not the electrolyte loss. In dynamic test mode, it was observed a rapid response of power and current output even at the lower step-time (10 s). In the static mode at 125 °C and 1 atm, the stack reached a power density peak of 0.29 W cm⁻² (43.5 W) at 1 V.     

Direct hybrid glucose-oxygen enzymatic fuel cell based on tetrathiafulvalene-tetracyanoquinodimethane charge transfer complex as anodic mediator

TTF-TCNQ has been used for the first time as a mediator in a direct glucose fuel cell operating on gas-phase oxygen. It has been shown that TTF-TCNQ forms highly irregular porous structure, which emphasizes the importance of optimization of mass transport and kinetic resistance in the catalyst layer. Kinetics resistance can be optimized by variation of the mediator and/or enzyme loading, while mass transport resistance mainly by the variation of other structural parameters such as electrode thickness. The optimized anode reached limiting current densities of nearly 400 μA cm⁻² in presence of 5 mM glucose under rotation. The enzymatic fuel cell exhibited unexpectedly high OCV values (up to 0.99 V), which were tentatively ascribed to different pH conditions at the anode and the cathode. OCV was influenced by glucose crossover and was decreasing with an increase of glucose concentration or flow rate. Although the performance of the fuel cell is limited by the enzymatic anode, the long-term stability of the fuel cell is mainly influenced by the Pt cathode, while the enzymatic anode has higher stability. The fuel cell delivered power densities up to 120 μW cm⁻² in presence of 5 mM glucose, depending on the glucose flow rate.     

Cathode contact optimization and performance evaluation of intermediate temperature-operating solid oxide fuel cell stacks based on anode-supported planar cells with LaNi0.6Fe0.4O3 cathode

This paper reports the development of intermediate temperature-operating solid oxide fuel cell stacks using anode-supported planar cells with LaNi_0.6Fe_0.4O₃ (LNF)cathode. We developed metallic separators with radial gas flow channels and an anode seal structure. To achieve good power-generating characteristics, we propose two cathode contact methods. According to a performance evaluation at 800 °C, power density of 0.5 W cm⁻² is obtained at the current density of 1.0 A cm⁻² when operating with a sufficient fuel amount, and power conversion efficiency of over 50% LHV is obtained at the current density of more than 0.2 A cm⁻² when operating at a high fuel utilization rate.     

Effects of Nafion loading in anode catalyst inks on the miniature direct formic acid fuel cell

Nafion, within the anode and cathode catalyst layers, plays a large role in the performance of fuel cells, especially during the operation of the direct formic acid fuel cell (DFAFC). Nafion affects the proton transfer in the catalyst layers of the fuel cell, and studies presented here show the effects of three different Nafion loadings, 10 wt.%, 30 wt.% and 50 wt.%. Short term voltage-current measurements using the three different loadings show that 30 wt.% Nafion loading in the anode shows the best performance in the miniature, passive DFAFC. Nafion also serves as a binder to help hold the catalyst nanoparticles onto the proton exchange membrane (PEM). The DFAFC anode temporarily needs to be regenerated by raising the anode potential to around 0.8 V vs. RHE to oxidize CO bound to the surface, but the Pourbaix diagram predicts that Pd will corrode at these potentials. We found that an anode loading of 30 wt.% Nafion showed the best stability, of the three Nafion loadings chosen, for reducing the amount of loss of electrochemically active area due to high regeneration potentials. Only 58% of the area was lost after 600 potential cycles in formic acid compared to 96 and 99% for 10 wt.% and 50 wt.% loadings, respectively. Lastly we present cyclic voltammetry data that suggest that the Nafion adds to the production of CO during oxidation of formic acid for 12 h at 0.3 V vs. RHE. The resulting data showed that an increase in CO coverage was observed with increasing Nafion content in the anode catalyst layer.     

High performance metal-supported solid oxide fuel cells fabricated by thermal spray

Metal-supported solid oxide fuel cells (SOFCs) have been fabricated and characterized in this work. The cells consist of porous NiO-SDC as anode, thin SDC as electrolyte, and SSCo as cathode on porous stainless steel substrate. The anode and electrolyte layers were consecutively deposited onto porous metal substrate by thermal spray, using standard industrial thermal spray equipment, operated in an open-air atmosphere. The cathode materials were applied to the as-sprayed half-cells by screen-printing and heat-treated at 800 °C for 2 h. The cell components and performance were examined by scanning electron microscopy (SEM), X-ray diffraction, leakage test, ac impedance and electrochemical polarization at temperatures between 500 and 700 °C. The half-inch button cells exhibit a maximum power density in excess of 0.50 W cm⁻² at 600 °C and 0.92 W cm⁻² at 700 °C operated with humidified hydrogen fuel, respectively. The half-inch button cell was run at 0.5 A cm⁻² at 603 °C for 100 h. The cell voltage decreased from 0.701 to 0.698 V, giving a cell degradation rate of 4.3% kh⁻¹. Impedance analysis indicated that the cell degradation included 4.5% contribution from ohmic loss and 1.4% contribution from electrode polarization. The 5 cm × 5 cm cells were also fabricated under the same conditions and showed a maximum power density of 0.26 W cm⁻² at 600 °C and 0.56 W cm⁻² at 700 °C with dry hydrogen as fuel, respectively. The impedance analysis showed that the ohmic resistance of the cells was the major polarization loss for all the cells, while both ohmic and electrode polarizations were significantly increased when the operating temperature decreased from 700 to 500 °C. This work demonstrated the feasibility for the fabrication of metal-supported SOFCs with relatively high performance using industrially available deposition techniques. Further optimization of the metal support, electrode materials and microstructure, and deposition process is ongoing.     

Experimental analysis of spatio-temporal behavior of anodic dead-end mode operated polymer electrolyte fuel cell

During the anodic dead-end mode operation of fuel cells, the inert gases (nitrogen and water) present in the cathode side gas channel permeate to the anode side and accumulate in the anode gas channel. The inert gas accumulation in the anode decreases the fuel cell performance by impeding the access of hydrogen to the catalyst. The performance of fuel cell under potentiostatic dead-end mode operation is shown to have three distinct regions viz. time lag region, transient current region and a steady state current region. A current distribution measurement setup is used to capture the evolution of the current distribution as a function of time and space. Co- and counter-flow operations of dead-end mode confirm the propagation of inert gas from the dead-end of anode channel to the inlet of anode. Experiments with different oxidants, oxygen and air, under dead-end mode confirm that nitrogen which permeates from cathode to anode causes the performance drop of the fuel cell. For different starting current densities of 0.15 A cm⁻², 0.3 A cm⁻² and 0.6 A cm⁻² the inert gas occupies 35%, 45% and 57%, respectively of anode channel volume at the end of 60 min of dead-end mode operation.