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.     

The effect of low concentrations of CO on H2 adsorption and activation on Pt/C. Part 1: In the absence of humidity

The presence of CO in the H₂-rich gas used as fuel for hydrogen fuel cells has a detrimental effect on PEMFC performance and durability at conventional operating conditions. This paper reports on an investigation of the effect of CO on H₂ activation on a fuel cell Pt/C catalyst close to typical PEMFC operating conditions using H₂-D₂ exchange as a probe reaction and to measure hydrogen surface coverage. While normally limited by equilibrium in the absence of impurities on Pt at typical fuel cell operating temperatures, the presence of ppm concentrations of CO increased the apparent activation energy (E_a) of H₂-D₂ exchange reaction (representing H₂ activation) from approximately 4.5-5.3 kcal mole⁻¹ (Bernasek and Somorjai (1975) [24], Montano et al. (2006) [25]) (in the absence of CO) to 19.3-19.7 kcal mole⁻¹ (in the presence of 10-70 ppm CO), similar to those reported by Montano et al. (2006) [25]. Calculations based on measurements indicate a CO surface coverage of approximately 0.55 ML at 80 °C in H₂ with 70 ppm CO, which coincide very well with surface science results reported by Longwitz et al. (2004) [5]. In addition, surface coverages of hydrogen in the presence of CO suggest a limiting effect on hydrogen spillover by CO. Regeneration of Pt/C at 80 °C in H₂ after CO exposure showed only a partial recovery of Pt sites. However, enough CO-free Pt sites existed to easily achieve equilibrium conversion for H₂-D₂ exchange. This paper establishes the baseline and methodology for a series of future studies where the additional effects of Nafion and humidity will be investigated.     

The effect of H2S on the performance of Ni-YSZ anodes in solid oxide fuel cells

Biomass-derived fuel, e.g. biogas, is a potential fuel for solid oxide fuel cells (SOFCs). At operating temperature (∼850 °C) reforming of the carbon-containing biogas takes place over the Ni-containing anode. However, impurities in the biogas, e.g. H₂S, can poison both the reforming and the electrochemical activity of the anode.Tests of single anode-supported planar SOFCs were carried out in the presence of H₂S under current load at 850 °C. The cell voltage dropped as we periodically added 2-100 ppm H₂S to an H₂-containing fuel in 24 h intervals, but it regenerated to the initial value after we turned off the H₂S. Evaluation of the changes of the cell voltage suggests that saturation coverage was reached at approximately 40 ppm H₂S. A front-like movement of S-poisoning over the anode was seen by monitoring the in-plane voltage in the anode. Furthermore, impedance spectra showed that mainly the polarization resistance increased when adding H₂S. These changes in resistance were found to happen at 1212 Hz, which is related to reactions at the anode-electrolyte interface. These findings can be used to identify S-related effects on the performance, when an SOFC is fuelled with biogas or other fuels with H₂S impurities and thus help in the development of more sulfur tolerant SOFCs.     

Effect of sulfur contaminants on MCFC performance

Molten carbonate fuel cells (MCFC) used as carbon dioxide separation units in integrated fuel cell and conventional power generation can potentially reduce carbon emission from fossil fuel power production. The MCFC can utilize CO₂ in combustion flue gas at the cathode as oxidant and concentrate it at the anode through the cell reaction and thereby simplifying capture and storage. However, combustion flue gas often contains sulfur dioxide which, if entering the cathode, causes performance degradation by corrosion and by poisoning of the fuel cell. The effect of contaminating an MCFC with low concentrations of both SO₂ at the cathode and H₂S at the anode was studied. The poisoning mechanism of SO₂ is believed to be that of sulfur transfer through the electrolyte and formation of H₂S at the anode. By using a small button cell setup in which the anode and cathode behavior can be studied separately, the anodic poisoning from SO₂ in oxidant gas can be directly compared to that of H₂S in fuel gas. Measurements were performed with SO₂ added to oxidant gas in concentrations up to 24 ppm, both for short-term (90 min) and for long-term (100 h) contaminant exposure. The poisoning effect of H₂S was studied for gas compositions with high- and low concentration of H₂ in fuel gas. The H₂S was added to the fuel gas stream in concentrations of 1, 2 and 4 ppm. Results show that the effect of SO₂ in oxidant gas was significant after 100 h exposure with 8 ppm, and for short-term exposure above 12 ppm. The effect of SO₂ was also seen on the anode side, supporting the theory of a sulfur transfer mechanism and H₂S poisoning. The effect on anode polarization of H₂S in fuel gas was equivalent to that of SO₂ in oxidant gas.     

Tolerance tests of H2S-laden biogas fuel on solid oxide fuel cells

Biogas is a variable mixture of methane, carbon dioxide and other gases. It is a renewable resource which comes from numerous sources of plant and animal matter. Ni-YSZ anode-supported solid oxide fuel cell (SOFC) can directly use clean synthesized biogas as fuel. However, trace impurities, such as H₂S, Cl₂ and F₂ in real biogas can cause degradation in cell performance. In this research, both uncoated and coated Ni-YSZ anode-supported cells were exposed to three different compositions of synthesized biogases (syn-biogas) with 20 ppm H₂S under a constant current load at 750-850 °C and their performance was evaluated periodically using standard electrochemical methods. Postmortem analysis of the SOFC anode was performed using X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The results show that H₂S causes severe electrochemical degradation of the cell when operating on biogas, leading to both complete electrochemical and mechanical failure. The Ni-CeO₂ coated cell showed excellent stability during CH₄ reforming and some tolerance to H₂S contamination.     

The study of Au/MoS2 anode catalyst for solid oxide fuel cell (SOFC) using H2S-containing syngas fuel

Au/MoS₂ is a promising anode catalyst for conversion of all components of H₂S-containing syngas in solid oxide fuel cell (SOFC). MoS₂-supported nano-Au particles have catalytic activity for conversion of CO when syngas is used as fuel in SOFC systems, thus preventing poisoning of MoS₂ active sites by CO. In contrast to use of MoS₂ as anode catalyst, performance of Au/MoS₂ anode catalyst improves when CO is present in the feed. Current density over 600 mA cm⁻² and maximum power density over 70 mW cm⁻² were obtained at 900 °C, showing that Au/MoS₂ could be potentially used as sulfur-tolerant catalyst in fuel cell applications.     

Durability of solid oxide fuel cells using sulfur containing fuels

The usability of hydrogen and also carbon containing fuels is one of the important advantages of solid oxide fuel cells (SOFCs), which opens the possibility to use fuels derived from conventional sources such as natural gas and from renewable sources such as biogas. Impurities like sulfur compounds are critical in this respect. State-of-the-art Ni/YSZ SOFC anodes suffer from being rather sensitive towards sulfur impurities. In the current study, anode supported SOFCs with Ni/YSZ or Ni/ScYSZ anodes were exposed to H₂S in the ppm range both for short periods of 24 h and for a few hundred hours. In a fuel containing significant shares of methane, the reforming activities of the Ni/YSZ and Ni/ScYSZ anodes were severely poisoned already at low H₂S concentrations of ∼2 ppm H₂S. The poisoning effect on the cell voltage was reversible only to a certain degree after exposure of 500 h in the state-of-the-art cell, due to a loss of percolation of Ni particles in the Ni/YSZ anode layers closest to the electrolyte. Using SOFCs with Ni/ScYSZ anodes improved the H₂S tolerance considerably, even at larger H₂S concentrations of 10 and 20 ppm over a few hundred hours.     

The effect of internal air bleed on CO poisoning in a proton exchange membrane fuel cell

It is found that carbon monoxide (CO) poisoning could be mitigated by increasing only cathode backpressure for a proton exchange membrane fuel cell (PEMFC) with ultra-thin membranes (≤25 μm). This mitigation can be explained by a heterogeneous oxidation of CO on a Pt-Ru/C anode by the permeated O₂ which is known as “internal air bleed” in his paper. A steady-state model which accounts for this internal air bleed has been developed to model the Pt-Ru/C anode polarization data when 50 ppm CO in H₂ is used as anode feed gas. The modeling results show that the mitigation of CO poisoning by the internal air bleed even exists at ambient conditions for a PEMFC with an ultra-thin membrane. Therefore, the effect of internal air bleed must be considered for modeling fuel cell performance or anode polarization data if an ultra-thin membrane and a low level of CO concentration are used for a Pt-Ru/C anode. An empirical relationship between the amount of internal air bleed used for the mitigation of CO poisoning and the fraction of free Pt sites is provided to facilitate the inclusion of an internal air bleed term in the modeling of anode polarization and the fuel cell performance.     

The effects of hydrogen sulfide on the polymer electrolyte membrane fuel cell anode catalyst: H2S-Pt/C interaction products

The performance of a polymer electrolyte membrane fuel cell (PEMFC) operating on a simulated hydrocarbon reformate is described. The anode feed stream consisted of 80% H₂, ∼20% N₂, and 8 ppm hydrogen sulfide (H₂S). Cell performance losses are calculated by evaluating cell potential reduction due to H₂S contamination through lifetime tests. It is found that potential, or power, loss under this condition is a result of platinum surface contamination with elemental sulfur. Electrochemical mass spectroscopy (EMS) and electrochemical techniques are employed, in order to show that elemental sulfur is adsorbed onto platinum, and that sulfur dioxide is one of the oxidation products. Moreover, it is demonstrated that a possible approach for mitigating H₂S poisoning on the PEMFC anode catalyst is to inject low levels of air into the H₂S-contaminated anode feeding stream.     

A novel proton exchange membrane fuel cell anode for enhancing CO tolerance

A novel proton exchange membrane fuel cell (PEMFC) anode which can facilitate the CO oxidation by air bleeding and reduce the direct combustion of hydrogen with oxygen within the electrode is described. This novel anode consists of placing Pt or Au particles in the diffusion layer which is called Pt- or Au-refined diffusion layer. Thus, the chemical oxidation of CO occurs at Pt or Au particles before it reaches the electrochemical catalyst layer when trace amount of oxygen is injected into the anode. All membrane electrode assemblies (MEAs) composed of Pt- or Au-refined diffusion layer do perform better than the traditionary MEA when 100 ppm CO/H₂ and 2% air are fed and have the performance as excellent as the traditionary MEA with neat hydrogen. Furthermore, CO tolerance of the MEAs composed of Au-refined diffusion layer was also assessed without oxygen injection. When 100 ppm CO/H₂ is fed, MEAs composed of Au-refined diffusion layer have the slightly better performance than traditionary MEA do because Au particles in the diffusion layer have activity in the water gas shift (WGS) reaction at low temperature.     

Effect of carbon deposition by carbon monoxide disproportionation on electrochemical characteristics at low temperature operation for solid oxide fuel cells

The deterioration by carbon deposition was evaluated for electrolyte- and anode-supported solid oxide fuel cells (SOFCs) in comparison with carbon monoxide disproportionation and methane cracking. The polarization resistance of the nickel-yttria stabilized zirconia (Ni-YSZ) anode increased with a rise in CO concentration in H₂-CO-CO₂ mixture for the electrolyte-supported cells at 923 K. The resistance, however, did not change against CO concentration for the anode-supported cells. In a methane fuel with a steam/carbon (S/C) ratio of 0.1, the cell performance decreased for both of the cells at 1073 K. A large amount of agglomerated amorphous carbon was deposited from the anode surface to the interface between the anode and the electrolyte after power generation at S/C = 0.1 in methane fuel. On the other hand, the crystalline graphite was deposited only at the anode surface for the anode-supported cell after power generation in CO-CO₂ mixture. These results suggest that the reaction rate of CO disproportionation is faster than that of methane cracking. The deposited carbon near the anode/electrolyte interface caused the increase in the polarization resistance.     

The effect of phosphine in syngas on Ni-YSZ anode-supported solid oxide fuel cells

Ni-YSZ cermet is commonly used as the anode of a solid oxide fuel cell (SOFC) because it has excellent electrochemical performance, not only in hydrogen fuel, but also in a clean blended synthetic coal syngas mixture (30% H₂, 26% H₂O, 23% CO, and 21% CO₂). However, trace impurities, such as phosphine (PH₃), in coal-derived syngas can cause degradation in cell performance [J.P. Trembly, R.S. Gemmen, D.J. Bayless, J. Power Sources 163 (2007) 986-996]. A commercial solid oxide fuel cell was exposed to a syngas with 10 ppm PH₃ under a constant current load at 800 °C and its performance was evaluated periodically using electrochemical methods. The central part of the anode was exposed directly to the syngas without an intervening current collector. Post-mortem analyses of the SOFC anode were performed using Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The results show that the impurity PH₃ caused a significant loss of the Ni-YSZ anode electrochemical performance and an irreversible Ni-YSZ structural modification. Ni₅P₂ was confirmed to be produced on the cell surface as the dominant nickel phosphorus phase.     

Synthesis and characterization of new ternary transition metal sulfide anodes for H2S-powered solid oxide fuel cell

A number of ternary transition metal sulfides with general composition AB₂S₄ (where A and B are different transition metal atoms) have been prepared and investigated as potential anode catalysts for use in H₂S-powered solid oxide fuel cells (SOFCs). For the initial screening, polarization resistance of the materials was measured in a two electrode symmetrical cell at 700–850 °C. Vanadium-based materials showed the lowest polarization resistance, and so were chosen for subsequent full cell tests using the configuration [H₂S, AV₂S₄/YSZ/Pt, air] (where A = Ni, Cr, Mo). MoV₂S₄ anode had superior activity and performance in the full cell setup, consistent with results from symmetrical cell tests. Polarization curves showed MoV₂S₄ had the lowest potential drop, with up to a 200 mA cm⁻² current density at 800 °C. The highest power density of ca. 275 mW cm⁻² at 800 °C was obtained with a pure H₂S stream. Polarization resistance of materials was a strong function of current density, and showed a sharp change of slope attributable to a change in the rate-limiting step of the anode reaction mechanism. MoV₂S₄ was chemically stable during prolonged (10 days) exposure to H₂S at 850 °C, and fuel cell performance was stable during continuous 3-day operation at 370 mA cm⁻² current density.     

Anode performance of LST–xCeO2 for solid oxide fuel cells

La-doped SrTiO₃ (LST)–xCeO₂ (x = 0, 30, 40, 50) composites were evaluated as anode materials for solid oxide fuel cells in terms of chemical compatibility, electrical conductivity and fuel cell performance in H₂ and CH₄. Although the conductivity of LST–xCeO₂ composite slightly decreased from 4.6 to 3.9 S cm⁻¹ in H₂ at 900 °C as the content of CeO₂ increased, the fuel cell performance improved from 75.8 to 172.3 mW cm⁻² in H₂ and 54.5 to 139.6 mW cm⁻² in CH₄ at 900 °C. Electrochemical impedance spectra (EIS) indicated that the addition of CeO₂ into LST can significantly reduce the fuel cells polarization thus leading to a higher performance. The result demonstrated the potential ability of LST–xCeO₂ to be used as SOFCs anode.     

In situ Van der Pauw measurements of the Ni/YSZ anode during exposure to syngas with phosphine contaminant

Solid oxide fuel cells (SOFCs) represent an option to provide a bridging technology for energy conversion (coal syngas) as well as a long-term technology (hydrogen from biomass). Whether the fuel is coal syngas or hydrogen from biomass, the effect of impurities on the performance of the anode is a vital question. The anode resistivity during SOFC operation with phosphine-contaminated syngas was studied using the in situ Van der Pauw method. Commercial anode-supported solid oxide fuel cells (Ni/YSZ composite anodes, YSZ electrolytes) were exposed to a synthetic coal syngas mixture (H₂, H₂O, CO, and CO₂) at a constant current and their performance evaluated periodically with electrochemical methods (cyclic voltammetry, impedance spectroscopy, and polarization curves). In one test, after 170 h of phosphine exposure, a significant degradation of cell performance (loss of cell voltage, increase of series resistance and increase of polarization resistance) was evident. The rate of voltage loss was 1.4 mV h⁻¹. The resistivity measurements on Ni/YSZ anode by the in situ Van der Pauw method showed that there were no significant changes in anode resistivity both under clean syngas and syngas with 10 ppm PH₃. XRD analysis suggested that Ni₅P₂ and P₂O₅ are two compounds accumulated on the anode. XPS studies provided support for the presence of two phosphorus phases with different oxidation states on the external anode surface. Phosphorus, in a positive oxidation state, was observed in the anode active layer. Based on these observations, the effect of 10 ppm phosphine impurity (or its reaction products with coal syngas) is assigned to the loss of performance of the Ni/YSZ active layer next to the electrolyte, and not to any changes in the thick Ni/YSZ support layer.     

Effects of coal syngas and H2S on the performance of solid oxide fuel cells: Part 2. Stack tests

The performance of two-cell planar solid oxide fuel cell stacks using coal syngas, with and without hydrogen sulfide (H₂S), was studied. All cells were tested at 850 °C with a constant current load of 15.2 A (current density of 0.22 A cm⁻² per cell) and 30% fuel utilization. The H₂S injection immediately and significantly affected the power degradation of the stack system regardless of the carrier fuel. Results for the test with only H₂ and N₂ in the presence of H₂S (119–120 ppm) indicated that the power decay and area-specific resistance (ASR) degradation values were lower than those for the tests where simulated syngas containing CO and increased water content was used. The results indicate that contact points in the stack contributed to the power degradation of the system. Other factors, including contamination from the upstream fuel gas tubing, may have contributed to the higher degradation under simulated syngas conditions. In general the data confirm previous results for single cell testing, and showed that for this specific short stacks (two-cells) arrangement both a fast and a slow response to H₂S injection that eventually stabilized.     

The influence of CO2, CO and air bleed on the current distribution of a polymer electrolyte fuel cell

The influence of CO₂, CO and air bleed on current distribution was studied during transient operation, and the dynamic response of the fuel cell was evaluated. CO causes significant changes in the current distribution in a polymer electrolyte fuel cell. The current distribution reaches steady state after approximately 60 min following addition of 10 ppm CO to the anode fuel stream. Air bleed may recover the uneven current distribution caused by CO and also the drop in cell voltage due to CO and CO₂ poisoning. The recovery of cell performance during air bleed occurs evenly over the electrode surface even when the O₂ partial pressure is far too low to fully recover the CO poisoning. The O₂ supplied to the anode reacts on the anode catalyst and no O₂ was measured at the cell outlet for air bleed levels up to 2.5%.     

Syngas reactivity over (LaAg)(CoFe)O3 and Ag-added (LaSr)(CoFe)O3 anodes of solid oxide fuel cells

The syngas, H₂ + CO gas mixture with various H₂/CO ratios, is used as the anode fuel of solid oxide fuel cell with La_0.7Ag_0.3Co_0.2Fe_0.8O₃ (LACF) and 2 wt% Ag-added La_0.58Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) as the anode, respectively, both being in composite with 50 wt% Ce_0.9Gd_0.1O_1.95 (GDC). Both the current-voltage and the fixed-voltage measurements are performed at 800 °C. The reactivity with H₂ as the fuel is larger than that with CO. The syngas reactivity increases with increasing H₂ content. The results of the current-voltage and the fixed-voltage measurements are in agreement with each other. Ag-added LSCF-GDC has better reactivity with H₂, CO and syngas and better stability in the H₂ atmosphere than LACF-GDC as the anode material.     

Solid-oxide fuel cell operated on in situ catalytic decomposition products of liquid hydrazine

Hydrazine was examined as a fuel for a solid-oxide fuel cell (SOFC) that employed a typical nickel-based anode. An in situ catalytic decomposition of hydrazine at liquid state under room temperature and ambient pressure before introducing to the fuel cell was developed by applying a Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) oxide catalyst. Catalytic testing demonstrated that liquid N₂H₄ can be decomposed to gaseous NH₃ and H₂ at a favorable rate and at a temperature as low as 20 °C and H₂ selectivity reaching values as high as 10% at 60 °C. Comparable fuel cell performance was observed using either the in situ decomposition products of hydrazine or pure hydrogen as fuel. A peak power density of ∼850 mW cm⁻² at 900 °C was obtained with a typical fuel cell composed of scandia-stabilized zirconia and La_0.8Sr_0.2MnO₃ cathode. The high energy and power density, easy storage and simplicity in fuel delivery make it highly attractive for portable applications.     

Investigation of the temperature‐related performance of proton exchange membrane fuel cell stacks in the presence of CO

H₂ is generally used as the fuel in proton exchange membrane fuel cells (PEMFCs). However, H₂ produced from reformate gas usually contains a trace of CO, which may severely affect the fuel cell performance. With the adoption of domestic short side chain, low equivalent weight perfluorosulphonic acid (PFSA) membrane, a 100 W stack is built and evaluated at elevated temperature of 95 °C for the purpose of improving its CO tolerance. The stack is operated with 5 ppm, 10 ppm and 20 ppm CO/H₂, respectively; better performance is obtained as expected. Furthermore, a 5 kW PEMFC stack is prepared with home‐made Ir–V/C and Pt/C as anode catalysts for the membrane electrode assemblies to compare their CO tolerance. Physical and electrochemical characterizations, such as transmission electron microscope and linear scan voltammogram are employed for catalyst investigation. The results demonstrate that the employment of domestic PFSA membrane enables the stack to be operated at 95 °C, which can improve the CO tolerance of all the anode catalysts. In addition, the effect of CO on cell polarization is insignificant at lower current densities. Under the same operating conditions, cells with Ir–V/C catalyst show better CO tolerance. Copyright © 2013 John Wiley & Sons, Ltd.