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.     

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.     

A prefilter for mitigating PH3 contamination of a Ni-YSZ anode

Ni-YSZ is used as the anode of a solid oxide fuel cell (SOFC) because it has excellent electrochemical performance for operation with coal-derived syngas. However, trace impurities, PH₃ H₂S AsH₃, and Sb in coal-syngas can cause SOFC degradation. Described here is a means of removing PH₃ impurity from syngas by using a Ni-based prefilter. In one test, a thin Ni-based filter was set upstream of a Ni-YSZ anode-supported SOFC. The SOFC was exposed to syngas with PH₃ under a constant current load at 800 °C. The filter decreased 20 ppm PH₃ in the feed to a level which did not degrade the SOFC for over 400 h until the filter became saturated. In another test, both H₂S and PH₃ were co-fed to the cell with Ni-based and Fe/Ni-based filters. The interaction between these two impurities did not significantly impact the filter performance with respect to PH₃ removal for both filter formulations. The cell performance was evaluated by current-voltage measurements and impedance spectroscopy. Post-mortem analyses of the cell and filter were performed by means of XRD, SEM/EDS and XPS. With proper filter design, the Ni-YSZ SOFC can operate on contaminated coal-syngas without degradation over a prescribed period of time.     

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

The Ni-YSZ cermet anode of the solid oxide fuel cell (SOFC) has excellent electrochemical performance in a clean blended synthetic coal syngas mixture. However, chloride, one of the major contaminants existing in coal-derived syngas, may poison the Ni-YSZ cermet and cause degradation in cell performance. Both hydrogen chloride (HCl) and chlorine (Cl₂) have been reported to attack the Ni in the anode when using electrolyte-supported SOFCs. In this paper, a commercial anode-supported SOFC was exposed to syngas with a concentration of 100 ppm HCl under a constant current load at 800 °C for 300 h and 850 °C for 100 h. The cell performance was evaluated periodically using electrochemical methods. A unique feature of this experiment is that the active central part of the anode was exposed directly to the fuel without an intervening current collector. Post-mortem analyses of the SOFC anode were performed using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The results show that the 100 ppm concentration of HCl causes about 3% loss of performance for the Ni-YSZ anode-supported cell during the 400 h test. Permanent changes were noted in the surface microstructure of the nickel particles in the cell anode.     

Effect of PH3 poisoning on a Ni-YSZ anode-supported solid oxide fuel cell under various operating conditions

The Ni-YSZ anode-supported solid oxide fuel cell (SOFC) can generate electrical power by using coal-derived syngas as the fuel. However, trace contamination of phosphine (PH₃) in the syngas can cause irreversible degradation in cell performance. A series of tests at 10 ppm PH₃ in the fuel gas was carried out under a variety of operating conditions, viz, with/without electrochemical reaction in syngas and with/without H₂O in H₂ fuel at 750 °C, 800 °C and 850 °C. The poisoning effects were evaluated by both electrochemical methods and chemical analyses. The post-mortem analyses of the SOFC anode were performed by means of XRD, SEM/EDS, and XPS. The results show that the degradation rate is larger at the higher cell working temperature using syngas with PH₃ in a 200 h test though PH₃ is more reactive with Ni in the anode at lower working temperature and produces a secondary nickel phosphide (Ni_xP_y) phase. The dominant compositions of Ni_xP_y on the cell anode are Ni₅P₂ with the presence of H₂O, and Ni₁₂P₅ without the presence of H₂O. The production of Ni_xP_y can be generated on the cell anode using syngas or dry H₂ fuel with 10 ppm PH₃ contaminant. Further, the appearance of Ni_xP_y phases is independent of the electrochemical reactions in the cell.     

The effect of coal syngas containing AsH3 on the performance of SOFCs: Investigations into the effect of operational temperature,current density and AsH3 concentration

The performance of solid oxide fuel cells (SOFCs) using simulated coal-derived syngas, with and without arsine (AsH₃), was studied. Anode-supported SOFCs were tested galvanostatically at 0.25 and 0.5 A cm⁻² at 750 and 800 °C with simulated coal syngas containing 0.1, 1, and 2 ppm AsH₃. The tests with simulated coal syngas containing 1 ppm AsH₃ show little degradation over 100 h of operation. The tests with simulated coal syngas containing 2 ppm AsH₃ show some signs of degradation, however no secondary arsenide phases were found. Extended trial testing with 0.1 ppm AsH₃ showed degradation as well as the formation of a secondary nickel arsenide phase in the anode of the SOFC.     

Effects of coal syngas impurities on anodes of solid oxide fuel cells

A literature review is conducted to summarize the studies on the identification of impurities in coal syngas and their effects on the performance of Ni-yttria stabilized zirconia (Ni-YSZ) anode of solid oxide fuel cells (SOFCs). Coal syngas typically contains major species, CO, H₂, CO₂, H₂O, CH₄, N₂, and H₂S as well as trace impurities. Thermodynamic equilibrium calculations have indicated that trace impurities species such as Be, Cr, K, Na, and V in the coal syngas form condensed phases under warm gas cleanup conditions and can be effectively removed by the cleanup processes. For meaningful data comparison, a practical parameter is formulated to quantify the level of degradation normalized with respect to the relevant experimental parameters. Experimental results show that the existence of Hg, Si, Zn and NH₃ in the coal syngas does not significantly affect the performance of the Ni-YSZ anode. The presence of Cd and Se in the syngas impacts the SOFC anode performance to some extent. Impurity species such as Cl, Sb, As, and P cause severe cell voltage degradation due to attack on the Ni-YSZ anode. Sb, As and P have the potential to react with Ni to form secondary phases in the Ni-YSZ anode, which deteriorate the catalytic activity of the anode.     

Degradation of LaSr2Fe2CrO9−δ solid oxide fuel cell anodes in phosphine-containing fuels

The performance and stability of La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-δ-electrolyte supported solid oxide fuel cells with composite LaSr₂Fe₂CrO_9-δ-Gd_0.1Ce_0.9O₂ anodes were studied in wet H₂ and coal syngas containing phosphine impurity. Introduction of 5-20 ppm PH₃ into the fuels caused an initial slow cell performance degradation followed by a very rapid complete cell degradation that initiated within 11-24 h - earlier at higher PH₃ concentration. There was no recovery after removing PH₃ impurity from the fuels. Electrochemical impedance analysis suggested that the initial gradual performance degradation was due to conductivity loss of the oxide anode due to chemisorption and reaction of phosphine. X-ray diffraction analysis showed the formation of FeP_x and LaPO₄ compounds. The rapid degradation presumably occurred when most or all of the Fe initially present in the LaSr₂Fe₂CrO_9−δ was consumed. Thermodynamic calculations confirmed that Fe is highly reactive with PH₃ at 800 °C, even at concentrations below 1 ppm.     

Elementary reaction kinetic model of an anode-supported solid oxide fuel cell fueled with syngas

In this paper, a detailed one-dimension transient elementary reaction kinetic model of an anode-supported solid oxide fuel cell (SOFC) operating with syngas based on button cell geometry is developed. The model, which incorporates anodic elementary heterogeneous reactions, electrochemical kinetics, electrodes microstructure and complex transport phenomena (momentum, mass and charge transport) in positive electrode|electrolyte|negative electrode (PEN), is validated with experimental performance for various syngas compositions at 750, 800 and 850 °C. The comparisons show that the simulation results agree reasonably well with the experimental data. Then the model is applied to analyze the effects of temperature and operation voltage on polarizations in each component of PEN, electronic current density in both electrodes and species concentrations distributions in anode. The numerical results of carbon deposition simulation indicate that higher temperature and lower operation voltage are helpful to reduce the possibility of carbon deposition on Ni surfaces by Bouduard reactions. Furthermore, a sensitivity analysis of cell performance on syngas composition is performed for the typical syngas from entrained-flow coal gasifier and natural methane thermochemical reforming processes. The cell performance increases with the increasing of effective compositions (e.g. H₂ and CO) in syngas and the large N₂ content introduced by using air as oxidant leads to significant deterioration of performance.     

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.     

One thousand-hour long term characteristics of a propane-fueled solid oxide fuel cell hot zone

One thousand-hour continuous test of a propane-fueled portable solid oxide fuel cell (SOFC) based hot zone has been successfully performed in order to assess the degradation characteristics of its performance. Comparing the different operating modes, the degradation rate based on constant current mode was three times lower than that based on constant voltage mode. The stack power output initially increased 3.7% during the first 34 h probably due to electrode activation processes improving cell performance under polarization during the early stage of operation, and then gradually decreased. It has been clearly illustrated that operating condition of constant current is more beneficial to the long term performance test. Further, based on thermodynamics analysis, the electromotive force of nickel oxidation is 13.2 V for the stack voltage at the stack temperature of 740 °C. From the initial current-power curve data, it can be derived that if the hot zone durability test was performed at constant current of 9 A from the beginning, the stack degradation rate would be 15% per 1000 h. The 1000-h durability test and analysis can better understand how to run longer term stability on the hot zone and guide the optimization of hot zone operating conditions.     

Design of highly efficient coal-based integrated gasification fuel cell power plants

Integrated gasification fuel cell (IGFC) technology combining coal gasification and solid oxide fuel cell (SOFC) is believed to be the only viable solution to achieving U.S. Department of Energy (DOE)’s performance goal for next generation coal-based power plants, producing electricity at 60% efficiency (coal HHV-AC) while capturing more than 90% of the evolved CO₂. Achieving this goal is challenging even with high performance SOFCs; design concepts published to date have not demonstrated this performance goal. In this work an IGFC system concept consisting of catalytic hydro-gasification, proven low-temperature gas cleaning and hybrid fuel cell-gas turbine power block (with SOFC operating at about 10 bar) is introduced. The system is demonstrating an electricity efficiency greater than 60% (coal HHV basis), with more than 90% of the carbon present in the syngas separated as CO₂ amenable to sequestration. A unique characteristic of the system is recycling de-carbonized, humidified anode exhaust back to the catalytic hydro-gasifier for improved energy integration. Alternative designs where: (1) anode exhaust is recycled directly back to SOFC stacks, (2) SOFC stack operating pressure is reduced to near atmospheric and (3) methanation reactor in the reactor/expander topping cycle is removed, have also been investigated and the system design and performance differences are discussed.     

Reversible poisoning of nickel/zirconia solid oxide fuel cell anodes by hydrogen chloride in coal gas

The performance of anode-supported solid oxide fuel cells (SOFC) was evaluated in synthetic coal gas containing HCl in the temperature range 650-850 °C. Exposure to up to 800 ppm HCl resulted in reversible poisoning of the Ni/zirconia anode by chlorine species adsorption, the magnitude of which decreased with increased temperature. Performance losses increased with the concentration of HCl to ∼100 ppm, above which losses were insensitive to HCl concentration. Neither cell potential, nor current density had any effect on the extent of poisoning. No evidence was found for long-term degradation that can be attributed to HCl exposure. Similarly, no evidence of microstructural changes or formation of new solid phases as a result of HCl exposure was found. From thermodynamic calculations, solid nickel chloride phase formation was shown to be highly unlikely in coal gas containing HCl. The presence of HCl at even the highest anticipated concentrations in coal gas would minimally increase the volatility of nickel.     

Electrochemical study of a planar solid oxide fuel cell: Role of support structures

This paper presents a performance analysis of a planar solid oxide fuel cell (SOFC) with different support structures, i.e., electrode (anode and cathode) and electrolyte supports. An electrochemical model, taking into account structural and operational parameters and gas diffusion at the electrodes, is used to analyze the characteristics of the planar SOFC. Simulation results demonstrate that under cell operation at an intermediate temperature (1073 K), an anode-supported SOFC is superior to an electrolyte- and cathode-supported SOFC. Analysis of individual cell voltage loss indicates that ohmic loss dominates the performance of an electrolyte-supported SOFC whereas activation and ohmic overpotentials constitute the major loss in an electrode-supported counterpart. Sensitivity analyses of the anode-supported SOFC show that decreasing the electrolyte and anode thickness can improve cell performance. A decrease in operating temperature causes the cell to operate at a lower range of current density due to an increase in ohmic and activation overpotentials. Further, increasing the operating pressure and degree of pre-reforming reduces the concentration overpotential and thereby enhances cell performance.     

The effect of coal syngas containing HCl on the performance of solid oxide fuel cells: Investigations into the effect of operational temperature and HCl concentration

The performance of solid oxide fuel cells (SOFCs) using simulated coal-derived syngas, with and without hydrogen chloride (HCl), was studied. Electrolyte-supported SOFCs were tested potentiostatically at 0.7 V at 800 and 900 °C with simulated coal syngas containing 0, 20, and 160 ppm HCl. The results from the tests without HCl show good performance with little degradation over 100 h of operation. Both 20 and 160 ppm HCl were shown to cause performance losses in the SOFCs after injection into the system. Although the tests presented in this paper show that HCl does cause degradation to SOFC performance, the cell performance was recoverable upon the removal of HCl from the fuel. Also recent results from anticipated Integrated Gasification Combined Cycle IGCC warm/hot-gas-cleanup technologies suggest that HCl will be removed to levels that will not cause any significant performance losses in SOFCs.     

Evaluation of carbon deposition behavior on the nickel/yttrium-stabilized zirconia anode-supported fuel cell fueled with simulated syngas

The nickel/yttrium-stabilized zirconia (Ni/YSZ) anode-supported solid oxide fuel cells (SOFCs) have been operated under various simulated syngases at different temperatures to investigate the degradation behavior of the cells caused by carbon deposition. The results show that the carbon morphology and the cell performance degradation are influenced significantly by the operation temperature. The stability of the cell fueled with syngas can be improved by applying a constant current, but the cell degraded quickly after carbon deposition. The microstructure damage is close to the anode surface and leads to a conductivity decrease, which is an important reason for the cell degradation and failure at 750 °C. Conversely, the degradation behavior at 650 °C is mainly due to solid carbon deposits inside of the anode that impede fuel diffusion and electrochemical reactions on the anodic side. The effect of carbon deposition on the microstructure degradation is also investigated using transmission electron microscope.     

Application of a Cu-CeO2/Ni-yttria-stabilized zirconia multi-layer anode for anode-supported Solid Oxide Fuel Cells operating on H2-CO syngas fuels

A Ni-yttria-stabilized zirconia (YSZ) anode and a Cu-CeO₂/Ni-YSZ multi-layer anode have been fabricated for use in anode-supported Solid Oxide Fuel Cells (SOFCs), and their performances and stabilities in H₂-CO syngas have been studied at 750 °C. A high CO content has been found to cause carbon deposition and crack formation in the Ni-YSZ anode after long-term operation, but the Cu-CeO₂ catalyst layer on the Ni-YSZ anode surface improves its stability in syngas with high CO content by facilitating the water gas shift reaction. The optimized single cell has run in syngas with a composition of 48.5%H₂-48.5%CO-3%H₂O for 460 h without obvious degradation of its performance, however, its performance decreases after 630 h due to carbon deposition in the anode functional layer and subsequent crack formation on the anode and electrolyte.     

Effect of nickel-phosphorus interactions on structural integrity of anode-supported solid oxide fuel cells

An integrated experimental/modeling approach was utilized to assess the structural integrity of Ni-yttria-stabilized zirconia (YSZ) porous anode supports during the solid oxide fuel cell (SOFC) operation on coal gas containing trace amounts of phosphorus impurities. Phosphorus was chosen as a typical impurity exhibiting strong interactions with the nickel followed by second phase formation. Tests were performed using Ni-YSZ anode-supported button cells exposed to 0.5-10 ppm of phosphine in synthetic coal gas at 700-800 °C. The extent of Ni-P interactions was determined by a post-test scanning electron microscopy (SEM) analysis. Severe damage to the anode support due to nickel phosphide phase formation and extensive crystal coalescence was revealed, resulting in electric percolation loss. The subsequent finite element stress analyses were conducted using the actual anode support microstructures to assist in degradation mechanism explanation. Volume expansion induced by the Ni phase alteration was found to produce high stress levels such that local failure of the Ni-YSZ anode became possible under the operating conditions.     

High temperature electrolyte supported Ni-GDC/YSZ/LSM SOFC operation on two-stage Viking gasifier product gas

This paper presents the results from a 150 h test of a commercial high temperature single planar solid oxide fuel cell (SOFC) operating on wood gas from the Viking two-stage fixed-bed downdraft gasifier, which produces an almost tar-free gas, that was further cleaned for particulates, sulphur and tar traces. The chosen SOFC was electrolyte supported with a nickel/gadolinium-doped cerium oxide (Ni-GDC) anode, known for its carbon deposition resistance. Through humidification the steam to carbon ratio (S/C) was adjusted to 0.5, which results in a thermodynamically carbon free condition at the SOFC operating temperature T = 850 °C. The cell operated with a fuel utilisation factor (U_f) around 30% and a current density of 260 mA cm⁻² resulting in an average power density of 207 mW cm⁻². Throughout the duration of the test, only a minor cell overpotential increase of 10 mV was observed. Nevertheless, the V–j (voltage–current density) curves on H₂/N₂ before and after the wood gas test proved identical. Extensive SEM/EDS examination of the cell's anode showed that there was neither carbon deposition nor significant shifts in the anode microstructure or contamination when compared to an identical cell tested on H₂/N₂ only.     

Interactions of nickel/zirconia solid oxide fuel cell anodes with coal gas containing arsenic

The performance of anode-supported and electrolyte-supported solid oxide fuel cells was investigated in synthetic coal gas containing 0-10 ppm arsenic at 700-800 °C. Arsenic was found to interact strongly with nickel, resulting in the formation of nickel-arsenic solid solution, Ni₅As₂ and Ni₁₁As₈, depending on temperature, arsenic concentration, and reaction time. For anode-supported cells, loss of electrical connectivity in the anode support was the principal mode of degradation, as nickel was converted to nickel arsenide phases that migrated to the surface to form large grains. Cell failure occurred well before the entire anode was converted to nickel arsenide, and followed a reciprocal square root of arsenic partial pressure dependence that is consistent with a diffusion-based rate-limiting step. Failure occurred more quickly with electrolyte-supported cells, which have a substantially smaller nickel inventory. For these cells, time to failure varied linearly with the reciprocal arsenic concentration. Failure occurred when arsenic reached the anode/electrolyte interface, though agglomeration of nickel reaction products may have also contributed. Test performed with nickel/zirconia coupons showed that arsenic was essentially completely captured in a narrow band near the fuel gas inlet. Arsenic concentrations of ∼10 ppb or less are estimated to result in acceptable rates of fuel cell degradation.