Mathematical modeling of ammonia-fed solid oxide fuel cells with different electrolytes

An electrochemical model was developed to study the ammonia (NH₃)-fed solid oxide fuel cells with proton-conducting electrolyte (SOFC-H) and oxygen ion-conducting electrolyte (SOFC-O). Different from previous thermodynamic analysis, the present study reveals that the actual performance of the NH₃-fed SOFC-H is considerably lower than the SOFC-O, mainly due to higher ohmic overpotential of the SOFC-H electrolyte. More analyses have been performed to study the separate overpotentials of the NH₃-fed SOFC-H and SOFC-O. Compared with the NH₃-fed SOFC-H, the SOFC-O has higher anode concentration overpotential and lower cathode concentration overpotential. The effects of temperature and electrode porosity on concentration overpotentials have also been studied in order to identify possible methods for improvement of SOFC performance. This study reveals that the use of different electrolytes not only causes different ion conduction characteristics at the electrolyte, but also significantly influences the concentration overpotentials at the electrodes. The model developed in this article can be extended to 2D and 3D models for further design optimization.     

Electrochemical modeling of ammonia-fed solid oxide fuel cells based on proton conducting electrolyte

An electrochemical model was developed to study the NH₃-fed and H₂-fed solid oxide fuel cells based on proton conducting electrolyte (SOFC-H). The modeling results were consistent with experimental data in literature. It is found that there is little difference in working voltage and power density between the NH₃-fed and the H₂-fed SOFC-H with an electrolyte-support configuration due to an extremely high ohmic overpotential in the SOFC-H. With an anode-supported configuration, especially when a thin film electrolyte is used, the H₂-fed SOFC-H shows significantly higher voltage and power density than the NH₃-fed SOFC-H due to the significant difference in concentration overpotentials. The anode concentration overpotential of the NH₃-fed SOFC-H is found much higher than the H₂-fed SOFC-H, as the presence of N₂ gas dilutes the H₂ concentration and slows down the transport of H₂. More importantly, the cathode concentration overpotential is found very significant despite of the thin cathode used in the anode-supported configuration. In the SOFC-H, H₂O is produced in the cathode, which enables complete fuel utilization on one hand, but dilutes the concentration of O₂ and impedes the diffusion of O₂ to the reaction sites on the other hand. Thus, the cathode concentration overpotential is the limiting factor for the H₂-fed SOFC-H and an important voltage loss in the NH₃-fed SOFC-H. How to reduce the concentration overpotentials at both electrodes is identified crucial to develop high performance SOFC-H.     

Thermodynamic analysis of ammonia fed solid oxide fuel cells: Comparison between proton-conducting electrolyte and oxygen ion-conducting electrolyte

A thermodynamic analysis has been performed to compare the theoretical performance of ammonia fed solid oxide fuel cells (SOFCs) based on proton-conducting electrolyte (SOFC-H) and oxygen ion-conducting electrolyte (SOFC-O). It is found that the ammonia fed SOFC-H is superior to SOFC-O in terms of theoretical maximum efficiency. For example, at a fuel utilization of 80% and an oxygen utilization of 20%, the efficiency of ammonia fed SOFC-H is 11% higher than that of SOFC-O. The difference between SOFC-H and SOFC-O becomes more significant at higher fuel utilizations and higher temperatures. This is because an SOFC-H has a higher hydrogen partial pressure and a lower steam partial pressure than an SOFC-O. In addition, an increase in oxygen utilization is found to increase the efficiency of ammonia fed SOFCs due to an increase in oxygen molar fraction and a reduction in steam molar fraction. With further development of new ceramics with high proton conductivity and effective fabrication of thin film electrolyte, the SOFC based on proton-conducting electrolyte is expected to be a promising approach to convert ammonia fuel into electricity.     

Importance of pressure gradient in solid oxide fuel cell electrodes for modeling study

The pressure gradients in the electrodes of a solid oxide fuel cell (SOFC) are frequently neglected without any justification in calculating the concentration overpotentials of the SOFC electrodes in modeling studies. In this short communication, a comparative study has been conducted to study the effect of pressure gradients on mass transfer and the resulting concentration overpotentials of an SOFC running on methane (CH₄) fuel. It is found that the pressure gradients in both anode and cathode are significant in the fuel cell electrochemical activities. Neglecting the anode pressure gradient in the calculation can lead to underestimation of the concentration overpotential by about 20% at a typical current density of 5000 A m⁻² and at a temperature of 1073 K. The deviation can be even larger at a higher temperature. At the cathode, neglecting the pressure gradient can result in overestimation of the concentration overpotential by about 10% under typical working conditions.     

An improved electrochemical model for the NH3 fed proton conducting solid oxide fuel cells at intermediate temperatures

An improved electrochemical model is developed to study the ammonia fed solid oxide fuel cell based on proton conducting electrolyte (SOFC-H). Including the chemical reaction kinetics of NH₃ catalytic thermal decomposition, the present model can be used to predict the performance of the NH₃ fed SOFC-H at an intermediate temperature (i.e. 773 K). Comparison between the simulation results using the present model and experimental data from literature validates the accuracy of this model. Parametrical analyses reveal that at a high operating temperature (i.e. 1073 K), the NH₃ fuel is completely decomposed to H₂ and N₂ within a very thin layer (30 μm) near the anode surface of an SOFC-H. It is also found that operating the NH₃ fed SOFC-H at an intermediate temperature of 773 K is feasible due to sufficiently high rate of NH₃ decomposition. However, further decreasing the temperature to 673 K is not recommended as less than 10% NH₃ fuel can be decomposed to H₂ and N₂ in the SOFC-H. The effects of current density and electrode microstructure on the performance of the NH₃ fed SOFC-H are also studied. It is found that increasing electrode porosity and pore size is beneficial to increase the partial pressure of H₂ at the anode–electrolyte interface. The model developed in this paper can be extended to 2D or 3D models to study practical tubular or planar SOFCs.     

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.     

Effect of bi-layer interconnector design on mass transfer performance in porous anode of solid oxide fuel cells

We propose a novel interconnector design, termed bi-layer interconnector, for solid oxide fuel cells (SOFCs). It can disturb the fuel gas and air on the planes normal to the SOFC three-phase-boundary (TPB) layer. In this paper, a two-dimensional half-cell model is developed to study the concentration overpotentials in the fuel side of the SOFC stack with conventional and novel bi-layer interconnectors. The numerical results show that the novel bi-layer interconnector can increase the velocity of the fuel gas in the porous anode. The results of mole fraction distribution illustrate that the novel bi-layer interconnector can effectively disturb the fuel flow. The average H₂ mole fraction in the porous anode of SOFC with bi-layer interconnector is about 4.7% higher than that of conventional SOFC. The average H₂ mole fraction at TPB interface is about 9.2% higher. The concentration overpotential of the novel SOFC design is lower than that of the conventional SOFC design by 5%. It can enhance the mass transfer in porous electrode and improve the performance of SOFC.     

Modeling of a planar solid oxide fuel cell based on proton‐conducting electrolyte

A 2D computational fluid dynamics (CFD) model is developed to study the performance of an advanced planar solid oxide fuel cell based on proton conducting electrolyte (SOFC‐H). The governing equations are solved with the finite volume method (FVM). Simulations are conducted to understand the transport phenomena and electrochemical reaction involved in SOFC‐H operation as well as the effects of operating/structural parameters on SOFC‐H performance. In an SOFC based on oxygen ion conducting electrolyte (SOFC‐O), mass is transferred from the cathode side to the anode side. While in an SOFC‐H, mass is transferred from the anode to the cathode, which causes different velocity fields of the fuel and oxidant gas channels and influences the distributions of temperature and gas composition in the cell. It is also found that increasing the inlet gas velocity leads to an increase in the local current density and a slight decrease in the SOFC‐H temperature due to stronger cooling effect of the gas species at a higher velocity. Another finding is that the electrode structure does not significantly affect the heat and mass transfer in an SOFC‐H at typical operating voltages. Copyright © 2009 John Wiley & Sons, Ltd.     

A general electrolyte–electrode-assembly model for the performance characteristics of planar anode-supported solid oxide fuel cells

A general electrode–electrolyte-assembly (EEA) model has been developed, which is valid for different designs of solid oxide fuel cells (SOFCs) operating at different temperatures. In this study, it is applied to analyze the performance characteristics of planar anode-supported SOFCs. One of the novel features of the present model is its treatment of electrodes. An electrode in the present model is composed of two distinct layers referred to as the backing layer and the reaction zone layer. The other important feature of the present model is its flexibility in fuel, having taking into account the reforming and water–gas shift reactions in the anode. The coupled governing equations of species, charge and energy along with the constitutive equations in different layers of the cell are solved using finite volume method. The model can predict all forms of overpotentials and the predicted concentration overpotential is validated with measured data available in literature. It is found that in an anode-supported SOFC, the cathode overpotential is still the largest cell potential loss mechanism, followed by the anode overpotential at low current densities; however, the anode overpotential becomes dominant at high current densities. The cathode and electrolyte overpotentials are not negligible even though their thicknesses are negligible relative to the anode thickness. Even at low fuel utilizations, the anode concentration overpotential becomes significant when chemical reactions (reforming and water–gas shift) in the anode are not considered. A parametric study has also been carried out to examine the effect of various key operating and design parameters on the performance of an anode-supported planar SOFCs.     

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.     

Ammonia‐fed solid oxide fuel cells for power generation—A review

Ammonia has been identified as a promising sustainable fuel and hydrogen source for solid oxide fuel cells (SOFC). This paper aims to provide a literature review on ammonia‐fed SOFCs. Both experimental studies and mathematical modeling investigations on NH₃‐fed SOFC are included and discussed. It is found that NH₃ is a technically feasible fuel for direct use in SOFCs and the performance of NH₃‐fed SOFC is comparable with that of the H₂ fed SOFC. Experimental study in literature also demonstrates that both oxygen ion‐conducting electrolyte (SOFC‐O) and proton‐conducting electrolyte (SOFC‐H) can be used in NH₃‐fed SOFC, as the amount of NO_x generated in a SOFC‐O is negligible. Fabricating thin film electrolyte and developing more reactive electrode materials are important to improve the performance of NH₃‐fed SOFCs. Mathematical models are useful design tools for understanding the coupled transport and reaction phenomena and for optimizing the SOFC performance. Thermodynamic and pioneering 1D electrochemical models have been developed, validated and demonstrated to be reliable by the present author. Copyright © 2009 John Wiley & Sons, Ltd.     

High-performance SO2-depolarized electrolysis cell using advanced polymer electrolyte membranes

Three different proton conducting polymeric membrane materials (Nafion® 115, Nafion® 212, and sulfonated Diels-Alder polyphenylene [SDAPP]) were evaluated for use in SO₂-depolarized electrolyzers for the production of hydrogen via the hybrid sulfur cycle. Their performance was measured using different water feed strategies to minimize overpotential losses while maintaining high product acid concentration. Both thin membranes (Nafion® 212 and SDAPP) showed performance superior to that of the thicker Nafion® 115. The SDAPP membrane electrode assembly (MEA) performed well at higher acid concentrations, maintaining low ohmic and kinetic overpotentials. Finally, short-term (100-h) stability tests under constant current conditions showed minimal degradation for the SDAPP and Nafion® 212 MEAs. SDAPP MEA performance approached the targets needed to make the hybrid sulfur cycle a competitive process for hydrogen production (product acid concentration ≥65 wt% H₂SO₄ at ≤ 0.6-V cell potential and ≥0.5 A-cm^?2 current density).     

Performance of an anode-supported solid oxide fuel cell with direct-internal reforming of ethanol

A theoretical study of a solid oxide fuel cell (SOFC) fed by ethanol is presented in this study. The previous studies mostly investigated the performance of ethanol-fuelled fuel cells based on a thermodynamic analysis and neglected the presence of actual losses encountered in a real SOFC operation. Therefore, the real performance of an anode-supported SOFC with direct-internal reforming operation is investigated here using a one-dimensional isothermal model coupled with a detailed electrochemical model for computing ohmic, activation, and concentration overpotentials. Effects of design and operating parameters, i.e., anode thickness, temperature, pressure, and degree of ethanol pre-reforming, on fuel cell performance are analyzed. The simulation results show that when SOFC is operated at the standard conditions (V = 0.65 V, T = 1023 K, and P = 1 atm), the average power density of 0.51 W cm⁻² is obtained and the activation overpotentials represent a major loss in the fuel cell, followed by the ohmic and concentration losses. An increase in the thickness of anode decreases fuel cell efficiency due to increased anode concentration overpotential. The performance of the anode-supported SOFC fuelled by ethanol can be improved by either increasing temperature, pressure, degree of pre-reforming of ethanol, and steam to ethanol molar ratio or decreasing the anode thickness and fuel flow rate at inlet. It is suggested that the anode thickness and operating conditions should be carefully determined to optimize fuel cell efficiency and fuel utilization.     

Combined methane reforming by carbon dioxide and steam in proton conducting solid oxide fuel cells for syngas/power co-generation

Methane and carbon dioxide mixture can be used as the fuel in a proton conducting solid oxide fuel cell (SOFC) for power/syngas co-generation and greenhouse gas reduction. However, carbon deposition and low conversion ratio are potential problems for this technology. Apart from using functional catalytic layer in the SOFC to enhance CH₄ dry reforming, adding H₂O into the fuel stream could facilitate the CH₄ conversion and enhance the co-generation performance of the SOFC. In this work, the effects of adding H₂O to the CO₂CH₄ fuel on the performance of a tubular proton conducting SOFC are studied numerically. Results show that the CH₄ conversion is improved from 0.830 to 0.898 after adding 20% H₂O to the anode. Meanwhile, the current density is increased from 2832 A m⁻² to 3064 A m⁻² at 0.7 V. Sensitivity studies indicate that the H₂:CO ratio can be effectively controlled by the amount of H₂O addition and the H₂ starvation can be alleviated, especially at high current density conditions.     

Effects of anodic gas conditions on performance and resistance of a PBI/H3PO4 proton exchange membrane fuel cell with metallic bipolar plates

In this study, polybenzimidazole (PBI) is used as membrane material of the high-temperature membrane electrode assembly which has the features of high-performance stability and high CO tolerance. Moreover, compared to graphite bipolar plates, metallic bipolar plates have better mechanical properties and seismic capacity, as well as lighter weight. We thus use metallic bipolar plates and a PBI-based membrane electrode assembly to setup a single cell and examine its performance. The experimental results show that the cell temperature has a significant effect on the cell performance. When the temperature increases from 120 °C to 180 °C, the performance is significantly enhanced. Moreover, the CO tolerance of the fuel cell increases along with the temperature. At the same time, methane is fed in the anode stream to assess the performance of the cell under different simulated methane reformate gases. The test of various CH₄/H₂ mixtures reveals the residual methane in the reformate gases only decreases fuel cell performance slightly due to the dilution effect. We also examined H₂/CO/N₂/CH₄ mixtures in this study, and these had only a small effect on the fuel cell performance at cell temperatures higher than 160 °C. As such, it is recommended that the cell temperature should be kept higher than 160 °C.     

Numerical modelling and comparative analysis of direct ammonia fuelled protonic and oxygen- ion conducting tubular solid oxide fuel cell

The main emphasis of this work is developing a 3D numerical model and investigating the performance characteristic of a direct ammonia fuelled protonic-conducting tubular solid oxide fuel cell (NH₃-T–SOFC–H) in comparison with the corresponding hydrogen-fuelled one and direct ammonia feed oxygen -ion conducting tubular solid oxide fuel cell (NH₃-T–SOFC–O) under the same operating parameters and geometrical shape. The findings revealed that NH₃-T–SOFC–H has outstanding performance over T–SOFC–O counterparts at intermediate temperature (973 K) when operated under similar working conditions and geometrical designs. On the other hand the NH₃-T–SOFC–O is promising for higher operating temperatures. The outcomes of the study are also confirmed that the power performance of NH₃-AS-T–SOFC–O is better than the other supports of both electrolytes when the anode electrode is constructed at the outside portion of the tubular cell. Yet, the other remarkable result found in this study is that NH₃– CS- T–SOFC–O has outstanding performance compared to all supports of both electrolytes when the fuel electrode is built in the inner portion of the tube. In addition, the finding indicates that the power performance of ammonia-fuelled tubular cells is strongly influenced by the anode position, operating temperatures, and pressures in both electrolytes yet the effect of cell temperature is more influential in the protonic-conducting cell. It is also observed that the performance of ES-T-SOFC is lower than AS- and CS-T-SOFC in both electrolytes and anode positions.     

Is steam addition necessary for the landfill gas fueled solid oxide fuel cells?

Landfill gas in Hong Kong – a mixture of about 50% (by volume) CH₄ and 50% CO₂ – can be utilized for power generation in a solid oxide fuel cell (SOFC). Conventional way of utilizing CH₄ in a SOFC is by adding H₂O to CH₄ to initiate methane steam reforming (MSR) and water gas shift reaction (WGSR). As the methane carbon dioxide reforming (MCDR: CH₄ + CO₂ ↔ 2CO + 2H₂) is feasible in the SOFC anode, it is unknown whether H₂O is needed or not for landfill gas fueled SOFC. In this study, a numerical model is developed to investigate the characteristics of SOFC running on landfill gas. Parametric simulations show that H₂O addition may decrease the performance of short SOFC at typical operating conditions as H₂O dilute the fuel concentration. However, it is interesting to find that H₂O addition is needed at reduced operating temperature, lower operating potential, or in SOFC with longer gas channel, mainly due to less temperature reduction in the downstream and easier oxidation of H₂ than CO. This preliminary study could help identify strategies for converting landfill gas into electrical power in Hong Kong.     

Theoretical analysis of reversible solid oxide fuel cell based on proton-conducting electrolyte

A single reversible solid oxide fuel cell (RSOFC) can accomplish two functions: (1) as a solid oxide steam electrolyzer (SOSE) for hydrogen production and (2) as a solid oxide fuel cell (SOFC) for power generation. An electrochemical model was developed to study the performance of an RSOFC based on a proton-conducting electrolyte (RSOFC-H). In both SOSE and SOFC modes, the hydrogen electrode-supported configuration was identified as the most favorable design to achieve high energy conversion efficiency of RSOFC-H. For comparison, in a previous study on conventional RSOFC based on an oxygen ion-conducting electrolyte (RSOFC-O), the hydrogen electrode-supported configuration was found to be favorable in the SOFC mode but such configuration would cause high concentration overpotential in the SOSE mode. Thus, the oxygen electrode-supported configuration was desirable for RSOFC-O operating in the SOSE mode. The results obtained in this study show that RSOFC-H has a natural advantage over RSOFC-O in terms of structural design. The modeling study signifies the difference between RSOFC-H and RSOFC-O and can serve as a useful tool for further design optimization.     

The effect of overpotential on performance degradation of the solid oxide fuel cell Ni/YSZ anode during exposure to syngas with phosphine contaminant

Phosphine (PH₃) as a contaminant in coal syngas has been shown to cause permanent degradation on solid oxide fuel cell (SOFC) anode performance. Previous studies on the performance degradation have been performed at constant current or constant voltage over the entire experiment. In this work, the effect of overpotential (difference between the open circuit voltage and the applied voltage) on rates of degradation of SOFC performance is examined. A commercial SOFC from MSRI is exposed in sequence to first hydrogen, then coal syngas and then coal syngas with 10 ppm PH₃. The rates of cell power density loss rates are monitored for three overpotentials (0.1, 0.2 and 0.3 V). There is no apparent correlation between the degradation rates and overpotential values. Post-mortem studies including SEM, XRD and XPS confirm the migration of nickel to the anode surface and the formation of a nickel phosphide phase.     

A new phenomenon of a fuel-free current during intermittent fuel flow over Ni-YSZ anode in direct methane SOFCs

A solid oxide fuel cell (SOFC) test unit was constructed with YSZ electrolyte as the support, and with Ni-YSZ anode (Ni:YSZ = 3:5 in weight) and Pt cathode. Direct methane SOFC operation at 800 °C with 10% CH₄ in argon was carried out. A new phenomenon of the generation of the electrical current without the fuel was observed and termed the fuel-free current. An operation of intermittent methane supply was designed to take advantage of three driving forces, i.e. methane in the gas phase, the deposited carbon at the anode surface, and a deficiency of the bulk lattice-oxygen concentration on the anode side, for the generation of the electrical current. A continuous generation of the electrical current is obtained with a methane pulse of only one-fifth of the total operation time. The operation of intermittent methane flow can reduce or even avoid SOFC deactivation by the carbon deposition; at the same time, the deposited carbon can be fully utilized for the power generation. It was also found that hydrogen from methane has been mostly evolved to the outlet gaseous product and the amount of CO formation is much higher than that of CO₂; the operation of intermittent methane flow can further increase the amount of CO over that of CO₂; these are beneficial for the co-generation of synthesis gas.