Heat-up and start-up modeling of direct internal reforming solid oxide fuel cells

In this paper, a transient heat transfer model to simulate the heat-up and start-up periods of co- and counter-flow direct internal reforming solid oxide fuel cells is developed and presented. In this comprehensive model, all the heat transfer mechanisms, i.e. conduction, convection, and radiation, and all the polarization nodes, i.e. ohmic, activation, and concentration, are considered. The heat transfer model is validated using the results of a benchmark test and two numerical studies obtained from the literature. After validating the model, the heat-up, start-up, and steady-state behaviors of the cell are investigated. In addition, the first principal thermal stresses are calculated to find the probability of failure of the cell during its operation. The results of the present model are in good agreement with the literature data. It is also shown for the given input data that counter-flow case yields a higher average current density and power density, but a lower electrical efficiency of the cell. For the temperature controlled heat-up and start-up strategy, the maximum probability of failure during the operation of the cell is found to be 0.068% and 0.078% for co- and counter-flow configurations, respectively.     

Modelling of solid oxide fuel cells with internal glycerol steam reforming

The direct application of glycerol in solid oxide fuel cell (SOFC) for power generation has been demonstrated experimentally but the detailed mechanisms are not well understood due to the lack of comprehensive modeling study. In this paper, a numerical model is developed to study the glycerol-fueled SOFC. After model validation, the simulated SOFC demonstrates a performance of 7827 A m^?2 at 0.6 V, with a glycerol conversion rate of 49% at 1073 K. Then, parametric analyses are conducted to understand the effects of operation conditions on cell performance. It is found that the SOFC performance increases with decreasing operating voltage or increasing inlet temperature. However, increasing either the fuel flow rate or steam to glycerol ratio could decrease the cell performance. It is also interesting to find out that the contribution of H₂ and CO to the total current density is significantly different under various operating conditions, even sometimes CO dominates while H₂ plays a negative role. This is different from our conventional understanding that usually H₂ contributes more significantly to current generation. In addition, cooling measures are needed to ensure the long-term stability of the cell when operating at a high current density.     

Development of paper-structured catalyst for application to direct internal reforming solid oxide fuel cell fueled by biogas

A flexible paper-structured catalyst (PSC) that can be applied to the anode of a solid oxide fuel cell (SOFC) was examined for its potential to enable direct internal reforming (DIR) operation. The catalytic activity of three types of Ni-loaded PSCs: (a) without the dispersion of support oxide particles in the fiber network (PSC-A), (b) with the dispersion of (Mg,Al)O derived from hydrotalcite (PSCB), and (c) with the dispersion of (Ce,Zr)O_2-δ (PSCC), for dry reforming of CH₄ was evaluated at operating temperatures of 650–800 °C. Among the PSCs, PSC-C exhibited the highest CH₄ conversion with the lowest degradation rate. The electrochemical performance of an electrolyte-supported cell (ESC) was evaluated under the flow of simulated biogas at 750 °C for cases without and with the PSCs on the anode. The application of the PSCs improved the cell performance. In particular, PSC-C had a remarkably positive effect on stabilizing DIRSOFC operation fueled by biogas.     

Durability of direct internal reforming of methanol as fuel for solid oxide fuel cell with double-sided cathodes

Direct internal reforming of methanol is applied as fuel for a Ni-YSZ anode-supported solid oxide fuel cell with a flat tube based on double-sided cathodes. It achieves a power density (PD) of 0.25 W/cm² at 0.8 V, reaching about 90% of that is fueled by H₂. And the cell has been operated for more than 120 h by the direct internal reforming of methanol. The durability and apparent advantage for using humidified methanol may lead to widespread applications by direct internal reforming method for this new designed SOFC in the future.     

Two-dimensional dynamic simulation of a direct internal reforming solid oxide fuel cell

This study presents a two-dimensional mathematical model of a direct internal reforming solid oxide fuel cell (DIR-SOFC) stack which is based on the reforming reaction kinetics, electrochemical model and principles of mass and heat transfer. To stimulate the model and investigate the steady and dynamic performances of the DIR-SOFC stack, we employ a computational approach and several cases are used including standard conditions, and step changes in fuel flow rate, air flow rate and stack voltage. The temperature distribution, current density distribution, gas species molar fraction distributions and dynamic simulation for a cross-flow DIR-SOFC are presented and discussed. The results show that the dynamic responses are different at each point in the stack. The temperature gradients as well as the current density gradients are large in the stack, which should be considered when designing a stack. Further, a moderate increase in the fuel flow rate improves the performances of the stack. A decrease in the air flow rate can raise the stack temperature and increase fuel and oxygen utilizations. An increased output voltage reduces the current density and gas utilizations, resulting in a decrease in the temperature.     

Electrochemical properties and thermal neutral state of solid oxide fuel cells with direct internal reforming of methane

Solid oxide fuel cells (SOFCs) with direct internal reforming (DIR) provide a promising method to realize clean and efficient utilization of hydrocarbon fuels. Thse endothermic reforming reactions occur simultaneously with exothermic electrochemical reactions at the anode, making thermal neutral state achievable inside a fuel cell, providing reference to the thermal management. In this study, a calculation model combining experimental data and thermodynamic results was established, validating the possibility of achieving thermal neutral state in DIR-SOFCs. In the process of modeling, the electrochemical and thermodynamic characteristics in direct internal steam and dry reforming were elaborately compared, contributing to a more scientific understanding of anode reaction mechanism. Detailed experimental investigation was carried out to determine the influence of H₂O/CO₂ on the electrochemical properties of DIR-SOFCs, based on which the optimum steam-carbon ratio (S/C) and CO₂ to CH₄ ratios were obtained. Besides, analysis of distribution of relaxation times (DRT) combined with elementary reactions in CH₄H₂O and CH₄CO₂ atmospheres were proposed to distinguish different physical and chemical processes within anodes. The results of this study can be conducive to a more precise understanding of reaction mechanism on SOFC anodes and meaningful for practical application of DIR-SOFCs.     

Performance degradation of solid oxide fuel cells due to sulfur poisoning of the electrochemical reaction and internal reforming reaction

Hydrogen sulfide is known to degrade the solid oxide fuel cell (SOFC) performance by adsorbing on the nickel anode catalyst. In this research, the mechanism underlying such SOFC degradation was evaluated based on a theoretical mathematical modeling approach and the sulfur coverage was calculated from a Temkin-like isotherm which is related to both temperature and hydrogen sulfide (H₂S) concentration. The influences of the cell temperature, H₂S concentration and electrochemical performance on both the sulfur coverage and cell polarization are studied in detail. Two specific models were considered to identify whether sulfur poisoning has a larger impact on cell performance through its effect on the electrochemical reaction or on the internal reforming reaction. It was found that sulfur poisoning has different effects on the hydrogen oxidation reaction and internal reforming reaction, leading to competing changes in cell performance with temperature and H₂S concentration.     

An additional layer in an anode support for internal reforming of methane for solid oxide fuel cells

Anode supported solid oxide fuel cells (SOFCs) have been extensively investigated for their ease of fabrication, robustness, and high electrochemical performance. SOFCs offer a greater flexibility in fuel choice, such as methane, ethanol or hydrocarbon fuels, which may be supplied directly on the anode. In this study, SOFCs with an additional Ni–Fe layer on a Ni–YSZ support are fabricated with process variables and characterized for a methane fuel application. The addition of Ni–Fe onto the anode supports exhibits an increase in performance when methane fuel is supplied. SOFC with a Ni–Fe layer, sintered at 1000 °C and fabricated using a 20 wt% pore former, exhibits the highest value of 0.94 A cm⁻² and 0.85 A cm⁻² at 0.8 V with hydrogen and methane fuel, respectively. An impedance analysis reveals that SOFCs with an additional Ni–Fe layer has a lower charge transfer resistance than SOFCs without Ni–Fe layer. To obtain the higher fuel cell performance with methane fuel, the porosity and sintering temperature of an additional Ni–Fe layer need to be optimized.     

Numerical analysis of electrical power generation and internal reforming characteristics in seal-less disk-type solid oxide fuel cells

For seal-less type solid oxide fuel cells, its power generation characteristics and distribution of the gas composition depend on not only the electrochemical reaction, but also complex kinetics and transport phenomena, because the internal reforming reaction and the water-gas shift reaction take place together with reverse diffusion of the ambient gas from the surroundings of the cell. The purpose of this paper is to theoretically explain the experimental results of the anodic concentration profile of gaseous species previously reported in a practical seal-less disk-type cell which used pre-reforming methane with steam as a fuel. A numerical model that takes into account the transport phenomena of the gaseous species and the internal reforming reaction with the water-gas shift reaction together with the assumption of the cell outlet boundary condition was constructed to numerically analyse the gas composition distribution and power generation characteristics. Numerical analyses by the model were conducted for the several cases reported as the experiment. The calculated results in the anode gas concentration profile and in the voltage–current characteristics show good agreement with the experimental data in every case, and then the validity of the simulation model was verified. Therefore, the model is useful for a seal-less disk-type cell which is operated by a fuel including non-reformed methane.     

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.     

Thermodynamic analysis of direct internal reforming of methane and butane in proton and oxygen conducting fuel cells

We present results of a thermodynamic analysis of direct internal reforming fuel cells, based on either a proton conducting fuel cell (FC-H⁺) or an oxygen ion conducting fuel cell (FC-O²⁻). We analyze the option of methane as fuel as well as butane. The model self-consistently combines all chemical equilibria in both the anode and cathode compartments with the proton or oxygen transfer rates through the membrane without predefining fuel utilization.     

Multi-physics modeling of a symmetric flat-tube solid oxide fuel cell with internal methane steam reforming

Methane is regarded as one of the ideal fuels for solid oxide fuel cells (SOFCs) due to its huge reserves and transportation properties. In this study, a 3D numerical model coupling with chemical reaction, electrochemical reaction, mass transfer, charge transfer, and heat transfer is developed to understand the heat and mass transfer processes of methane steam direct internal reforming based on double-sided cathodes (DSC) SOFC. After the model verification, the parametric simulations are performed to study the effects of operating voltage, inlet temperature, and steam to carbon (S/C) ratio on the performance of a DSC. It is found that the non-uniform distribution of flow rate among channels results in the non-uniform distribution of each physical field. Increasing the inlet temperature significantly enhances the performance of DSC, however, when the temperature is above 1073 K, the concentration loss and the temperature gradient of DSC increase, which is not conducive to the long-term operation of the DSC. In addition, we revealed the effect of the S/C ratios on the heat and mass transfer process. This study provides an insight into the heat and mass transfer process of SOFC with a mixture of steam and methane and operating conditions for enhancing the performance.     

Feasibility of palm‐biodiesel fuel for a direct internal reforming solid oxide fuel cell

The feasibility of a direct internal reforming (DIR) solid oxide fuel cell (SOFC) running on wet palm‐biodiesel fuel (BDF) was demonstrated. Simultaneous production of H₂‐rich syngas and electricity from BDF could be achieved. A power density of 0.32 W cm^?2 was obtained at 0.4 A cm^?2 and 800 °C under steam to carbon ratio of 3.5. Subsequent durability testing revealed that a DIR‐SOFC running on wet palm‐BDF exhibited a stable voltage of around 0.8 V at 0.2 A cm^?2 for more than 1 month with a degradation rate of approximately 15 % / 1000 h. The main cause of the degradation was an increase in the ohmic resistance. Copyright © 2012 John Wiley & Sons, Ltd.     

Three-dimensional modeling of pressure effect on operating characteristics and performance of solid oxide fuel cell

A three-dimensional (3-D) model for planar, anode-supported, solid oxide fuel cell (SOFC) is developed to investigate the effect of operating pressure on cell characteristics. The results show that the elevated operating pressure can improve cell performance by increasing open circuit voltage and reducing activation overpotential, and enhance the electrochemical reaction in the vicinity of electrolyte. Besides, the high pressure can also change the distributions of species and internal reforming reactions. Compared to the case using syngas as fuel, the operating pressure has more significant effects on temperature gradient along flow direction when partly pre-reformed gas is supplied. In addition, efficient control of cell temperature could be achieved by decreasing fuel utilization in the case of partly pre-reformed gas, but this is achieved at the expense of cell efficiency, especially under high pressure condition. Another way to reduce the temperature gradient is to adopt higher air ratio. Moreover, when partly pre-reformed gas is used, the counter-flow configuration has a better performance due to the higher overall temperature.     

NiMo-calcium-doped ceria catalysts for inert-substrate-supported tubular solid oxide fuel cells running on isooctane

A calcium-doped ceria (Ce_1-xCa_xO_2−δ, 0 ≤ x ≤ 0.3) has been applied as a ceramic support in NiMo-based catalysts for an internal reforming tubular solid oxide fuel cell running on isooctane. Introducing calcium into the CeO₂-based ceramic was found to improve conductivity of Ce_1-xCa_xO_2−δ. The Ce_0.9Ca_0.1O_2−δ (x = 0.10) sample exhibited an optimum conductivity of 0.045 S cm⁻¹ at 750 °C. The transport of oxygen ions in Ce_1-xCa_xO_2−δ promoted the catalytic partial oxidation of isooctane in the NiMo–Ce_1-xCa_xO_2−δ catalyst, which increased the fuel conversion as well as H₂ and CO yields. As a result, the NiMo–Ce_0.9Ca_0.1O_2−δ (x = 0.10) catalyst exhibited a high isooctane conversion of 98%, and the H₂ and CO yields achieved 74% and 83%, respectively, for reforming of isooctane and air at the O/C ratio of 1.0 at 750 °C. Furthermore, the NiMo–Ce_0.9Ca_0.1O_2−δ catalyst has been applied as an internal reforming layer for an inert-substrate-supported tubular solid oxide fuel cell running on isooctane/air. Due to its high reforming activity, the single cell presented an initial maximum power density of 355 mW cm⁻² in isooctane/air at 750 °C and displayed stable electrochemical performance during ~30 h operation. These results demonstrated the application feasibility of the NiMo–Ce_0.9Ca_0.1O_2−δ catalyst for direct internal reforming solid oxide fuel cells running on isooctane/air.     

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.     

Temperature effect on electrochemical promotion of syngas cogeneration in direct-methane solid oxide fuel cells

Syngas cogeneration in direct-methane solid oxide fuel cells with Ni–yttria-stabilized zirconia (YSZ) anodes was studied with temperature varying from 700 to 900 °C. A phenomenon of electrochemical promotion of bulk lattice-oxygen extraction from the YSZ electrolyte was observed. With increasing temperature, this promotion effect increases while both the rate enhancement ratios of CO and CO₂ formations decrease. The activation energy of CO and CO₂ formation under close circuit is lower than that under open circuit. The activation energy for the lattice-oxygen extraction from the YSZ bulk is higher than that for the oxygen transport through the YSZ bulk. The process of lattice-oxygen extraction from YSZ is rate determining in direct-methane oxidation under the condition of either close circuit or open circuit. The dependence of CO formation rate on the oxygen supply rate is stronger than that of CO₂ formation rate. Electrochemical promotion of bulk lattice-oxygen extraction enhances syngas cogeneration.     

Analysis of reformate syngas mixture fed solid oxide fuel cell through experimental and 0-D thermodynamic modeling studies

In this study, the performance assessment of a solid oxide fuel cell (SOFC) fed with a reformate syngas mixture and having anode off-gas recirculation is done in terms of energy and exergy analyses. In this regard, a zero-dimensional (0-D) mathematical model for SOFCs is developed. This model is validated by the results of the in-house experimental studies. In addition, parametric studies are carried out to assess the effect of operating parameters on fuel cell performance. The results show that the proposed model is very agreeable with experimental studies. The maximum error found in the validated model is 6.8% at the operating temperature of 800 °C. In addition, it is shown that the anode off-gas recirculation ratio does not have a significant effect on the performance of the SOFC at low current densities. Furthermore, the exergy destruction rate of SOFC increases by 23.2% under the high current density condition (i = 1.4 A/cm²) when the fuel utilization ratio increases from 0.75 to 0.95.     

Modelling of tubular-designed solid oxide fuel cell with indirect internal reforming operation fed by different primary fuels

Mathematical models of an indirect internal reforming solid oxide fuel cell (IIR-SOFC) fed by four different primary fuels, i.e., methane, biogas, methanol and ethanol, are developed based on steady-state, heterogeneous, two-dimensional and tubular-design SOFC models. The effect of fuel type on the thermal coupling between internal endothermic reforming with exothermic electrochemical reactions and system performance are determined. The simulation reveals that an IIR-SOFC fuelled by methanol provides the smoothest temperature gradient with high electrochemical efficiency. Furthermore, the content of CO₂ in biogas plays an important role on system performance since electrical efficiency is improved by the removal of some CO₂ from biogas but a larger temperature gradient is expected.Sensitivity analysis of three parameters, namely, a operating pressure, inlet steam to carbon (S:C) ratio and flow direction is then performed. By increasing the operating pressure up to 10 bar, the system efficiency increases and the temperature gradient can be minimized. The use of a high inlet S:C ratio reduces the cooling spot at the entrance of reformer channel but the electrical efficiency is considerably decreased. An IIR-SOFC with a counter-flow pattern (as based case) is compared with that with co-flow pattern (co-flow of air and fuel streams through fuel cell). The IIR-SOFC with co-flow pattern provides higher voltage and a smoother temperature gradient along the system due to superior matching between heat supplied from electrochemical reaction and heat required for steam reforming reaction; thus it is expected to be a better option for practical applications.