Numerical modelling of methane-powered micro-tubular, single-chamber solid oxide fuel cell

An experimentally validated, two-dimensional, axisymmetric, numerical model of micro-tubular, single-chamber solid oxide fuel cell (MT-SC-SOFC) has been developed. The model incorporates methane full combustion, steam reforming, dry reforming and water-gas shift reaction followed by electrochemical oxidation of produced hydrogen within the anode. On the cathode side, parasitic combustion of methane along with the electrochemical oxygen reduction is implemented. The results show that the poor performance of single-chamber SOFC as compared to the conventional (dual-chamber) SOFC (in case of micro-tubes) is due to the mass transport limitation on the anode side. The gas velocity inside the micro-tube is far too low when compared to the gas-chamber inlet velocity. The electronic current density is also non-uniform over the cell length, mainly due to the short length of the anode current collector located at the cell outlet. Furthermore, the higher temperature near the cell edges is due to the methane combustion (very close to the cell inlet) and current collection point (at the cell outlet). Both of these locations could be sensitive to the silver current collecting wire as silver may rupture due to cell overheating.     

A right-angular configuration for the single-chamber solid oxide fuel cell

A right-angular configuration for the single-chamber solid oxide fuel cell (SC-SOFC) has been proposed and operated successfully in a methane-oxygen mixture (CH₄:O₂ = 2:1) with a total flow rate of 300 mL min⁻¹. It was fabricated by attaching the Ni/yttria-stabilized zirconia (YSZ) anode and the Sm_0.2Ce_0.8O_1.9-impregnated La_0.7Sr_0.3MnO₃ (LSM) cathode on two mutually perpendicular planes of a YSZ electrolyte substrate. Effect of the relative position of the electrodes on the ohmic resistance has been investigated. It is shown that the cell exhibits the smallest ohmic resistance when the two electrodes are symmetrically located on the two planes. Compared with the conventional coplanar SC-SOFC, this configuration can make full use of the edge area of the electrolyte substrate and shorten the conductive channel of oxygen ion, leading to a remarkable reduction in ohmic resistance, an elevation of the open-circuit voltage, and, ultimately, an improved performance. The simple stack, consisting of two right-angular cells connected in series on an electrolyte, generated an open-circuit voltage 1.4 V at 700 °C and a maximum power 14.9 mW at 800 °C.     

Silver modified cathode for a micro-tubular, single-chamber solid oxide fuel cell

Micro-tubular, solid oxide fuel cells consisting of nickel, yttria-stabilized zirconia (Ni-YSZ) anode, yttria-stabilized zirconia (YSZ) electrolyte and lanthanum strontium cobaltite ferrite-gadolinium doped ceria (LSCF-GDC) cathode have been developed and operated under single-chamber conditions, utilizing methane/air mixture. The cell performance was compared with a silver modified cathode by the addition of 10wt% silver-paste in LSCF-GDC cathode. The cells with and without silver addition yielded maximum power densities of 118.75 mW cm⁻² and 61.53 mW cm⁻² at 700 °C, respectively. The results demonstrate that silver is a good candidate for enhancing the oxidation reduction kinetics via improved adsorption, desorption, dissociation and subsequent diffusion. However, long term performance of the silver modified cathode is not guaranteed under single-chamber conditions.     

Structural stability of silver under single-chamber solid oxide fuel cell conditions

In the present study, structural stability of silver under single-chamber conditions has been examined. Micro-tubular cells made of conventional solid oxide fuel cell materials (Ni-YSZ/YSZ/LSM) with silver paste and silver current-collecting wires (for both electrodes) were prepared. The cells were operated with methane/air mixture of 25/60 mL min⁻¹, furnace temperature of 750 °C, and at an operating voltage of 0.5 V. The results showed increasing porosity in the current-collecting silver wire with time, leading to rupture, finally. It is postulated that the porosity formation could be due to the formation of silver oxide which is highly unstable (volatile) at operating temperature considered in this study. Furthermore, vaporization and melting of silver due to cell overheating under mixed-reactant conditions is expected. Based on experimental evidences, it is concluded that silver may not be a good choice to be employed under the above specified operating conditions, as it lacks long-term structural stability.     

Micro-tubular, solid oxide fuel cell stack operated under single-chamber conditions

A micro-tubular, solid oxide fuel cell stack has been developed and operated under single-chamber conditions. The stack, made of three single-cells, arranged in triangular configuration, was operated between 500 and 700 °C with varying methane/air mixtures. The results show that the operating conditions for the stack differ significantly than the single-cell operation reported in our earlier study. The stack operated at 600 °C with methane/oxygen mixture of 1.0 gives stable performance for up to 48 h, whereas for the single-cell, this mixing ratio was not suitable. The increase in the inert gas flow rate improves the stack performance up to a certain extent, beyond that; the power output by the stack reduces due to extensive dilution of the reactants. It is concluded that both, the operating conditions and the addition of inert gas, need to be tuned according to the number of cells present within the stack.     

Cell temperature measurements in micro-tubular, single-chamber, solid oxide fuel cells (MT-SC-SOFCs)

Anode supported, micro-tubular, solid oxide fuel cells made of nickel, yttria-stabilized zirconia (Ni-YSZ) anode, yttria-stabilized zirconia (YSZ) electrolyte and lanthanum strontium manganite (LSM) cathode have been prepared and operated under single-chamber conditions. Four different cells with varying cathode location/size, i.e. inlet, center, outlet and full size have been compared. The highest temperature rise of ∼93 °C and the highest power density of ∼36 mW cm⁻² (at a furnace temperature of 750 °C with methane/air = 25/60 mL min⁻¹) was observed in the case of cathode-inlet configuration. The scanning electron microscope (SEM) analysis shows that both the anode and cathode were badly damaged near the cell inlet in case of cathode-inlet configuration. On the contrary, both of the electrodes remained undamaged in case of cathode-outlet configuration.     

Mixed-reactant, micro-tubular solid oxide fuel cells: An experimental study

Anode-supported, micro-tubular solid oxide fuel cells were prepared and operated, utilizing mixed-reactant (methane and air mixture) supply. The cells were composed of conventional materials, i.e. nickel, yttria-stabilized zirconia (Ni-YSZ) as anode supported material, yttria-stabilized zirconia (YSZ) as electrolyte, and lanthanum strontium manganite (LSM) as cathode material. The cells were operated at various temperatures in between 550 and 800 °C with varying methane/air ratio (1:1-1:4.76). Cell performance was found to be strongly dependent on flow rate and mixing ratio. At 750 °C, the maximum open circuit voltage (OCV) of the cell was 1.05 V at a methane/air ratio of 1:4.76, with a maximum power output of 122 mW cm⁻². The degradation test shows 0.05% performance loss per 24 h, thereafter, fluctuations in current density were observed due to oxidation-reduction cycles over nickel surface. It is therefore concluded that although the methane/air ratio of 1:4.76 gives the best performance but the long-term performance is not guaranteed under such conditions.     

Influence of patterned electrode geometry on performance of co-planar,single-chamber,solid oxide fuel cell

Co-planar, single-chamber, solid oxide fuel cells (SC-SOFCs) with linearly patterned electrode structures on one surface of the electrolyte are fabricated via a robo-dispensing method. The SC-SOFCs with various electrode patterns are prepared to investigate the relationship between electrode geometry and cell performance. The open-circuit voltage (OCV) for cells with a single electrode pair is unaffected by the anode-to-cathode distance. By contrast, for cells with multiple electrode pairs, increasing the number of electrode pairs leads to a gradual decrease in OCV. These observations confirm that the inter-mixing of product gases causes a loss in OCV and power density, which in turn reduces the oxygen partial pressure gradient between the anode and cathode. Keeping the electrode pairs apart by ∼4 mm permits cells with complex electrode geometry to exhibit higher OCVs and power densities.     

Efficiency and fuel utilization of methane-powered single-chamber solid oxide fuel cells

The single-chamber solid oxide fuel cell (SC-SOFC) is a simplification of the conventional dual-chamber SOFC and has great potential for meeting portable power generation needs. While the high energy density of hydrocarbon fuels makes SC-SOFC a promising candidate as a power source for scenarios where portability is most preferred, the low efficiency and fuel utilization reported by many experimental groups have presented a major barrier keeping it from real application.     

Alternative perovskite materials as a cathode component for intermediate temperature single-chamber solid oxide fuel cell

This paper exploits the suitability of three perovskite materials Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF), GdBaCo₂O_5+δ (GBC) and Ba_0.5Sr_0.5Mn_0.7Fe_0.3O_3−δ (BSMF) as SOFC cathodes in the single-chamber configuration operating at the intermediate temperature range. TG analysis showed high thermal stability depending on the crystalline phases of the materials. The catalytic activity of these three materials for hydrocarbon conversion was investigated under a realistic feed, i.e. with hydrocarbon, oxygen, water and carbon dioxide. Electrochemical impedance spectroscopy of the various cathodes tested in symmetric cell configuration revealed a B-site dependence of the electrode catalytic activity for oxygen reduction. High temperature (1000 °C) powder reactivity tests over a gadolinium doped-ceria (CGO) and perovskite cathode revealed excellent chemical compatibility of BSMF and CGO. Catalytic tests associated with thermal and structural characterization attest to the suitability of these materials in the single-chamber configuration.     

Analysis of a perovskite-ceria functional layer-based solid oxide fuel cell

A fuel cell based on a functional layer of perovskite Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ (BSCF) composited samarium doped ceria (SDC) has been developed. The device achieves a peak power density of 640.4 mW cm^?2 with an open circuit voltage (OCV) of 1.04 V at 560 °C using hydrogen and air as the fuel and oxidant, respectively. A numerical model is applied to fit the experimental cell voltage. The kinetics of anodic and cathodic reactions are modeled based on the measurements obtained by electrochemical impedance spectroscopy (EIS). Modeling results are in well agreement with the experimental data. Mechanical stability of the cell is also examined by using analysis with field emission scanning electron microscope (FESEM) associated with energy dispersive spectroscopy (EDS) after testing the cell performance.     

A durability model for solid oxide fuel cell electrodes in thermal cycle processes

Despite the intense interest in solid oxide fuel cells, many details of their durability remain a mystery. Here, we present the insight see on electrode degradation in thermal cycle processes. Our model interprets the degradation to the stresses induced by thermal expansion mismatch of the electrocatalyst and electrolyte in a composite electrode that undergoes a temperature change. Such stresses might break the particle-particle interfaces (grain boundaries), thus reduce oxygen-ionic conductivity, electronic conductivity, and three-phase boundaries within the electrode, and consequently, degrade its performance. The model formulates the degradation rate as a function of cycle number, thermal expansion coefficient, composition, and particle size, providing a remarkable ability to balance thermal expansion restriction and catalytic activity of electrode materials, to optimize the electrode structure and composition, and to predict thermal-cycle durability. The model explicitly demonstrates that, in addition to their excellent electrochemical activity, nanostructured electrodes exhibit exceptional durability in thermal cycle processes.     

A review of numerical modeling of solid oxide fuel cells

The solid oxide fuel cell (SOFC) is one of the most promising fuel cells for direct conversion of chemical energy to electrical energy with the possibility of its use in co-generation systems because of the high temperature waste heat. Various mathematical models have been developed for three geometric configurations (tubular, planar, and monolithic) to solve transport equations coupled with electrochemical processes to describe the reaction kinetics including internal reforming chemistry in SOFCs. In recent years, considerable progress has been made in modeling to improve the design and performance of this type of fuel cells. The numbers of the contributions on this important type of fuels have been increasing rapidly. The objective of this paper is to summarize the present status of the SOFC modeling efforts so that unresolved problems can be identified by the researchers.     

Fabrication and testing of coplanar single-chamber micro solid oxide fuel cells with geometrically complex electrodes

Coplanar single-chamber micro solid oxide fuel cells (SC-μSOFCs) with curvilinear microelectrode configurations of arbitrarily complex two-dimensional geometry were fabricated by a direct-write microfabrication technique using conventional fuel cell materials. The electrochemical performance of two SC-μSOFCs with different electrode shapes, but comparable electrode and inter-electrode dimensions, was characterized in a methane–air mixture at 700 °C. Both cells exhibited stable open circuit voltage and peak power density of 0.9 V and 2.3 mW cm⁻², respectively, indicating that electrode shape did not have a significant influence on the performance of these fuel cells.     

Numerical simulation of intermediate-temperature direct-internal-reforming planar solid oxide fuel cell

A numerical model for an anode-supported intermediate-temperature direct-internal-reforming planar solid oxide fuel cell (SOFC) was developed. In this model, the volume-averaging method is applied to the flow passages in the SOFC by assuming that a porous material is inserted in the passages as a current collector. This treatment reduces the computational time and cost by avoiding a full three-dimensional simulation while maintaining the ability to solve the flow and pressure fields in the streamwise and spanwise directions. In this model, quasi-three-dimensional multicomponent gas flow fields, the temperature field, and the electric potential/current fields were simultaneously solved. The steam-reforming reaction using methane, the water-gas shift reaction, and the electrochemical reactions of hydrogen and carbon monoxide were taken into account. It was found that the endothermic steam-reforming reaction led to a reduction in the local temperature near the inlet and limited the electrochemical reaction rates therein. Computational results indicated that the local temperature and current density distributions can be controlled by tuning the pre-reforming rate. It was also found that a small amount of heat loss from the sidewall can cause significant nonuniformity in the flow and thermal fields in the spanwise direction.     

Experimental and numerical studies on chemically reacting gas flow in the porous structure of a solid oxide fuel cells internal fuel reformer

This paper presents experimental and numerical studies on the fuel reforming process on an Ni/YSZ catalyst. Nickel is widely known as a catalyst material for Solid Oxide Fuel Cells. Because of its prices and catalytic properties, Ni is used in both electrodes and internal reforming reactors. To optimize the reforming reactors, detailed data about the entire reforming process is required. In the present paper kinetics of methane/steam reforming on the Ni/YSZ catalyst was experimentally investigated. Measurements including different thermal boundary conditions, the fuel flow rate and the steam-to-methane ratios were performed. The reforming rate equation derived from experimental data was used in the numerical model to predict synthetic gas composition at the outlet of the reformer.     

A novel direct carbon fuel cell by approach of tubular solid oxide fuel cells

A direct carbon fuel cell based on a conventional anode-supported tubular solid oxide fuel cell, which consisted of a NiO-YSZ anode support tube, a NiO-ScSZ anode functional layer, a ScSZ electrolyte film, and a LSM-ScSZ cathode, has been successfully achieved. It used the carbon black as fuel and oxygen as the oxidant, and a preliminary examination of the DCFC has been carried out. The cell generated an acceptable performance with the maximum power densities of 104, 75, and 47 mW cm⁻² at 850, 800, and 750 °C, respectively. These results demonstrate the feasibility for carbon directly converting to electricity in tubular solid oxide fuel cells.     

Performance analysis of solid oxide fuel cell using reformed fuel

Fuelling SOFC with reformed fuel can be beneficial due to it being cheaper compared to pure hydrogen. A biomass fuel can be easily modeled as a reformed fuel, as it can be converted into H₂ and CO using gasification or biodegradation, the main composition of product from a reformer. Hence in this study it is assumed that feed to the fuel cell contains only H₂ and CO. A closed parametric model is formulated. Performance is analyzed with changes in temperature, pressure and fuel ratio; considering the possible voltage losses, like ohmic, activation, mass transfer and fuel crossover. Performance curves consisting of operating voltage, fuel utilization, efficiency, power density and current density are developed for both pure hydrogen and mixture of CO and H₂. Variations of open circuit voltage with temperature, power density with current density, operating voltage with current density and maximum power density with fuel utilization are also evaluated.