A direct-flame solid oxide fuel cell (DFFC) operated on methane,propane, and butane

This paper presents an experimental study of a direct-flame type solid oxide fuel cell (DFFC). The operation principle of this system is based on the combination of a combustion flame with a solid oxide fuel cell (SOFC) in a simple, no-chamber setup. The flame front serves as fuel reformer located a few millimeters from the anode surface while at the same time providing the heat required for SOFC operation. Experiments were performed using 13-mm-diameter planar SOFCs with Ni-based anode, samaria-doped ceria electrolyte and cobaltite cathode. At the anode, a 45-mm-diameter flat-flame burner provided radially homogeneous methane/air, propane/air, and butane/air rich premixed flames. The cell performance reaches power densities of up to 120 mW cm⁻², varying systematically with flame conditions. It shows a strong dependence on cell temperature. From thermodynamic calculations, both H₂ and CO were identified as species that are available as fuel for the SOFC. The results demonstrate the potential of this system for fuel-flexible power generation using a simple setup.     

Entropy generation analysis in a monolithic-type solid oxide fuel cell (SOFC)

The aim of the paper is to investigate possible improvements in the geometry design of a monolithic solid oxide fuel cells (SOFCs) through analysis of the entropy generation terms. The different contributions to the local rate of entropy generation are calculated using a computational fluid dynamic (CFD) model of the fuel cell, accounting for energy transfer, fluid dynamics, current transfer, chemical reactions and electrochemistry. The fuel cell geometry is then modified to reduce the main sources of irreversibility and increase its efficiency.     

Fabrication of hydrogen electrode supported cell for utilized regenerative solid oxide fuel cell application

A utilized regenerative solid oxide fuel cell (URSOFC) provides the dual function of performing energy storage and power generation, all in one unit. When functioning as an energy storage device, the URSOFC acts like a solid oxide electrolyzer cell (SOEC) in water electrolysis mode; whereby the electric energy is stored as (electrolyzied) hydrogen and oxygen gases. While hydrogen is useful as a transportation fuel and in other industrial applications, the URSOFC also acts as a solid oxide fuel cell (SOFC) in power generation mode to produce electricity when needed. The URSOFC would be a competitive technology in the upcoming hydrogen economy on the basis of its low cost, simple structure, and high efficiency. This paper reports on the design and manufacturing of its anode support cell using commercially available materials. Also reported are the resulting performance, both in electrolysis and fuel cell modes, as a function of its operating parameters such as temperature and current density. We found that the URSOFC performance improved with increasing temperature and its fuel cell mode had a better performance than its electrolysis mode due to a limited humidity inlet causing concentration polarization. In addition, there were great improvements in performance for both the SOFC and SOEC modes after the first test and could be attributed to an increase in porosity within the oxygen electrode, which was beneficial for the oxygen reaction.     

Performance of cone-shaped tubular anode-supported segmented-in-series solid oxide fuel cell stack fabricated by dip coating technique

A simple and feasible technique is developed successfully to fabricate the cone-shaped tubular segmented-in-series solid oxide fuel cell (SOFC) stack. The cone-shaped tubular anode substrates and yttria-stabilized zirconia (YSZ) electrolyte films are fabricated by dip coating technique. After sintering at 1400 °C for 4 h, a dense and crack-free YSZ film with a thickness of about 35.9 μm is successfully obtained. The single cell, NiO–YSZ/YSZ/LSM–YSZ, provides a maximum power density of 1.08 and 1.35 W cm⁻² at 800 and 850 °C, respectively, using moist hydrogen (75 ml/min) as fuel and ambient air as oxidant.A two-cell-stack based on the above-mentioned cone-shaped tubular anode-supported SOFC was assembled and tested. The maximum total power at 800 °C was about 3.7 W.     

Crack severity in relation to non-homogeneous Ni oxidation in anode-supported solid oxide fuel cells

The full oxidation of Ni-YSZ anode-supported cells at high temperatures (>700 °C) is shown here to lead to much more severe degradation (larger quantity and wider cracks in the electrolyte) than at lower temperatures. This correlates with the linear mass gain/time profile observed in TGA experiments at high temperatures, indicative of diffusion controlled Ni oxidation and thus the presence of O₂ (and Ni/NiO) concentration gradients into the depth of the anode layer. At low partial pressures of O₂, the severity of cracking also increases. SEM studies of partially oxidized anode layers confirmed that Ni oxidation is non-homogeneous when carried out at either high temperatures or low pO₂, in which case the outer regions of the anode (near the anode/air interface) become almost fully oxidized, while the inner regions (near the electrolyte) remain metallic. Under these conditions, the continued volume expansion associated with NiO formation can then only occur towards the electrolyte, increasing the compressive stress inside the anode as the Ni continues to be oxidized, leading to electrolyte cracking and warping (convex to the electrolyte). To prevent severe degradation to the cell, efforts should therefore be made to avoid gradients in NiO/Ni content during oxygen exposure of Ni-YSZ anode-supported cells at high temperatures.     

Chemo-mechanical coupling model of solid oxide fuel cell under high-temperature oxidation

Solid oxide fuel cell (SOFC), which is a generation device that converts chemical energy into electrical energy, has been regarded as a new generation device. The diffusion mechanism of metal cations and anions during the high-temperature oxidation process of SOFC is proposed. Based on the equilibrium expression and diffusion equation, the chemo-mechanical coupling relationship between oxide stress and thickness growth of the oxide layer is established by considering the influences of viscoplastic effect and oxide growth effect. The present theoretical result is consistent with the previous experimental results. In addition, the stress critical points corresponding to different parameters are different in initial oxidation stage. The oxide stress varies dramatically with time in the compressive stress phase, but it changes slowly in the tensile stress phase. The compressive stress that exists in the oxide layer increases with the growth coefficient (D_NiO = 1000-15 000 m⁻¹) of the oxide layer. The oxide stresses in oxide layer and electrolyte reduce with viscoplastic coefficient of the oxide layer from J_NiO = 8.97 × 10⁻⁵ Pa⁻¹ s⁻¹ to J_NiO = 16.97 × 10⁻⁵ Pa⁻¹ s⁻¹ and anode-oxide layer thicknesses from H = 30 μm to H = 660 μm, while they increase with viscoplastic coefficient of the anode from J_Ni = 3.81 × 10⁻⁵ Pa⁻¹ s⁻¹ to J_Ni = 12.81 × 10⁻⁵ Pa⁻¹ s⁻¹ and kinetic parabolic constant from k _p = 2.9 × 10⁻¹⁵ m²s⁻¹ to k _p = 12.9 × 10⁻¹⁵ m²s⁻¹ in whole oxidation stage. The oxide thickness increases with kinetic parabolic constant in the whole oxidation stage and this changing trend accords with parabolic diffusion law. The oxide thickness increases with temperatures increasing. The results obtained from this study will provide the reference to the researches of the chemo-mechanical coupling model and performance optimization of SOFC under high-temperature oxidation.     

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.     

Nickel zirconia cerate cermet for catalytic partial oxidation of ethanol in a solid oxide fuel cell system

Ni + Ce_xZr_1−xO₂ (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) cermets were synthesized and their catalytic performance for partial oxidation of ethanol (POE) reaction was studied. The structure, reducibility properties and carbon deposition behavior of the various catalysts were investigated. Among the various catalysts, Ni + Ce_0.8Zr_0.2O₂ displayed the best catalytic activity in terms of H₂ selectivity and also the highest coking resistance. The fuel cell with Ni + Ce_0.8Zr_0.2O₂ catalyst layer delivered a peak power density of 692 mW cm⁻² at 700 °C when operating on ethanol–O₂ gas mixtures, comparable to that applying hydrogen fuel. The fuel cell also showed an improved operation stability on ethanol–O₂ fuel for 150 h at 700 °C. Ni + Ce_0.8Zr_0.2O₂ is promising as an active and coke-tolerant catalyst layer for solid oxide fuel cells operating on ethanol-O₂ fuel, which makes it highly attractive by applying biofuel in an SOFC system for efficiency electric power generation.     

Performance of a Ni/Al2O3 cermet-supported tubular solid oxide fuel cell operating with biomass-based syngas through supercritical water

Thermochemical gasification of biomass through the supercritical water gasification (SCWG) has high gasification efficiency at lower temperatures and can deal directly with wet biomass without drying. Besides, solid oxide fuel cells (SOFCs) appear to be an important technology in the future as they can operate at a high efficiency. Therefore, the combination of biomass gasification through supercritical water with SOFC represents one of the most potential applications for highly efficient utilization of biomass.     

An error in solid oxide fuel cell stack modeling

This paper points out an error in the literature and analyzes its effect on electrochemical models of solid oxide fuel cell stacks. A correction is presented.     

Performance analysis of a solid oxide fuel cell with reformed natural gas fuel

In the present study a two‐dimensional model of a tubular solid oxide fuel cell operating in a stack is presented. The model analyzes electrochemistry, momentum, heat and mass transfers inside the cell. Internal steam reforming of the reformed natural gas is considered for hydrogen production and Gibbs energy minimization method is used to calculate the fuel equilibrium species concentrations. The conservation equations for energy, mass, momentum and voltage are solved simultaneously using appropriate numerical techniques. The heat radiation between the preheater and cathode surface is incorporated into the model and local heat transfer coefficients are determined throughout the anode and cathode channels. The developed model has been compared with the experimental and numerical data available in literature. The model is used to study the effect of various operating parameters such as excess air, operating pressure and air inlet temperature and the results are discussed in detail. The results show that a more uniform temperature distribution can be achieved along the cell at higher air‐flow rates and operating pressures and the cell output voltage is enhanced. It is expected that the proposed model can be used as a design tool for SOFC stack in practical applications. Copyright © 2009 John Wiley & Sons, Ltd.     

High performance praseodymium nickelate oxide cathode for low temperature solid oxide fuel cell

The praseodymium nickelate oxide Pr₂NiO_4+δ, a mixed conducting oxide with the K₂NiF₄-type structure, was evaluated as cathode for low temperature solid oxide fuel cells (T = 873 K). The electrochemical performance of the cathode has been improved by optimization of the microstructure of the porous cathode combined with the use of a ceria barrier layer in between the cathode and zirconia electrolyte. Both low polarization and ohmic resistances were obtained using Pr₂NiO_4+δ-powders with a median particle size of 0.4 μm, and sintering the screen printed layer at a sintering temperature of about 1353 K for 1 h. These manufacturing conditions resulted in a cathode microstructure with well established connections between the cathode particles and good adhesion of the cathode on the electrolyte. Full-sized anode supported cells have been manufactured using the same process conditions for the Pr₂NiO_4+δ cathode and tested. The best results were obtained when using a dense Ce_0.8Gd_0.2O_1.9 (20CGO) barrier layer. While a complete optimization of the cell preparation has not yet been achieved, the electrochemical performances of anode supported cells with Pr₂NiO_4+δ are higher than those with the well known state-of-the-art La_0.6Sr_0.4Fe_0.8Co_0.2O_3−δ (LSFC) material.     

A novel catalytic layer material for direct dry methane solid oxide fuel cell

The perovskite structured oxide La_0.75Sr_0.25Cr_0.5−xFe_xMn_0.5O_3−δ (LSCFMx, x = 0.05, 0.1, 0.15, 0.2, 0.25) powder is prepared by the liquid phase method, using iron as dopant to replace the chromium. According to XRD patterns, perovskite-like LSCFMx are stable in pure H₂, except for LSCFM0.25. Thus the maximum content of Fe doping is 0.2. The calculated lattice volume increases along with the content of iron and the powders show excellent chemical compatibility with yttria-stabilized zirconia (YSZ). The electrical conductivities for LSCFM0.15 and LSCFM0.2 are very comparative, and they exhibit similar performance as catalytic materials. In contrast, the different sintered temperature with the LSCFM0.2 catalytic layer, at 1300 °C exhibits higher electrochemical performance. When dry methane is used as the fuel, the ohmic resistance and polarization resistance are 0.15 and 0.55 Ω cm², respectively, and the power density reaches 550 mW cm⁻².     

Dynamic modeling and evaluation of solid oxide fuel cell - combined heat and power system operating strategies

Operating strategies of solid oxide fuel cell (SOFC) combined heat and power (CHP) systems are developed and evaluated from a utility, and end-user perspective using a fully integrated SOFC-CHP system dynamic model that resolves the physical states, thermal integration and overall efficiency of the system. The model can be modified for any SOFC-CHP system, but the present analysis is applied to a hotel in southern California based on measured electric and heating loads. Analysis indicates that combined heat and power systems can be operated to benefit both the end-users and the utility, providing more efficient electric generation as well as grid ancillary services, namely dispatchable urban power.Design and operating strategies considered in the paper include optimal sizing of the fuel cell, thermal energy storage to dispatch heat, and operating the fuel cell to provide flexible grid power. Analysis results indicate that with a 13.1% average increase in price-of-electricity (POE), the system can provide the grid with a 50% operating range of dispatchable urban power at an overall thermal efficiency of 80%. This grid-support operating mode increases the operational flexibility of the SOFC-CHP system, which may make the technology an important utility asset for accommodating the increased penetration of intermittent renewable power.     

A novel design and performance of cone-shaped tubular anode-supported segmented-in-series solid oxide fuel cell stack

A novel design of cone-shaped tubular segmented-in-series solid oxide fuel cell (SOFC) stack is presented in this paper. The cone-shaped tubular anode substrates are fabricated by slip casting technique and the yttria-stabilized zirconia (YSZ) electrolyte films are deposited onto the anode tubes by dip coating method. After sintering at 1400 °C for 4 h, a dense and crack-free YSZ film with a thickness of about 7 μm is successfully obtained. The single cell, NiO-YSZ/YSZ (7 μm)/LSM-YSZ, provides a maximum power density of 1.78 W cm⁻² at 800 °C, using moist hydrogen (75 ml min⁻¹) as fuel and ambient air as oxidant.A two-cell-stack based on the above-mentioned cone-shaped tubular anode-supported SOFC is fabricated. Its typical operating characteristics are investigated, particularly with respect to the thermal cycling test. The results show that the two-cell-stack has good thermo-mechanical properties and that the developed segmented-in-series SOFC stack is highly promising for portable applications.     

Transient modeling of anode-supported solid oxide fuel cells

An isothermal 2-D transient model is developed for an anode-supported solid oxide fuel cell. The model takes into account the transient effects of both charge migration and species transport in PEN assembly. Due to the lack of transient experimental data, the transient model, under steady state operating conditions, is validated using experimental results from open literature. Numerical results show that the cell can obtain very quick transient current response when subjected to a step voltage change, followed by a slow current transient period due to species diffusion effects within porous electrodes. It is also found that the transient response of the cell current is sensitive to oxygen concentration change at cathode/channel interface, whereas the current response is slow when step change of hydrogen concentration is applied at anode/channel interface. The cell transient performance can be improved by increasing porosity or decreasing tortuosity of electrodes.     

A study of solid oxide fuel cell stack failure by inducing abnormal behavior in a single cell test

It is well known that cell imbalance can lead to failure of batteries. Prior theoretical modeling has shown that similar failure can occur in solid oxide fuel cell (SOFC) stacks due to cell imbalance. Central to failure model for SOFC stacks is the abnormal operation of a cell with cell voltage becoming negative. For investigation of SOFC stack failure by simulating abnormal behavior in a single cell test, thin yttria-stabilized zirconia (YSZ) electrolyte, anode-supported cells were tested at 800 °C with hydrogen as fuel and air as oxidant with and without an applied DC bias. When under a DC bias with cell operating under a negative voltage, rapid degradation occurred characterized by increased cell resistance. Visual and microscopic examination revealed that delamination occurred along the electrolyte/anode interface. The present results show that anode-supported SOFC stacks with YSZ electrolyte are prone to catastrophic failure due to internal pressure buildup, provided cell imbalance occurs. The present results also suggest that the greater the number of cells in an SOFC stack, the greater is the propensity to catastrophic failure.     

Kinetic Monte Carlo simulation of the elementary electrochemistry in a hydrogen-powered solid oxide fuel cell

A hydrogen-powered solid oxide fuel cell (SOFC), with a Pt cathode and a Ni anode, is modeled with a kinetic Monte Carlo (KMC) simulation technique. A series of reversible elementary steps are adopted from experiments and theories for simulating the oxygen reduction reaction near the cathode-electrolyte interface and the hydrogen-oxidation mechanism near the anode-electrolyte interface. By studying the change in the ionic current density, the sensitivity of the kinetic parameters is analyzed, and the influence of various operating conditions and different material properties are also explored. The results show that the dominant elementary process is the oxygen incorporation into the yttria-stabilized zirconia (YSZ) electrolyte at the cathode. Increasing the applied bias voltage, operating temperature, and relative permittivity of the YSZ, but reducing the thickness of the YSZ enhance the ionic current density and improve the efficiency of the SOFC.     

On the nanostructuring and catalytic promotion of intermediate temperature solid oxide fuel cell (IT-SOFC) cathodes

Solid oxide fuel cells (SOFCs) are highly efficient energy converters for both stationary and mobile purposes. However, their market introduction still demands the reduction of manufacture costs and one possible way to reach this goal is the decrease of the operating temperatures, which entails the improvement of the cathode electrocatalytic properties. An ideal cathode material may have mixed ionic and electronic conductivity as well as proper catalytic properties. Nanostructuring and catalytic promotion of mixed conducting perovskites (e.g. La_0.58Sr_0.4Fe_0.8Co_0.2O_3−δ) seem to be promising approaches to overcoming cathode polarization problems and are briefly illustrated here. The preparation of nanostructured cathodes with relatively high surface area and enough thermal stability enables to improve the oxygen exchange rate and therefore the overall SOFC performance. A similar effect was obtained by catalytic promoting the perovskite surface, allowing decoupling the catalytic and ionic-transport properties in the cathode design. Noble metal incorporation may improve the reversibility of the reduction cycles involved in the oxygen reduction. Under the cathode oxidizing conditions, Pd seems to be partially dissolved in the perovskite structure and as a result very well dispersed.