Validation of a physically-based solid oxide fuel cell anode model combining 3D tomography and impedance spectroscopy

Ni-Sm 2O 3 cermet anodes for intermediate-temperature solid oxide fuel cells with stabilized zirconia electrolytes

This paper presents electrochemical impedance simulation of a solid oxide fuel cell (SOFC) anode in order to investigate the effect of mass transport processes on the impedance spectra. The current model takes in to account the gas-phase transport processes both in the gas channel and within the porous electrode and couples the gas transport processes with the electrochemical kinetics. The impedance simulation is carried out in time domain, and the correlation between the anode harmonic responses to the sinusoidal excitation and the impedance spectra is analyzed. In order to solve the system of non-linear equations, an in-house code based on the finite difference method is developed and utilized. Results show a depressed semicircle in the Nyquist plot, which originates from gas transport processes in the gas channel, in addition to a Warburg diffusion impedance originates from gas transport in the thick porous anode. The influence of parameters such as electrode thickness, inlet gas composition, and temperature is also investigated and the results are discussed. The simulation results are in good agreement with published data.

3D imaging and quantification of interfaces in SOFC anodes

Solid oxide fuel cells (SOFCs) are being extensively researched for clean power generation from coal-derived syngas. Some of the contaminants in syngas such as phosphine (PH3) may interact with the SOFC anode material, and degrade its electrochemical performance and material properties. In this paper, a modified Sagnac interferometry method is utilized to monitor the anode surface transient temperature as a function of applied current densities under hydrogen and simulated coal syngas. Moreover, the poisoning effects of PH3 contaminant on the SOFCs performance are investigated in dry and moist conditions. The experimental results indicate that the Ni-cermet-based SOFC anode is more susceptible to degradation due to PH3 in the presence of steam than under dry conditions. These experiments are valuable for the validation and the development of SOFC electrochemical models, and understanding the anode-contaminant interaction.

(La0.8Sr0.2)0.95MnO3−δ (LSM)–Gd0.1Ce0.9O2−δ (gadolinium-doped ceria, GDC) composite cathode material was developed and characterized in terms of chemical stability, sintering behaviour, electrical conductivity, mechanical strength and microstructures to assess its feasibility as cathode support applications in cathode-supported fuel cell configurations. The sintering inhibition effect of LSM, in the presence of GDC, was observed and clearly demonstrated. The mechanical characterization of developed composites revealed that fracture behaviour is directly affected by pore size distribution. The Weibull strength distribution showed that for bimodal pore size distribution, two different fracture rates were present. Furthermore, the contiguity of LSM and GDC grains was calculated with image analysis, and correlation of microstructural features with mechanical and electrical properties was established. Subsequently, an LSM/GDC-based cathode-supported direct carbon fuel cell (DCFC) with Ni/ScSZ (scandia-stabilised zirconia) anode was successfully fabricated via slurry coating and co-firing techniques. The microstructures of electrodes and electrolyte layers were observed to confirm the desired morphology after co-sintering, and a single cell was electrochemically characterized in solid oxide fuel cell (SOFC) and DCFC mode with ambient air as oxidant. The higher values of open-circuit voltage indicated that the electrolyte layer prepared by vacuum slurry coating is dense enough. The corresponding peak power densities at 850 °C were 450 and 225 mW cm−2 in SOFC and DCFC mode, respectively. Electrochemical impedance spectroscopy was carried out to observe electrode polarization and ohmic resistance.

Direct comparison between X-ray nanotomography and scanning electron microscopy for the microstructure characterization of a solid oxide fuel cell anode

Biomass gasification has acquired considerable interest as a sustainable and environmentally friendly way to produce heat, hydrogen or electricity from agro-industrial wastes or other kinds of biomass. A very effective solution for the achievement of high electrical efficiency (up to 55%) is the integration of biomass gasification with solid oxide fuel cell (SOFC) technology, including the necessary gas cleanup to avoid degradation of the SOFC. For this reason, this paper first shows in detail the risk and the impact of carbon deposition, exposure to tar, hydrogen sulphide, hydrogen chloride and alkali metals on SOFC anode and then, considering the tolerance limit for inorganic and organic contaminants (<1 ppmv for H2S, HCl and alkali and <10 ppmv for tar), offers an overview of the most relevant and effective technologies to remove these contaminants and to feed safely a SOFC system.

Solid Oxide Fuel Cells (SOFCs) is one of the most attractive energy conversion devices because of their high efficiency, low pollution, and fuel flexibility. La0.2Sr0.8TiO3 (LST) anode material shows its potential utilization in direct oxidation of methane fuel without carbon formation. In this paper, LST powders were synthesized by traditional solid-state method, and then mixed with scandia-stabilized zirconia (SSZ) in mass ratio of 5: 5 to prepare the composite anode materials. Symmetrical cells with LST-SSZ composite anode were fabricated and measured. Their polarization resistances in hydrogen at 700°C, 750°C and 800°C were 5.3, 3.0 and 2.0 Ω·cm, respectively. Considering the insufficient conductivity of LST, 10wt%Ni was impregnated into the composite anode to improve the anode performance. The polarization resistance of the symmetrical cell with 10wt% Ni impregnation load is obviously reduced. The maximum power density of a cathode supported single cell with 10wt%Ni-LST-SSZ composite anode are 225 mW/cm and 175 mW/cm in hydrogen and in methane at 750°C, respectively, and the single cell shows its stability running in methane fuels.

High operating temperature affords solid oxide fuel cells (SOFCs) fuel flexibility, favorable kinetics, enhanced transport properties and high quality heat for secondary thermodynamic cycles.1 Elevated temperatures, however, present challenges to ensuring cell durability.2 Coarsening of nickel in the Ni-YSZ anode is one such challenge that can lead to significant performance degradation. The fundamental driving force Δμ for coarsening phenomena is given by Eq. 1.3 The expression, which assumes isotropic interfacial energy, indicates that the chemical potential μ of a curved interface differs from that of a flat interface μ 0 by the factor VmγH, where H is mean curvature, γ interfacial energy and Vm molar volume. Δμ = μ - μ 0 = VmγH (1) Eq. 1 makes evident that variations in interface curvature, i.e., interface shape, directly correspond to variations in chemical potential. Furthermore, it follows from Eq. 1 that microstructural coarsening is fundamentally related to variations in interface shape. The link between interface shape and coarsening propensity is well known and methods have been developed to directly measure interfacial curvature distributions for complex morphologies in 3-D.4,5 In this work, these techniques are applied to 3-D images obtained by x-ray nanotomography to study coarsening in microstructures obtained from Ni-YSZ solid oxide fuel cell anodes aged for varying lengths of time. This work builds on a previous characterization of the same samples.6 The curvature measurements collected suggest that a combination of coarsening and morphological instability, which leads to channel pinch-off, severely diminish the connectivity of the anode’s Ni network and, in addition, lead to a significant loss of both nominal and effective triple-phase boundary (TPB) density. Both the loss of connectivity and TPB density coincide with cell performance degradation that was observed in the aging experiment7 from which the anode samples were taken. References Singhal, S. C.; Kendall, K. High Temperature Solid Oxide Fuel Cells, Elsevier, 2003.Yokokawa, H.; Tu, H.; Iwanschitz, B.; Mai, A. Fundamental mechanisms limiting solid oxide fuel cell durability. J. Power Sources 2008, 400-412.Voorhees, P. W. The Theory of Ostwald Ripening. J. Stat. Phys. 1985, 231-252.Glicksmann, M. E.; Voorhees, P. W. Ostwald Ripening and Relaxation in Dendritic Structures. Metall. Trans. A, 1984, 995-1001.Mendoza, R.; Savin, I.; Thornton, K.; Voorhees, P. W. Topological complexity and the dynamics of coarsening. Nat. Mater., 2004 385-388.Nelson, G. J.; Grew, K. N.; Izzo, J. R. Jr.; Lombardo, J. J.; Harris, W. M.; Faes, A.; Hessler-Wyser, A.; Van herle, J.; Wang, S.; Chu, Y. S.; Virkar, A. V.; Chiu, W. K. S. Three-dimensional microstructural changes in the Ni-YSZ solid oxide fuel cell anode during operation. Acta Mater., 2012 3491-3500. 7. Faes, A.; Hessler-Wyser, A.; Presvytes, D.; Vayenas, C. G.; Van herle, J. Nickel-Zirconia Anode Degradation and Triple Phase Boundary Quantification from Microstructural Analysis. Fuel Cells, 2009 841-851. Acknowledgements Financial support from the National Science Foundation (Award CBET-1134052) and an Energy Frontier Research Center on Science Based Nano-Structure Design and Synthesis of Heterogeneous Functional Materials for Energy Systems (HeteroFoaM Center) funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (Award DE-SC0001061) is gratefully acknowledged. X-ray nanotomography was performed with Dr. Steve Wang at the Advanced Photon Source supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract No. DE-AC02-06CH11357. Ni-YSZ samples were provided by MER Dr. J. Van herle (Ecole Polytechnique Federale de Lausanne, Switzerland).

The electrochemical reduction of CO2 was studied via solid oxide electrolysis cell (SOEC), a type of device that can work reversely into a solid oxide fuel cell (SOFC) to generate electricity. Application of SOEC for CO2 electrolysis possesses potential rewards both in energy and environmental aspects, as it offers a way to recycle CO2 into chemicals and value-added fuels, which helps to reduce the accumulation of atmospheric CO2 and realize the carbon neutral cycling of fuels. Secondly, SOEC techniques provide a means to utilise the intermittent renewable sources, such as wind, tide, etc., as energy input to store excess electricity in the form of H2, CO and hydrocarbons and use these chemicals when necessary. Yet it is a challenging task to realize an efficient reduction of CO2 by SOEC due to the non-polar nature of CO2 fuels which are hard to be chemically absorbed and activated in high temperature range. The CO product from CO2 reduction is also demanding for the choice of fuel electrode (i.e. cathode in SOEC and anode in SOFC) materials, which has been an issue for the CO/hydrocarbon-fuelled SOFCs. To date, the CO2 electrolysis by SOEC is still at the starting point, and the mechanisms on the electrochemical reduction of CO2through SOECs are not fully understood. Extensive efforts need to be dedicated to the material developments, mechanism study, and system designs etc. Effort was made in our lab to find a highly performed, long-term durable cathode material for electrochemical reduction of CO2 by SOEC and to obtain more understandings of the mechanism of CO2 electrochemical reduction process. Different cathode materials were employed, including Ni-8 mol% yttria stabilised zirconia (YSZ) cermet, (La,Sr)(Cr,Mn)O3 (LSCM)-YSZ composite, and LSCM-(Gd, Ce)O2 (GDC) composite. Focus was casted on LSCM based cathodes which were found to be carbon-resistive, and the microstructure of LSCM-based cathodes was tuned to high performance and efficient CO2 electrolysis by the strategy of applying a gradient composite cathode and of adopting wet impregnation as cell fabrication procedures. The electrochemical performance of CO2 electrolysis was characterized in various CO2-CO mixtures and applied potentials in 900-750oC with the aid of impedance spectroscopy, on YSZ electrolyte supported three-electrode SOECs. In this paper, impedance behaviour of the electrochemical reduction reaction of CO2 from different cathode SOECs was correlated with the variations in gas composition, operating temperature and loading potential. As both charge transfer and surface adsorption/desorption equilibration and surface diffusion of activated species were found to be dominant processes taking place in the scope of cathodes under examination, with the later being significant in CO2-rich fuels, areas of discussion will be the effects of operational conditions on the impedance arcs associated with these steps, and how the cathode microstructure impacts the impedance behaviour and the corresponding elementary steps from CO2electrochemical reduction. By introducing a LSCM-YSZ 30-70/LSCM-YSZ 60-40 graded cathode and by incorporating extra catalyst into LSCM-GDC composite, the cathode performance was greatly improved, and the surface activity was profoundly accelerated. However, the most effective way to promote cathode performance was to introduce the cathode components in separate steps via wet impregnation. A competitive CO2 electrolysis performance to Ni-YSZ cermet was obtained from the GDC impregnated LSCM-YSZ cathode with 0.5% Pd extra catalyst, which also showed a comparable performance between SOEC and SOFC when operating in CO2-CO 50-50 mixture.

Evaluation of Sc2O3–CeO2–ZrO2 electrolyte-based tubular fuel cells using activated charcoal and hydrogen fuels

Physicochemical impedance modeling of solid oxide fuel cell anode as an alternative tool for equivalent circuit fitting

Solid oxide fuel cells (SOFCs) operate under harsh environments, which cause the deterioration of anode material properties and service life. In addition to electrochemical performance, the structural integrity of the SOFC anode is essential for successful long-term operation. The SOFC anode is subjected to stresses at high temperature, thermal/redox cycles, and fuel gas contaminant effects during long-term operation. These mechanisms can alter the anode microstructure and affect its electrochemical and structural properties. In this research, anode material degradation mechanisms are briefly reviewed and an anode material durability model is developed and implemented in finite-element analysis. The model takes into account thermomechanical and fuel gas contaminant degradation mechanisms for predicting the long-term structural integrity of the SOFC anode. The proposed model is validated experimentally using a NexTech Probostat™ SOFC button cell test apparatus integrated with a Sagnac optical setup for simultaneously measuring electrochemical performance and in situ anode surface deformation.

The purpose of the current study is to simulate the behavior of a solid oxide fuel cell (SOFC) anode under sinusoidal excitation. The obtained harmonic response is used as a base for electrochemical impedance spectra simulation. The electrochemical impedance spectroscopy (EIS) is a powerful non-destructive tool for SOFC researches. In order to evaluate the EIS experimental results, efforts are devoted to develop EIS numerical simulation tools. In this study, a planar SOFC is modeled, and the steady state behavior and frequency response, as well as the electrochemical spectra of the anode, are obtained. The developed model couples the electrochemical kinetics with mass transport. The Butler–Volmer equation is used for the anode electrochemistry, and the species equations are used for gas transport in the anode channel. In order to solve the system of the nonlinear equations, an in-house code based on finite difference method is developed and utilized. A parametric study is also carried out, and the results are discussed. The simulation results are in good agreement with published data. Results show a capacitive semicircle in the Nyquist plot, which is identical to the gas diffusion impedance as reported in literatures.

Carbon tolerance, electrochemical performance and stability of solid oxide fuel cells with Ni/yttria stabilized zirconia anodes impregnated with Sn and operated with methane