Quantitative estimation of triple phase boundaries in solid oxide fuel cell electrodes via artificial neural network

Design of optimal microstructures for infiltrated solid oxide fuel cell (SOFC) electrodes is a complicated process because of the multitude of the electrochemical and physical phenomena taking place in the electrodes in different temperatures, current densities and reactant flow rates. In this study, a stochastic geometric modeling method is used to create a range of digitally realized infiltrated SOFC electrode microstructures to extract their geometry-related electrochemical and physical properties. Triple Phase Boundary (TPB), active surface density of particles along with the gas transport factor is evaluated in those realized models to adapt for various infiltration strategies. Recently, additive manufacturing or freeze type casting methods enable researchers to investigate the performance of directional electrodes to get the maximum electrochemical reaction sites, gas diffusivity and ionic conductivity simultaneously. A series of directional backbones with different amount of virtually deposited electrocatalyst particles are characterized in the first step. The database of microstructural parameters (inputs) and effective geometric properties (outputs) is used to train a range neural network. A microstructure property hull is created using the best neural network model to discover the range of effective properties, their relative behaviour and optimum microstructure. The characteristics of models is shown that there is not any contradiction between the high level of TPB and contact surface density of particles, but the highest amount of gas diffusivity can be found in the microstructures with lower level of reaction sites. Also increasing the contact surface density has a negative effect on gas transport but the high level of TPB density is feasible in the full range of microstructures. In the other hand, TPB density and gas diffusion into the models are inversely related, although there are a limited number of microstructures with high level of reaction sites and acceptable gas diffusivity. Finally, using a simple optimization process, the microstructures with the highest level of reaction sites and gas transport factor are identified which have the backbone porosity of about 50%, and extremely higher gain growth rate normal to the electrolyte. Additive manufacturing and 3D printing methods will enhance researchers in the future to create the real directional electrodes on the base of these proposed models.

Polarization resistance of solid oxide fuel cell electrodes consists of resistances due to mass transfer and chemical reaction. Therefore, higher ion conductivity, electron conductivity, and gas diffusivity and larger triple-phase boundary (TPB) density lead to lower polarization resistance. To increase effective conductivities and diffusivity, tortuosity factors in each mass-transfer path should be reduced. In this study, magnetic alignment method is developed to align the mass-transfer paths in the electrode microstructure. Since Ni as an electron-conducting material in anode has high magnetic permeability, the particles are polarized and aligned by a magnetic field. Therefore, the tortuosity factors can be reduced. In addition, this Ni alignment is expected to reduce the tortuosity factors of yttria-stabilized zirconia (YSZ) and pore phases as well. However, there is a risk for a decrease in TPB density. The effect of magnetic field on resultant microstructure and polarization resistance of Ni-YSZ anode are investigated by impedance measurement of anode symmetrical cells and by reconstruction of three-dimensional microstructure. The tortuosity factors of Ni and YSZ decreased and TPB density decreased by the magnetic field. As a result, the polarization resistance of anode was kept nearly unchanged. The effect of reducing Ni volume fraction is also investigated.

Microstructural stability of supported metal catalysts: A phase field approach

Synthetical designing of solid oxide fuel cell electrodes: Effect of particle size and volume fraction

Solid Oxide Fuel Cells (SOFCs) are widely considered to be an ideal power source across a range of industries in the near future due to their high efficiency, high power density, and fuel flexibility. However, for widespread usage of SOFCs to be feasible, certain disadvantages, such as their high operating temperature, electrochemical losses, and high cost of manufacturing, must be solved. In particular, the field of materials research occupies a unique position of being able to quickly and simultaneously solve many of these issues through the development of material compositions and structures that do not currently exist in the industry. Especially relevant to solid oxide fuel cells in particular, is the impact that the electrodes’ geometries and compositions have on the operating performance. The electrodes’ ability to quickly move reactants to the interface of the electrolyte and remove products to the bulk flow comes into play as the fuel cell operates at higher current densities and concentration losses become prominent. Therefore, the microstructures present throughout the electrodes’ depth plays a vital role in improving overall cell performance. However, current fuel cell research has not yet effectively captured and defined the connections of the microstructure parameters and measured their impact on cell behavior. Additionally, homogeneous electrode design and implementation have dominated the research and commercial space thus far. The technique of functional material grading, which has begun to see wide research and commercial usage for such problems as acoustic impedance matching, thermal control, and mechanical design will be leveraged for the enhancement of SOFC electrodes. Functionally graded electrodes have been used in solid oxide fuel cell research in recent years in an effort to improve the cell performance by altering the microstructure including porosity, particle size, and composition of electronic and ionic conductors near the triple phase boundary region. Normally the functional grading process adds additional fabrication steps making it less desirable as an optimization process and easy manufacturing method. However, by using an additive manufacturing process it eliminates the need for multiple discrete graded layers to be deposited to obtain a graded electrode functional layer. This study seeks to explore the correlations of geometry and structure parameters from the meso-scale through to the micro-scale level, together with mass transfer, ionic and electronic transport, and gas-surface electrochemical reactions inside the electrodes to guide future additive manufacturing of SOFCs. Outlined is the development of an effective medium model for simulating the performance of fuel cell microstructures as a function of specific operating ranges in temperature, pressure, and in fuels used. Smooth and continuous linear and nonlinear functional gradation profiles of porosity and material composition are studied within the framework of an effective medium boundary value problem where the electrochemical relations, such as the Butler-Volmer equation, percolating conduction paths, and gas diffusion are solved using the finite difference method. The form of these relations for homogeneous electrodes was analyzed by Costamagna, et. al [1], who also defined outstanding problems with regards to optimizing SOFC electrodes [2]. Globally optimal linear and nonlinear gradation profiles and cell parameters are derived as a function of particle sizes, ratio of conductivities, and desired operating conditions and scored based on their reduction of cell overpotentials.[1] Costamagna, P., P. Costa, and V. Antonucci, Micro-modelling of solid oxide fuel cell electrodes. Electrochimica Acta, 1998. 43(3-4), pp.375-394.[2] Costamagna, P., P. Costa, and E. Arato, Some more considerations on the optimization of cermet solid oxide fuel cell electrodes. Electrochimica Acta, 1998. 43(8), pp.967-972. Figure 1

Reconstruction of solid oxide fuel cell electrode microstructure and analysis of its effective conductivity

The stability of interfacial structure between air electrode and ceria‐based electrolyte (Sm2O3–CeO2, SDC) was evaluated under various polarization conditions at 1,000 °C. This is because the structural change at the interface is strongly related to the diffusion of constituent elements and has the potential to affect the long‐term stability. In this study, (La,Sr)MnO3 (LSM) and (La,Sr)(Co,Fe)O3 (LSCF) were applied as air electrodes. The cell with LSM/SDC interface showed the performance enhancement after cathodic polarization for 5 h, accompanied with the change in interfacial structure. The magnitude of the microstructural change as well as activation was dependent on the current density and the oxygen partial pressure. However, the active triple phase boundary (TPB)‐length decreased at every condition studied. On the other hand, no appreciable change in interfacial structure was confirmed for the LSCF/SDC system regardless of polarization conditions. In response to this phenomenon, the total TPB‐length was almost identical to the active one. The difference in morphological evolution at the interface depending on the electrode material was discussed.

Solid oxide fuel cells are among the most thermodynamically efficient energy conversion devices. They are critical for the future if we are to meet rising energy demands and increasing selectivity over our future energy mix. Traditionally, solid oxide fuel cell performance has been assessed using bulk parameters, and the microstructure-bulk properties relationship is yet to be well understood. Here, we use time-lapse 3D imaging to probe 3D electrode structure and move towards intelligently designing structures with specific performance attributes. Using 3D imaging allows for characterisation and quantification of parameters that are not well described in 2D, such as triple-phase boundary lengths, tortuosity and phase percolation. In this work, the parameters for an optimised porous nickel-scandia stabilized zirconia anode (Ni-ScSZ) were calculated using an electrochemical model to maximise triple-phase boundary length and density, gas permeation and electronic and ionic transport. Ni-ScSZ scaffolds were then produced using screen-printing and impregnation and characterized with FIB-SEM to obtain 3D microstructural parameters such as actual percolation of the phases, tortuosity and connectivity of the phases, and the length and density of triple-phase boundaries (Figure 1). The experimental microstructural parameters were then compared to the modelled optimised microstructure, allowing for an examination of the accuracy of the manufacturing parameters. Symmetrical cells were set up to compare the anode performance with the performance predicted by the electrochemical model. Early iterations of impregnated scaffolds show triple-phase boundary densities increased by approximately an order of magnitude and allowed for a critical assessment of the electrochemical model. The degraded electrode morphology was also characterized in 3D to link its changes during cycling to performance degradation. This approach enables us to move towards designing optimised electrodes with specific performance attributes. Figure 1

Composite electrodes comprising a rare-earth nickelate phase and a doped rare-earth ceria phase with a high level of rare-earth doping have been studied as oxygen electrodes. While rare-earth nickelates have shown great promise as oxygen electrodes in both solid oxide fuel cells (SOFC) and solid oxide electrolysis cells (SOECs), they become unstable in contact with rare-earth doped ceria. In this work we describe a strategy to eliminate this instability and enable the use of these electrodes as stable high performance oxygen electrodes in both SOFC and SOEC applications. The performance of such composite electrodes is explored using a symmetrical cell approach, and through the electrical conductivity relaxation (ECR) method and compare it to state-of-the-art oxygen electrodes comprising strontium doped lanthanum manganite (LSM) – yttria stabilized zirconia (YSZ) composite electrodes. The symmetrical cell tests which reveal the stabilized nickelate-ceria electrodes to be superior, are also well-correlated with the results of testing complete cells in both SOFC and SOEC modes. Based on these results we make the case for deploying these stabilized nickelate-ceria composite electrodes as oxygen electrodes in reversible SOFC-SOEC systems.

Investigation of the active thickness of solid oxide fuel cell electrodes using a 3D microstructure model

Using a large-scale, experimentally captured 3D microstructure data set, we implement the generative adversarial network (GAN) framework to learn and generate 3D microstructures of solid oxide fuel cell electrodes. The generated microstructures are visually, statistically, and topologically realistic, with distributions of microstructural parameters, including volume fraction, particle size, surface area, tortuosity, and triple-phase boundary density, being highly similar to those of the original microstructure. These results are compared and contrasted with those from an established, grain-based generation algorithm (DREAM.3D). Importantly, simulations of electrochemical performance, using a locally resolved finite element model, demonstrate that the GAN-generated microstructures closely match the performance distribution of the original, while DREAM.3D leads to significant differences. The ability of the generative machine learning model to recreate microstructures with high fidelity suggests that the essence of complex microstructures may be captured and represented in a compact and manipulatable form.

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).

Geometrical modeling of microstructure of solid oxide fuel cell composite electrodes

Topology-informed machine learning for efficient prediction of solid oxide fuel cell electrode polarization

A modeling study of porous composite microstructures for solid oxide fuel cell anodes