Search

Solid Oxide Cell (SOC) is a high-temperature electrochemical device that can be operated in both fuel and electrolysis modes. It is constituted of a dense electrolyte in Yttria Stabilized Zirconia (YSZ) sandwiched between two porous electrodes. The hydrogen electrode is classically made of a cermet composed of Nickel and YSZ (Ni-YSZ). Because of system failures in operation (e.g. a fuel shortage or air re-introduction during the system shutdown), the Nickel is liable to be re-oxidized inducing its volume expansion. The Ni swelling within the cermet leads to a mechanical damage in the YSZ backbone [1] resulting in a degradation of the overall cell performances [2]. Therefore, it is still required to enhance the hydrogen electrode robustness for a higher redox tolerance. For this purpose, it is essential to predict accurately the formation and distribution of micro-cracks in the YSZ network during the re-oxidation. Nevertheless, the modeling of the initiation and propagation of cracks in complex microstructures of porous ceramics is still a subject of investigation. Moreover, there is also a lack of data on fracture properties for the porous YSZ material. In this frame, the present study was focused to propose a relevant model for the initiation and the growth of cracks in porous ceramics in order to simulate the fracture induced by Ni re-oxidation. For this purpose, a coupled experimental and modeling approach has been adopted (Fig.1). For the experimental part, the mechanical characterizations have been performed on thin YSZ membranes of different porosities representative of SOC microstructures. The compression test has been chosen as it generates a quasi-uniform stress field in the tested samples. To this end, micro-pillars of few tens of micro-meters in section have been milled in the YSZ membrane using a xenon plasma focused ion beam. For each investigated porosity, the compressive fracture strength has been measured on several pillars. The tested samples have been carefully characterized to assess the damage in the microstructure. As expected, the compressive strength was found to decrease with increasing the porosity. Moreover, a transition has been observed from a brittle behaviour at low porosity towards a local damage at high porosity [3]. All these experimental data have been used to validate a numerical tool to simulate the fracture in porous microstructure. In this study, a model based on the Phase Field Method (PFM) has been developed. In this approach, the crack is modeled implicitly through a smooth scalar damage variable and its width is controlled by a length scale parameter. Therefore, this method is well adapted to solve the fracture problem in complex and heterogeneous materials since it is mesh independent. The implemented model corresponds to the one proposed by C. Miehe et al. [4] who proposed a staggered scheme for the numerical resolution. A special attention has been paid in this work to evaluate the model capability to accurately predict the crack initiation for porous electrode material. For this purpose, the results of the PFM simulations have been compared to the mixed criterion proposed by D. Leguillon [5]. The study has been conducted on notched samples with different opening angles and for macro-cracks blunted by different cavity sizes. It has been highlighted that the two approaches provide consistent predictions for the crack initiation. Moreover, it has been checked that the PFM model is able to reproduce accurately the expected decrease of the fracture toughness when increasing the material porosity. Once these studies completed, the PFM model has been used to simulate the micro-compression test using a multiscale approach. It has been found that the model is able to reproduce correctly the decrease of the measured compressive fracture strength with the sample porosity. Moreover, the distribution of cracks in the simulations has enabled analysing the transition from a brittle to a local damage detected during the experiments. The validated model has been applied to simulate the fracture induced by the Ni re-oxidation. The repartition and density of micro-cracks in the YSZ backbone has been computed during the Ni reoxidation and the results have been confronted with an available tomographic data set. Finally, the impact on the cermet redox tolerance of the Yttrium content in YSZ has been discussed thanks to the modelling. [1] Faes, A. et al. J. Power Sources 193, 55–64. [2] Laurencin, J. et al. J. Power Sources 192, 344–352. [3] Meille, S. Et al . J. Eur. Ceram. Soc. 32, 3959–3967. [4] Miehe, C. et al. Comput. Methods Appl. Mech. Eng. 199, 2765–2778. [5] Leguillon, D. J. Mech. – A/Solids 21, 61–72. Figure 1

International audience; An elementary kinetic model was developed to predict the electrochemical response of porous LSCF and LSCF-CGO electrodes. The model was validated thanks to experiments performed on symmetrical cells using a three-electrode setup. After the model calibration on polarization curves, it has been shown that the model is able to simulate accurately the experimental impedance diagram at OCP and under polarization without additional fitting. Moreover, the evolution of the electrode polarization resistance with the oxygen partial pressure is well reproduced by the model. The electrodes reaction mechanism was thoroughly analyzed and it has been shown that the transition from the bulk path to the surface path depends on the temperature, the polarization and the oxygen partial pressure. The rate-determining steps for the LSCF electrode have been identified at OCP as function of the oxygen partial pressure. Finally, a sensitivity analysis has been performed to study the impact of LSCF demixing on the electrode performances. For a given decomposition, it has been highlighted that the surface passivation would be more impacting than the decrease of the ionic conductivity. Moreover, the impact of the LSCF decomposition would be more detrimental for the electrode performances evaluated in electrolysis mode.

International audience; Three long-term experiments have been performed in SOEC and SOFC modes at different operating temperatures. The durability tests confirm a higher degradation in electrolysis mode with respect to fuel cell operation. In addition, a larger increase of the ohmic resistance is observed for the cell operated at higher temperature in electrolysis mode. The oxygen electrodes of the pristine and tested cells have been characterized by synchrotron X-ray micro-diffraction and micro-fluorescence to assess the relation between the material destabilization and the formation of insulating phases due to interlayer diffusion. The analyses of the pristine cell confirm the presence after the electrode sintering of strontium zirconate and a Gd-rich inter-diffusional layer in the electrolyte just below the zirconates. Moreover, evolutions in the LSCF unit cell volume reveal strontium segregation after aging. The associated material destabilization is linked to the accumulation of SrZrO 3 at the barrier layer-inter-diffusional layer interface in operation and both phenomena are found to be thermally-activated and promoted in electrolysis mode. Finally, the crystallographic evolution of the inter-diffusional layer in electrolysis mode has been investigated by X-ray diffraction. A slight increase of the phase peaks intensity detected at the highest temperature is correlated to the largest formation of SrZrO 3 observed in this condition. Based on these preliminary results, it is proposed that the loss of Zr 4+ from the electrolyte due to the zirconates formation could facilitate the inter-diffusion of Gd, reducing the local ionic conductivity and thus significantly contributing to the largest increase in the ohmic resistance observed in this case.

This work reports a durability study in galvanostatic mode at 700 °C for 900–960 h related to structural and microstructural evolution of LaPrNiO4+δ (LPNO) oxygen electrode. The performances of the electrode, deposited by electrostatic spray deposition (ESD) and screen printing (SP), are not changed when operated under electrolysis current whereas a degradation is observed in fuel cell mode. Small quantities of secondary phases (La,Pr)3Ni2O7-δ in the fine ESD microstructure and Pr6O11 on both ESD and SP layers are detected in the pristine electrode by synchrotron μ-X-ray diffraction and fluorescence. The destabilization of LPNO electrode, which slightly occurs in the ESD layer after thermal aging in air, is strongly accelerated under anodic and cathodic currents. Indeed, the formation of a new phase (La,Pr)4Ni3O10-δ on both ESD and SP layers occurs with the extension of (La,Pr)3Ni2O7-δ in the SP layer, and a significant increase in the amount Pr6O11 at high current density. Nevertheless, the electrode microstructure, determined by FIB-SEM tomography, remains stable under current whereas severe delamination is observed after aging in fuel cell mode. Based on these characterizations, the mechanisms of electrode aging have been discussed to explain the different behavior in fuel cell and electrolysis modes.

A set of long-term tests (t ≥ 1000 h) have been carried out in fuel cell and electrolysis modes on typical Ni-YSZ//YSZ//LSCF-CGO cells. The degradation rates were found to be higher in electrolysis than in fuel cell operation. Post-test analyses have revealed that Sr diffusion and formation of SrZrO3 at YSZ/CGO interface occur mainly during electrolysis operation, whereas the process is very limited in fuel cell mode. As a consequence, LSCF destabilization is found to be not involved in the degradation of cell performances during fuel cell operation while it could explain the highest degradation rates recorded in electrolysis mode. An in-house multi-scale model has been used to interpret the role of the cell operating mode on the LSCF demixing mechanism. The simulations have shown that the electrolysis operation leads to a strong depletion of oxygen vacancies in LSCF material (while the fuel cell condition results in an increase in the concentration of oxygen vacancies). It has been proposed that the depletion in oxygen vacancies under electrolysis polarization could drive the Sr release from the structure, and in turn, could explain the experimental results. Based on this proposition, a possible mechanism for the LSCF destabilization and SrZrO3 formation is detailed.

Ceramic high-temperature fuel cells and electrolysers are efficient energy conversion systems for electrical power generation and hydrogen production. Their core components are constituted by a stack of electroactive Solid Oxide Cells (SOCs) in which the electrochemical reactions take place. Thanks to their flexibility, the same stack can be alternatively operated in both fuel cell and electrolysis modes. However, the insufficient durability of SOCs still constitutes a major limitation for the technology. The present study addresses this issue and aims to bring some new insights on the effect of the Solid Oxide Fuel Cell (SOFC) versus Solid Oxide Electrolysis Cell (SOEC) operating modes on degradation of a typical Ni-YSZ//YSZ//CGO//LSCF-CGO cell. The electrochemical degradations are generally attributed to several underlying phenomena such as electrode microstructural evolution, material chemical decomposition or electroactive sites poisoning by contaminants. Among them, it is generally considered that Ni agglomeration in the Ni-YSZ cermet and Lanthanum Strontium Cobalt Ferrite (LSCF) material destabilization are two prevalent mechanisms involved in the cell performance deterioration. Therefore, these two mechanisms have been specifically investigated by a coupled approach of long-term testing in both SOFC and SOEC modes (1000 ≤ t (h) ≤9000) and post-test characterizations. The experimental results have then been analyzed in the frame of an in-house multi-scale model with the purpose to interpret them and to quantify the effect of material ageing on cell performances. The extent of Ni agglomeration has been characterized by three-dimensional electrode reconstructions obtained by X-ray nano-holotomography at European Synchrotron Radiation Facility (ESRF) (on the new Nano-Imaging beamline ID16A-NI). The new set-up and protocol enable the reconstructions of valuable 3D volumes (Fig. 1) with a large field of view (~50 µm) along with a high spatial resolution (~50 nm). The electrode morphological properties, which have been measured on the 3D volumes, have revealed a substantial Ni coarsening over time at 850°C and 750°C, whereas no Ni depletion was detected at the electrolyte interface. The increase of the Ni particle size is found to induce a decrease in both (i) the density of Triple Phase Boundary (TPBs) lines and (ii) the interfacial surface area between Ni and gas. Moreover, it was found that the Ni/YSZ interfacial surface area does not evolve during the experiments. This statement indicates that the ceramic backbone in the cermet prevents a massive Ni agglomeration at the SOFC/SOEC operating temperature. The compilation of all experimental data have allowed fitting the parameters of a physically-based law for Ni coarsening that was introduced in the modelling framework. The simulations have revealed that Ni agglomeration explains around 20-25% of the electrochemical degradation at 850°C after 1000 hrs of operation. However, the electrode microstructural evolution is found not to be affected by the cell polarizations. Therefore, the mechanism cannot explain the higher degradation rates recorded in electrolysis mode compared to the fuel cell ones. To explain the impact of the operating modes (SOFC or SOEC) on the degradation rates, several post-test analyses (i.e. Scanning Electron Microscopy, Transmission Electron Microscopy, X-ray µfluorescence and µdiffraction techniques) have been employed to investigate the phase reactivity in the region of the CGO barrier layer. The characterizations have revealed that Sr diffusion across the barrier layer and formation of SrZrO3 secondary phase occur mainly during electrolysis operation, whereas the process is very limited in fuel cell mode (Fig. 2). As a consequence, LSCF destabilization is found not to be involved in the degradation of cell performances during fuel cell operation while it could explain the highest degradation rates recorded in electrolysis mode. The post-test analyses have also revealed a diffusion and an accumulation of Co in the region of the barrier layer which is concomitant with the formation of SrZrO3. The formation of these Co-rich segregates in contact with SrZrO3 grains have been identified as cobalt-ferrite type compound. The in-house multi-scale model has been used to interpret the role of the cell operating mode on the LSCF destabilization mechanism. The cell polarization curves and the local quantities within the O2 electrode have been computed in both fuel cell and electrolysis modes. The simulations have shown that the electrolysis operation leads to a strong depletion of oxygen vacancies in the LSCF material. It has been proposed that the depletion in oxygen vacancies under electrolysis polarization could drive the Sr release from the structure, and in turn, could explain the experimental results. Based on this proposition, a possible mechanism for the LSCF destabilization and SrZrO3 formation has been detailed. Figure 1

International audience; Two types of solid oxide cells with different Ni-YSZ cermet microstructures have been aged in electrolysis and fuel cell modes for operating times ranging from 1000 to 15000 hours. The pristine and aged cermets have been reconstructed by synchrotron X-ray holotomography. Nickel agglomeration has been observed in the bulk of the operated samples inducing a significant loss of triple phase boundary lengths. The inspection of the microstructural properties has confirmed the stabilizing role of YSZ on Ni coarsening. Furthermore, the gradients of properties quantified at the electrolyte interface have revealed a depletion of Ni only in the electrochemically active region of the electrode. The process is strongly promoted for a coarse cermet microstructure when operated under electrolysis current. The evolution of the microstructural properties has been implemented in an in-house multiscale model. The simulations have shown that the loss of performance is dominated by the depletion of Ni in case of a coarse microstructure. Thanks to the computations, it has been shown that the Ni depletion is controlled by the cathodic overpotential. To explain this dependency, it has been proposed that the accumulation of oxygen vacancies in the double layer could deteriorate the Ni/YSZ interface and trigger the Ni depletion.

Chapter 11: Cell, Stack, and System Modeling and Simulation; International audience; As it plays a key role on the performances and durability of solid oxide cells, the electrode microstructure has to be finely characterized and modelled. In this frame, a plurigaussian random field model and an original sphere packing algorithm have been developed to simulate a large variety of electrode microstructures. The two stochastic geometrical models have been validated on various electrode reconstructions obtained by synchrotron X-ray holotomography including the microstructures of thin functional layers and a thick current collector. Afterwards, semi-analytical microstructural correlations have been proposed and validated on a large dataset of representative synthetic microstructures. These equations allow establishing the links between the microstructural properties controlling the performances (Triple Phase Boundary lengths density and specific surface areas) to the ‘basic’ geometric attributes of the electrode (composition, porosity and particle size distribution). These correlations have been used to model the loss of active TPBl due to the Ni agglomeration.

International audience; Rare earth nickelate, LaPrNiO4+δ (LPNO), is one of the most suitable oxygen electrode materials for Intermediate Temperature Solid Oxide Cells (IT-SOC). By using Electrostatic Spray Deposition (ESD) and Screen Printing (SP), various architectural designs of electrodes are fabricated on Ce0.9Gd0.1O2-δ (GDC) electrolyte. Three electrode configurations are investigated based on a single Active Functional Layer (AFL), a double layer of the same composition which is an AFL topped by a current collecting layer (CCL) and a triple layer which is mainly the double layer with an LPNO/GDC composite interface. For each configuration, the electrode response and properties are analyzed by using Electrochemical Impedance Spectroscopy (EIS), X-ray diffraction and Scanning Electron Microscopy (SEM). The electrochemical properties are discussed as a function of the electrode design, microstructure, and composition with the presence of a higher order nickelate such as (La,Pr)3Ni2O7-δ. The electrochemical performance is enhanced thanks to better adhesion of the electrode onto the electrolyte, the presence of an LPNO/GDC composite interface, a more homogeneous distribution of fine grains, and a flatter electrode surface. A significant decrease in the polarization resistance (Rpol) is measured from 0.72, 0.50, and down to 0.20 Ω cm2 at 600 °C from single to triple layer, respectively.

International audience; La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) electrode deposited on Gadolinium Doped Ceria (GDC) has been characterized by cyclic voltammetry and impedance spectroscopy in the temperature range of 300 to 700 °C. We demonstrate that the LSCF microstructure has a strong influence on the shape of the voltammograms and on the variation of the series resistance, Rs, measured on the impedance diagrams as a function of the dc bias. LSCF was deposited with two different microstructures, either porous layer (~10 μm thick) by screen-printing (SP) or almost dense layer (~2 μm thick) by Electrostatic Spray Deposition (ESD). For the denser film, one cathodic peak and one reverse anodic peak were evidenced under air at 300 and 500°C. The Rs value was also found to increase with the dc cathodic bias. On the contrary, no peak was observed with the porous film under the same conditions and Rs was independent on the applied potential from 300 to 700°C. Decreasing the oxygen partial pressure allowed the peaks to be evidenced and Rs to vary. The results are discussed in terms of oxygen exchange rate at the LSCF/gas interface, which depends on the LSCF specific surface area and the oxygen partial pressure.

The durability and efficiency of Solid Oxide Fuel Cells or Electrolysis Cells (SOFC/SOEC) depend on the reaction mechanisms taking place within the electrodes. These mechanisms combine a series of elementary steps including mass and charge transfers along with chemical and electrochemical reactions. These processes are still not precisely understood as they involve complex physical phenomena occurring at the atomic scale. Therefore, it is still required to carry out some fundamental studies to better unravel the basic mechanisms involved in the material properties such as the electronic or ionic conductivity, etc. For such basic investigations, the ab-initio modeling is nowadays recognized as a powerful and relevant method. In this context, this work aims to provide deeper insights into the mechanisms at atomic scale by using Density Functional Theory (DFT) calculations. La1-xSrxCoyFe1-yO3-δ (LSCF) and LSCF-based materials are Mixed Ionic-Electronic Conductors, which are commonly used as oxygen electrode for the SOFCs/SOECs [1]. LSCF is a perovskite oxide that contains two transition metals, i.e. cobalt and iron. Owing to the complexity of this system, our work was first devoted to the parent material La1-xSrxFeO3 (LSF), which was here studied by DFT+U calculations. A special focus was paid to finely describe the localization of holes and the formation of oxygen vacancies as a function of the oxygen partial pressure. Electronic structure calculations were carried out at different strontium contents x (x=0.0, x~0.1, x~0.4, x~0.6). Progressive changes during Sr substitution were evaluated in the Density Of State (DOS). The probability densities of the gap-state wave functions were visualized in order to describe the spatial extension of the localized electron holes. The oxygen vacancy concentration, which is related to the oxygen diffusion coefficient, was calculated and coupled to a defect model in order to give at any temperature and partial oxygen pressure the defect concentration. This work will be extended to the typical LSCF material to provide some essential insights into the chemistry of this imperfect solid. [1] S. P. Jiang, International Journal of Hydrogen Energy, 2019, 44, 7448 – 7493

Due to the mixed ionic electronic conductive properties of the Lanthanum Strontium Cobalt Ferrite (LSCF) La0.6Sr0.4Co0.2Fe0.8O3−δ compound, it is of great scientific and technological interest. Especially in the Solid Oxide Fuel Cell (SOFC) technology, this compound has receiving great attention as a cathode material. However, its chemical reactivity with the Yttria-stabilized Zirconia (YSZ) electrolyte still remains one of the main challenges, which demands a comprehension in the μm and sub-μm range. In order to address the reactivity issues locally in the micrometre scale range, 2D and 3D X-ray μ-diffraction and μ-fluorescence analysis have been performed on a pristine LSCF cathode layer. The cathode was deposited on a dense YSZ electrolyte substrate spaced by a thin Gadolinium doped Ceria Oxide (CGO) barrier layer in between LSCF and YSZ to limit the reactivity. The present approach offers a larger field of view in comparison to electron microscopy techniques. The method can provide a more representative information and may offer some insights on the reactivity distribution along the interfaces. The formation of micro SrZrO3 inclusions in LSCF layer is then indubitably identified, as well as in the CGO/YSZ interface.

This work aims at investigating through a modeling approach the difference in thermal and electrochemical responses between high temperature H 2 O electrolysis and H 2 O+CO 2 co-electrolysis in solid oxide cells. The study has been conducted by considering a typical planar stack configuration with cathode supported cells. The influence of the local temperature on the polarization curve is discussed. Operating maps are simulated for both electrolysis modes depending on cell voltage and inlet gas flow rate, covering a complete range of gas conversion rates. The optimum domains of operating conditions combining high performances and reasonable temperature elevations are identified. In overall, higher performances are found in steam electrolysis. Indeed, the co-electrolysis process is found to be strongly limited by mass transport through the thick cathode. However, co-electrolysis exhibits an easier thermal management. Finally, the composition of the syngas produced by co-electrolysis is found to be highly flexible through adjustments of the operating parameters.

In order to finally and systematically address the growing need for accelerated stress tests, given the longer lifetimes of solid oxide cells – both in fuel cell and electrolysis operation – the Fuel Cells and Hydrogen Joint Undertaking has launched an international initiative to overcome this epic challenge. The overall objective of the project that was awarded the task is the development of protocols that allow quantitative identification and prediction of critical degradation mechanisms, correlating them with overall performance variables in selected stack components (fuel electrode, oxygen electrode and interconnect). These will build firstly on the analysis of numerous field-tested samples of SOC stacks provided by the industrial partners, followed by applying existing and developing improved testing and modelling methods based on ex-situ component ageing and aggravated stack testing.

To manage the grid with renewable electrical sources and ensure their storage, hydrogen chains have to be considered. However, hydrogen must be pressurized before being used or stored. The first levels of compression are less energetic for liquids than for the hydrogen gas, therefore the electrolysis of steam directly under pressure has to be studied. On one hand, with the solid oxide technology, the Open Circuit Voltage (OCV) presents the drawback of increasing with pressure. On the other hand, the pressure might improve the reactive species supply to the electrochemical sites and reduce the related losses. Thus, what are the electrolysis performances under pressure? And is there an energetic gain at the system level to produce pressurized hydrogen? In this context, experimental and modelling approaches have been adopted in order to understand the basic underlying mechanisms of pressurized electrolysis operation. In this frame, SOEC performance tests were realized under pressure in the range of 1 to 10 bars on two types of single commercial cells. They were based on conventional materials and differentiated by their microstructure. Concerning the set-up, the test platform requirements were achieved by developing an innovative mechanical design associated to a specific steam management. Moreover, a previously proposed electrochemical model of solid oxide electrolysis cell was adapted to take into account the pressure effects. The model allows computing all the most important operation parameters such as local current densities, local molar fraction, overpotentials and also the cell microstructural parameters [1]. According to the complete I-V curves from 0 to -1.3 A/cm2 at 800°C with high steam conversion, it has been observed that OCVs respect the Nernst relation under pressure while the limit current appears at higher current values. This work shows that the hydrogen production can be increased thanks to a 10 bars operation at the autothermal voltage. Moreover, these trends have been analyzed with the model. The impact of pressure on the electrochemical performances is much more important in the range of 1 to 5 bars than above. In our experimental conditions, the diffusion improvement in the porous cathode alone can explain this behavior. Finally, the impact of each microstructural parameter on the cell performances with pressure is discussed. The research leading to these results has received funding from the European Union's Seventh Framework Programme (FP7/2007-2013) Fuel Cells and Hydrogen Joint Undertaking (FCH-JU-2013-1) under grant agreement 621173. [1] J. Laurencin, D. Kane, G. Delette, J. Deseure, F. Lefebvre-Joud, Modelling of solid oxide steam electrolyser : impact of the operating conditions on hydrogen production, 2011, Journal of Power Sources, 196, 2080-2093. Figure 1

This work highlights an experimental and modeling approach devoted to a better understanding of H2O and CO2 co-electrolysis mechanisms at 800 °C. A standard Cathode Supported Cell (CSC) was used in this study. Through numerical adjustments on experimental polarization curves, the cathode microstructural parameters and exchange current densities for H2O and CO2 reductions were determined and subsequently implemented in an in-house co-electrolysis model. Additionally, micro gas chromatography (μGC) analyses were performed in co-electrolysis operating mode for different cell polarizations (from i = 0 to i = −1.75 A cm−2). μGC analyses at Open Circuit Voltage (OCV) were used to validate the kinetic constants of the Water Gas Shift (WGS) reaction implemented in the model. Predictions of both co-electrolysis polarization curves and outlet gas compositions were then compared to the experimental measurements. The good agreement between simulated and experimental data proves the relevance of the macroscopic representation of electrochemical processes through a “surface ratio” that takes into account the H2O and CO2 electrolyzes competition. A sensitivity analysis was performed to ensure a better understanding of co-electrolysis mechanisms and further investigate the influence of the reverse WGS reaction over CO production.

International audience; The relevance of micro Laue diffraction tomography (mu-LT) to investigate heterogeneous polycrystalline materials has been studied. For this purpose, a multiphase solid oxide fuel cell (SOFC) electrode composite made of yttria-stabilized zirconia and nickel oxide phases, with grains of about a few micrometres in size, has been analyzed. In order to calibrate the Laue data and to test the technique's sensitivity limits, a monocrystalline germanium sample of about 8 x 4 mu m in cross-section size has also been studied through mu-LT. The SOFC and germanium Laue diffraction pattern analyses are compared and discussed. The indexing procedure has been successfully applied for the analysis of the germanium Laue data, and the depth-resolved two-dimensional cartographies of the full deviatoric strain tensor components were obtained. The development and application of an original geometrical approach to analyze the SOFC Laue data allowed the authors to resolve grains with sizes of about 3 mu m and to identify their individual Laue patterns; by indexing those Laue patterns, the crystalline phases and orientations of most of the grains identified through the geometrical approach could be resolved

International audience; Long-term experiments have been carried out to investigate the impact of Nickel (Ni) coarsening on the performance of Solid Oxide Cell. Durability tests have been performed with H2 electrode supported cells at 850 °C and 750 °C in fuel cell and electrolysis modes. Microstructural changes in the composite electrode of Nickel and Yttria Stabilized Zirconia (YSZ) have been characterized by synchrotron X-ray nanotomography. Analysis of the reconstructions have revealed that Ni coarsening induces a significant decrease of both the density of Triple Phase Boundary lengths (TPBls) and the Ni/gas specific surface area. However, the contact surface between Ni and YSZ is not changed upon operation, meaning the Ni sintering is inhibited by the YSZ backbone. Moreover, the Ni coarsening rate is independent of the electrode polarization. The evolution of TPBls in operation has been fitted by a phenomenological law implemented in an electrochemical model. Simulations have shown that microstructural changes in the H2 electrode explain 30% of the total degradation in fuel cell mode and 25% in electrolysis mode at 850 °C after 1000-2000 h. Moreover, it has been highlighted that the temperature at which the degradation is estimated after the durability experiment plays a major role on the result.

Session 1:Image Analysis - SPIE : Society of Photo-Optical Instrumentation Engineers; International audience; A strong correlation exists between the performance of Solid Oxide Cells (SOCs), working either in fuel cell or electrolysis mode, and their electrodes microstructure. However, the basic relationships between the three-dimensional characteristics of the microstructure and the electrode properties are not still precisely understood. Thus, several studies have been recently proposed in an attempt to improve the knowledge of such relations, which are essential before optimizing the microstructure, and hence, designing more efficient SOC electrodes. In that frame, an original model has been adapted to generate virtual 3D microstructures of typical SOCs electrodes. Both the oxygen electrode, which is made of porous LSCF, and the hydrogen electrodes, made of porous Ni-YSZ, have been studied. In this work, the synthetic microstructures are generated by the so-called 3D Gaussian ‘Random Field model’. The morphological representativeness of the virtual porous media have been validated on real 3D electrode microstructures of a commercial cell, obtained by X-ray nano-tomography at the European Synchrotron Radiation Facility (ESRF). This validation step includes the comparison of the morphological parameters like the phase covariance function and granulometry as well as the physical parameters like the ‘apparent tortuosity’. Finally, this validated tool will be used, in forthcoming studies, to identify the optimal microstructure of SOCs.

This work details an in-house 2D electrochemical and thermal model of solid oxide electrolysis cell (SOEC) dedicated to the simultaneous electrolysis of steam and carbon dioxide. The apparent exchange current densities for both H2O and CO2 electrochemical reductions have been fitted on single electrolysis polarization curves obtained on a standard cathode supported cell (CSC). By using these values, predictive simulations have been performed in a co-electrolysis mode. The results have been compared to experimental data obtained in the same conditions. A good agreement is found between the simulated points and the experimental polarization curves, meaning that the model stands to predict accurately the SOEC response in co-electrolysis mode. Simulations have been performed to investigate co-electrolysis mechanisms in terms of partial pressures, current densities, and overpotentials distributions along the cell. The relative influence of both water gas shift (WGS) reaction and CO2 electrolysis on the global CO production is also discussed.

Microstructural evolution of a Solid Oxide Electrolyser Cell (SOEC) La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) anode is investigated using 3D reconstruction techniques both on a reference and a long-term tested cell. In this framework, reconstructions have been obtained from focused ion beam-scanning electron microscopy and synchrotron X-ray nano-tomography techniques. Microstructural properties extracted from the 3D reconstructions exhibit a slight evolution during the test. Synchrotron X-ray Absorption Spectroscopy (XAS) was also performed, and a modification of the cobalt oxidation state is found. LSCF conductivity decrease due to the change in Co mixed valence has been discussed. Evolutions of both morphological parameters and electrical conductivity were introduced in an in-house micro model to evaluate their impacts on the electrode degradation.

An in-house micro model has been built to describe the electrochemical mechanisms governing both H2 and O2 electrodes operating in SOEC mode. A special attention has been paid to take into account the microstructure properties of the ionic, electronic and gas phases as well as the processes occurring therein. A commercial LSM–YSZ symmetrical cell has been tested at 700, 750 and 850 °C in air. Simulations have been carried out to interpret the experimental data. It is suggested that the kinetic of O2 formation is controlled by a single charge transfer. A sensitivity analysis has been performed using the micro model to quantify the role of the microstructure in the electrode behaviour. Transport of oxygen ions in the functional layer has a strong impact on the cell response since it governs the delocalization of the electrochemical reactions. The density of TPB length is also a key parameter controlling the electrode efficiency. Evolutions of the microstructural parameters in operation have been associated to the degradation of the electrochemical performances. The decrease in TPB length due to Ni agglomeration has a moderate impact whereas the decrease in ionic conductivities of 8YSZ or LSFC could explain a large amount of the cell degradation.

International audience; Experiments have been performed in pressurized co-electrolysis mode at 800 °C on a typical Ni-YSZ//YSZ//CGO-LSCF cell. The polarization curves and the composition of the produced syngas have been measured at 1 bar and 10 bar. It has been found that the cell performances are improved under pressure at 1.3 V. The gas analyses have revealed that the methane formation is only activated under polarization and pressure. These experimental results have been used to validate a model which encompasses a chemical and electrochemical description of the co-electrolyser combined with a mass transport module. It has been found that the model is able to predict accurately the polarization curves as well as the syngas compositions at the cell outlet. Once validated, the model has been used to analyze the operating mechanisms in pressurized co-electrolysis. The impact of pressure on the mass transfer, the electrochemical and chemical reactions has been discussed. The close interaction between the electrochemical and chemical reactions for the internal production of CH4 has been specifically highlighted. Finally, operating maps have been computed at 10 bar from 700 °C to 800 °C. These simulations have shown that formation of CH4 in the co-electrolyser remains limited at 700 °C.

Nickel with yttria stabilised zirconia (Ni-YSZ) is usually used as anode material for the solid oxide fuel cells (SOFCs) technology. Upon cyclic reduction and oxidation of Ni-YSZ ceramic–metal (cermet), the induced cell degradation constitutes one of the main limitations to the SOFCs lifetime. In this study, the effect of anode reduction and oxidation cycling on typical electrolyte supported cell (ESC) has been investigated. The electrochemical degradation has been followed by impedance spectroscopy. The cell damage has been characterised after testing with scanning electron microscopy (SEM). It has been shown that cells can withstand several ‘redox’ cycles without major decrease in electrochemical performances. The ‘redox’ cycling induces only a slight degradation rate estimated to ∼70 mΩ cm2 per cycle. The microstructural observations are found to be consistent with the impedance diagram analysis. Both reveal that the damage is restricted to bulk cermet microstructure change, whereas no cracking is initiated at the anode/electrolyte interface.

An in-house-model has been developed to study the thermal and electrochemical behaviour of a planar SOFC fed directly with methane and incorporated in a boiler. The usual Ni-YSZ cermet has been considered for the anode material. It has been found that methane reforming into hydrogen occurs only at the cell inlet in a limited depth within the anode. A sensitivity analysis has allowed establishing that anode thicknesses higher than ∼400–500 μm are required to achieve both the optimal methane conversion and electrochemical performances. The direct internal reforming (DIR) mechanisms and the impact of operating conditions on temperature gradients and SOFC electrical efficiencies have been investigated considering the anode supported cell configuration. It has been shown that the temperature gradient is minimised in the autothermal mode of cell operation. Thermal equilibrium in the stack has been found to be strongly dependent on radiative heat losses with the stack envelope. Electrochemical performance and cell temperature maps have been established as a function of methane flow rates and cell voltages.

Improving the oxygen electrode performances of the single solid oxide electrolysis cell (SOEC) is of peculiar interest as it contributes to a large extent to the cell polarization resistance. The present study focuses on alternative oxygen electrode materials: the oxygen overstoichiometric rare-earth nickelate oxides Ln 2 NiO 4+δ (Ln = La, Pr or Nd). Their electrochemical properties are measured on three-electrode symmetrical half-cells under zero dc conditions and under anodic polarization. The electrochemical characteristics are compared to those of the usual perovskite La 0.6 Sr 0.4 Fe 0.8 Co 0.2 O 3-δ (LSFC) electrode. Under polarization, in the temperature range from 600 °C to 800 °C, the Pr 2 NiO 4+δ -based cells exhibit the highest performances. At the same anodic overpotential of 0.15 V/Pt/air, the current densities measured through Pr 2 NiO 4+δ nickelate-based cells are more than ten times larger than those obtained with a cell based on LSCF. The modeling of the anodic overpotential phenomena (activation and concentration terms) occurring at the oxygen electrode is achieved and discussed.

International audience; For many industrial applications, hydrogen must be pressurized before being used or stored. Because compressing liquid water is less energetic than the first levels of gaseous H2 compression, High Temperature Steam Electrolysis (HTSE) performed under pressure might represent an advantageous way for hydrogen production. With the goal of improving the electrolysis efficiency, an experimental and modeling approach has been adopted in order to better understand the basic underlying mechanisms of pressurized electrolysis operation. Experiments were carried on two different single commercial solid oxide cells at 800 °C in the pressure range of 1–10 bar. As a first result, according to the i–V curves, two main pressure effects have been observed. First, as expected, the Open Circuit Voltage is higher under pressure. Then, the limiting current density is increased with increasing the pressure, meaning that the hydrogen production can be improved. The electrochemical model, which has been adjusted on the experimental i–V curves obtained at atmospheric conditions, has been validated for the pressurized operation. Simulations have shown that the improvement of the limiting current is related to the decrease of cathode's concentration overpotential with pressure. Moreover, an optimal pressure can be defined depending on the cell polarization. Higher pressures than the optimal one lead to slightly decrease the hydrogen production rate, mainly due to Open Circuit Voltage increase that cannot be balanced enough by the cathode's concentration overpotential decrease. Finally, this study demonstrates that cell performances under pressure are less sensitive to the variation of cermet-support microstructural properties.

Introduction The integration of renewable energies to the global energy market implies electricity storage. However, the available technologies for electricity storage have a low energy capacity and a short time-span. In this context, H2 or carbon molecules produced via water and/or water+CO2 electrolysis open up excellent perspectives for storing renewable electricity, especially the High Temperature Electrolysis (HTE). This technology, based on Solid Oxide Cell (SOC), consumes less electrical energy than low temperature electrolysis because of the energy demand is significantly lowered by the vaporization of water1. The required electrical power is also reduced at high temperature since the steam electrolysis is increasingly endothermic with temperature. Moreover HTE can also directly convert a mix of water and CO2 into syngas, (CO+H2) (co-electrolysis), which can be converted into methane or other hydrocarbon molecules. Moreover, this type of co-electrolyzer can operate under pressure which increases the energy efficiency of the system, reducing the compression costs of the downstream chemical processing unit and increasing cells performance.2 In addition, as nickel present in SOC is known to catalyze CO and CO2 (COx) methanation and water gas shift reactions3, a pressure increase in the electrolyser leads to higher rates of these reactions. HTE cells can also be used in fuel cell mode to generate electricity from methane and water4. In this case, nickel catalyzes steam reforming leading to syngas which can be used to produce electricity. However, the contribution of these catalytic reactions are not well-known in co-electrolysis and fuel cell modes. In this view, we propose to evaluate their impact in a SOC fed with carbonated gases by establishing a kinetic model necessary for a complete electrochemical SOC modelling. This work was carried out on two different SOCs to establish kinetic models for co-electrolysis and steam reforming at atmospheric pressure and then under pressure. Catalytic tests The cells studied come from two different suppliers (A and B). In order to study the catalytic reactions, induced by nickel in the hydrogen electrode, other layers have been removed by sandblasting. COX methanation catalytic tests were performed at 400°C with the cells reduced into powder with different inlet mixtures (CO and/or CO2 with H2 with COx/H2 molar ratio around 0.3). Tests were carried out with a total flow rate of 35NmL.min-1 (equivalent to 346NmL.min-1.cm-2 cell and 245NmL.min-1.cm-2 cell for cells A and B, respectively). These flowrates are far from those commonly used for electrochemical tests, but they allow to distinguish the catalytic activity of the two cells. The results showed that cells are not equivalent to each other regarding COx conversion whatever the conditions used (CO and/or CO2) (Figure 1). It also can be noticed that the CO2 hydrogenation activity is reduced after exposure to a CO/H2mixture (Figure. 2) due to carbon deposition blocking the active sites. Secondly, catalytic tests were achieved to demonstrate the influence of water at the inlet (up to 15mol.% of water). The temperature was varied from 400 to 800°C after initial stabilization at 400°C. These tests confirmed the negative effect of water due to a less favorable thermodynamic. Finally, methane steam reforming catalytic tests were carried out to simulate fuel cell feeding conditions (H2O/CH4 molar ratio around 2) with a total flow rate of 5.3NmL.min-1 (equivalent to 52NmL.min-1/cm-2 cell and 37NmL.min-1.cm-2 cell for cells A and B, respectively). These conditions make it possible to approach the operating conditions of an electrolyser. The temperature was varied from 600 to 800°C after initial stabilization at 600°C. It appears that the A cell is close to thermodynamic equilibrium up to 700°C followed by a decrease at higher temperature whereas the B cell does not exhibit this decrease (Figure 5). Conclusions and outlooks The cells exhibit similar catalytic activities with respect to COX methanation and methane reforming. Simulations carried out using the COMSOL software allowed to select three kinetic models for atmospheric SOC operation5 , 6. To discriminate these models and propose a quantitative kinetic model for the SOCs operating under pressure, catalytic and electrochemical tests will be carried out up to 15 bars. Simulations will then be performed (COSMOL) to simulate the functioning of a cell by coupling catalysis, electrochemistry, gaseous and thermal flows. 1. Ni M. et al. Int. J. Hydrogen Energy 33,2337–2354 (2008). 2. Bernadet L. et al. Int. J. Hydrogen Energy 40,12918–12928 (2015). 3. Gao J. et al. RSC Adv. 5,22759–22776 (2015). 4. Er-rbib H. et al. Energy 75,81–88 (2014). 5. Wang Y. et al. Int. J. Hydrogen Energy 34,3885–3893 (2009). 6. Peters R. et al. J. Power Sources 106, 238–244 (2002). Figure 1

International audience; A 2D multi-physic in-house-model has been developed to analyse the performances of Solid Oxide Electrolysis Cell (SOEC) stack This model encompasses a combined electrochemical and thermal description of the electrolyser An analytical solution for multi-species diffusion across the porous cathode has been implemented in the model This numerical tool is useful to provide all the important parameters of the stack operation distribution of temperature heat fluxes local current densities gas concentrations and overpotentials Simulations show that thermal equilibrium of the stack is strongly dependant on radiative heat losses whereas convective heat transfers are limited In the exothermic operation mode the cell warming depends on the radiation efficiency A parametric study has been carried out to analyse SOEC irreversible losses It is found that the anode activation overpotential is significant whereas the polarisation due to the cathode activation remains much more limited Anode concentration overpotentials are found to be insignificant whatever the operating condition Cathode concentration overpotentials are found to be moderate in the case of Electrolyte Supported Cell (ESC) while they can increase drastically with current density in the case of Cathode Supported Cell (CSC) Addition of diluent gases into the H(2) H(2)O mixture is found to increase the concentration overpotentials

International audience; Highly porous ceramics are critical components of Solid Oxide Fuel Cells. Nevertheless, their mechanical properties are poor and not fully understood. Herein, Discrete Element simulations are used to quantitatively assess the relation between the particulate microstructure of highly porous ceramics and their mechanical properties. Partially sintered ceramics are numerically generated with complex microstructures including pore formers and bilayers. These microstructures are then tested in tension and compression to obtain their elastic and fracture behavior. Compiling experimental data from the literature and simulations results, an Orowan-Petch type relation between strength and particle size is proposed for highly porous ceramics. It is based on the local fracture model at the length scale of solid bonds between sintered particles.

International audience; The effects of Ni-YSZ cermet re-oxidation in anode supported Solid Oxide Fuel Cells (SOFCs) have been investigated. Damage mechanisms have been studied in both cases of direct oxidation in air (i.e., fuel shutdown) or by an ionic current (i.e., fuel starvation). Direct oxidation tests show that the electrolyte cracks for a conversion degree of Ni into NiO ranging between similar to 58 and similar to 71%. This failure mode has been modelled considering both the bulk expansion of the cermet induced by the transformation of the Ni phase and the change of mechanical stresses in the multilayered cell. In the case of fuel starvation, a thin layer of the cermet was electrochemically re-oxidised at 800 degrees C and then reduced under a hydrogen stream. This 'redox' cycle was repeated until the degradation of the cell. The evolution of the impedance diagrams recorded after each cycle suggests that the cermet damages in an area close to anode/electrolyte interface. The mechanical modelling states that a delamination can occur along the interface between the Anode Functional Layer(AFL) and the Anode Current Collector (ACC) substrate. This theoretical result confirms the experimental trends observed by impedance spectroscopy. (C) 2009 Elsevier B.V. All rights reserved.

A dynamic physically based model has been developed to unravel the complex relationships between the overall Solid Oxide Cells (SOCs) response and the reaction mechanisms taking place in the electrodes. This numerical tool combines modules for different length-scales from the electrode microstructure up to the single repeat unit. First, models have been developed to emulate digital twins of electrode microstructures made of the classical SOCs materials [1]. The microstructural properties of the active layers and the current collectors are then computed on the synthetic volumes and used as inputs in the electrochemical models. The microscale models for the active layers take into account the mass and the charge transport phenomena for the solid and gas phases. For each electrode, the proposed reaction mechanism is split in a sequence of elementary steps with different pathways that can be activated depending on the polarization [2, 3]. The electrode models are finally coupled with a macroscopic description including the cell geometry and the design of the gas channels [4]. This model allows computing the cell polarization curves, the overpotentials and the EIS together with the distribution of the local current density and gas composition in the single repeat unit. This multiscale model has been used to study a typical cell made of the classical SOCs materials: the electrolyte was in Yttria Stabilized Zirconia (YSZ) whereas the hydrogen and oxygen electrodes were respectively composed by a cermet of Nickel and YSZ (Ni-YSZ) and a composite of Lanthanum doped Strontium Cobaltite Ferrite and Ceria doped Gadolinium Oxide (LSCF-CGO). For this cell, the representativeness of the electrodes synthetic microstructures have been checked on reconstructions obtained by tomographic techniques. It has been shown that the synthetic electrodes reproduce accurately the real microstructures. Moreover, the models at the electrode level have been carefully validated on polarizations curves and Electrochemical Impedance Spectra (EIS) measured on symmetrical cells using a three-electrode setup. It is worth noting that the electrodes of the tested symmetrical cells were manufactured using the same materials and composition than the complete cell. Finally, a specific attention has been paid in this work to validate the approach with an original experimental setup allowing the measurement of the local current densities on the full cell without electrode segmentation. This setup is composed of nine symmetrical-spaced pins that perform the measurement of local polarization curves from the inlet to the cell outlet. A campaign of tests has been carried out in fuel cell and electrolysis mode with different temperatures and flow rates. A good agreement has been found between the experimental and simulated data. It has been shown that the model is able to reproduce the evolution of the local polarization curves with a higher current density at the cell inlet. Furthermore, the simulated EIS for the cell have been found to be consistent with the experimental ones. The fully validated model has been used to analyze the cell operation in electrolysis and fuel cell mode. The reaction pathways associated to the elementary steps in the active layers have been discussed depending on the position within the electrodes and the polarizations. This model will then be used to implement the degradation laws such as the Ni agglomeration and compute the loss of cell performances and the remaining useful lifetime [5]. Moreover, the model could be applied to interpret the evolution of the EIS upon operation. [1] H. Moussaoui, J. Laurencin, Y. Gavet, G. Delette, M. Hubert, P. Cloetens, T. Le Bihan, J. Debayle, Stochastic geometrical modeling of solid oxide cells electrodes validated on 3D reconstructions, Computational Materials Science. 143 (2018) 262-276. [2] F. Monaco, E. Effori, M. Hubert, E. Siebert, G. Geneste, B. Morel, E. Djurado, D. Montinaro, J. Laurencin, Electrode Kinetics of Porous Ni-3YSZ Cermet Operated in Fuel Cell and Electrolysis Modes for Solid Oxide Cell Application. Under review. [3] E. Effori, J. Laurencin, E. Da Rosa Silva, M. Hubert, T. David, M. Petitjean, L. Dessemond, E. Siebert, An elementary kinetic model for the LSCF and LSCF-CGO electrodes for solid oxide cells: impact of oxygen partial pressure and degradation on the electrode response. Under review. [4] J. Laurencin, D. Kane, G. Delette, J. Deseure, F. Lefebvre-Joud, Modelling of solid oxide steam electrolyser: Impact of the operating conditions on hydrogen production. Journal of Power Sources. 196 (2011) 2080-2093. [5] M. Hubert, J. Laurencin, P. Cloetens, B. Morel, D. Montinaro, F. Lefebvre-Joud, Impact of Nickel agglomeration on Solid Oxide Cell operated in fuel cell and electrolysis modes. Journal of Power Sources. 397 (2018) 240-251. Figure 1

Microstructural evolution of Nickel in Ni-YSZ fuel electrodes is one of the main limiting degradation mechanisms in solid oxide cells [1]. The redistribution of Nickel is ascribed to its high mobility and low wettability with YSZ, related to interfacial surface tensions. Practically, the degradation manifests as the agglomeration of Ni, potentially accompanied by its migration, mainly reported in electrolysis mode. Extensive efforts have been made to understand Ni agglomeration and relocation. In this frame, advanced imaging techniques have been employed to characterize the microstructure of electrodes after aging in a wide range of conditions. In order to support these observations and gain fundamental insights, a number of computer simulations methods such as: multistate kinetic Potts-Monte Carlo models, cellular automata, phase field, and topological boundary dynamics have been successfully employed in modelling grain growth and recrystallization phenomena. Nevertheless, questions still remain on the exact underlying mechanisms of Ni migration. In the shadow of this lack of clear understanding, a morphological modelling approach aiming at mimicking Ni depletion based on the most fundamental definition of chemical potential and surface curvature minimization would be very helpful to guide researchers into gaining clearer insights of this phenomenon. Moreover, the morphological simulations are very fast compared to the physically based models. Therefore, they can offer the possibility to emulate large database of numerical microstructures in order to study the impact of Ni evolution on the microstructural properties [2]. The current work falls within this framework and aims at modelling the two main Ni degradation phenomena, namely coarsening and migration. For this purpose, a novel model based on morphological operations from mathematical morphology [3] has been developed and adapted to the Ni-YSZ specificities. The considered driving force for Ni evolution is the minimization of its surface curvature, and implicitly its chemical potential, which strongly depends on the local operating conditions. After calibration, the model showed a capability to predict, starting from an initial 3-D microstructure as input data, Ni relocation that was in agreement with that observed in a large dataset of 3-D reconstructions from pristine and aged cells. This helps understanding the associated microstructural evolutions which are linked to the cell Area Specific Resistance (ASR) through an adapted in-house model. This coupling of microstructural and electrochemical models allows giving clearer insights and practical recommendations for the design of fuel electrodes with improved stability and electro-catalytic activity. [1] M. Hubert, J. Laurencin, P. Cloetens, B. Morel, D. Montinaro, F. Lefebvre-Joud, Journal of Power Sources, 397 (2018) 240-251. [2] H. Moussaoui, R.K. Sharma, J. Debayle, Y. Gavet, G. Delette, J. Laurencin, Journal of Power Sources, 412 (2019) 736-748. [3] J. Serra, Image Analysis and Mathematical Morphology: Theoretical Advances, Academic Press, Cornell University (1988). Figure 1