Mathematical approaches to modelling the mass transfer process in solid oxide fuel cell anode

Fatigue resistance of steels: Boardman, B. Metals Handbook 10th Edn (ASM International, Materials Park, Ohio, 1990) Vol. 1, pp 673–688

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

Different solutions adopted in producing Solid Oxide Cells (SOCs) have proven to be scalable and the technology is now approaching commercialization. The high energy conversion efficiency, coupled with the fuel flexibility and the reduced use of expensive catalyst materials promoted by the favorable thermodynamics at the operative temperatures, are making the technology increasingly attractive and stacks are finding applications in more fields. Large scale power-to-X plants, particularly the ones devoted to hydrogen production (Solid Oxide Electrolysis Cells – SOEC), are among the solutions that are gaining most momentum in the energy market. X-to-power (Solid Oxide Fuel Cells – SOFC) solutions such as decentralized heat and electricity production, auxiliary power systems and heavy duty transport propulsion are spreading as well, facing challenges such as power density and dynamic load operation.Advancement in the SOC technology is opting at substituting ceramic materials with mechanical support function, in favor of metal. A lower amount of ceramic materials not only reduces the raw material costs, but also allows rapid thermal cycling without compromising the mechanical integrity of the cells – hence allowing faster start-ups and load regulations. Furthermore, our recent studies demonstrated a scalable and innovative layer integration process that allows to fabricate complex 3D multilayer structures with internal gas channels and cavities of different geometries, using conventional tape casting. The monolithic SOC stacks rising from this process, combined with the integration of metallic parts in the great majority of their volume, may achieve groundbreaking power densities and the dynamic load operation desired for the mentioned applications, while decreasing CapEX and resources necessary to produce high performing SOCs of the future.The monolithic SOC stacks obtained within this work are made of three standard repetitive units (SRUs). Each SRU consists of a SOC backbone, composed by two porous zirconia based electrode backbones to be infiltrated with appropriate electro-catalysts, a dense thin zirconia based electrolyte, two sets of ferritic steel gas channel structures – one at the fuel side and one at the oxygen side – conferring enhanced gas diffusion to the triple phase boundaries, mechanical support and electronic conductivity and composite metal/ceramic interconnect plates connecting in series the SRUs. The total number of layers co-fired to produce monoliths within this work is 19 and the monoliths are denoted as “MNx3” (nomenclature defined for a monolith stack with 3x SRUs). The cross section is showed in Figure, where scanning electron microscopy is complemented by qualitative energy dispersive x-ray spectroscopy (EDS) to highlight the material composition of the three SRUs. This work presents the challenges and a solid framework for the solutions adopted to fabricate monolithic stacks aimed at hydrogen production, using the conventional tape casting shaping technique integrated with the innovative assembly process developed. Among the challenges, focus is given to i) the shaping of internal gas channels, ii) structural integrity during fabrication and operation and iii) the use of non-critical raw materials. Detailed electrochemical characterization is currently in progress and the results will be presented at the conference. Besides the real initial performance of the stacks at this development stage, it is speculated that SRU cells performance could get close to the ones of state of the art metal supported cells, also relying on electrocatalyst infiltration. Figure 1

Review: 22 refs.

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.

Reversible solid oxide electrochemical cell (RSOC) is a competitive option which has attracted increasing focus on alleviating some environmental problems and energy crisis with the capability of reversibly operating in solid oxide fuel cell (SOFC) mode and solid oxide electrolysis cell (SOEC) mode [1].Solid oxide cells (SOCs) have received increasingly attention due to their high efficiency and broad applications. However, electrodes with rapid hydrogen oxidation reaction (HOR), oxygen reduction reaction (ORR), carbon dioxide reduction reaction (CO2RR), oxygen evolution reaction (OER) and sufficient durability play a key role in solid oxide cells. A multifunctional perovskite oxide La0.6Ca0.4Fe0.8Ni0.2O3-δ (LCFN) has been investigated as an electrode for SSOCs in our previous work. The results confirm that LCFN shows excellent ORR, OER, CO2-RR and HOR catalytic activity [2-3]. However, the investigation of LCFN for SOCs has been hindered due to the lack of stability. Herein, a novel perovskite La0.6Ca0.4Fe0.7Sc0.1Ni0.2O3-δ (LCFSN) is investigated as an electrode of SOCs. Its structural stability has been improved under H2 atmosphere. The polarization resistance (Rp) of the electrode LCFSN is only 0.147 Ω cm2 at 800 °C under air. The single cell Ni-YSZ/YSZ/GDC/LCFSN displays a peak power density of 1.36 W/cm2 in fuel cell mode and a low Rp value of 0.131 Ω cm2. Most importantly, the cell exhibits admirable durability of 130 h without apparent degradation. All these results suggest that LCFSN is a promising candidate electrode for SOCs.

Solid oxide fuel cells (SOFCs) excel by high efficiencies in fuel cell as well as electrolysis modes, and by being able to operate in both modes as a reversible cell (solid oxide cell – SOC). This allows for production of electricity and heat from a green fuel, and for storage of electricity as gas or use as fuel. Lifetime and costs are major factors enabling such reversible SOCs to enter green energy systems. Metal supported SOCs (MSCs) provide cost-competitive materials within the cell. Furthermore, targeting the lower operating temperatures around 650 oC, MSCs will allow for cheaper stack and balance of plant components as well. Lowering operating temperatures leads to a reduction of thermally activated degradation processes, thereby prolonging the lifetime. The present study investigates the option to operate MSCs, fabricated at DTU Energy by tape casting, lamination, and screen-printing, in reversible mode between fuel cell (FC) and electrolysis (EC). Emphasis is on the effect of reversible operation on performance and durability of the MSC, compared to steady state operation in either mode, and to the behavior of state-of-the-art (SoA) fuel electrode supported SOC with Ni/YSZ fuel electrode. The MSCs are composed of a FeCr support, a Ni/GDC (gadolinium-doped ceria) infiltrated LSFNT (lanthanum-doped strontium iron nickel titanate) fuel electrode, a YSZ (yttria-stabilized zirconia) electrolyte, a GDC barrier layer, and an in situ sintered LSC (lanthanum-doped strontium cobaltite) air electrode. The reversible operation was carried out by switching between FC and EC modes at current densities of 0.25 and -0.25 A/cm2, respectively, at 650 oC using a gas mixture of 50/50 H2O/H2 to the fuel electrode and air to the oxygen electrode.Figure 1 shows the evolution of the cell voltages for the SoA cell and the MSC. The degradation rate of the SoA cell was larger during operation in EC as compared to FC mode. Similar observations were made previously, even though these tests were typically carried out at temperatures higher than 650 oC as in this work [1]. Furthermore, the degradation rate decreases over time, more particularly in EC mode, which is also a known phenomenon at this type of cells [2, 3]. In the final ca. 200 h, both degradation rates are in the range of 3%/1000 h, which is an interesting observation, i.e., the longer-term degradation rates are similar in both modes (EC and FC). The analysis of electrochemical impedance spectroscopy (EIS) recorded under current allowed to conclude that the main contribution to the degradation is the increase of polarization resistance, i.e., related to electrodes degradation.In the initial ca. 400 h hundred hours, the cell voltage degradation on the MSC is larger in fuel cell mode, while there is nearly no degradation in electrolysis mode. The good stability in EC mode over a few hundred hours confirms the findings of steady-state electrolysis tests with the same type of cells [4]. In the final period from ca. 600 h, both degradation rates increase but stay fairly constant with ca. 4%/1000 h in EC and ca. 16%/1000 h in FC mode, when calculated as linear increase. EIS reveals that both, the serial and the polarization resistances increase in parallel, which indicates a combination of degradation of electrode and probably corrosion and/or interface attachment. Details will be presented, including comprehensive EIS evaluation combined with micro-structural characterization.Figure 1. Cell voltage vs. operating time under current in reversible mode at 650 oC, 0.25 A/cm2 in fuel cell and -0.25 A/cm2 in electrolysis mode, 50/50 H2O/H2 fuel and air to the oxygen electrode, (a) SoA cell, (b) MSC, gaps in the cell voltage are interruptions of operation due to technical issues in the labReferences[1] X. Sun, B.R. Sudireddy, X. Tong, M. Chen, K. Brodersen, A. Hauch, Optimization and Durability of Reversible Solid Oxide Cells, ECS Trans. 91 (2019) 2631.[2] A. Hagen, R. Barfod, P.V. Hendriksen, Y.-L. Liu, S. Ramousse, Degradation of anode supported SOFCs as a function of temperature and current load, J. Electrochem. Soc. 153(6) (2006) A1165.[3] A. Hauch, K. Brodersen, M. Chen, C. R. Graves, S. H. Jensen, P. S. Jørgensen, P. V. Hendriksen, M. B. Mogensen, S. Ovtar, X. Sun, A Decade of Solid Oxide Electrolysis Improvements at DTU Energy, ECS Transactions, 75(42) (2017) 3.[4] A. Hagen, R. Caldogno, F. Capotondo, X. Sun, Metal Supported Electrolysis Cells, Energies 15 (2022) 2045. Figure 1

High-temperature solid oxide cells (SOCs) is in the center of scientific attention for a while as a promising technology related to sustainable society. In this case, SOCs consist of two closely interlinked technologies: solid oxide fuel cells and solid oxide electrolysis cells. Both technologies share several similar traits such as high electrical efficiency and fast reaction kinetics due to the high operating temperature (600–900 °C) without the need for PGM catalysts. These cells basically consist of two porous composite electrodes and a dense ion conducting electrolyte. In particular, the inner microstructure of the electrodes predetermines the SOCs performance owing to its governing effect on the electrical conductivity and/or electrocatalytic activity. Despite its importance, contemporary understanding of the development of the emerging microstructure during the fabrication of these composite materials is far from sufficient.Lanthanum-strontium-manganite (LSM, La1-xSrxMnO3-δ) paired with yttria stabilized zirconia (YSZ, ZrO2:Y2O3) is the typical example of the state-of-the art porous oxygen electrode exhibiting a mixed ion-electron conductivity suitable for SOCs. The fabrication process of LSM:YSZ electrodes involves a crucial step – the sintering, which principle lies in the thermal treatment of the precursor particles for a defined period of time. The LSM:YSZ composite is usually sintered at 1150 °C. At this temperature, exclusively LSM particles tend to soften and form an interlinked solid framework between individual particles, while the YSZ particles remain unaffected by the temperature treatment due to their high melting point (around 2500 °C).Despite the sintering process belongs among the oldest known fabrication techniques, there is no hard evidence on how the sintering proceeds over time at different temperatures while employing materials with significantly different melting points, such as LSM and YSZ. In addition, the sintering temperature along with the sintering time directly influences the resulting inner microstructure and consequently the electrical conductivity of such electrode. Prediction of the resulting inner microstructure is frequently performed by postmortem analyses of multiple samples sintered at different temperatures. However, such practice results only in indirect proofs of the impact of the sintering temperature and is significantly time consuming. The goal of this study is, therefore, to investigate the sintering process of LSM:YSZ composite in situ and to set into relation the resulting inner microstructure with the applied thermal treatment.To answer the present goal, a novel combination of SEM paired with inbuilt MEMS heating chip was developed. This setup allows for online monitoring of the LSM:YSZ sintering process. The results show that at 900 °C the LSM particle agglomerates begin to shrink as the individual LSM particles start to adhere to each other. At this point, significant porosity emerges in the composite, which is considered essential to ensure a sufficient mass transfer during the SOCs operation. On the other hand, the degree of the emerged porosity can be beyond the threshold of mechanical stability of the electrode body, rendering such an electrode unusable. At 1150 °C the densification of the composite occurs, which is essentially a self-healing process resulting in a well-interlinked and mechanically stable composite. The densification is related to the adhesion of the LSM particles to the YSZ particles, thus forming a solid framework, ensuring ample mixed ionic-electronic conductivity of the fabricated electrode. Based on the results, a slight variation in sintering temperature and/or time leads to a significant difference in the electric conductivity of the electrode due to a different sintering degree or, in other words, due to the different void fraction in the body of the electrode. Within the literature, this outcome is reflected by a major inconsistency in reported electric conductivity of the commonly utilized 50:50 wt.% ratio of LSM:YSZ.An interesting insight into the sintering process of the LSM:YSZ composite has provided the SEM paired with inbuilt MEMS heating chip. This experimental technique is very promising for in situ studies of sintering and/or synthesis processes of various materials related to numerous technologies.This work was supported by the Technology Agency of the Czech Republic under project no. TK04030143.

Complementary techniques for solid oxide electrolysis cell characterisation at the micro- and nano-scale

Yttria-stabilized zirconia (YSZ) is the most common and the most reliable electrolyte material for solid oxide fuel cells (SOFCs) and solid oxide electrolysis cells (SOECs), collectively referred to as solid oxide cells (SOCs). Typical SOCs for practical applications are of the fuel-electrode-supported cell variety because these type of cells could be operated under high current densities. Here, the YSZ electrolyte is co-sintered with porous NiO-YSZ support at temperatures as high as 1400 °C to obtain dense electrolyte layer on the anode. In this process, NiO is expected to diffuse into the YSZ electrolyte. The influence of dissolved NiO into YSZ electrolyte has been investigated in AIST [1-3]. For the YSZ electrolyte with intentionally dissolved NiO, the phase transformation from cubic phase to tetragonal phase is accelerated in the lower oxygen potential range where NiO is reduced to Ni metal in the YSZ electrolyte, consequently, degradation in the conductivity of YSZ electrolyte occurs. In this study, the influence of co-sintering process of YSZ electrolyte with the NiO-YSZ support, i.e. NiO diffusion into YSZ electrolyte under co-sintering process, and its influence on the oxide ion diffusivity of YSZ electrolyte are examined.YSZ electrolyte layers were prepared on the NiO-YSZ substrates by screen-printing method or dip-coating method, and then co-sintered at high temperatures between 1370 °C to 1550 °C. The co-sintered YSZ/NiO-YSZ half-cells were reduced under dry H2 flow for 5 to 300 hours. The crystal structure and Ni distribution of the YSZ electrolyte layer were analyzed using Raman spectroscopy and high-spatial-resolution SIMS (secondary ion mass spectrometry), respectively. Lastly, the oxide ion diffusivity of the YSZ electrolyte layer was obtained using the oxygen isotope exchange method and high-spatial-resolution SIMS technique.By co-sintering of YSZ electrolyte and NiO-YSZ support, NiO uniformly diffused into YSZ electrolyte layer, and the amount of dissolved Ni (NiO) increased with increasing sintering temperature. When the half-cell was reduced at 900 °C, a phase transformation of the YSZ electrolyte was clearly observed, moreover, the oxide ion diffusivity of the YSZ electrolyte also decreased. By reduction of the half-cell at 700 °C, such phase transformation could not be observed, however, the oxide ion diffusivity is slightly but clearly decreased. In the presentation, the mechanisms of phase transformation and conductivity degradation will be discussed. H. Yokokawa et. al., Fuel Cells, 19 (2019) 311–339.T. Ishiyama, H. Kishimoto, K. D. Bagarinao, K. Yamaji, T. Horita, H. Yokokawa, ECS Transactions, 78 (2017) 321–326.T. Shimonosono, H. Kishimoto, M.E. Brito, K. Yamaji, T. Horita, H. Yokokawa, Solid State Ionics,225, 69 (2012).

A novel system for the production of pure hydrogen from natural gas based on solid oxide fuel cell–solid oxide electrolyzer

The aim of this presentation is to address three fundamental questions related to solid oxide cells: Are the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) indeed the rate-limiting steps in the high-performance of solid oxide cells, and how can we accurately quantify the area specific resistance of the oxygen electrode?What causes the phenomenon known as “electrochemically driven phase transformation,” and how can our understanding of this process be applied to create electrodes that are both high-performing and durable?How can we develop reliable accelerated testing protocols for both solid oxide fuel cells and solid oxide electrolysis cells, and which physical processes are being accelerated through these tests? The accurate quantification of electrode polarization in fuel cells and electrolyzers holds critical importance but presents a significant challenge due to the extensive overlap in polarizations from both the anode and cathode, whether in DC or AC measurements. This overlap creates a notable gap in our understanding of electrode behavior and in the development of electrochemical devices that are both high-performing and durable. In this presentation, I will introduce a reliable method for measuring the polarization of individual electrodes within a solid oxide cell. This technique is versatile and can be easily adapted for use in various types of electrochemical cells. Additionally, we will explore the limitations associated with using the distribution of relaxation times analysis for determining the polarization of individual electrodes.We will then address the origin for the phase transformation observed in an oxygen electrode during operation, as opposed to what is seen with thermally annealed materials. By integrating electronic conduction at the interface layer, we can significantly reduce the occurrence of phase transformation. This understanding of “electrochemically driven phase change” is crucial for the development of reliable accelerated testing protocols. Such protocols are essential in solid oxide fuel cell research to speed up the investigation of durability issues, quickly identify potential failure mechanisms, and ultimately estimate the lifespan of electrochemical cells. In our study, we compared solid oxide fuel cells operated at constant current density with those subjected to accelerated testing methods, which involve intermittent current injections. We have formulated a general accelerated testing framework, which will be presented in detail.Finally, we will present a theoretical model that underlies those three questions and can be used to address stability and durability issues in solid oxide cells. Acknowledgements: The presenter would like to thank Prof. Anil Virkar, Dr. Emir Dogdibegovic, and Dr. Yudong Wang, for their invaluable contributions to the work presented. This work was made possible through the support of projects DE-FE0026097, DE-FE0031667, DE-AR0001346, and DE-FE0032110.

Introduction With the recent enhancement of renewable energy utilization, large scale energy conversion and storage become more important to control the surplus electric power due to the unsteady power generation. Reversible hydrogen energy storage system via solid oxide electrolysis cell (SOEC) and solid oxide fuel cell (SOFC) are expected as a high efficient device because of its high operating temperature (600℃~1000℃). It is possible to unify them to one device as reversible system (RSOFC/EC), but it is necessary to understand the mechanism of FC/EC reactions and design the device with a good balance between FC and EC in order to apply them for an actual energy system. While SOFC reaction models and many electrochemical data of electrodes have been developed and reported by many researchers, there are few reports to investigate the reaction model of SOEC. Thus, it is possible to predict the performance of SOEC based on a comprehensive SOFC/EC models and experimental data of SOFC, because the reactions of SOFC and SOEC are a reversible relationship and the equal value of IR loss can be applied. However, the comprehensive SOFC/EC electrochemical model has not been established. A series of experimental data of anodic and cathodic current density vs. the potential should be investigated at various conditions to develop the SOFC/EC model. In this work, a series of anodic and cathodic electrode performance was taken using a SOFC in various conditions. Furthermore, attempting to predict SOEC performance from SOFC performances, we proposed and discussed a new model of electrolysis based on our developed SOFC model. Experimental The Disks of 8 mol% Y2O3-ZrO2 (YSZ; 0.25 mm thickness, 20 mm diameter) were used as the electrolyte and the anode was a Ni/YSZ or Ni/GDC composite, and the cathode was a La0.8Sr0.2MnO3/ScSZ composite. We measured the dependence of the current density of anodes on oxygen activity with wide range to get both power generation and electrolysis data for various gas composition (PH2=0.3~0.99 atm, PH2O=0.01, 0.03, 0.05 atm). Results and Discussion 1. Method to fit parameters on the SOFC/EC model We have developed the electrochemical reaction model on the fuel electrode (=anode) based on the equilibrium of competitive adsorption and oxygen activity, ao , specified by anode potential (Eq.1, Table.1) [1]. The SOFC model was constructed by assuming competitive adsorption equilibrium of H2, H2O and O on Ni surfaces at three-phase boundary and the rate-determining step to be Langmuir-type reactions of H with O (Table.1). We obtained an equation of the electrical current density, i, as a function of the oxygen activity (ao ) calculated from the anode potential which is simply measured from experiments. To confirm effectiveness of the model, we fitted the model to actual experimental data described by i vs. ao . From the equations of model on Table.1, each current density of SOFC (ia ) and SOEC(ic ) are described as Eq.2. To draw the plot of i vs. ao on the model, the rate constants (ka, kc ) and the equilibrium constants (KO, KH, KH2O ) need to be defined as reliable value. Thus, from the equilibrium potential vs. 1 atm O2 (Eq.3), we defined the rate constant of kc as Eq.4. When the kc became a dependent variable of ka , then we fitted ia to power generation experimental data described by i vs. ao so that the values of KHKO/KH2O were fitted approximately. Finally, i c model could be drawn on the plot of i vs. ao and the maximum value of i c was obtained by Eq.5 which is independent of ao and Eq.6 was obtained using Eq.4. 2. Experimental results and parameter fitting on the SOFC/EC model As the expreimental results, the maximum power density of SOFC with Ni/YSZ was 588.5 mW/cm2 for FC mode at PH2=0.99 atm, PH2O=0.01 atm, and ic(max) was 0.285 A/cm2 for EC mode at PH2O=0.03 atm. However, ic(max) calculated by the model (Eq.6) was 0.050 A/cm2. Also, in case of SOFC with Ni/GDC, ic(max) was 0.400 A/cm2 for EC mode at PH2O=0.03 atm, while ic(max) calculated by the model (Eq.6) was 0.055 A/cm2. The electrolysis current density measured by our RSOFC/EC showed 6 times higher than model values approximately. This result suggested the possibility that additional parallel reaction path was existed. In this presentation, we will discuss the possible electrochemical paths to explain the disagreement between the model and the experimental data. Finally, the comprehensive SOFC/EC model will be proposed to predict EC performance using SOFC data.

Increasing demand for long-term energy storage, reduced carbon emissions, more resilient grid, and the lowest cost grid balancing solutions promotes solid oxide electrolysis cell (SOEC) and reversible solid oxide cell (RSOC) technologies. These systems can achieve high hydrogen production rates with near 100 percent stack electrical efficiency while co-electrolysis of carbon dioxide and water leads to production of syngas. RSOC can serve as a grid storage device (hydrogen production) and power production plant (provide electricity during peak demand). With over 25 years’ experience building and testing solid oxide cell materials, components and stacks, Nexceris has a proven track-record of commercializing products to major OEMs. The established manufacturing platforms at Nexceris enable smooth expansion into new applications.In this talk, development of cells, stack components and stacks will be discussed. Performance and durability improvements from single cell to short stacks will be addressed. Cells with downselected electrode sets were implemented into short stacks with active cell area of 42 cm2 and 96 cm2. Stacks were operated continuously in SOEC mode at ~1.3 V for ≥ 500 hours with <5%/kh degradation and improving. The resulting short stack demonstrations show promising baseline performance and durability platform for future cell and stack development. RSOC tests were recently initiated with dynamic operation. Nexceris’ ChromLok coatings for bipolar plates were also integrated to stacks to enhance durability.

To improve solid oxide electrolysis cell (SOEC) system designs and fabrication quality, endurance testing of SOEC systems provides a proving ground on which real-world usage can be simulated, and quality assurance issues can be identified early on. A test facility at Idaho National Laboratory (INL) was designed, built, and operated to facilitate endurance testing of a reversible system by Oxeon Energy. Designated Emerald, the test facility is currently the only test facility at INL designed to allow both SOEC and solid oxide fuel cell (SOFC) testing of the same module. To safely operate a reversible SOEC test facility, several safety features are required, and a hazard and operability analysis is of Emerald is discussed here. Design challenges due to differences in the endothermic SOEC and exothermic SOFC reactions were addressed in the process recuperators. Controls for the Emerald test facility were built in an open-source JavaScript runtime environment, Node.js and executed on a Linux-based industrial controller. The Oxeon Energy module has been successfully brought up to SOEC ready conditions. Initial operations of the Emerald test facility are being improved to eventually achieve non-stop operations and thousands of hours of testing of both SOEC and SOFC.