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

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

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

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

Review: 22 refs.

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

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.

Introduction Reversible solid oxide cells (r-SOCs) are attractive electrochemical energy devices that can operate as both solid oxide fuel cells (SOFCs) for power generation, and solid oxide electrolysis cells (SOECs) for steam electrolysis (1). Renewable power generation, such as wind and solar, depends on daily weather conditions and so that it is desirable to adjust the supply of fluctuating electricity to match demand using reversible energy devices such as r-SOCs. The operational concept of r-SOCs is schematically described in Figure 1. The aim of this study is to examine the electrochemical properties and durability of r-SOCs using alternative fuel electrode materials. Experimental Various r-SOCs were prepared using conventional and alternative fuel electrode materials. As the conventional materials, Ni-cermet with Sc2O3-doped ZrO2 (ScSZ) was used for the fuel electrode; dense 200 mm thick ScSZ membrane for the electrolyte; and La0.6Sr0.4Co0.2Fe0.8O0.3 oxide (LSCF) air electrode with Gd-doped CeO2 (Gd0.1Ce0.9O2) acting as a buffer layer between the ScSZ electrolyte and the LSCF air electrode. As alternative fuel electrode materials, GDC and/or La0.1Sr0.9TiO3 (LST) were used as the fuel electrode backbone. By applying the co-impregnation procedure of Ni and GDC, fuel electrodes with highly dispersed nanoparticles of Ni catalysts and GDC, denoted as Ni-GDC/LST-GDC, were prepared (2,3). A Pt-based reference electrode was deposited beside the air electrode, such that the fuel electrode potential was measured as the voltage between the fuel and reference electrodes.Current-voltage characteristics were characterized, including voltage cycle tests performed by switching the direction of current simulating r-SOC operation. Long-term durability tests in SOEC and SOFC modes were conducted at 800°C. Air was supplied to the air electrode, while 50%-humidified hydrogen gas was supplied to the fuel electrode. The current density in the SOFC and SOEC modes is denoted as positive and negative values, respectively. Results and discussion Figure 2 shows fuel electrode potential as a function of current density in both SOFC and SOEC modes. The cells with the Ni-zirconia cermet, GDC, LST, LST-GDC, and Ni-GDC/LST-GDC could be operated in both modes. In the SOFC mode, the conventional Ni-zirconia cermet exhibited the highest fuel electrode voltage among these materials studied. In contrast, in the SOEC mode, the GDC-containing materials exhibited lower (i.e. better) fuel electrode voltage compared to Ni-zirconia cermet even without Ni catalysts, indicating enhanced electrocatalytic activity of mixed-conducting GDC for the electrode reactions with water vapor at the fuel electrodes. Voltage cycle durability up to 1,000 cycles and long-term durability up to 1,000 hours could be measured. Latest results on the durability with various electrode materials will be presented. Acknowledgements A part of this study was supported by “Research and Development Program for Promoting Innovative Clean Energy Technologies Through International Collaboration” of the New Energy and Industrial Technology Development Organization (NEDO) (Project No. JPNP20005). References Q. Minh and M. B. Mogensen, Electrochem. Soc. Interface, 22, 55 (2013).Futamura, Y. Tachikawa, J. Matsuda, S. M. Lyth, Y, Shiratori, S. Taniguchi, and K. Sasaki, J. Electrochem. Soc., 164 (10), F3055 (2017).Futamura, A. Muramoto, Y. Tachikawa, J. Matsuda, S. M. Lyth, Y, Shiratori, S. Taniguchi, and K. Sasaki, International J. Hydrogen Energy, 44 (16), 8502 (2019). Figure 1

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

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.

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.

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.

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.

Technology readiness levels (TRLs) of electrolysis systems have dramatically increased in recent years as the interest in clean hydrogen production and decarbonization of transportation, industrial and other sectors increases across the globe. This is especially true of high temperature steam electrolysis (HTSE) / solid oxide electrolysis cell (SOEC) systems which show promise of much higher system efficiencies than other more developed electrolysis technologies. This possibility of higher efficiencies of HTSE / SOEC systems has been previously assumed to be theoretically possible but in recent years it has become less theoretical and more realistic as an increasing amount of suppliers complete lab and pilot tests showing very promising results. Research in the areas of manufacturing techniques, material selection, electrode and electrolyte compositions, and balance of plant size and integration continues at a fast pace as an increasing number of suppliers both internationally and domestically become involved. The advantages of HTSE become more pronounced when HTSE is coupled with nuclear power plants (NPPs). This is because thermal energy produced by the nuclear reactor can be used in a series of heat transfer loops and heat exchangers to vaporize HTSE feedwater, which drastically improves the economics of the process. Idaho National Laboratory (INL) has been very involved in the research and modeling of HTSE systems for a number of years, in collaboration with other national laboratories, academia, and industry stakeholders both on the hydrogen production as well as the hydrogen demand side. The modeling completed over the years on a large variety of projects has led to a wealth of knowledge at INL including in the area of the technoeconomic assessment (TEA) of HTSE systems. TEAs include process modeling of the HTSE systems to calculate system energy requirements and equipment sizing, followed by estimation of capital and operating costs to enable calculation of the levelized cost of hydrogen (LCOH). The TEA work performed has produced incremental improvements and tuning of the methods, assumptions, models, and results of the analyses as well as providing some opportunities for validating these results. The purpose of this document is to record the current baseline HTSE analyses led by INL to show the current status of assumptions and costs of these systems. Given the rapid development of this technology, the variety of suppliers entering the space, and the increasing attention government and industry are giving to such systems, this document may be updated on a periodic basis with updated analysis and assumptions. This document compiles various analyses results and approaches completed over a period of years into a single document to be used as a baseline going forward. It represents what the INL HTSE analysis group assumes to be the internal best estimate of the current operation, costs, and landscape of the HTSE industry state of the art capability for current SOEC technology in an Nth-of-a-Kind (NOAK) plant, which in this study is defined as existence of the manufacturing capacity to support previous deployment of N = 100 count of 25 MWe modular HTSE blocks (with modular equipment component cost reductions specified as following a 95% learning curve). That said, Tthis is a public document and as such so no proprietary data was used or included in this report. There may be HTSE suppliers that have performance specifications, and cost estimates, and test data that differ from the analysisose presented in this document. This document is meant to be a best conservative estimate of the technology and not an absolute reference.

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).

Electrolyte degradation in anode supported microtubular yttria stabilized zirconia-based solid oxide steam electrolysis cells at high voltages of operation