A one dimensional mass transfer analysis was performed for convective transport as well as mass transport within a porous media. This analysis was based on the analogous average heat transfer within a duct. Equations were developed to calculate the concentration of gas species at the triple phase boundary sites present at the interface of a porous electrode and a nonporous electrolyte. The mass transport analyzed on the steam side electrode of a solid oxide electrolysis cell was performed for a ternary gas mixture. In this analysis two gas species were actively diffusing in the presence of a third inert carrier gas. Multicomponent diffusion coefficients were determined for each species in the steam side electrode mixture. The mass transport analysis performed on the air side electrode utilized a binary gas mixture, namely air. At less than one percent of the total mixture of air, the combined effects of Argon and Carbon Dioxide were assumed to be negligible. This assumption allowed us to consider air a binary mixture. A comprehensive model was developed to determine cell performance under various operating condition and multiple cell geometries. The output of this model was used to optimize various physical features of the cell. Tests were performed on electrode supported solid oxide electrolysis cells at the Idaho National Laboratory. These cells were subjected to various operating temperatures and inlet steam mole fractions. Voltage vs. current density experimental data were collected and compared to computational data in order to validate the model.

The need for energy and fuels is predicted to grow within the next decades, in parallel to the need of decreasing the emissions to air and water to operate within the planetary boundaries. The alternatives to consider as energy or fuel options need to be environmentally friendly, evaluated over the whole life cycle. Hydrogen is one of the considered alternatives because it contains no carbon and has a good environmental performance when produced from renewable sources. It can be produced by a variety of methods, where electrolyzers have a good potential environmental impact if powered by renewable energy. Electrolyzers cleave water into hydrogen and oxygen, by using electricity and water. There are currently four technologies on the market or under development but there is a lack of LCA-studies that compare these. This study is an attributional LCA-study, evaluating the potential environmental performance of two electrolyzers: PEMEC and SOEC. The result from this study is thereafter compared to a parallel study of one other electrolyzer: Alkaline. The LCA study considers six impact categories: Abiotic Depletion (element), Abiotic Depletion (fossil), Acidification Potential, Eutrophication Potential, Global Warming Potential and Photochemical Ozone Creation Potential. The system boundary is set as cradle to gate. The electricity source for hydrogen production is evaluated in a sensitivity analysis, together with a scenario of future estimated developments. The electricity during hydrogen production has the highest impact of the life cycle for PEMEC and SOEC, where the energy source has a great impact on the result. PEMEC has the lowest potential environmental impact, in comparison to Alkaline and SOEC, which comes from low energy consumption and low weight of materials with high environmental impact. / Energi- och bränslebehovet förväntas öka inom de närmsta decennierna, samtidigt som utsläpp till luft och vatten måste minska för att nå uppsatta klimatmål. De alternativ som tas fram behöver vara miljövänliga, med bra klimatresultat sett över hela livscykeln. Vätgas är ett alternativ som övervägs, på grund av högt energiinnehåll och låga utsläpp till följd av att den är fri från kol. Vätgas kan produceras med en mängd metoder, där genom elektrolys anses vara en av de bästa teknikerna ur miljösynpunkt. En elektrolysör producerar vät- och syrgas genom att sönderdela vatten med hjälp av elektricitet. Det finns fyra elektrolys-varianter på marknaden och under utveckling, men det saknas LCA-studier där dessa jämförs mot varandra. Denna studie är en bokförings LCA av två elektrolyser: PEMEC och SOEC, som jämförs med resultatet från en parallell studie av en annan elektrolys-typ: Alkalisk. Potentiell miljöpåverkan mättes i sex stycken kategorier: resursutarmning (fossila resurser och ämnen), försurning, övergödning, global uppvärmning och fotokemiskt marknära ozon. Systemgränsen är satt från råmaterialutvinning till vätgasproduktion. Valet av elektricitetskälla för vätgasproduktion utvärderas i en känslighetsanalys, tillsammans med påverkan av framtida teknikers konstruktion. Livscykelfasen ”produktion av vätgas” har övervägande högst påverkan över livscykeln för SOEC och PEMEC, där elektriciteten är den bidragande faktorn. Elektrolysmodellen PEMEC har uppskattningsvis lägst miljömässig påverkan över livscykeln. Den låga påverkan för PEMEC kan härledas till låg elektricitetsförbrukning under vätgasproduktionen samt låga vikter av material med hög miljömässig påverkan.

Ce travail porte sur l’étude de la dégradation des convertisseurs électrochimiques haute température à oxydes solides. Une approche couplant des tests électrochimiques, des caractérisations post-mortem avancées et une modélisation multi-échelle a été mise en place afin d’établir les liens entre les performances, la microstructure des électrodes et leur dégradation. Dans ce but, des essais de durabilité de plus de mille heures ont été menés dans différentes conditions opératoires. La microstructure des électrodes a été reconstruite par nano-holotomographie des rayons X pour la cellule de référence avant et après vieillissement. Une attention particulière a été apportée à la mesure de la résolution spatiale et à la fiabilisation du protocole expérimental. Grâce aux volumes 3D, les propriétés microstructurales de l’électrode H2 en Ni-YSZ ont été quantifiées pour les cellules à l’état initial et vieillies. Un modèle physique d’agglomération des particules de Nickel a ensuite été ajusté sur les analyses tridimensionnelles et intégré dans une structure de modélisation multi-échelle développée au laboratoire. Il a auparavant été nécessaire de compléter l’outil numérique avec un module spécifique dédié aux matériaux composant l’électrode à oxygène fait avec un conducteur mixte ionique-électronique. Une fois le modèle validé sur des courbes de polarisation expérimentales, il a été utilisé pour quantifier la contribution de l’agglomération du Nickel sur les pertes de performances mesurées expérimentalement en mode pile à combustible et électrolyse. / This work aims at a better understanding of the high temperature Solid Oxide Cells degradation. An approach based on electrochemical tests, advanced post-test characterizations and multi-scale models has been used to investigate the links between the performances, the electrodes microstructure and their degradation. In that goal, long-term durability tests have been performed over thousand hours in different operating conditions. Electrode microstructures have been reconstructed by X-ray nano-holotomography for the pristine and the aged cells. It is worth noting that a special attention has been paid to improve both the process reliability for the tomographic experiments as well as the spatial resolution of the 3D reconstructed images. Thanks to the valuable 3D volumes, the Ni-YSZ microstructural properties of the H2 electrode have been quantified for the fresh and the aged samples. Then, a physically-based model for Nickel particle agglomeration has been adjusted on the microstructural parameters obtained by the 3D analysis and implemented in an in-house multi-scale modelling framework. Beforehand, it has been necessary to enrich the available numerical tool with a specific module dedicated to the oxygen electrode made in Mixed Ionic Electronic Conducting materials. Once validated on polarisation curves, the completed model has been used to quantify the contribution of Nickel agglomeration on the experimental degradation rates recorded in fuel cell and electrolysis modes.

Ces travaux visent à évaluer la possibilité technique, la performance énergétique et la compétitivité économique d'un procédé Power-to-SNG dans le contexte actuel et à déterminer si la réversibilité en mode Gas-to-Power est pertinente tant énergétiquement qu'économiquement, ce type de procédé étant proposé comme une solution à l'intégration des ressources renouvelables dans le mix énergétique. Les grandes étapes identifiées pour le procédé Power-to-SNG sont l'électrolyse de l'eau pour la production d'hydrogène, l'hydrogénation du dioxyde de carbone pour la production de méthane et une étape de mise aux spécifications pour satisfaire aux exigences de composition pour l'injection sur le réseau de gaz naturel. La technologie retenue pour l'électrolyse est celle des cellules à oxydes solides SOEC s'appliquant à la vapeur d'eau. L'étude énergétique du procédé Power-to-SNG réalisée par simulation avec ProsimPlus 3 montre que le couplage thermique entre la méthanation et l'électrolyse de la vapeur d'eau à haute température est pertinent, l'efficacité du procédé atteignant 75,8 % sur PCS. Concernant le procédé Gas-to-Power, il est choisi de fonctionner en pression afin de mettre en œuvre des cycles thermodynamiques complémentaires. Le choix d'alimenter la pile à combustible en hydrogène pur pour des aspects de réversibilité conduit à des limitations sur l'efficacité énergétique du procédé qui, au mieux, vaut 44,6 %. L'analyse économique des procédés Power-to-SNG et réversible est basée sur les résultats de simulations et fait appel à des performances électrochimiques observées lors de travaux expérimentaux sur monocellule avec pour point de fonctionnement un fort taux de conversion à la tension thermoneutre. Cela permet de proposer un coût actualisé du SNG produit par le procédé Power-to-SNG et un coût de l'électricité produite par le procédé réversible en considérant un couple performance électrochimique - valeur de dégradation associée cohérent et en accord avec une conduite industrielle. L'investissement et le coût d'exploitation de ces installations sont importants, conduisant à coût actualisé de l'électricité restituée au réseau électrique élevé, cela étant accentué par l'investissement supplémentaire dû à la fonction Gas-to-Power à l'installation Power-to-SNG. / The present work focuses on a Power-to-SNG process, especially on its energy efficiency and its economic competitiveness in the current context. It also aims at determining if the reversibility with a Gas-to-Power working mode is interesting from energy and financial considerations. The main steps required into a Power-to-SNG process, identified thanks to a review of the state of the art, are steam electrolysis for hydrogen production, followed by methane production thanks to the Sabatier reaction and a final step of gas purification to meet the composition requirements for gas network injection. Here, electrolysis is led into solid oxide cells. Power-to-SNG process simulations, led with ProsimPlus 3, indicate that the thermal coupling between methanation and the generation of steam to feed the electrolyzer is pertinent, the process energy efficiency achieving 75.8%. Concerning the Gas-to-Power process, its solid oxide fuel cell is pressurized to use additional thermodynamic cycles. The fuel cell is fed with pure hydrogen stream due to reversibility considerations, this limiting the energy efficiency, which highest value here is evaluated at 44.6%. The economic analysis includes experimental based data concerning electrochemical performances and degradation. They are obtained on a commercial cell tested at the thermoneutral voltage with a high steam conversion rate, these conditions being close to what can be expected for industrial process. They are used to calculate the levelized cost of the SNG produced by the Power-to-SNG process and the levelized cost of electricity produced by the reverse process. Investment and operating cost of these processes are important, leading to a high levelized cost of electricity. In the conditions of this study, adding the Gas-to-Power working mode to a Power-to-SNG process is not economically pertinent

The global need to eliminate CO2 emissions and its consequent reduction in the use of fossil fuels drives the ongoing energy transition that highly involves the research achievements of the scientific community to reach the goals of this purpose. Renewable sources like photovoltaic and wind energy, are central to this endeavor, however, the intermittency of natural resources makes it non-dispatchable and energy storage is fundamental. According to the European Roadmap [1] just a 60% of the CO2 emissions reduction goal can be achieved with available technologies and existing energy. However, the production, use and specially storage opportunities that hydrogen offers can drive non-dispatchable renewable sources to achieve its full potential by clearing up the intermittency problem as well as covering the remained 40% gap. This master's thesis aims to investigate the techno-economic feasibility of integrating a Solid Oxide Electrolyzer Cell (SOEC) into a hybrid PV-CSP(sCO2) plant. The study focuses on assessing various indicators related to electricity, energy, and hydrogen production prices. To achieve this, three different integration strategies within the hybrid PV-CSP(sCO2) plant were selected for analysis: Soec using heat from the particles coming from the receiver, soec using heat coming from the particles available in the thermal energy storage (TES) and soec recovering heat from the sCO2 power block. A sensitivity analysis was conducted on different PV sizes (MWp), battery capacities (MWh), and SOEC installed capacities (MWh) to investigate the technology's potential in the plant and determine optimal sizing of subsystems. However, the individual optimization of economic indicators presented technical and economic challenges. Scenarios allowing individual optimization of hydrogen production prices (€/kg H2) resulted in 10.9, 11.7, and 14.6 €/kg h2 for receiver, TES, and sCO2 integration strategy, respectively. These scenarios, however, require high SOEC installed capacities, leading to elevated electricity and energy production prices. On the other hand, the individual optimization of electricity and energy production prices led to better and lower results when no hydrogen production presence within the plant. However, this analysis also showed that soec capacities below 5MWh together with no installation of batteries and a new definition for calculating hydrogen production prices (LCOH) allows feasible integration of hydrogen production within the plant. LCOH(€/kg h2) results were 10.2€/kg h2, 7.6€/kg h2, and 9.4€/kg h2 for receiver, TES, and sCO2, respectively, for a soec installed capacity of 0.5MWh (119m2 size) along with energy production values not exceeding 101€/MWh. While the results present a favorable outlook for SOEC installations based on literature review data [2] [3] [4] they still face challenges when competing with the cost-efficient PEM technology, which offers 4.5-5.5€/kg H2 [5] without storage. Nonetheless, this research contributes valuable insights into the integration of SOEC technology within hybrid renewable energy systems and provides a comprehensive analysis of the techno-economic aspects related to hydrogen production following different integration strategies. The findings may inform decision-making processes and promote further advancements in sustainable energy solutions. / Det globala behovet av att eliminera CO2utsläpp och därmed minska användningen av fossila bränslen driver pågående energiomställning, som starkt involverar forskningsresultaten från vetenskapssamhället för att nå syftet med detta mål. Förnybara källor som solceller och vindkraft är centrala i detta arbete, men intermittensen hos naturliga resurser gör dem icke disponibla och energilagring är grundläggande. Enligt den europeiska vägkartan [1] kan endast 60% av målet att minska CO2-utsläppen uppnås med tillgängliga teknologier och befintlig energi. Produktionen, användningen och särskilt lagringsmöjligheterna som väte erbjuder kan emellertid driva icke-disponibla förnybara källor att nå sin fulla potential genom att lösa intermitt ensproblemet och täcka den återstående 40% klyftan. Detta examensarbete syftar till att undersöka den tekniskekonomiska genomförbarheten av att integrera en fastoxid elektrolysör (SOEC) i en hybrid PV CSP(sCO2)-anläggning. Studien fokuserar på att utvärde ra olika indikatorer relaterade till el-, energi- och vätgasproduktionspriser. För att uppnå detta har tre olika integrationsstrategier inom hybrid PV CSP(sCO2) anläggningen valts för analys: SOEC med hjälp av värme från partiklar som kommer från mottagaren, SOEC med hjälp av värme från partiklar som finns i termisk energilagring (TES) och SOEC som återvinner värme från sCO2-kraftblocket. En känslighetsanalys har genomförts för olika PVstorlekar (MWp), batterikapaciteter (MWh) och SOEC installerade kapacit eter (MWh) för att undersöka teknologins potential i anläggningen och bestämma optimal dimensionering av delsystem. Resultaten från individuell optimering av ekonomiska indikatorer ledde dock till flera tekniska och ekonomiska utmaningar. Scenarier som tillåter individuell optimering av vätgasproduktionspriser (€/kg H2) resulterade i 10, 9, 11, 7 respektive 14,6 €/kg H2 för mottagare, TES och sCO2 integrationsstrategi. Dessa scenarier kräver dock höga SOEC installerade kapaciteter, vilket leder till höga el och energipriser. Å andra sidan ledde individuell optimering av el och energiproduktionspriser till bättre och lägre resultat när ingen vätgasproduktion fanns i anläggningen. Denna analys visade också att SOEC kapaciteter under 5MWh tillsammans med ingen installation av batterier och en ny definition för beräkning av vätgasproduktionspriser (LCOH) möjliggör genomförbar integration av vätgasproduktion i anläggningen. LCOH (€/kg H2) resultaten var 10,2 €/kg h2 , 7 ,6 €/kg h2 respektive 9,4 €/kg h2 för mottagare, TES och sCO2, för en SOEC installerad kapacitet på 0,5 MWh (storlek 119m2) tillsammans med energiproduktionsvärden som inte överstiger 101 €/MWh. Medan resultaten visar en gynnsam utsikt för SOECinstallationer baserat på data från litteraturöversikter [2] [3] [4], står de ändå inför utmaningar när de konkurrerar med den kostnadseffektiva PEM teknologin, som erbjuder 4,5-5,5 €/kg H2 [5] utan lagring. Trots detta bidrar forskningen med värdefulla insikter i integrationen av SOEC teknologi i hybrid förnybara energisystem och ger en omfattande an alys av de teknisk-ekonomiska aspekterna relaterade till vätgasproduktion enligt olika integrationsstrategier. Resultaten kan informera beslutsprocesser och främja ytterligare framsteg inom hållbara energilösningar.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24106号 / 工博第5028号 / 新制||工||1785(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 江口 浩一, 教授 安部 武志, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Solid oxide cells are best known in the energy sector as novel power generation devices through solid oxide fuel cells (SOFCs), which enable the direct conversion of chemical energy to electrical energy and result in high efficiency power generation. However, solid oxide electrolysis cells (SOECs) are receiving increased attention as a hydrogen production technology through high temperature electrolysis applications. The development of higher fidelity methods for modeling transport phenomena within solid oxide cells is necessary for the advancement of these key technologies. The proposed thesis analyzes the increased transport path lengths caused by constriction resistance effects in prevalent solid oxide cell designs. Such effects are so named because they arise from reductions in active transport area. Constriction resistance effects of SOFC geometry on continuum level mass and electronic transport through SOFC anodes are simulated. These effects are explored via analytic solutions of the Laplace equation with model verification achieved by computational methods such as finite element analysis (FEA). Parametric studies of cell geometry and fuel stream composition are performed based upon the models developed. These studies reveal a competition of losses present between mass and electronic transport losses and demonstrate the benefits of smaller SOFC unit cell geometry. Furthermore, the models developed for SOFC transport phenomena are applied toward the analysis of SOECs. The resulting parametric studies demonstrate that geometric configurations that demonstrate enhanced performance within SOFC operation also demonstrate enhanced performance within SOEC operation. Secondarily, the electrochemical degradation of SOFCs is explored with respect to delamination cracking phenomena about and within the critical electrolyte-anode interface. For thin electrolytes, constriction resistance effects may lead to the loss of electro-active area at both anode-electrolyte and cathode-electrolyte interfaces. This effect (referred to as masking) results in regions of unutilized electrolyte cross-sectional area, which can be a critical performance hindrance. Again analytic and computational means are employed in analyzing such degradation issues.

Ce travail porte sur l’analyse du comportement en durabilité d’une cellule à oxydes solides en fonctionnement en mode Electrolyse de la vapeur d’eau à Haute Température (EHT). Il s’agit plus particulièrement d’identifier les paramètres influant sur la durabilité de la cellule et de comprendre les mécanismes associés, de manière à établir le meilleur compromis durabilité-performance. Un premier axe de recherche correspond à la caractérisation électrochimique initiale de la mono-cellule choisie pour l’étude, à savoir une cellule à électrode support de type LSFC/YDC/8YSZ/Ni-YSZ dont le comportement électrochimique est étudié sous diverses températures, conditions de gaz et densités de courant. Ensuite, la dégradation des performances est étudiée in situ par spectroscopie d’impédance électrochimique et voltampérométrie lors de diverses études séquentielles par paliers de 200 heures. L’influence du taux de conversion et de la densité de courant sur la dégradation des performances est ainsi analysée. Pour compléter cette étude, des analyses physico-chimiques et microstructurales post tests ont été réalisées sur des échantillons ayant fonctionné 1000 heures afin de faire le lien entre les modifications électrochimiques observées et les changements de structure et de composition des matériaux de cellule. Des hypothèses de mécanismes de dégradation ont ainsi pu être formulées. / This work is dedicated to the study on the long term behavior of a solid oxide electrolysis cell (SOEC). More specifically, the target is to identify and understand the influence of main working parameters on the cell durability in order to find the best compromise between performances and durability. The initial part of this work is to characterize electrochemically the single cell selected for the study, that is to say a cathode supported cell of the type LSFC/YDC/8YSZ/Ni-YSZ at different gas conditions, temperature and current density. Then, the degradation of the cell performances has been studied by Electrochemical Impedance Spectroscopy (EIS) and voltamperometry (i-V) curves during sequential tests of 200h. The influence of the most important working parameters like the current density and the steam conversion has been analyzed. To complete this study, physico-chemical and microstructural analyses have been performed on cells that have been operated over 1000 hours, to make a link between electrochemical degradation observed on the cell and composition and structural changes of cell materials.