Ces travaux de thèse portent sur l’étude du comportement sous pression d’une cellule à oxydes solides fonctionnant à haute température en mode électrolyse de H2O et en mode co-électrolyse de H2O et CO2. Une étude expérimentale sur mono-cellule associée au développement de modèles multi-physiques a été mise en place. Les essais, réalisés à partir d’une installation unique présente au CEA-Grenoble, sur deux types de cellules entre 1 et 10 bar et de 700 à 800 °C, ont permis d’identifier dans les deux modes de fonctionnement, que la pression a un effet positif ou négatif sur les performances selon le point de fonctionnement (courant, tension) de la cellule. De plus, des analyses de gaz conduites en mode co-électrolyse ont permis de détecter une production de CH4 in-situ sous pression. Ces effets de la pression ont été correctement simulés par les modèles calibrés à pression atmosphérique. L’analyse des simulations a ensuite permis l’identification des mécanismes impactés par la pression et la proposition de conditions opératoires de fonctionnement grâce à l’établissement de cartographies de fonctionnement. / This thesis work investigates the behavior of a solid oxide cell operating under pressure in high temperature steam electrolysis and co-electrolysis mode (H2O and CO2). The experimental study of single cell associated with the development of multi-physical models have been set up. The experiments, carried out using an original test bench developed by the CEA-Grenoble on two types of cells between 1 and 10 bar and 700 to 800 °C, allowed to identify in both operating modes that the pressure has a positive or negative effect on performance depending on the cell operating point (current, voltage). In addition, gas analyzes performed in co-electrolysis led to detect in situ CH4 production under pressure. These pressure effects were simulated by models calibrated at atmospheric pressure. Simulations analysis helped identify the pressure dependent mechanisms and propose operating conditions thanks to the establishment of operating maps.

High-temperature Co-electrolysis of H2O and CO2 in a solid-oxide electrolyser (Co-SOE) for syngas production is a high-efficiency renewable electricity conversion and storage method part of the Power-to-X technologies. Syngas, a mixture of H2, CO and CO2, is a critical building block to make several chemical and synthesis fuels. The thesis aimed to model the Co-electrolysis process in a steady-state process modelling tool called Aspen Plus. The model was designed at thermoneutral mode and four cases with electrolysis temperatures of 700 °C, 750 °C, 800 °C and 850°C. The results from the model were used to perform an economic assessment and check the feasibility of Co-SOE. The analysis included calculation of Net Present Value (NPV), Internal Rate of Return (IRR) and the Levelised cost of Syngas (LCOS). The LCOS from Co-SOE was compared to the benchmark technology of syngas production in a Reverse Water Gas Shift (RWGS) reactor. The H2 feed to the RWGS reactor was assumed to be obtained from a Proton Exchange Membrane Electrolyser(PEME). A sensitivity analysis was performed to check the effect of electricity price, electrolyser stack price, electrolyser lifetime, CO2 feed price, by-product O2 revenue and discount rate on the LCOS. The LCOS was calculated to be 0.697, 0.727, 0.752 and 0.783 €/kg at 700 °C, 750 °C, 800 °C and 850 °C, respectively, increased with temperature due to increased electricity consumption at thermoneutral mode. The average LCOS from Co-SOE was 18.5% cheaper than the benchmark technology due to the high investment in the PEME and low conversion efficiency of the RWGS process. There was a trade-off between LCOS and system efficiency due to the effect of internal methanation occurring on the cathode side of the SOE. 750 °C was found to be the optimum design temperature to minimise the LCOS and maximise the efficiency. LCOS was most sensitive to electricity price, followed by O2 revenue and discount rate, while other parameters were less significant. The thesis also discussed key challenges to overcome in the future development of the Co-SOE technology. Co-SOE was found to be a promising technology for green syngas production. However, challenges concerning low stack lifetime, high capital investment and high cost of electricity have yet to be overcome to demonstrate it at a commercial scale.

This study mainly explores the development of alternative cathode materials for the electrochemical reduction of CO₂ by high temperature solid oxide electrolysis cells (HTSOECs), which operate in the reverse manner of solid oxide fuel cells (SOFCs). The conventional Ni-yttria stabilized zirconia (YSZ) cermets cathode suffered from coke formation, whereas the perovskite-type (La, Sr)(Cr, Mn)O₃ (LSCM) oxide material displayed excellent carbon resistance. Initial CO₂ electrolysis performance tests from different cathode materials prepared by screen-printing showed that LSCM based cathode performed poorer than Ni-YSZ cermets, due to non-optimized microstructure. Efforts were made on microstructure modification of LSCM based cathodes by means of various fabrication methods. Among the LSCM/YSZ graded cathode, extra catalyst (including Pd, Ni, CeO₂, and Pt) aided LSCM/GDC (Gd₀.₁Ce₀.₉O₁.₉₅) cathode, LSCM impregnated YSZ cathode, and GDC impregnated LSCM cathode, the GDC impregnated LSCM cathode, with porous LSCM as backbone for finely dispersed GDC nanoparticles, was found to possess the desired microstructure for CO₂ splitting reaction via SOEC. Incorporating of 0.5wt% Pd into GDC impregnated LSCM cathode gave rise to an Rp of 0.24 Ω cm² at open circuit voltage (OCV) at 900°C in CO₂-CO 70-30 mixture, comparable with the Ni/YSZ cermet cathode operated in the identical conditions. Meanwhile, the cathode kinetics and possible mechanisms of the electrochemical reduction of CO₂ were studied, and factors including CO₂/CO composition, operation temperature and potential were taken into account. The current-to-chemical efficiency of CO₂ electrolysis was evaluated with gas chromatography (GC). The high performance Pd and GDC co-impregnated LSCM cathode was also applied for CO₂ electrolysis without protective CO gas in feed. This cathode also displayed superb performance towards CO₂ electrochemical reduction under SOEC operation condition in CO₂/N₂ mixtures, though it had OCV as low as 0.12V at 900°C. The LSCM/GDC set of SOEC cathode materials were investigated in the application of steam electrolysis and H₂O-CO₂ co-electrolysis as well. For the former, adequate supply of steam was essential to avoid the appearance of S-shaped I-V curves and limited steam transport. The 0.5wt% Pd and GDC co-infiltrated LSCM material has been found to be a versatile cathode with high performance and good durability in SOEC operations.