Dynamics of a very high temperature heat pump coupled to a thermal storage system. Experimental and numerical study.
In the context of an electricity mix with a high proportion of intermittent renewable energy sources, massive energy storage solutions will be of major interest. For the vast majority of these solutions, electricity is converted into energy that can be stored on a large scale (e.g. pressure energy, chemical or electrochemical energy, etc.), then converted back into electricity. Losses occur during each of these stages (conversion, storage), so the efficiency of the complete system is an important issue and requires a good understanding of each conversion and storage stage.
The innovative system that we want to study is a Carnot battery, i.e. a thermal battery associated with thermodynamic conversion cycles (electrical energy to thermal energy to electrical energy). The anticipated advantages are numerous: the possibility of integrating thermal flows, the absence of geographical constraints, a degree of freedom in the choice of temperatures and storage materials, the use of alternators for inertia, etc. The identified challenges are reactivity and overall efficiency.
The research will focus on the charging cycle (very high temperature heat pump) and its coupling with thermal storage, initially from a static and then a dynamic perspective. Unsteady numerical modelling will be developed and used to design the Carnot battery system. Tests carried out on an experimental installation at the CEA will be used to validate and enhance the modelling results.
High yield strength austenitic stainless steels for nuclear applications: numerical design and experimental study
The PhD thesis is part of a project that aims at designing new austenitic stainless steels grades for nuclear applications, which are specifically suitable to in-service conditions encountered by the components and to the manufacturing process. More precisely, the subject deals with bolt steels achieved by controlled nitriding of powders which are then densified by hot isostatic pressing. Indeed, current bolt steel grades may suffer from stress corrosion cracking, while nitriding allows to increase the chromium content, which is beneficial from that point of view.
The study will start by the definition of specifications and associated criteria, then CALPHAD calculations in the Fe-Cr-Ni-Mo-X-N-C system will be done to define promising compositions. Then, selected compositions will be supplied as powders. The behaviour of powders during nitriding will be studied and modelled. Samples will be nitrided, densified and heat treated. One grade will be then selected and fully characterised: mechanical properties and deformation mechanisms, corrosion behaviour. One important objective is to demonstrate the advantages of the new grade compared to the industrial solution.
Analysis of solid oxide cell degradation by transmission electron microscopy and atomic probe tomography
Nowadays, high-temperature electrolysis is considered as one of the most promising technology for producing green hydrogen. The electrolysis reaction takes place in a Solid Oxide Cell (SOC) composed of an oxygen electrode (made of LSCF or PrOx) and a hydrogen electrode (made of Ni-YSZ) separated by an electrolyte (made of YSZ). To accompany industrialization f SOCs, the durability still needs to be improved. The main performance losses are due to the degradation of the two electrodes. In order to propose an improvement, it is essential to gain a precise understanding of electrode degradation mechanisms. In this thesis, we thus propose to apply high-resolution transmission electron microscopy and atom probe tomography (SAT) to study electrode degradation after aging under current. On the one hand, advanced electron microscopy techniques coupled with energy dispersive X-ray spectroscopy (EDX) and electron energy loss spectroscopy (EELS) will be applied. In addition, analyses carried out on a SAT will provide three-dimensional information particularly suited to the complex structure of the electrodes.
This work should provide a better understanding of the degradation mechanisms of high-temperature electrolysis cells. Recommendations for their manufacture can then be made to improve their lifespan.
Modeling and experimental validation of a catalytic reactor and optimization of the process for the production of e-Biofuels
During the past 20 years, « Biomass-to-liquid » processes have considerably grown. They aim at producing a large range of fuels (gasoline, kerozene, diesel, marine diesel oil) by coupling a biomass gazéification into syngaz unit (CO+CO2+H2 mixture) and a Fischer-Tropsch (FT) synthesis unit. Many demonstration pilots have been operated within Europe. Nevertheless, the low H/C ratio of bio-based syngaz from gasification requires the recycling of a huge quantity of CO2 at the inlet of gaseification process, which implies complex separation and has a negative impact on the overall valorization of biobased carbon. Moreover, the possibility to realize, in the same reactor, the Reverse Water Gas Shift (RWGS) and Fischer-Tropsch (FT) reaction in the same reactor with promoted iron supported catalysts has been proved (Riedel et al. 1999) and validated in the frame of a CEA project (Panzone, 2019).
Therefore, this concept coupled with the production of hydrogen from renewable electricity opens new opportunities to better valorize the carbon content of biomass.
The PhD is based on the coupled RWGS+FT synthesis in the same catalytic reactor. On the one hand a kinetic model will be developed and implemented in a multi-scale reactor model together with hydrodynamic and thermal phenomena. The model will be validated against experimental data and innovative design will be proposed and simulated. On the other hand, the overall PBtL process will be optimized in order to assess the potential of such a process.
Understanding the fundamental properties of PrOx based oxygen electrodes through ab-initio and electrochemical modelling for solid oxide cells application
Solid Oxide Cells (SOCs) are reversible and efficient energy-conversion systems for the production of electricity and green hydrogen. Nowadays, they are considered as one of the key technological solutions for the transition to a renewable energy market. A SOC consists of a dense electrolyte sandwiched between two porous electrodes. To date, the large-scale commercialization of SOCs still requires the improvement of both their performances and lifetime. In this context, the main limitations in terms of efficiency and degradation of SOCs have been attributed to the conventional oxygen electrode in La0.6Sr0.4Co0.2Fe0.8O3. To overcome this issue, it has recently been proposed to replace this material with an alternative electrode based on PrOx. Indeed, this material has a high electro-catalytic activity for the oxygen reduction and good transport properties. The performance of cells incorporating this new electrode is promising and might enable to reach the targets required for large-scale industrialization (i.e. -1.5A/cm2 at 1.3V at 750°C and a degradation rate of 0.5%/kh). However, it has been shown that PrOx undergoes phase transitions depending on the cell operating conditions. The impact of these phase transitions on the electrode properties and on its performance and durability are still unknown. Thus, the purpose of the PhD is to gain an in-depth understanding of the physical properties for the different PrOx phases in order to investigate their role in the electrode reaction mechanisms. The study will contribute to validate whether PrOx based electrodes are good candidates for a new generation of SOCs and help to identify an optimized electrode using a methodology combining ab-initio calculation with electrochemical modelling.