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.
Physical modelling of Solid-State Batteries exposed to long cycling and fast-charge protocols
CEA-Leti, a leader in the development and manufacturing of integrated solid-state batteries, is collaborating with InjectPower, a cutting-edge start-up, to develop an innovative power solution for miniaturized implantable medical devices. Thin-film all-solid-state battery technology currently stands out as the leading choice for delivering high energy density and customizable form-factor power sources. However, despite this advantage, capacity retention during cycling remains insufficient, with the goal of 1,000 cycles and less than 10% capacity loss still unmet. Additionally, a comprehensive understanding of the physical mechanisms driving performance degradation in microbatteries is lacking.
During this PhD, you will contribute to the development and refinement of our physical model, focusing on accurately describing microbattery behavior during cycling and fast charging. You will also apply our physically informed Bayesian machine learning model to identify key factors that influence battery performance, including charge-discharge protocols, storage conditions, and device architecture. Model training and validation will be based on data collected from automatic probers on silicon wafers containing thousands of microbatteries.
Development of Single-Ion Eutectogel Electrolytes through Polymerization of Deep Eutectic Solvents (DES)
The proposed PhD thesis focuses on the development of innovative polymer electrolytes for next-generation batteries, aimed at improving the safety and performance of energy storage systems.
Polymer electrolytes represent a promising solution to replace traditional liquid electrolytes. However, their development is limited by challenges related to ionic conductivity and low ion transport numbers. The addition of Deep Eutectic Solvents (DES) into the polymer matrix enhances ionic conductivity. Furthermore, the "single-ion" approach, based on grafting the counter-ion onto the polymer chain, leads to unipolar conduction.
CEA has recently developed "single-ion eutectogel" electrolytes, obtained by polymerizing a DES composed of a single-ion monomer and a hydrogen bond donor (HBD). These electrolytes exhibit very promising performance, achieving unipolar ionic conductivities greater than 0.1 mS/cm at room temperature. However, it is essential to further explore the relationships between formulation, structure, and properties, as well as the conduction mechanisms within these materials, in order to continue their development.
The thesis will be structured in three main phases:
Study of the reference system: Establish a research methodology to link polymerizable formulations, polymer structure, and their electrochemical properties. This will include the study of the starting DES and the electrolyte resulting from its polymerization. The study of conduction mechanisms within these electrolytes will be a central focus of this phase.
Optimization of properties: Based on the results from the previous phase, optimize the properties of the electrolytes through formulation work to select the most promising electrolyte for the next phase.
Integration into a complete system: Explore the integration of the electrolyte into a battery cell, using the in situ polymerization process to synthesize the electrolyte directly within the cell.
Physicochemical techniques (NMR, DSC, TGA, FTIR, RAMAN, SEC, SAXS, ...) and electrochemical techniques (EIS, CV, GCPL, ...) will be used throughout the project.
The PhD will be carried out in collaboration with CEA and LEPMI, providing access to state-of-the-art infrastructures and recognized expertise in formulation, polymer chemistry, and polymer electrolyte electrochemistry.
Compréhension et modélisation du transport des gaz dans un combustible UO2 présentant plusieurs familles de porosités
Sans objet (candidats français uniquement pour cette thèse)
Analysis and experimental study of capillary structures to mitigate the influence of magnetogravitational forces on liquid helium cooling for future HTS superconducting magnets
As physics requires increasingly higher magnetic fields, CEA is called upon to develop and produce superconducting magnets capable of generating magnetic field of more than 30 T. The windings of these electromagnets are made from superconducting materials whose electrical resistance is extremely low at cryogenic temperatures (a few Kelvins). This enables them to carry high currents (>10 kA) while dissipating a minimum of heat by Joule effect. Cooling at these low temperatures is achieved using liquid helium. But helium is diamagnetic. Magnetic fields will therefore induce volumetric forces that add to or oppose gravity within the helium. These magneto-gravity forces disrupt the convective phenomena required to cool the superconducting magnet. This can lead to a rise in their temperature and a loss of their superconducting state, which is essential for their proper operation. In order to circumvent this phenomenon, a new cooling system never used in cryomagnetism will be studied. This cooling system will be developed using heat pipes whose operation is based on capillary forces that are theoretically independent of the magneto-gravity forces induced by strong magnetic fields. These capillary structures can take several forms (microchannels, foam, mesh, etc.). In the framework of the thesis these different structures will be studied theoretically and then experimentally, both with and without magnetic forces, in order to determine the most suitable structures for the future superconducting magnets.
Development of a multi-criteria comparison tool for electrochemical stationary storage systems
Use of stationary storage systems is now essential to keep pace with changes in the electricity grid and the growing integration of intermittent renewable energies such as solar and wind power. The choice of a storage solution is based on a number of criteria, including performance, lifetime, environmental impact, safety, regulatory constraints and, of course, economics.
The laboratory possesses comparative data on these different criteria, via experimental studies and feedback on existing systems. In addition, an initial software tool has been developed to assess environmental impact using LCA (Life Cycle Assessment). The aim of this thesis work is to integrate these different components into a broader comparison tool with a multi-criteria approach, targeting specific case studies and a limited number of storage technologies that have reached sufficient maturity for the available data to be reliable.
Designing a fast reactor burnup credit validation experiment in the JHR reactor
The primary mission of the Jules Horowitz experimental nuclear Reactor (JHR) is to meet the irradiation needs of materials and fuels for the current nuclear industry and future generations. It is expected to start around 2032. The design of the first wave of experimental devices for RJH already includes specifications for GEN2 and 3 industrial constraints. On the other hand, the field of experiments essential to GEN4 Fast Breeder Reactor remains quite open in the longer term, while no fast-spectrum irradiation facility is currently available.
The objective of this thesis is to study the feasibility of integral experiments in the JHR or another light water reactor, for validation of the reactivity loss with innovative FBR fuels.
In the first part of this thesis, fission products (FPs) that contribute to the loss of reactivity in a typical FBR will be identified and ranked by importance. The second part is the activation measurement and evaluation of the capture cross section of stable FPs in a fast spectrum. It involves the design, specification, implementation and achievement of a “stable” FBR-FP target in the ILL reactor or in the CABRI reactor fuel recovery station (potentially with thermal neutron shields). The third and final part is the design of an experiment in the JHR to generate and characterize FBR FPs. This experiment should be sufficiently representative of fuel irradiation conditions in a FBR. The goal is to access the FP inventory by underwater spectrometry in the JHR and integral reactivity weighing before/after irradiation in CABRI or another available facility.
The thesis will be carried out in a team experienced in the physics and thermal-hydraulics characterization of the JHR. The candidate will be advised by several experts based in the department. The candidate will have the opportunity to promote his/her results before the nuclear industry partners (CEA, EDF, Framatome, Orano, Technicatome etc.).
Modeling and upscaling of sodium boiling flow within a 4th generation nuclear reactor core
The stabilized boiling in sodium is a subject that has been studied for many years at CEA in order to improve the validation of scientific calculation tools such as CATHARE3. Being able to reproduce properly this phenomena is a key safety related question for liquid metal liquid 4th generation reactors. When an unprotected loss of flow (ULOF) happens in the reactor and the safety measures are not deployed, the coolant can reach saturation, which can ultimately lead to a degradation of the subassembly. In order to avoid this situation, new fuel assembly designs provide negative neutronic feedback as the void fraction is generated. To understand how this void fraction evolves in the sub-assembly (within the rod bundle or the top plenum), the code requires a state of the art sodium modeling in terms of momentum, heat and mass transfer.
To improve the qualification of the CATHARE3 code for such situations, the doctoral student will implement CFD models allowing a better understanding of the boiling mechanisms in sodium-cooled subassemblies. New CFD models, such as large interface modelling, wall boiling, heat and mass exchange at the interface will be applied, yielding detailed information on local variables. Subsequently, this detailed information will be transferred to the 1D system code during an upscaling operation. Once this information is properly gathered and transferred, new models will be developed and implemented into the system code. Finally, these new models will be confronted to experimental data in a validation exercise over the CATHARE code validation database. Ultimately, the aim is to increase the confidence in the CATHARE3 1-D simulation tool for predicting the specific physics of sodium boiling during an unprotected loss of flow transient.
The doctoral student will be based in a research unit on innovative nuclear systems at CEA/IRESNE Cadarache, in a dynamic and international environment. Travel to CEA-Saclay and EDF-Chatou is planned during the thesis, as well as participation in international conferences.
CTC electrolyte pour LiS system
Lithium-Sulfur (Li-S) Batteries are among the most promising energy storage technologies for the fifth generation of batteries, often referred to as post-Li-ion. With a theoretical energy density five times higher than that of conventional Li-ion batteries and an abundant availability of sulfur, the Li-S system offers a unique potential to meet the growing demand for sustainable energy storage. However, current technology is limited by major challenges related to the dissolution of polysulfides in the electrolyte, leading to active sulfur loss, poor cycle life, and insufficient electrochemical performance. These limitations currently hinder the market deployment of this technology.
This thesis aims to explore an alternative approach based on an all-solid electrochemical sulfur conversion mechanism. To achieve this, a next-generation organic solid electrolyte developed in the laboratory will be implemented. This electrolyte features a unique lithium-ion conduction mechanism within a crystalline lattice, preventing polysulfide solubilization. The main objectives are:
1. To understand and control the ionic conduction mechanisms in these electrolytes.
2. To integrate this solid electrolyte into an innovative Li-S system.
3. To optimize the cathode structure for the solid-state mechanism and evaluate the electrochemical performance on a representative prototype scale.
The PhD candidate will use a wide range of characterization and analysis techniques to carry out this project:
• Formulation and characterization of the organic solid electrolyte: Techniques such as FT-IR and NMR to analyze chemical structures and identify the properties of synthesized materials (DSC, TGA, XRD, etc.).
• Electrochemical characterization: Analyses using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and symmetric cell cycling tests to study ionic conduction properties and electrolyte stability.
• Formulation and performance study of the cathode: Formulation of carbon/sulfur composites and sulfur cathodes integrating the solid electrolyte; galvanostatic cycling tests and advanced interface analyses to understand and optimize solid-state sulfur conversion.
The research will progress in three main phases:
1. Development and characterization of the solid electrolyte: Material development, analysis of conduction mechanisms, and optimization of ionic and mechanical properties.
2. Design and optimization of the cathode structure: Improving electrolyte/cathode interfaces for solid-state sulfur conversion.
3. Electrochemical performance evaluation: Experimental validation of prototypes through in-depth tests, including cyclability and power performance.
Multiphe hydrogen injection at anode side of PEMFC
The alternating feeding architecture (known as Ping-Pong) was developed by the CEA. This architecture emerged in 2013 and has been implemented in several fuel cell systems. Following the latest tests on this architecture, questions remained unanswered. First, it is a question of understanding how species (hydrogen, nitrogen, liquid and gaseous water) move in cells operating with alternating feeding. Control laws influences these movements, it will be necessary to identify the levers to make the most out of it and then to propose methods to promote the evacuation of water and nitrogen while avoiding the evacuation of hydrogen.
The thesis work will aim to optimize the anode architecture with alternating feeding and to bring this architecture to maturity. The key points are the search for an optimum control of this architecture, the achievement of a hydrogen rejection rate of less than 1%. Finally, this optimization will also have to maximize the durability of the stack.
The doctoral student will have to model the movements of species at different time scales (10ms to 10 minutes), understand the mechanisms, adapt the control laws and validate the new control laws on a test bench.
This work will identify solutions to efficiently evacuate liquid water and nitrogen and minimize H2 rejection and then obtain superior performance compared to conventional architectures.