Development of an innovative anode based on non-critical and sustainable materials for anion-exchange membrane electrolysis
Anion-exchange membrane water electrolysis (AEMWE) is a recent and promising technology for producing green hydrogen, but it still faces major challenges in terms of performance and durability. Currently, the anodes used in AEMWE electrolyzers consist of two layers: a porous transport layer (PTL), which enables the circulation of electrolyte and gases, and an active layer made of catalysts and binders, where the electrochemical reactions take place. This configuration limits reactant diffusion and reduces the available active surface area, which negatively impacts overall performance.
This PhD project aims to develop an innovative anode based on non-critical materials by combining the advantages of both layers while minimizing their drawbacks. The idea is to functionalize the PTL directly by adding catalyst nanoparticles and/or by applying a surface activation treatment, in order to confer electrochemical activity. These modifications are expected to improve electron and reactant transport while increasing the active surface area for the oxygen evolution reaction (OER).
The work carried out in this thesis will involve functionalizing a pre-selected PTL and characterizing the resulting anodes through structural and electrochemical analyses. The expected outcomes include the development of an optimized anode with enhanced performance and limited degradation, as well as a deeper understanding of the limiting phenomena in AEMWE anodes. This project is part of a broader effort to develop sustainable technologies essential for the energy transition.
Contribution in the study of Power Partial Converters in Energy sources Hybridization
One of the key areas for reducing the carbon footprint is transport, particularly the development of electric mobility, which is currently growing rapidly. In this context, the hybrid electric transport market is growing. Hybridization applications have seen their power increase and with it that of power electronics converters allowing to adapt the voltage levels of energy sources and the energy exchanges between them. This increase in power is accompanied by higher losses to be evacuated, resulting in a significant impact firstly on the size of the converters, and therefore of the overall system, and then on the energy efficiency of the entire chain. Efforts have already been made at CEA-LITEN to develop high-efficiency DC-DC converters (in particular by using interleaved DC-DC converters). The objective of the thesis will be to go further by studying the so-called partial power converters (PPC). The different architectures/topologies will be studied for hybrid applications associating a fuel cell and a battery on the one hand, and applications associating 2 batteries (one power type battery and the other, energy type battery) on the other hand. The work aims to determine the best architecture/topologies for each of the typical applications allowing a significant reduction in the size of the converters and the improvement of the efficiency of the whole system
Advancing Lithium-Sulfur Batteries through the study of the Quasi-Solid Sulfur Conversion
Lithium–sulfur batteries are widely seen as one of the most promising candidates for the next generation of energy storage, offering the potential for significantly higher energy density than today’s batteries while using abundant and inexpensive sulfur. However, several scientific and technological challenges still prevent their large-scale industrial deployment.
One key issue is the formation of soluble lithium polysulfides during battery operation, which can migrate inside the cell and lead to rapid capacity loss. Recent research suggests that a different reaction pathway, known as a “quasi-solid mechanism”, could limit this dissolution and significantly improve battery stability.
This PhD project aims to design and study lithium–sulfur pouch cells operating through this quasi-solid mechanism. The work will combine materials development, electrochemical testing, and advanced characterization techniques to better understand the processes governing battery performance and durability.
The project will focus on two complementary research directions:
1. Design of advanced sulfur cathodes
The first part of the work will involve developing optimized sulfur-based cathodes. This includes exploring different conductive host materials and tuning their structure and surface properties to better confine sulfur and reduce unwanted reactions.
2. Development of improved electrolytes
The second part of the project will focus on electrolyte formulations that reduce the solubility of polysulfides while maintaining good battery performance. Current solutions often rely on dense, fluorinated solvents that increase cost and environmental impact. This project will explore alternative solvent systems and investigate how salt composition and concentration influence cell behaviour.
To gain deeper insight into the quasi-solid reaction mechanism, the project may also involve operando or in-situ characterization techniques, such as Raman spectroscopy, X-ray diffraction, and high-resolution X-ray tomography.
Li alloys for all solid-state batteries with sulfide electrolyte
Using lithium metal as a negative electrode would significantly increase the energy density of current batteries. However, today, this material quickly leads to short circuits during charge/discharge cycles, mainly due to the formation of dendrites and the instability of the interface with the electrolyte. All-solid-state batteries, particularly with sulfide electrolytes, are a promising alternative, but the limitations of lithium metal remain. Lithium alloys appear to be a solution for improving mechanical and interfacial properties while maintaining good energy densities.
The objective of the PhD is to develop and select lithium alloys suitable for sulfide electrolytes batteries, then integrate them into all-solid-state cells in order to study degradation mechanisms. The work will be focused on the synthesis of the alloys, their shaping in thin films and their integration into cells. The alloys will be finely characterized and then electrochemically tested in laboratory cells and pouch cells. Finally, degradation phenomena, particularly at interfaces, will be studied using advanced post-mortem characterizations.
Control & optimization of fuel cell temperature
Proton exchange membrane fuel cells (PEMFC) represent a key technology for the development of clean and sustainable energy systems, particularly for heavy-duty transport applications where their energy density is very attractive. However, in order to represent a viable industrial alternative, a number of obstacles still need to be overcome, including operating costs and, above all, the durability of the systems under real-world conditions. Among the levers for action, optimizing operating conditions is a promising avenue for limiting the degradation phenomena occurring within the cell. The operating temperature is a particularly key parameter because it affects all aspects of the system, from the kinetics of degradation mechanisms to the thermal capacity that the system can dissipate, including the water balance within the fuel cell. Despite the influence of this parameter on durability, it is generally only optimized at the system level to achieve the best performance, the shortest possible response time and to limit the size of the thermal management system.
The aim of this thesis is to work on optimizing the temperature management of a fuel cell within a system, taking into account not only performance but also sustainability criteria. To do this, the impact of operating temperature on degradation mechanisms will be analyzed using various simulation tools already available at LITEN and the teams' fifteen years of experience in studying PEMFC fuel cell degradation. Various thermal architectures will be proposed and evaluated in conjunction with the work on temperature control optimization. The latter will be implemented on a real fuel cell system in order to demonstrate the relevance of the proposed solution using concrete experimental data.
Diphasic thermoregulation system for ultra wide bandgap diamond semiconductors
The objective of this thesis is to study a diphasic thermoregulation system for ultra wide bandgap diamond semiconductors. One of the specific behavior of diamond semiconductors is the negative temperature coefficient of is on-state resistance. The thermoregulation proposed in this thesis aims to optimize the global losses of the system and to insure both temperature and electrical constraints between several diamond semiconductors in parallel.
Based on specifications that will be defined at the beginning of this theses (calories to dissipate, temperature range to control), the PhD candidate will have to:
- Define a temperature control strategy
- Define most appropriate materials and fluid of this system
- Design the thermoregulation system
- Realize and validate experimentally the proposed system
This thesis will tackle numerical simulation (component and thermoregulation system modelling) and experimental tests through the realization of a TRL 3-4 prototype of power converter system integrating diamond Schottky diodes.
The global objective to achieve is to put forward an innovative system modeled and experimentally demonstrated, where control strategy, dimensional and operative elements will be investigated and optimized.
Physics-Informed Deep Learning and Multi-Modal Sensor Fusion for Li-Ion and Na-Ion Battery degradation mechanisms predictive monitoring
Context:
Lithium-ion and emerging Sodium-ion batteries are crucial for energy transition and transportation electrification. Ensuring battery longevity, performance, and safety requires understanding degradation mechanisms at multiple scales.
Research Objective:
Develop innovative battery diagnostic and prognostic methodologies by leveraging multi-sensor data fusion (acoustic sensors, strain gauge sensors, thermal sensors, electrical sensors, optical sensors) and Physics-Informed Machine Learning (PIML) approaches, combining physical battery models with deep learning algorithms.
Scientific Approach:
Establish correlations between multi-physical measurements (internal sensors using optical fiber modality, and external sensors Embedded on the cell packaging) and battery degradation mechanisms
Explore hybrid PIML approaches for multi-physical data fusion
Develop learning architectures integrating physical constraints while processing heterogeneous data
Extend methodologies to emerging Na-Ion battery technologies
Methodology:
The research will utilize an extensive multi-instrumented cell database, analyzing measurement signatures and developing innovative PIML algorithms that optimize multi-sensor data fusion and validate performance using real-world data.
Expected Outcomes:
The thesis aims to provide valuable recommendations for battery system instrumentation, develop advanced diagnostic algorithms, and contribute significantly to improving the reliability and sustainability of electrochemical storage systems, with potential academic and industrial impacts.
Understanding the effect of doping on the lifespan of advanced Li-ion battery electrode materials
The development of new electrode materials for Li-ion batteries is primarily focused on two often contradictory objectives: increasing the energy density, and thus the range of vehicles, and reducing the cost of batteries. Disordered NaCl-structured materials, such as Li2MnO2F, thanks to the combination of their Mn-rich, low-cost composition and high Li-ion storage capacity, allow these two aspects to be reconciled. Unfortunately, these materials undergo rapid degradation during cycling, which limits their lifespan. It is therefore necessary to address this degradation to make these materials competitive. Recently, our group has developed a strategy for stabilizing the material by modifying its structure, which is the subject of a patent. The goal of this thesis is to deepen this strategy by improving the understanding of the stabilization mechanism by varying its parameters. The PhD student will have access to all synthesis tools to realize these new materials, as well as electrochemical characterization tools on our battery platform to evaluate their performance. The student will also be required to perform in-depth structural characterizations, notably via various X-ray diffraction methods (including synchrotron).
Direct lithium extraction from brine through adsorption
The development of electric vehicles due to climate and the decision to turn towards a greener energy has increased sharply the demand of lithium over the past decade and will continue to escalate. Thus, lithium extraction projects are proliferating worldwide. Since mining presents a quite highly energy-consuming and polluting solution, alternative lithium sources like brine deposits or seawater are being currently investigated. In this study, we will focus on the approach of a direct lithium extraction from brine sources with different concentrations by adsorption. The first step will be to synthesize and characterize a wide range of materials as adsorbents, from classic oxides (LMO, LTO, etc) to functionalized hybrid porous materials (ZIFs, MOFs, etc). It is also intended to shape these materials with the help of an extruder, in order to enhance performances. Then, these materials will be evaluated both in static and dynamic conditions. Various parameters like the concentration of lithium, the presence of other cations and their concentration will be also evaluated and optimized so that we obtain a facile, efficient and selective process. The results of this study will be valorized through the deposit of patents and the submission of scientific articles along the whole duration of the thesis.
Fast charging of lithium-ion batteries : Study of the lithium plating phenomenon using operando NMR
The focus of the thesis is the fast-charging process of lithium-ion batteries and, more specifically, the phenomenon of lithium plating, which will be studied using operando NMR. The target application is electric mobility. The objective of the thesis is to study the dynamics of lithium insertion and lithium metal deposition at the graphite or graphite/silicon-based negative electrode in order to understand the mechanisms leading to plating formation.
Operando NMR is an ideal technique for this study because it offers the unique possibility of simultaneously tracking the signals of the lithiated graphite phases and of deposited lithium during the electrochemical processes. The coupling of electrochemistry and operando NMR will allow us to determine the onset of plating, i.e. the potential of the negative electrode at which deposition begins, and the kinetics of lithium metal deposition and reinsertion at different temperatures and different charging current regimes. We will study Li-ion batteries with a pure graphite negative electrode, but also with graphite-silicon electrodes, in order to investigate the impact of silicon on this phenomenon. The data obtained on the onset mechanisms and the kinetics of lithium metal deposition and reinsertion will be used in a multiphysics model that has already been developed in the laboratory to improve the prediction of plating onset. We will then be able to evaluate the chargeability gains on an NMC 811 // Gr+Si system incorporating optimized electrodes and propose innovative charging protocols.