Evaluation of the impact of dry extrusion process on cathode microstructure and performances for polymer-based solid-state batteries
Solid-state batteries (SSB) are expected to outperform standard lithium-ion technology in terms of energy density and safety, with application in electric vehicles or stationary energy storage. Manufacturing of these new battery technologies can rely on existing infrastructure (solvent-based electrode slurry mixing and coating) or need new processing methods. In this context, twin-screw extrusion process exhibits several advantages when applied to SSB, particularly with polymer-based electrolytes.
To speed up the implementation of polymer-based SSB, a better understanding of extrusion process applied to positive electrode manufacturing is needed. The objective of this thesis is to develop new electrode formulations using hot-melt extrusion and understand the impact of process parameters on final performances. It should finally give a clear picture about the advantages and limitations of extrusion compared to standard wet casting.
This PhD project will be part of a collaboration between CEA and Stellantis on the development of new solid-state batteries. The study will focus on the development of extrusion-processed composite electrodes to be used in polymer-based SSB. First, materials will be selected and characterized for a preliminary screening of formulations using lab-scale extrusion. Then, a systematic evaluation of the impact of input materials and operational conditions during extrusion process will be undertaken to highlight the relationships between process, electrode microstructures and performances. Finally, the best performing electrode formulations will be integrated in a fully-extruded prototype and characterized by electrical tests as well as post-mortem analysis.
The PhD candidate will benefit from CEA-LITEN's multidisciplinary environment (Grenoble campus) and Stellantis industrial know-how. Battery Prototyping Platform will be used for extrusion trials and cell assembly, whereas access to advanced characterization equipment (SEM, XPS, rheometers, electrochemical methods, etc.) will guarantee deep understanding of underlying mechanisms.
Growth of 2D Ferromagnetic Chalcogenide Materials for Spintronics
Chalcogenide materials, particularly Ge-Sb-Te (GST) alloys, are essential for phase-change memory (PCMs).
Although high-performance, these memories consume a great deal of energy, which
is driving the search for alternative solutions. GST alloys offer unique opportunities in the field of spin-orbitronics as spin-charge conversion materials or as sources of spin-polarized current. Two-dimensional ferromagnetic alloys such as Fe-Ge-Te or Ge-Mn-Te offer promising avenues as sources of spin current for new types of more efficient memory devices. For efficient spin injection, we are seeking a material that not only exhibits a high Curie temperature (TC) and significant spin polarization, but is also fully compatible with existing silicon-based CMOS technology.
The aim of this thesis is to develop and master, on an industrial scale on 300 mm Si substrates, the van der Waals epitaxial growth of 2D ferromagnetic films based on Fe-Ge (Ga)Te2 (n=3, 5) or Ge_(1-x)Mn_xTe, for example to integrate them in situ with spin-charge conversion chalcogenide layers such as ferroelectric layers (a-GeTe(111)) or topological insulators (Bi_(2-x)Sb2Te3).
Development and characterization of a low-silver metallization for photovoltaic cells with high-efficiency passivated contacts
In order to decarbonize energy production and meet climate plan objectives, the production of photovoltaic (PV) modules must increase significantly. To sustain these production levels, the silver content in latest-generation cells must be drastically reduced. Some alternatives incorporate less expensive metals (nickel, aluminum, copper) into screen-printing pastes. These approaches require evaluation in terms of contact formation, electron transport, and reliability. In a TOPCon cell architecture, the electrode must be brought into direct contact with the active layers of the cell via thermal annealing. This step enhances device performance (through a hydrogenation phenomenon) while simultaneously generating potential degradation related to the introduction of metallic species. This is especially critical when using new metals (Ni, Cu, etc.) with higher diffusivities than silver. The objectives of this thesis are manifold: to evaluate the performance of these low-silver alternative pastes once integrated into TOPCon cells; to characterize the impact of the introduction of these metallic species on the lifetime of photogenerated carriers in silicon; and to assess the long-term stability of these metallizations while verifying the absence of cell degradation phenomena under prolonged illumination. If necessary, an alternative metallization technique more suitable for these pastes will be developed. During the PhD, the successful candidate will be required to fabricate, metallize via screen printing, and characterize devices within a cleanroom environment.
Enhancing Faradaic Efficiency in Protonic Ceramic Electrolysis Cells (PCCELs) through Electrolyte and Electrode–Electrolyte Interface Engineering
Proton conducting ceramic electrolysis cells (PCCELs), an advanced variant of solid oxide electrolysis cells (SOECs), enable the direct production of hydrogen through steam electrolysis using proton-conducting electrolytes. Unlike conventional SOECs, which rely on oxygen ion (O²?) conductors, PCCELs operate at lower temperatures (~400–600?°C vs. 750–850?°C for SOECs) due to their higher proton conductivity. This lower operating temperature helps reduce material degradation and overall system costs. While SOEC technology has reached industrial maturity, with large-scale deployment projects underway, the development of PCCELs remains limited by several scientific challenges. These include the difficulty of densifying electrolytes (such as BaCeO3–BaZrO3) without barium volatilization during high-temperature sintering; the proton transport limitations posed by grain boundaries; and the poor control of electrode–electrolyte interfaces. This thesis aims to improve the faradaic efficiency of PCCELs by optimizing the microstructure of the electrolyte and engineering high-quality interfaces through targeted surface treatments. The methodology includes cell fabrication, interface engineering, and electrochemical evaluation. The ultimate goal is to establish robust and scalable processing protocols that enable PCCELs to achieve faradaic efficiencies above 95%, compatible with industrial-scale deployment.
Controlling the composition and microstructure to achieve high magnetic performance in 1–12 rare earth-poor magnets
Permanent magnets based on rare earth elements (REEs), particularly neodymium-iron-boron (Nd-Fe-B) magnets, are strategically important for the development of more efficient motors and generators (electric vehicles, wind turbines). However, REEs, particularly Nd, are critical materials, with a high risk of supply disruption in the coming years. The growing demand for high-performance magnets requires the development of new types of magnets with reduce RE content. Iron-rich compounds, such as Sm-Fe12 (commonly known as phase 1-12), have very interesting intrinsic magnetic properties and are considered the best alternative to NdFeB magnets, allowing for a TR saving of around 35% by weight. However, achieving sufficient magnetic performance (remanence > 1 T and coercivity > 800 kA/m) depends on obtaining a suitable microstructure and remains the main challenge in the development of Sm-Fe12 magnets.
The aim of the thesis is therefore to improve the magnetic performance of this new family of magnets, in particular by controlling the composition and distribution of phases at grain boundaries. The doctoral work will combine an advanced experimental approach (development of Sm-Fe12 alloys, characterization of equilibrium phases, magnet manufacturing, magnetic characterization) with knowledge of phase diagrams to define compositions and optimal manufacturing conditions to achieve the targeted magnetic performances.
Potential synergy between NH3 and NaBH4 for improved H2 density and enhanced safety
The thesis focuses on the study of the hybrid ammonia–sodium borohydride system (NH3–NaBH4) as an innovative chemical energy carrier. The objective is to investigate the combination of ammonia (NH3), recognised for its high hydrogen density and mature industrial infrastructure, with sodium borohydride (NaBH4), a high-capacity chemical hydrogen storage material, in order to overcome certain limitations associated with each vector when considered separately.
The proposed work specifically addresses the safer storage and transport of ammonia through its coupling with sodium borohydride, enabling a reduction in vapour pressure (compared to 8.88 bar at 21 °C for liquid ammonia) and less restrictive operating conditions. In parallel, the thesis aims to improve the stability (relative to the H2O–NaBH4 system) and operability of sodium borohydride which, when combined with ammonia molecules (acting as inert species), forms stable liquid or viscous phases that are potentially pumpable, thereby facilitating integration into energy-related processes.
The fundamental goal of the thesis is to understand the physicochemical mechanisms governing this hybrid system, particularly the role of dihydrogen interactions between the N–H bonds of ammonia and the B–H bonds of borohydride, and their influence on stability, reactivity, transport properties, and hydrogen release pathways (thermal and/or hydrolytic).
Beyond its storage function, the thesis also explores the potential of the NH3–NaBH4 system as a novel hybrid material with high gravimetric and volumetric hydrogen capacity, while considering realistic operational constraints relevant to energy applications in a dual-use context. At this stage, exhaustive optimisation is not the primary objective.
Advancing All-Solid-State Microbatteries: Interface Stabilization and Degradation Mitigation for Long-Term Reliability
This PhD project focuses on advancing all-solid-state microbatteries for miniaturized energy storage applications, such as wearable electronics, IoT systems, and implantable medical technologies. The research aims to stabilize and mitigate degradation at the electrode/electrolyte interfaces, which are critical bottlenecks in solid-state microbattery performance. The project involves two main research axes: (1) the study and optimization of ultrathin films (sub-nanometer to nanometer scale deposited by ALD) for engineering the interfaces in LiCoO2/LiPON/Li stacks, and (2) a fundamental investigation of the mechanisms responsible for interface degradation. The study will involve the fabrication and characterization of partial and complete stacks using techniques like cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The incorporation of alloying metals (e.g., Ag, Au) between the buffer layer and lithium will also be explored to enhance lithium-metal interface stability. The expected outcomes include an optimized microbattery stack capable of exceeding 1,000 cycles with minimal increase in interfacial resistance and a comprehensive framework describing degradation mechanisms and buffer layer effects.
High-throughput screening of catalysts for the direct conversion of CO2 into synthetic fuels
This doctoral project aims to develop an innovative high-throughput screening approach for catalysts for the direct conversion of CO2 into synthetic fuels, known as CO2-FTS. This approach will combine a catalyst screening platform with in situ/operando characterization techniques and artificial intelligence methods to accelerate the discovery and optimization of high-performance catalysts. It aims to identify doped FeOx-type catalysts for the CO2-FTS reaction (>50% conversion, high selectivity towards C8-C16). Several high-throughput screening campaigns will allow for iterative optimization of compositions and reactive conditions. A numerical model of the parametric landscape will then be developed. This model will subsequently be coupled with multi-scale modeling from the active site to the reactor level. The developed catalysts will contribute to the energy transition by enabling a circular carbon economy.
Dies to wafer direct bonding: from physical mechanisms to the development of thin stackable dies
Direct dies-to-wafer bonding has become, in recent years, a major development axis in microelectronics and at the heart of many LETI projects, both in silicon photonics and for 3D applications involving hybrid bonding.
Due to their small size, die bonding allows the study of direct bonding edge effects and the implementation of new direct bonding processes that can shed original light on the mechanisms of direct bonding, which are already well studied at LETI. From a more technological perspective, the development of thin stackable chips will also be a very interesting technological key for many applications. This approach is a clever alternative to classical damascene processes to address the challenges related to the planarization of surfaces with low density of high topographies.
Hydrodynamic simulations of porous materials for ductile damage
The mechanical behavior of metallic materials under highly dynamical loading (schock) and especially their damage behavior is a topic of interest for the CEA-DAM. For tantalum, damage is ductile : by nucleation, growth and coalescence of voids within the material. Usual ductile damage models have been developed using the simplifying assumption that voids are isolated in the materials. However, recent studies by direct simulations explicitly describing a void population in the material (and experimental observations after failure) have shown the importance of void interaction for predicting ductile damage. Yet, the microscopical mechanisms of this interaction remain little known.
The objective of the PhD is to study the growth and coalescence phases of ductile damage through direct numerical simulations of a porous material undergoing dynamic loading. Hydrodynamic simulations, in which voids are explicitly meshed within a continuous matrix, will be used to study relevant scales of length and time. Monitoring the void population throughout the simulation will provide valuable information on the influence of void interaction during ductile damage. Firstly, the bulk behavior will be compared to the one predicted by usual models of isolated voids, showing the macroscopic effect of void interaction. Secondly, the evolution of the size distribution in the void population will be monitored. The last objective will be to understand microscopic void-to-void interaction. In order to take advantage of the wealth of simulation results, approaches based on artificial intelligence (neural networks on the graph associated with the pore population) will be used to learn the link between a void's neighborhood and its growth.
The doctoral student will have the opportunity to develop their skills in shock physics and mechanics, numerical simulations (with access to CEA-DAM supercomputers), and data science.