Elucidation of the Correlation between the Electrochemical Activity of Oxygen Reduction and the Molecular Structure of the Platinum/Ionomer Interface in Proton Exchange Membrane Fuel Cells

This thesis focuses on the Proton Exchange Membrane Fuel Cell (PEMFC), used in the transportation sector to generate electricity and heat from hydrogen and oxygen. Although promising for reducing CO2 emissions through the use of green hydrogen, the PEMFC needs to enhance its performance and durability to compete with combustion engines and batteries. The electrode plays a crucial role, but the molecular complexity of the electrochemical interface between the platinum-based catalyst and the ionomer makes characterization challenging. Currently, the qualitative understanding of this interface is limited, impeding progress and model predictability. The thesis aims to establish a correlation between the molecular structure of the electrochemical interface and the electrochemical kinetics, focusing on platinum oxidation and ionomer adsorption. A unique device developed at CEA allows simultaneous electrochemical and spectroscopic characterizations. The novelty lies in using Atomic Force Microscopy (AFM) coupled with Raman spectroscopy and synchrotron-based micro-infrared spectroscopy as original techniques to obtain crucial information for PEMFC applications.

Development of new anode materials for potassium-ion batteries

Classic Li-ion batteries are composed of a graphite anode and a cathode containing a lithiated layered oxide (formula LiNixMnyCozO2). The development and the generalization of the electric automobile market will generate stress on certain chemical elements source, especially for lithium, nickel, cobalt and copper. In addition, the production method consumes a lot of energy (multiple calcinations) and several solvents/products used are not respectful of the environment (NMP, ammonia).
The thesis aims to develop a battery technology based on potassium without using any critical element in order to significantly decrease the ecological footprint.
The insertion of potassium ion inside the graphite structure has been reported as an advantage in front of Na-ion batteries. However, due to the potassium size, the graphite structure expands (60%) and can limit the batterie cycle life.
The final target of the PhD thesis is to solve this issu following two approches : 1/ Find the link beetween graphites specifications and the resulting electrochemical performances in order to select the best graphite grade 2/ Develop new anode materials for K-ion application.

Physics-based ageing model of Li-ion batteries

In recent years, Li-ion batteries have become the benchmark technology for the global battery market, supplanting the older Nickel-Cadmium and Alkaline technologies. Although slightly inferior to fossil fuels in terms of massic energy capacity, Li-ion batteries have a major advantage for the development of electric vehicles: their exceptional lifespan. It has recently been demonstrated that particular electric vehicle technologies can exceed one million km. Beyond the promising performance of ideal prototypes, the question of battery lifespan is linked to industrial, economic and environmental issues that are crucial to the ecological transition and energy sovereignty of our country.

One of the major challenges in developing these long-life batteries is to anticipate and control the various internal degradation phenomena that occur during actual use. Although most degradation phenomena have been identified in laboratory on common battery materials, the question of their kinetics in a battery pack in real use remains open, as does the prediction of the battery's state of health and end-of-life.

CEA's teams draw on a unique expertise combining experimental data and modeling to build a predictive physico-chemical model of Li-ion battery degradation. As part of this thesis, you will design and carry out basic characterization experiments on battery degradation mechanisms in the laboratory, using a wide range of advanced experimental techniques (electrochemical titration, impedance spectroscopy, operando gas measurements, DRX, etc.). Your work will also involve integrating your results into aging models, and studying the predictions and validation of these models.

Advanced modeling of Gas Diffusion Layers for Fuel Cells: ink impregnation and drying, 3D phase distribution, and effective properties

In the frame of advanced H2 solutions for the energy transition, the Proton Exchange Membrane Fuel Cell (PEMFC) is a relevant solution for the production of low-carbon electrical energy. The European Project DECODE proposes to develop a fully digital chain of design tools, including raw material properties, manufacturing and assembly of the different components, to predict the performance of such ‘virtual’ stack. This will help reducing the development cost and time of improved materials/components suitable for different applications in the future.
The component considered in this thesis is the Gas Diffusion Layer (GDL), which is a combination of a fibrous microporous substrate and of a micro/nano porous layer (MPL for microporous layer). The work will be split into different steps: a) based on (real or virtual) 3D images of the substrate, simulation of the hydrophobic and MPL coating and drying to derive the 3D distribution of the components (fibers, hydrophobicity and MPL); b) simulation of single and two-phase transport properties of the GDL to supply inputs to upper scale performance models; c) sensitivity analysis of the main manufacturing processes (ink properties, drying parameters…)