Characterisation of reaction pathways leading to thermal runaway for new battery technologies

The development of all-solid-state cells is no longer a mere hypothesis today. As part of the Safelimove project, we assessed the safety of hybrid polymer cells of 1 Ah and 3 Ah, which led to a publication. Additionally, within the Sublime project, we evaluated the safety of 1 Ah sulfide-based cells (argyrodite), and a publication is currently being submitted.

With the arrival of these new cells, it becomes even more crucial to support their development with a detailed safety assessment and the identification of the complex mechanisms involved. Large-scale instruments such as synchrotrons and neutron reactors offer a powerful opportunity to achieve this goal, as they provide the best spatial and temporal resolutions. For example, thanks to fast X-ray radiography at ESRF, it is possible to visualize the inside of a cell during thermal runaway, thereby identifying the local impact of (electro)chemical reactions on the microstructure of components and validating our thermal runaway models. Moreover, with wide-angle X-ray scattering (WAXS), it is possible to monitor in situ the evolution of the crystalline structure of active materials during a very rapid thermal runaway reaction. Indeed, synchrotron radiation allows the acquisition of one diffractogram every 3 milliseconds. The neutron beam at ILL also enables us to track the evolution of lithium metal structure before, during, and after runaway. It is important to emphasize that these three techniques are currently mastered by the LAPS teams and have already led, or will lead, to publications.

Furthermore, new complementary techniques may be explored, such as studying the impact of thermal/mechanical stress on active materials using the BM32 beamline, or evaluating the oxidation states of metals via X-ray absorption spectroscopy (XAS) on ID26.

More conventional laboratory characterizations will also be carried out, such as DSC, TGA-MS, and XRD.

As part of our various collaborations, for the all-solid-state system, the active material of the positive electrode will most likely be NMC, or even LMFP in the event of supply difficulties. The electrolyte used will be sulphide-based, or even halide-based, while the anode will be composed of lithium metal or even a lithium alloy. If time permits, a post-Na-ion system will be considered from the second year onwards. Among other things, the thesis will aim to identify, based on the materials used, whether there are reactions prior to cathode destabilisation, whether the solid electrolyte reacts with the oxygen in the cathode or with the anode material, and whether these parallel reactions contribute to better or worse cell safety.

The three years of the PhD will be structured as follows: the first year will be dedicated to a literature review and the characterization of sulfide technology. Following the first milestones (1st CSI) and the evaluation of ongoing work on sulfides, the second year will focus either on sodium-ion technology or on further development of sulfide technology. Finally, the third year, in addition to the thesis writing, will concentrate more specifically on the impact of the identified materials on safety.

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.