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Technologie de protection active des électrodes par fluoration de surface

Abstract : A shift toward greener technologies has been impulsed by the European authorities and tremendous efforts are now engaged to drastically reduce our carbon footprint, by at least for 40 percent by 2030. The development of safe batteries with higher energy density is part of this shift, since this technology is critical for the commercialization and for the rise of electrical mobility and smart energy grid deployment. To do so, new materials need to be developed or existing materials need to be improved to reach higher specific capacities and working electrochemical potentials. The research prospects new electrode materials, new electrolytes and new ways to protect the electrode/electrolyte interphase within the batteries. Indeed, in secondary batteries, the anode/electrolyte interphase plays a key role in the electrochemical performances and life span. Since the classically used liquid organic electrolytes are not stable in the totality of the working potential window of Li-ion batteries, they undergo degradation on cycling of the battery, hence a Solid Electrolyte Interphase (SEI) is formed. This interphase passivates the negative electrodes from the electrolyte and prevents further aging processes, however as this passivation continues in cycling, it also lowers the coulombic efficiency and causes irreversible capacity loss. Knowing this, any modification of the SEI should be performed with parsimony as it could break the balance between the positive and negative aspect for the SEI. By synthetizing a chemisorbed thin fluorinated layer upon anode material, we managed to improve the passivating power of the SEI on TiO2 and Li4Ti5O12 (LTO) anodes, leading to enhanced electrochemical performance. We also determine that very low quantities of fluorine on the active electrode material surface leads to several beneficial effects. We demonstrated that the fluorination brings as well enhancement for positive electrode materials, such as LiNi0.8Co0.15Al0.05O2 (NCA). Indeed, NCA and NMC suffer structural surface instability, leading to self-heating and loss of performance. Improved cyclability is observed for fluorinated NCA electrodes as the fluorination stabilizes the surface structure.Surface fluorination was carried by a process using XeF2, for the first time applied to electrode materials. We aimed to prospect the influence of the surface fluorination on different aspect of a Li-ion battery, from the active material to the electrolyte interphase, thanks to a multi-scale probing approach. The chemical nature of the surface layer on negative and positive electrode materials was described by the mean of the XPS, as well as the fluorine distribution on the surface with both AES and SAM. The bulk and sub-surface properties of fluorinated LTO (LTO-F) were also investigated by coupling XRD, Raman Spectroscopy and NMR 19F, showing no modifications of the crystallographic structure. The influence of the surface fluorination on the electrochemical performance was investigated by galvanostatic cycling and by coupling XPS and SAM on cycled electrodes. We paid a specific attention to the impact of the fluorination on the SEI thickness and stability in charge and discharge. Indeed, LTO-F exhibits a new reactivity toward the electrolyte, leading to a thinner and stabilized SEI. Finally, the gas generation of the LTO-F electrodes has been investigated by Gas Chromatography – Mass Spectrometry (GC-MS), as gassing is known to be a roadblock to the commercialization of LTO. We demonstrated that the CO2 outgassing is reduced by the surface fluorination. Overall, the strategy implemented in this work, from synthesis to thorough characterization, offer new solutions to improve both SEI formed on negative electrode material as well as surface structural stability of positive electrode material, leading to improved Li-ion batteries.
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Youn Charles-Blin. Technologie de protection active des électrodes par fluoration de surface. Autre. Université Montpellier, 2019. Français. ⟨NNT : 2019MONTS068⟩. ⟨tel-02964680⟩

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