Lithium-ion batteries, widely present in our daily lives, have revolutionized portable applications and are now used in electric vehicles. The development of new generations of batteries for future applications in transport and storing electricity from renewable sources is therefore vital to mitigating climate change. Lithium-ion technology is generally considered as the preferred solution for applications requiring high energy density, while sodium-ion technology is particularly attractive for applications requiring power.

However, the intrinsic instability of liquid electrolytes results in safety issues. Faced with the requirements concerning the environment and safety, solid-state batteries based on solid electrolytes can provide an effective solution while meeting battery energy storage needs. The barriers to overcome allowing the development of all-solid-state battery technology consist mainly in the research of new chemically stable solid electrolytes with good electrical, electrochemical and mechanical performance. For this goal, this thesis project aims to develop “polymer/polymer” and “ceramic/polymer” composite solid electrolytes with high performance and enhanced safety. Characterizations by electrochemical impedance spectroscopy (EIS) will be carried out in order to understand the cation dynamics (by Li+ or Na+) at the macroscopic scale in composite electrolytes, while the local dynamics will be probed using advanced techniques of Solid-state NMR (23Na / 7Li relaxation, 2D NMR, in-situ NMR & operando). Other characterization techniques such as X-ray and neutron diffraction, XPS, chronoamperometry, GITT ... will be implemented for a perfect understanding of the structure of electrolytes as well as aging mechanisms at the electrolyte / electrolyte and electrolyte/electrode interfaces of the all-solid battery.

Key words: composite solid electrolyte, all-solid-state battery, interfaces, multiscale characterization, dynamics of Li + and Na + ions, electrochemical performance, solid-state NMR, X-ray / neutron diffraction.