Abstract
Hybrid solid electrolytes (HSEs) aim at combining the superior ionic conductivity of inorganic fillers with the scalable process of polymer electrolytes in a unique material for solid-state batteries. Pursuing the goal of optimizing the key metrics (σion ≥ 10-4 S.cm-1 at 25°C and selfstanding property), we successfully developed a HSE based on a modified poly(ethylene oxide):LiTFSI organic matrix which binds together a high loading (75 wt.%) of Li6PS5Cl particles, following a solvent-free route. A rational study of available formulation parameters has enabled us to understand the role of each component in the conductivity, the mixing and the mechanical cohesion. Especially, the type of activation mechanism (Arrhenius or Vogel-Fulcher-Tammann (VFT)) and its associated energy are proposed as a new metric to unravel the ionic pathway inside the HSE. We showed that a polymer-in-ceramic approach is mandatory to obtain enhanced conduction through the HSE ceramic network, as well as superior mechanical properties, revealed by tensile test. Probing the compatibility of phases, using electrochemical impedance spectroscopy (EIS) alongside 7 Li nuclear magnetic resonance (NMR), reveals the formation of an interphase, the quantity and resistivity of which grow with time and temperature. Finally, electrochemical performances are evaluated by assembling a HSE-based battery, which displays comparable stability as pure-ceramic ones but still suffers from higher polarization and thus lower capacity. Altogether, we hope these findings provide valuable knowledge to develop a successful HSE, by placing the optimization of the right metrics at the core of the formulation.