Phase Morphology Dependence of Ionic Conductivity and Oxidative Stability in Fluorinated Ether Solid-State Electrolytes

Solid-state polymer electrolytes can enable the safe operation of high energy density lithium metal batteries; unfortunately, they have low ionic conductivity and poor redox stability at electrode interfaces. Fluorinated ether polymer electrolytes are a promising approach because the ether units can solvate and conduct ions, while the fluorinated moieties can increase oxidative stability. However, current perfluoropolyether (PFPE) electrolytes exhibit deficient lithium-ion coordination and ion transport. Here, we incorporate cross-linked poly(ethylene glycol) (PEG) units within the PFPE matrix and increase the polymer blend electrolyte conductivity by 6 orders of magnitude as compared to pure PFPE at 60 °C from 1.55 × 10^–11 to 2.26 × 10^–5 S/cm. Blending varying ratios of PEG and PFPE induces microscale phase separation, and we show the impact of morphology on ion solvation and dynamics in the electrolyte. Spectroscopy and simulations show weak ion–PFPE interactions, which promote salt phase segregation into─and ion transport within─the PEG domain. These polymer electrolytes show promise for use in high-voltage lithium metal batteries with improved Li|Li cycling due to enhanced mechanical properties and high-voltage stability beyond 6 V versus Li/Li⁺. Our work provides insights into transport and stability in fluorinated polymer electrolytes for next-generation batteries.