The Influence of Charge Correlation and Ion Solvation on the Phase Behavior of Single-Ion Conducting Polymer Blend...

Single-ion conducting polymer blends (SICPBs) have demonstrated exceptional electrochemical performance as solid-state battery electrolytes; however, their nanoscale morphology and thermodynamic behavior remain unexplored. In this work, we investigate blends composed of deuterated poly-(ethylene oxide) and poly-[lithium sulfonyl-(trifluoromethane sulfonyl)-imide methacrylate], dPEO/P-(LiMTFSI), and report the first experimental study of the nanostructures of charge-neutral polymer blends using small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS). Despite the macroscopic miscibility indicated by a single glass-transition temperature, SANS and SAXS results reveal disordered, charge-correlated nanostructures that are strongly influenced by blend composition and temperature. At low concentrations of charge polymer, the scattering is dominated by concentration fluctuations, and the random phase approximation is applied to extract values of the Flory-Huggins interaction parameter, χ_SC. At higher charged polymer content, concentration fluctuations are suppressed, and a correlation model is used to characterize the nanostructures of the charge correlations. We find that the structures of the charge correlations are highly dependent on blend compositionconsistent with predictions from Sing's self-consistent field theory-liquid state models. Understanding these features is essential for uncovering the ion transport mechanism that leads to improved electrochemical performance previously reported in SICPB systems.