Critical Percolation Threshold for Solvation-Site Connectivity in Polymer Electrolyte Mixtures

Poly(ethylene oxide) (PEO)-based polymer electrolytes are often mixed with rigid, nonconductive polymers to improve mechanical strength. The suppressed conductivity of the mixture typically arises from a reduced segmental mobility and a diminished connectivity between conductive PEO sites. To decouple these two mechanisms, we compare transport in symmetric miscible blends and disordered block copolymers (BCP) of PEO and poly(methyl methacrylate) (PMMA). Because the two systems have identical physicochemical properties, differences in their conductivity directly reflect the underlying PEO network connectivity. We find that, at short distances (<5 Å), the Li⁺solvation networks are identical for the two systems; however, a distinct variation in the network connectivity arises at length scales between 5 and 10 Å. Specifically, the BCP exhibits a lower connectivity, and therefore a lower conductivity than the blend. A quantitative model is proposed that associates long-range Li⁺transport with local miscibility; the concept of network connectivity discussed here could be useful for designing polymer electrolyte systems.