Universal Relationship between Conductivity and Solvation-Site Connectivity in Ether-Based Polymer Electrolytes

We perform a joint experimental and computational study of ion transport properties in a systematic set of linear polyethers synthesized via acyclic diene metathesis (ADMET) polymerization. We measure ionic conductivity, σ, and glass transition temperature, Tg, in mixtures of polymer and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. While Tg is known to be an important factor in the ionic conductivity of polymer electrolytes, recent work indicates that the number and proximity of lithium ion solvation sites in the polymer also play an important role, but this effect has yet to be systematically investigated. Here, adding aliphatic linkers to a poly(ethylene oxide) (PEO) backbone lowers Tg and dilutes the polar groups; both factors influence ionic conductivity. To isolate these effects, we introduce a two-step normalization scheme. In the first step, Vogel–Tammann–Fulcher (VTF) fits are used to calculate a temperature-dependent reduced conductivity, σr(T), which is defined as the conductivity o...

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