Abstract
Fourier Transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies and Scanning Electron Microscopy (SEM) were used to investigate ionic association, hydrogen bonding and morphology in a family of sol–gel derived lithium triflate (LiCF 3SO 3)-doped di-urethane cross-linked poly( ε-caprolactone) (PCL(530))/siloxane hybrid electrolytes. The materials studied, with compositions ∞ > n ⩾ 0.5 (where n – composition – expresses the molar ratio of PCL(530) ester repeat units per Li + ion), are non-porous and homogeneous. The Li + ions interact with the urethane and ester carbonyl oxygen atoms within the whole range of salt concentration analyzed, promoting the formation of hydrogen-bonded aggregates. The composition dependence of the relative concentration of “free” anions and coordinated anions (weakly coordinated anions, Li + CF 3 SO 3 - ion pairs or [Li(CF 3SO 3) 2] − triplets, aggregates I ([Li 2(CF 3SO 3)] +) and aggregates II ([Li 3(CF 3SO 3)] 2+) in all the samples is in perfect agreement with the values of the room temperature ionic conductivity reported previously.
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