Phase behavior of binary and ternary fluoropolymer (PVDF-HFP) solutions for single-ion conductors.

A fluoropolymer poly(vinylidene fluoride--hexafluoropropylene) (PVDF-HFP) has a dielectric constant of ∼11, providing charge screening effects. Hence, this highly polar PVDF-HFP material has been employed as a matrix for solid polymer electrolytes (SPEs). In this study, the phase behavior of binary PVDF-HFP solutions was analyzed using the Flory-Huggins theory, in which ethylene carbonate, propylene carbonate, dimethyl carbonate, γ-butyrolactone, and acetone were employed as model solvents. In particular, for the binary PVDF-HFP/acetone system, the solid-liquid and liquid-liquid phase transitions were qualitatively described. Then, the phase diagram for ternary acetone/PVDF-HFP/polyphenolate systems was constructed, in which the binodal, spinodal, tie-line, and critical point were included. Finally, when a polyelectrolyte lithium polyphenolate was mixed with the PVDF-HFP matrix, it formed a single-ion conductor with a Li transference number of 0.8 at 23 °C. In the case of ionic conductivity, it was ∼10 S cm in solid state and ∼10 S cm in gel state, respectively.