Ion conduction and relaxation in PEO-LiTFSI-Al2O3 polymer nanocomposite electrolytes

Ion conduction and relaxation in PEO-LiTFSI-Al2O3 polymer nanocomposite electrolytes have been studied for different concentrations of Al2O3 nanoparticles. X-ray diffraction and differential scanning calorimetric studies show that the maximum amorphous phase of PEO is observed for PEO-LiTFSI embedded with 5 wt. % Al2O3. The maximum ionic conductivity ∼3.3 × 10−4 S cm−1 has been obtained for this composition. The transmission electron microscopic image shows a distribution of Al2O3 nanoparticles in all compositions with size of <50 nm. The temperature dependence of the ionic conductivity follows Vogel-Tamman-Fulcher nature, indicating a strong coupling between ionic and polymer chain segmental motions. The scaling of the ac conductivity implies that relaxation dynamics follows a common mechanism for different temperatures and Al2O3 concentrations. The imaginary modulus spectra are asymmetric and skewed toward the high frequency sides of the maxima and analyzed using Havriliak-Negami formalism. The temperature dependence of the relaxation time obtained from modulus spectra also exhibits Vogel-Tamman-Fulcher nature. The values of the stretched exponent obtained from Kohlrausch-Williams-Watts fit to the modulus data are fairly low, suggesting highly non-exponential relaxation for all concentrations of Al2O3 in these electrolytes.