Investigation of the free volume and ionic conducting mechanism of poly（ethylene oxide）-LiClO_4 polymeric electrolyte by positron annihilating lifetime spectroscopy

The positron annihilation lifetime and ionic conductivity are each measured as a function of organophilic rectorite（OREC） content and temperature in a range from 160 K to 300 K.According to the variation of ortho-positronium（o-Ps） lifetime with temperature,the glassy transition temperature is determined.The continuous maximum entropy lifetime（MELT） analysis clearly shows that the OREC and temperature have important effects on o-Ps lifetime and free volume distribution.The experimental results show that the temperature dependence of ionic conductivity obeys the Vogel-Tammann-Fulcher（VTF） and Williams-Landel-Ferry（WLF） equations,implying a free-volume transport mechanism.A linear least-squares procedure is used to evaluate the apparent activation energy related to the ionic transport in the VTF equation and several important parameters in the WLF equation.It is worthwhile to notice that a direct linear relationship between the ionic conductivity and free volume fraction is established using the WLF equation based on the free volume theory for nanocomposite electrolyte,which indicates that the segmental chain migration and ionic migration and diffusion could be explained by the free volume theory.

Investigation of the free volume and ionic conducting mechanism of poly(ethylene oxide)-LiClO4 polymeric electrolyte by positron annihilating lifetime spectroscopy

The positron annihilation lifetime and ionic conductivity are each measured as a function of organophilic rectorite (OREC) content and temperature in a range from 160 K to 300 K. According to the variation of ortho-positronium (o-Ps) lifetime with temperature, the glassy transition temperature is determined. The continuous maximum entropy lifetime (MELT) analysis clearly shows that the OREC and temperature have important effects on o-Ps lifetime and free volume distribution. The experimental results show that the temperature dependence of ionic conductivity obeys the Vogel-Tammann-Fulcher (VTF) and Williams-Landel-Ferry (WLF) equations, implying a free-volume transport mechanism. A linear least-squares procedure is used to evaluate the apparent activation energy related to the ionic transport in the VTF equation and several important parameters in the WLF equation. It is worthwhile to notice that a direct linear relationship between the ionic conductivity and free volume fraction is established using the WLF equation based on the free volume theory for nanocomposite electrolyte, which indicates that the segmental chain migration and ionic migration and diffusion could be explained by the free volume theory.