Abstract
The conductivity mechanism is studied in the LiCF3SO3-doped polyethylene oxide by monitoring the vibrations of sulfate groups and mobility of Li+ ion along the polymeric chain at different EO/Li molar ratios in the temperature range from 16 to 90 °С. At the high EO/Li ratio (i.e., 30), the intensity of bands increases and a triplet appears at 1,045 cm−1, indicating the presence of free anions, ionic pairs and aggregates. The existence of free ions in the polymeric electrolyte is also proven by the red shift of bands in Raman spectra and a band shift to the low frequency Infra-red region at 65 < T < 355 °С. Based on quantum mechanical modeling, (method MNDO/d), the energies (minimum and maximum) correspond to the most probable and stable positions of Li+ along the polymeric chain. At room temperature, Li+ ion overcomes the intermediate state (minimum energy) through non-operating transitions (maximum energy) due to permanent intrapolymeric rotations (rotation of C, H and O atoms around each other). In solid electrolyte (Li2SO4) the mobility of Li+ ions increases in the temperature range from 20 to 227 °С, yielding higher conductivity. The results of the present work can be practically applied to a wide range of compact electronic devices, which are based on polymeric or solid electrolytes.
Highlights
The physics and chemistry of solid electrolytes requires expanding investigations in a new way due to the fabrication of devices of which they are the basis
The main purpose of our work is to study ionic species (e.g., SO42− and Li+) in two conductive systems—polymeric and solid electrolytes
Spectroscopy of Polymeric Electrolytes Based on LiCF3SO3 and Polyethylene Oxide
Summary
The physics and chemistry of solid electrolytes requires expanding investigations in a new way due to the fabrication of devices of which they are the basis. Among them are high temperature phases of α-Li2SO4 (586–860 °C), α-Ag2SO4 (412–660 °C) sulfates of one-valent metals (Li+, Na+ and Ag+) and solids Li2SO4-Na2SO4 and Li2SO4- Ag2SO4, Na2SO4. Lithium α-orthosilicate has an ionic conductivity of 3 S∙cm−1 and is temperature sensitive, when doped with the metal oxides (e.g., titanium, zinc, magnesium or aluminum). The third class of polymeric electrolytes, which are polymers with lithium salt (e.g., LiCF3SO3), is least studied. Their conductivity is controlled by the change of the polymeric matrix, impurity salt and temperature [11,12,13,14,15,16]
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