Spectroscopic Investigation of Composite Polymeric and Monocrystalline Systems with Ionic Conductivity

Polymers

Darya V. Radziuk¹ 

关键词: polymer;    electrolyte;    lithium ion;    battery;    conductivity;   

DOI  :  10.3390/polym3020674

来源: mdpi

【 摘 要 】

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 °C. 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 °C. 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 °C, 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.

【 授权许可】

CC BY   
© 2011 by the authors; licensee MDPI, Basel, Switzerland.