Dielectric relaxation in PEO-based polymer electrolytes
Dielectric properties of cross-linked poly(ethylene oxide) (PEO) with different mesh sizes, doped with lithium salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), have been studied in frequency region between 0.1 and 107 Hz and in broad temperature range. Results were compared with linear PEO of 1000 g/mol. Dielectric responses of the systems are dependent on frequency and thermally activated. Systems exhibit different responses in semi-crystalline and molten state. Increase of temperature promotes polarization; whereas, increase of frequency lessens it. In other words, polarization is thermally activated and local conductivity reduced. Generally, one observes enhanced dc conductivity in linear PEO as compared to cross-linked PEO at high temperature and the opposite at low temperature. Resonance responses are observed in low-molecular cross-linked PEO and in linear PEO at low temperature. These responses lead to splitting of polarization relaxation at frequencies beyond low-frequency range. Salt-comprising systems display only relaxation-type dielectric response. Imaginary parts of response spectra show distribution of relaxation times. It turns out that this distribution is independent of temperature in the low-frequency range, but depends on concentration of salt in the cross-linked polymer. In both systems, neat cross-linked and linear polymer of low-molecular mass, one observes coexistence of non-local and local motions of charged entities even at very low temperature.
Publisher URL: https://link.springer.com/article/10.1007/s11581-017-2290-8
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