Characterization of polymer electrolytes by dielectric response using electrochemical impedance spectroscopy.

Authors present a phenomenological view on dielectric relaxation in polymer electrolytes, which is monitored by electrochemical impedance spectroscopy. Molecular interaction of polymer chains with salt molecules (or dipole-dipole interaction between segments and salt molecules) leads to dipolar molecular entities. Frequency-dependant impedance spectra are the key quantities of the interest for determination of electric properties of materials and their interfaces with conducting electrodes. Salt concentration serves as parameter. Bulk and interfacial properties of the samples are discussed in terms of impedance (<italic>Z</italic>*) and modulus (<italic>M</italic>*) spectra. We focus on two different classes of systems, i.e. high molar mass of poly(ethylene oxide) (PEO)+lithium perchlorate (LiClO4) (i.e. the inorganic salt) and epoxidized natural rubber (ENR-25) with 25 mol% of epoxide content+LiClO4. Impedance spectra with salt content as parameter tell us that we have interaction between dipolar entities leading to dispersion of relaxation times. However, as scaling relations show, dispersion of relaxation times does not depend on salt content in the PEO system. The relaxation peak for the imaginary part of electric modulus (<italic>M</italic>″) provides information on long-range motion of dipoles. Summarizing the results from imaginary part of impedance spectrum (<italic>Z</italic>″), tan <italic>δ</italic> (imaginary/real of permittivities) and <italic>M</italic>″ for the two systems under the discussion, PEO behaves like a mixture of chains with dipoles. There are interactions between the dipoles, but they are relaxing individually. Therefore, we see PEO-salt system as a polymer electrolyte where only a tiny fraction of added salt molecules becomes electrically active in promoting conductance. However, ENR-25-salt system behaves just as a macroscopic dipole and it can not display electrode polarization or electric relaxation because there is no mobility of individual dipoles. Hence, ENR-25-salt does not form a polymer electrolyte in the classic sense. [ABSTRACT FROM AUTHOR]