Low Frequency Dielectric Relaxation and Conductance of Solid Polymer Electrolytes with PEO and Blends of PEO and PMMA.

Solid polymer electrolytes are mixtures of polymer and inorganic salt. There are quite a number of studies dealing with the relationship between electric conductivity and structural relaxation in solid polymer electrolytes. We present a phenomenological approach based on fluctuation-dissipation processes. Phase heterogeneity appears in poly(ethylene oxide) (PEO) of high molecular mass and its blends due to crystallization and accompanying phase segregation. Addition of salt hampers crystallization, causing dynamic heterogeneity of the salt mixtures. Conductivity is bound to amorphous phase; the conductivity mechanism does not depend on content of added salt. One observes dispersion of conductivity relaxation only at low frequency. This is also true for blends with poly(methyl methacrylate) (PMMA). In blends, the dynamics of relaxation depend on glass transition of the system. Glassy PMMA hampers relaxation at room temperature. Relaxation can only be observed when salt content is sufficiently high. As long as blends are in rubbery state at room temperature, they behave PEO-like. Blends turn into glassy state when PMMA is in excess. Decoupling of long-ranging and dielectric short-ranging relaxation can be observed. Conductivity mechanism in PEO, as well as in blends with PMMA were analyzed in terms of complex impedance Z*, complex permittivity, tangent loss spectra and complex conductivity.