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We present the analysis of the impedance spectra for a binary electrolyteconfined between blocking electrodes with dielectric layers. An expression forthe impedance is derived from Poisson-Nernst-Planck equations in the linearapproximation taking into account the voltage drop on the dielectric layer. Theanalysis shows, that characteristic features of the frequency dependence of theimpedance are determined by the ratio of the Debay length and the effectivethickness of the dielectric layer. The impact of the dielectric layer isespecially strong in the case of high concentrated electrolytes, where theDebay length is small and thus comparable to the effective thickness of thedielectric layer. To verify the model, measurements of the impedance spectraand transient currents in a liquid crystal 4-n-pentyl-4'-cyanobiphenyl (5CB)confined between polymer-coated electrodes in cells of different thicknessesare performed. The estimates for the diffusion coefficient and ionconcentration in 5CB obtained from the analysis of the impedance spectra andthe transient currents are consistent and agree with previously reported data.We demonstrate that calculations of the ion parameters from the impedancespectra without taking into account the dielectric layer contribution lead inmost cases to incorrect results. Application of the model to analyze violationsof the low-frequency impedance scaling and contradictions in the estimates ofthe ion parameters recently found in some ionic electrolytes are discussed.

Influence of dielectric layers on estimates of diffusion coefficients and concentrations of ions from impedance spectroscopy