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This research paper presents a study on dielectric properties of ZnO‐P2O5‐SeO2 glass ceramics containing varied contents of silver oxide. The structural analysis of the prepared samples was performed using XRD, TEM, DSC, FT‐IR spectra, and optical absorption (OA) techniques. These studies indicated the samples were embedded with Ag3PO4, Ag2SeO3 and Zn3(PO4)2 anisotropic crystal phases along with Ag+ ions and Ag0 metallic particles. Dielectric properties, a.c. conductivity (σ ac ) and dielectric breakdown strength (DBS) were investigated as functions of Ag2O concentration over wide ranges of temperature and frequency. The results showed that the maximal concentration of Ag+ ions and Ag0 metallic particles in the sample doped with 0.6 mol % of Ag2O. Dielectric parameters and σ ac were found to increase with an increase in Ag2O content up to 0.6 mol %, while the DBS and electrical impedance gradually decreased. The dipolar effects exhibited by these samples were quantitatively analysed and the possible dipoles for such effects were recognised. The ionic contribution to a.c. conduction was predominant up to 0.6 mol % of Ag2O, beyond which the polaronic tunnelling phenomenon prevailed. Based on these findings, it was concluded that 0.6 mol % of Ag2O is the optimal concentration for using these glass ceramics as solid electrolytes in ionic batteries. Moreover, glass ceramics containing Ag2O beyond 0.6 mol%, have exhibited larger polaronic conductivity, hence such samples can be considered as suitable candidates for electrodes in ionic batteries.This article is protected by copyright. All rights reserved.

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