A.c. conductivity and dielectric study of LiNiPO₄ synthesized by solid-state method

Abstract

LiNiPO₄ compound was prepared by the conventional solid-state reaction. The sample was characterized by X-ray powder diffraction, infrared, Raman analysis spectroscopy and electrical impedance spectroscopy. The compound crystallizes in the orthorhombic system, space group Pnma with a = 10·0252(7) Å, b = 5·8569(5) Å and c = 4·6758(4) Å. Vibrational analysis was used to identify the presence of $\mathrm{PO}_4^{3- }$ – group in this compound. The complex impedance has been measured in the temperature and frequency ranges 654–716 K and 242 Hz–5 MHz, respectively. The Z′ and Z″ vs frequency plots are well-fitted to an equivalent circuit consisting of series of combination of grains and grain boundary elements. Dielectric data were analysed using complex electrical modulus M* for the sample at various temperatures. The modulus plots are characterized by the presence of two peaks thermally activated. The frequency dependence of the conductivity is interpreted in terms of equation: ${\sigma_{\mathrm{a}.\mathrm{c}.}}\left( \omega \right)=\left[ {{{{{\sigma_{\mathrm{g}}}}} \left/ {{\left( {1+{\tau^2}{\omega^2}} \right)}} \right.}+\left( {{{{{\sigma_{\infty }}{\tau^2}{\omega^2}}} \left/ {{1+{\tau^2}{\omega^2}}} \right.}} \right)+A{\omega^{\mathrm{n}}}} \right]$. The near values of activation energies obtained from the analysis of M″, conductivity data and equivalent circuit confirms that the transport is through ion hopping mechanism dominated by the motion of Li⁺ in the structure of the investigated material.