Bond character, optical properties and ionic conductivity of Li2O/B2O3/SiO2/Al2O3 glass: Effect of structural substitution of Li2O for LiCl

Abstract

A glass of composition (20 - x)Li2O-xLiCl-65B2O3-10SiO2-5Al2O3 where 0 ≤ x ≤ 12.5 wt% is prepared using the normal melt-quenching technique. The optical constants and electrical conductivity and their correlation are investigated, furnished and discussed with the substitution of Li2O for LiCl. The mechanism of the optical absorption and the calculated Urbach energy follow the rule of phonon-assisted transitions. The ionic conduction mechanism is determined by activation energy process. Substitution up to 10 wt% LiCl provides high ionic conductivity (1.9 × 10-2 Ω-1 m-1) due to the high average electronegativity of LiCl which increases the polarizability of lithium ions. The small cation-anion distance approach confirmed the enhancement in ionic conductivity of LiCl containing glass compared to that of Li2O. Due to the large size of Cl- ions, there is an expansion of the lattice which in turn broadens the available path windows. For 12.5 wt% LiCl, anomalous density behavior is observed and a reduction in conductivity is occurred, σ = 5.4 × 10-3 Ω-1 m-1. Owing to the model of bond fluctuation, the reduction is attributed to the increase in the alkali halide concentration which creates bottlenecks that hinder the motion of Li+ ions. The ionic conductivity character is strongly supported by the behavior of the glass ionicity factor, density, molar volume, refractive index, average boron-boron separation, molar refraction, metallization criterion and non-bridging oxygen concentration of the studied glass. © 2008 Elsevier B.V. All rights reserved.