Glasses of the formula 40Li2O⋅xSb2O3⋅(60–x)B2O3 (0 ≤ x ≤ 40 mol%) were prepared using the melt quenching technique. XRD, FTIR spectroscopy, SEM, density and dc conductivity were studied. A phase separation was observed in as-prepared glass samples that contain a concentration of Sb2O3 ≥ 25 mol%. Moreover, crystalline phases of Li5Sb3O8, Li3SbO4 and LiSbO3 were found in the 40Li2O⋅40Sb2O3⋅20B2O3 glass sample after thermal treatment at 600 oC for 4 h. N 4 decreased slightly with increasing Sb2O3 content. The contribution to N 4 from Li2O and Sb2O3 was separated. The negative contribution of Sb2O3 to N 4 was due to the association of Sb2O3 and Li2O to form Li5Sb3O8, Li3SbO4 and LiSbO3 phases and acting as a former. The formed Li5Sb3O8, Li3SbO4 phases having low migration energy and rich with Li+ ions exhibited a high mobility. Density and molar volume increased with increasing Sb2O3 content. The abrupt increase in the conductivity by about 4 orders in magnitude for Sb2O3 ≥ 25 mol% is correlated with the presence of clusters rich by Li+ and Sb+3 ions that have low migration energies and the increase in the free volume.
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