Abstract
A new lithium-ion conducting oxide, hexagonal Li4GeO4, with a space group of P63/mmc, was prepared by mechanochemical treatment and subsequent heat treatment at 250 °C. The crystal structure was found in sulfide Li4SnS4, and this is the first study to report an oxide system. In addition, (100-x)Li4GeO4·xLi2MO4 (M = S or W; x = 10, 20, 30, and 40 mol%) glass-ceramic electrolytes with the hexagonal phase were prepared by crystallization of their mother glasses. The formability of the electrolytes improved as the quantity of Li2SO4 increased, and the 90Li4GeO4·10Li2SO4 glass-ceramic electrolyte showed the highest ionic conductivity of 2.9 × 10−6 S cm−1 at 25 °C. Compared with the experimental results, the bond valence sum (BVS) analysis results indicated that ionic conduction paths are easily connected along the c-axis in the hexagonal phase, suggesting that the relatively small lattices in the a- and b-axes are more advantageous for three-dimensional ionic conduction.
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