화학공학소재연구정보센터
Solid State Ionics, Vol.291, 1-7, 2016
Mechanism of lithium ion diffusion in the hexad substituted Li7La3Zr2O12 solid electrolytes
The Li6.4La3Zr1.7M0.3O12 (M = Mo and Cr) and Li7 - 2xLa3Zr2 - xWxO12 (X = 0.1-0.5) solid lithium-ion conductors were prepared by conventional solid state reaction method. The results indicate that partial substitutions by W and Mo ions can stabilize the garnet-like cubic phase of Li-La-Zr-0 at room temperature, while the Cr ions substitution cannot even at a content of 15 mol%. The total conductivity of the Li7 - 2xLa3Zr2 - xWxO12 lithium conductor is the highest at x = 0.2 (8.7 x 10(-5) S/cm), and decreases with the increasing W substituting concentration. The Li6.4La3Zr1.7Mo0.3O12 has a higher total conductivity than that of Li6.4La3Zr1.7W0.3O12. Different from one apparent peak in the Li7La3Zr2O12 samples, two prominent relaxation-type internal friction peaks related to the short range diffusion of lithium ions were observed in each W or Mo substituted Li7La3Zr2012 compounds. The high-temperature IF peaks locate at about 365.9 K and 358.9 K at 1 Hz, corresponding to an activation energy of 0.49 and 0.51 eV for the W and Mo substituted Li7La3Zr2O12 compounds, respectively. Considering the crystalline structure, it was suggested that the lithium ionic diffusion between 48g(96h)-24d corresponds to the low-temperature peak and 48g(96h)-48g(96h) to the high-temperature peak. (C) 2016 Elsevier B.V. All rights reserved.