Phase stability of a garnet-type lithium ion conductor Li7La3Zr2O12

作者：Matsui M^*; Takahashi K; Sakamoto K; Hirano A; Takeda Y; Yamamoto O; Imanishi N

来源：Dalton Transactions, 2014, 43(3): 1019-1024.

DOI：10.1039/c3dt52024b

The phase stability of Li7La3Zr2O12 (LLZ) was investigated using high temperature X-ray diffraction (HT-XRD). An Al-free tetragonal LLZ phase transformed into a non-quenchable cubic phase around 650 degrees C. The phase transformation process between the tetragonal phase and the new cubic phase showed perfect reversibility. The thermal analysis showed a pair of endothermic and exothermic peaks around 640 degrees C that is in good agreement with the phase transformation process observed in the HT-XRD study. The non-quenchable high temperature cubic phase showed high ionic conductivity with extraordinarily low activation energy (0.117 eV). The tetragonal phase showed another phase transformation to a low temperature (LT) cubic phase around 150-200 degrees C in air by absorbing CO2 into the structure. The preferred temperature for the CO2 absorption process was around 200 degrees C and the absorbed CO2 was extracted once the temperature reached 450 degrees C or above resulting in the phase transformation back to the tetragonal phase. On the other hand the high temperature (HT) cubic phase which shows high ionic conductivity was stabilized by Al substitution. A Li-poor LLZ containing impurity phases such as La2Zr2O7 and La2O3 effectively reacted with gamma-Al2O3 resulting in the formation of a pure Al-stabilized cubic LLZ, while the stoichiometric LLZ took a much longer time to complete the Al-substitution. The result suggested that the formation of Li vacancies is the primary step in the formation of the Al-stabilized cubic phase.

• 出版日期2014