Comparative Study of Stability against Moisture for Solid Garnet Electrolytes with Different Dopants
Li Huang, Jian Gao, Zhijie Bi, Ning Zhao, Jipeng Wu, Qiu Fang, Xuefeng Wang, Yong Wan, Xiangxin Guo
Abstract
The cubic garnet Li7La3Zr2O12 (c-LLZO) is one of the most promising solid electrolytes due to its high ionic conductivity and large electrochemical window. However, the critical issue of Li2CO3 formation on the c-LLZO surface when exposed to air is problematic, which is detrimental to the ionic conductivity and storage. Herein, comparative studies were carried out on the air stability of Al-doped Li7La3Zr2O12 (Al-LLZO), Al-Ta-doped Li7La3Zr2O12 (Al-LLZTO), and Al-Nb-doped Li7La3Zr2O12 (Al-LLZNO). It was found that Al-LLZTO and Al-LLZNO are less reactive with air than Al-LLZO. The morphology of Li2CO3 on Al-LLZTO micro-sized powders after air exposure was island-like with ~1.5 μm in thickness. The interfacial resistance of Li/Al-LLZTO was also a factor of ~3 smaller than that of Li/Al-LLZO, leading to the improved cycle stability of Li/Al-LLZTO/Li symmetric cells. The first-principles calculations based on density functional theory (DFT) verified that the decomposition energy of Al-LLZTO was larger than that of Al-LLZO, inhibiting the reaction product of Li2O and, thus, the next step product of Li2CO3 following the reactions of Li2O + H2O → LiOH and LiOH + CO2 → Li2CO3.