A strategy of enhancing the ionic conductivity of Li7La3Zr2O12 under accurate sintering conditions

Abstract

Garnet-type Li₇La₃Zr₂O₁₂ (LLZO) oxide solid electrolytes are spotlighted as solid electrolytes for lithium-ion secondary batteries due to their high thermal and electrochemical stability. However, LLZO has a low ionic conductivity compared to liquid electrolytes, which is one of the biggest problems hindering the commercialization of all-solid-state batteries (ASSBs). Essential conditions for improving the ionic conductivity can be classified into two factors: (1) formation of a cubic LLZO phase related to bulk ionic conductivity and (2) formation of grain boundaries for low interfacial resistance. In this work, cubic LLZO phase formation conditions were first confirmed by TGA-DTA analysis. The LLZO phase was pre-formed via a holding range of furnace temperature profile (HRFTP) found by TGA-DTA analysis. The pre-formed LLZO phase could stabilize the cubic LLZO phase after a sintering process. This was confirmed by XRD analysis. Stabilized cubic LLZO under HRFTP conditions could enhance the bulk ionic conductivity, the main factor affecting the total ionic conductivity. In addition, to confirm the characteristics of sintering temperature changes, the grain boundaries of LLZO surfaces and the color of LZO pellets were investigated by SEM in detail. By setting the holding time process at 600 °C, the pre-formed LLZO phase stabilized the cubic LLZO phase formation after the sintering process. By optimizing the sintering temperature, both bulk and grain boundary ionic conductivities were improved. As a result, an ionic conductivity of 1.87 × 10⁻⁴ S cm⁻¹ of the cubic LLZO phase was confirmed by EIS analysis. These results provide an insight into the reproducibility of the facile synthesis of LLZO. This strategy can be successfully applied to next-generation ASSBs.