Influence of Powder Milling and Annealing Parameters on the Formation of Cubic Li7La3Zr2O12 Compound

Abstract

Li-ion batteries are widely used as energy storage devices due to their excellent electrochemical performance. The cubic Li7La3Zr2O12 (c-LLZO) compound is regarded as a promising candidate as a solid-state electrolyte for lithium-ion batteries due to its high bulk Li-ion conductivity, excellent thermal performance, and chemical stability. The standard manufacturing procedure involves the high-temperature and lengthy annealing of powders. However, the formation of the tetragonal modification of LLZO and other undesired side phases results in the deterioration of electrochemical properties. The mechanical milling of precursor powders can enhance the powders’ reactivity and can result in an easier formation of c-LLZO. The aim of this work was to study the influence of selected milling and annealing parameters on c-LLZO compound formation. The starting powders of La(OH)3, Li2CO3, and ZrO2 were subjected to milling in various ball mills, under different milling conditions. The powders were then annealed at various temperatures for different lengths of times. These studies showed that the phase transformation processes of the powders were not very sensitive to the milling parameters. On the other hand, the final phase composition and microstructure strongly depended on heat treatment conditions. Low temperature annealing (750 °C) for 3 h produced 90% of c-LLZO in the powder structure.