Phase Formation Study of Solid-State LLZNO and LLZTO via Structural, Thermal, and Morphological Analyses
Year: 2025
Type: article
Abstract: Garnet-type Li7La3Zr2O12 (LLZO) is a solid electrolyte candidate for ASSLBs, owing to its wide electrochemical window and intrinsic safety. Yet phase-pure LLZO remains difficult because secondary phases form, and the transition towards the tetragonal phase, aliovalent doping, mitigates these issues. Still, the phase formation pathway is not fully understood. Here, we present comparative in situ and ex situ studies of Nb- and Ta-doped LLZO (LLZNO and LLZTO) that were synthesized by a solid-state reaction. In situ/ex situ XRD reveals that the lithium precursor dictates the reaction path: differing decomposition temperatures of the lithium precursor define reaction windows that control cubic-phase purity and particle morphology. In air, limited Li diffusion favors oxycarbonates and pyrochlore, necessitating 950–1050 °C to achieve phase-pure cubic LLZO. Under N2, faster Li availability and diffusion enable uniform nucleation and a route to cubic LLZO without detectable secondary phases. These findings demonstrate the coupled effects of temperature, precursor, dopant, and atmosphere, guiding process optimization and scalable production.
Source: Ceramics
Authors: Chengjian Li, Frank Kern, Lianmeng Liu, Christopher Parr, Andreas Börger, Chunfeng Liu
Institutions: University of Stuttgart, Imerys (France), Imerys (Austria)
Language: English
Subfield: Electrical and Electronic Engineering
Field: Engineering
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $1,930
OpenAlex ID: W4415624577