skip to main content


Title: A study of suppressed formation of low-conductivity phases in doped Li7La3Zr2O12 garnets by in situ neutron diffraction

Doped Li7La3Zr2O12 garnets, oxide-based solids with good Li+ conductivity and compatibility, show great potential as leading electrolyte material candidates for all-solid-state lithium ion batteries. Still yet, the conductive bulk usually suffers from the presence of secondary phases and the transition towards a low-conductivity tetragonal phase during synthesis. Dopants are designed to stabilize the high-conductive cubic phase and suppress the formation of the low-conductivity phases. In situ neutron diffraction enables a direct observation of the doping effects by monitoring the phase evolutions during garnet synthesis. It reveals the reaction mechanism involving the temporary presence of intermediate phases. The off-stoichiometry due to the liquid Li2CO3 evaporation leads to the residual of the low-conductivity intermediate phase in the as-synthesized bulk. Appropriate doping of an active element may alter the component of the intermediate phases and promote the completion of the reaction. While the dopants aid to stabilize most of the cubic phase, a small amount of tetragonal phase tends to form under a diffusion process. Lastly, the in situ observations provide the guideline of process optimization to suppress the formation of unwanted low-conductivity phases.
 [1] ;  [2] ;  [3] ;  [2] ;  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Quantum Condensed Matter Division
Publication Date:
OSTI Identifier:
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 3; Journal Issue: 45; Journal ID: ISSN 2050-7488
Research Org:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); High Flux Isotope Reactor (HFIR); Spallation Neutron Source
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States