Probing the Phase Transition during the Formation of Lithium Lanthanum Zirconium Oxide Solid Electrolyte

Lithium lanthanum zirconium oxide (LLZO) has long been considered as a promising solid electrolyte for all-solid-state lithium (Li) metal batteries because of its interfacial stability when coupled with a Li metal anode. However, the cubic phase of LLZO (c-LLZO) with a higher Li-ion conductivity has a complex atomic structure and is subject to complicated phase transition during its processing and working conditions, which remain largely elusive. Here, we reveal the phase transition process during the formation of c-LLZO nanotubes through detailed microscopic characterization by scanning and transmission electron microscopy as well as X-ray diffraction. We find four typical stages during the formation of c-LLZO along with several intermediate phases including lanthanum (La)-rich cubic lanthanum zirconium oxide (La-rich c-LZO), c-LZO, and La-rich c-LLZO. We also reveal the role of m-Li₂CO₃ and h-Li₂O₂ as the "phase mediator".