Dual-Doped Cubic Garnet Solid Electrolytes with Superior Air Stability

Li₇La₃Zr₂O₁₂ (LLZO) garnet is one kind of solid electrolyte drawing extensive attention due to its good ionic conductivity, safety, and stability toward lithium metal anodes. However, the stability problem during synthesis and storage results in high interfacial resistance and prevents it from practical applications. We synthesized air-stable dual-doped Li_6.05La₃Ga_0.3Zr_1.95Nb_0.05O₁₂ ((Ga, Nb)-LLZO) cubic-phase garnets with ionic conductivity of 9.28 × 10^-3 S cm^-1. The impurity-phase species formation on the garnet pellets after air exposure was investigated. LiOH and Li₂CO₃ can be observed on the garnet pellets by Raman spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) once the garnets are exposed to humid air or come in contact with water. The (Ga, Nb)-LLZO garnet is found to form less LiOH and Li₂CO₃, which can be further reduced or removed after drying treatment. To confirm the stability of the garnet, an electrochemical test of the Li//Li symmetric cell was also performed in comparison with previously reported garnets (Li₇La_2.75Ca_0.25Zr_1.75Nb_0.25O₁₂, (Ca, Nb)-LLZO). The dual-doped (Ga, Nb)-LLZO showed less polarized and stable plating/stripping behavior than (Ca, Nb)-LLZO. Through Rietveld refinement of XRD patterns of prepared materials, dopant Ga was found to preferably occupy the Li site and Nb takes the Zr site, while dopant Ca mainly substituted La in the reference sample. The inherited properties of the dopants in (Ga, Nb)-LLZO and their structural synergy explain the greatly improved air stability and reduced interfacial resistance. This may open a new direction to realize garnet-based solid electrolytes with lower interfacial resistance and superior air stability.