Electrochemical Activation of LiGaO₂: Implications for Ga-Doped Garnet Solid Electrolytes in Li-Metal Batteries

Ga-doped Li₇La₃Zr₂O₁₂ garnet solid electrolytes exhibit the highest Li-ion conductivities among the oxide-type garnet-structured solid electrolytes, but instabilities toward Li metal hamper their practical application. The instabilities have been assigned to direct chemical reactions between LiGaO₂ coexisting phases and Li metal by several groups previously. Yet, the understanding of the role of LiGaO₂ in the electrochemical cell and its electrochemical properties is still lacking. Here, we are investigating the electrochemical properties of LiGaO₂ through electrochemical tests in galvanostatic cells versus Li metal and complementary ex situ studies via confocal Raman microscopy, quantitative phase analysis based on powder X-ray diffraction, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and electron energy loss spectroscopy. The results demonstrate considerable and surprising electrochemical activity, with high reversibility. A three-stage reaction mechanism is derived, including reversible electrochemical reactions that lead to the formation of highly electronically conducting products. The results have considerable implications for the use of Ga-doped Li₇La₃Zr₂O₁₂ electrolytes in all-solid-state Li-metal battery applications and raise the need for advanced materials engineering to realize Ga-doped Li₇La₃Zr₂O₁₂for practical use.