Understanding the Surface Regeneration and Reactivity of Garnet Solid-State Electrolytes

Garnet solid-electrolyte-based Li-metal batteries can be used in energy storage devices with high energy densities and thermal stability. However, the tendency of garnets to form lithium hydroxide and carbonate on the surface in an ambient atmosphere poses significant processing challenges. In this work, the decomposition of surface layers under various gas environments is studied by using two surface-sensitive techniques, near-ambient-pressure X-ray photoelectron spectroscopy and grazing incidence X-ray diffraction. It is found that heating to 500 °C under an oxygen atmosphere (of 1 mbar and above) leads to a clean garnet surface, whereas low oxygen partial pressures (i.e., in argon or vacuum) lead to additional graphitic carbon deposits. The clean surface of garnets reacts directly with moisture and carbon dioxide below 400 and 500 °C, respectively. This suggests that additional CO₂ concentration controls are needed for the handling of garnets. By heating under O₂ along with avoiding H₂O and CO₂, symmetric cells with less than 10 Ωcm² interface resistance are prepared without the use of any interlayers; plating currents of >1 mA cm^-2 without dendrite initiation are demonstrated.