Degradation Mechanism of Phosphate‐Based Li‐NASICON Conductors in Alkaline Environment

NASICON‐type Li conductors (Li‐NASICON) have traditionally been regarded as promising candidates for solid‐state Li‐air battery applications because of their stability in water and ambient air. However, the presence of water in the cathode of a Li‐air battery can induce a highly alkaline environment by modifying the discharge product from Li2O2 to LiOH which can potentially degrade cathode and separator materials. This study investigates the alkaline stability of common Li‐NASICON chemistries through a systematic experimental study of LiTixGe2‐x(PO4)3 (LTGP) with varying x = 0–2.0. Density functional theory calculations are combined to gain a mechanistic understanding of the alkaline instability. It is demonstrated that the instability of LTGP in an alkaline environment is mainly driven by the dissolution of PO43– groups, which subsequently precipitate as Li3PO4. The introduction of Ti facilitates the formation of a Ti‐rich compound on the surface that eventually passivates the material, but only after significant bulk degradation. Consequently, phosphate‐based Li‐NASICON materials exhibit limited alkaline stability, raising concerns about their viability in humid Li‐air batteries.