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

Abstract 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 LiTi_xGe_2‐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 PO₄^3– 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.