Li-NASICON solid-state superionic conductors have traditionally been regarded as promising candidates for Li-air applications because of their stability in ambient air and water [1], [2]. However, the presence of water in the cathode can change the discharge product from Li2O2 to LiOH [3], [4], inducing a highly alkaline environment which may degrade cathode and separator materials. Here, we investigate the impact of octahedral substitution on the alkaline stability of common Li-NASICON chemistries through a systematic experimental case study of LiTixGe2-x(PO4)3 (LTGP) with varying x = 0 - 2.0. Density functional theory calculations are combined to gain mechanistic understandings of the alkaline instability. We demonstrated that the alkaline instability of LTGP is mainly driven by the dissolution of PO4 polyanion 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 of their viability in humid Li-air batteries.[1] N. Imanishi, S. Hasegawa, T. Zhang, A. Hirano, Y. Takeda, and O. Yamamoto, “Lithium anode for lithium-air secondary batteries,” Journal of Power Sources, vol. 185, no. 2, pp. 1392–1397, Dec. 2008, doi: 10.1016/j.jpowsour.2008.07.080.[2] R. Chen, Q. Li, X. Yu, L. Chen, and H. Li, “Approaching Practically Accessible Solid-State Batteries: Stability Issues Related to Solid Electrolytes and Interfaces,” Chem. Rev., vol. 120, no. 14, pp. 6820–6877, Jul. 2020, doi: 10.1021/acs.chemrev.9b00268.[3] S. Ma, J. Wang, J. Huang, Z. Zhou, and Z. Peng, “Unveiling the Complex Effects of H2O on Discharge–Recharge Behaviors of Aprotic Lithium–O2 Batteries,” J. Phys. Chem. Lett., vol. 9, no. 12, pp. 3333–3339, Jun. 2018, doi: 10.1021/acs.jpclett.8b01333.[4] T. Liu et al., “Cycling Li-O2 batteries via LiOH formation and decomposition,” Science, vol. 350, no. 6260, pp. 530–533, Oct. 2015, doi: 10.1126/science.aac7730.
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