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

Lam, Benjamin X.; Li, Zhuohan; Mishra, Tara P.; Ceder, Gerbrand

doi:10.1002/aenm.202403596

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

Journal Article · Mon Nov 11 00:00:00 EST 2024 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.202403596· OSTI ID:2481712

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University of California, Berkeley, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2481712

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 11 Vol. 15; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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