Li+/H+ exchange in solid-state oxide Li-ion conductors
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arXiv
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| Main Authors: | , , , |
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| Format: | Preprint |
| Published: |
2025
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| _version_ | 1866915714889154560 |
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| author | Li, Zhuohan Lam, Benjamin X. Wang, Shilong Ceder, Gerbrand |
| author_facet | Li, Zhuohan Lam, Benjamin X. Wang, Shilong Ceder, Gerbrand |
| contents | Understanding the moisture stability of oxide Li-ion conductors is important for their practical applications in solid-state batteries. Unlike sulfide or halide conductors, oxide conductors generally better resist degradation when in contact with water, but can still undergo topotactic \ch{Li+}/\ch{H+} exchange (LHX). Here, we combine density functional theory (DFT) calculations with a machine-learning interatomic potential model to investigate the thermodynamic driving force of the LHX reaction for two representative oxide Li-ion conductor families: garnets and NASICONs. Li-stuffed garnets exhibit a strong driving force for proton exchange due to their high Li chemical potential. In contrast, NASICONs demonstrate a higher resistance against proton exchange due to the lower Li chemical potential and the lower O-H bond covalency for polyanion-bonded oxygens. Our findings reveal a critical trade-off: Li stuffing enhances conductivity but increases moisture susceptibility. This study underscores the importance of designing Li-ion conductors that possess both high conductivity and high stability in practical environments. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2509_13477 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Li+/H+ exchange in solid-state oxide Li-ion conductors Li, Zhuohan Lam, Benjamin X. Wang, Shilong Ceder, Gerbrand Materials Science Understanding the moisture stability of oxide Li-ion conductors is important for their practical applications in solid-state batteries. Unlike sulfide or halide conductors, oxide conductors generally better resist degradation when in contact with water, but can still undergo topotactic \ch{Li+}/\ch{H+} exchange (LHX). Here, we combine density functional theory (DFT) calculations with a machine-learning interatomic potential model to investigate the thermodynamic driving force of the LHX reaction for two representative oxide Li-ion conductor families: garnets and NASICONs. Li-stuffed garnets exhibit a strong driving force for proton exchange due to their high Li chemical potential. In contrast, NASICONs demonstrate a higher resistance against proton exchange due to the lower Li chemical potential and the lower O-H bond covalency for polyanion-bonded oxygens. Our findings reveal a critical trade-off: Li stuffing enhances conductivity but increases moisture susceptibility. This study underscores the importance of designing Li-ion conductors that possess both high conductivity and high stability in practical environments. |
| title | Li+/H+ exchange in solid-state oxide Li-ion conductors |
| topic | Materials Science |
| url | https://arxiv.org/abs/2509.13477 |