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DOE OSTI · 3021265

Decoupling Failure Pathways in Li-O 2 Cells Operated Under Lean Electrolyte Conditions

Córdoba, Daniel [Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of Buenos Aires (Argentina)] (ORCID:0000000168239972)·Li, Matthew [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000190933207)·Huang, Xiaozhou [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000276600382)·Gao, Yanan [Argonne National Laboratory (ANL), Argonne, IL (United States); National Institute for Materials Science (NIMS), Tsukuba (Japan)] (ORCID:0000000302176512)·Matsuda, Shoichi [Argonne National Laboratory (ANL), Argonne, IL (United States); National Institute for Materials Science (NIMS), Tsukuba (Japan)] (ORCID:0000000206403404)·Calvo, Ernesto Julio [Univ. of Buenos Aires (Argentina)] (ORCID:0000000303972406)·Amine, Khalil [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000192063719)
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Abstract

The operation of lithium-oxygen (Li-O 2 ) batteries under lean electrolyte conditions offers higher energy density but leads to rapid degradation and short cycle life. Although cathode passivation and electrolyte decomposition occur in all regimes, we show that under lean electrolyte conditions, failure is primarily driven by progressive electrolyte consumption at the lithium/solid electrolyte interphase (SEI), rather than by irreversible cathode passivation. Poor wetting of the lithium surface results in heterogeneous SEI growth and high local current densities, which accelerate electrolyte loss and cell failure. Strategies aimed at improving interfacial stability, including optimized wetting and SEI forming additives, significantly extend cycle life without compromising energy density. Our results establish anode-electrolyte interactions as the dominant degradation mechanism under lean electrolyte conditions, and emphasize the need to engineer a stable Li/SEI interface for long-lasting Li-O 2 batteries.

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Córdoba, Daniel [Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of Buenos Aires (Argentina)] (ORCID:0000000168239972), Li, Matthew [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000190933207), Huang, Xiaozhou [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000276600382), Gao, Yanan [Argonne National Laboratory (ANL), Argonne, IL (United States); National Institute for Materials Science (NIMS), Tsukuba (Japan)] (ORCID:0000000302176512), Matsuda, Shoichi [Argonne National Laboratory (ANL), Argonne, IL (United States); National Institute for Materials Science (NIMS), Tsukuba (Japan)] (ORCID:0000000206403404), Calvo, Ernesto Julio [Univ. of Buenos Aires (Argentina)] (ORCID:0000000303972406), Amine, Khalil [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000192063719). 2025-11-21. Decoupling Failure Pathways in Li-O 2 Cells Operated Under Lean Electrolyte Conditions. https://doi.org/10.1149/1945-7111/ae1ea5

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