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Title: How Transition Metals Enable Electron Transfer through the SEI: Part I. Experiments and Butler-Volmer Modeling

Journal Article · · Journal of the Electrochemical Society
DOI:https://doi.org/10.1149/2.0022001JES· OSTI ID:1558746
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Transition metal dissolution from high-voltage Li-ion battery cathodes disrupts the formation and performance of the solid-electrolyte interphase (SEI). SEI contamination by transition metals results in continual Li loss and severe capacity fade. Fundamental understanding of how metals undermine SEI passivation is necessary to mitigate this degradation. This two-part study interrogates the mechanisms by which transition metals facilitate through-film charge-transfer and SEI failure. Part I presents experimental results in which we intentionally contaminate SEIs with Mn, Ni, and Co. Rotating disk electrode voltammetry of a redox mediator quantifies how each metal impacts the charge-transfer characteristics of the SEI. A physics-based model finds that all three metals disrupt the electronic properties of the SEI more than the morphology. Surprisingly, the Butler-Volmer kinetics of charge-transfer through a Mn-contaminated SEI are an order of magnitude faster than for a Co-contaminated SEI, even with similar embedded metal concentrations. Such trends between metals are inconsistent with bandgap predictions from density functional theory, implying an alternative redox-cycling mechanism, which is mathematically developed and compared to experiment in Part II.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Univ. of Maryland, College Park, MD (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
SC0001160; NA0003525; NSF-1751553; DMR-1832808
OSTI ID:
1558746
Alternate ID(s):
OSTI ID: 1767501
Journal Information:
Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Vol. 167 Journal Issue: 1; ISSN 0013-4651
Publisher:
IOP Publishing - The Electrochemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science

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