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

Abstract

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.

Authors:
ORCiD logo; ; ; ; ORCiD logo
Publication Date:
Research Org.:
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 Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1558746
Alternate Identifier(s):
OSTI ID: 1767501
Grant/Contract Number:  
SC0001160; NA0003525; NSF-1751553; DMR-1832808
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Name: Journal of the Electrochemical Society Journal Volume: 167 Journal Issue: 1; Journal ID: ISSN 0013-4651
Publisher:
IOP Publishing - The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; bio-inspired; energy storage (including batteries and capacitors); defects; charge transport; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats

Harris, Oliver C., Lin, Yuxiao, Qi, Yue, Leung, Kevin, and Tang, Maureen H. How Transition Metals Enable Electron Transfer through the SEI: Part I. Experiments and Butler-Volmer Modeling. United States: N. p., 2019. Web. https://doi.org/10.1149/2.0022001JES.
Harris, Oliver C., Lin, Yuxiao, Qi, Yue, Leung, Kevin, & Tang, Maureen H. How Transition Metals Enable Electron Transfer through the SEI: Part I. Experiments and Butler-Volmer Modeling. United States. https://doi.org/10.1149/2.0022001JES
Harris, Oliver C., Lin, Yuxiao, Qi, Yue, Leung, Kevin, and Tang, Maureen H. Mon . "How Transition Metals Enable Electron Transfer through the SEI: Part I. Experiments and Butler-Volmer Modeling". United States. https://doi.org/10.1149/2.0022001JES.
@article{osti_1558746,
title = {How Transition Metals Enable Electron Transfer through the SEI: Part I. Experiments and Butler-Volmer Modeling},
author = {Harris, Oliver C. and Lin, Yuxiao and Qi, Yue and Leung, Kevin and Tang, Maureen H.},
abstractNote = {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.},
doi = {10.1149/2.0022001JES},
journal = {Journal of the Electrochemical Society},
number = 1,
volume = 167,
place = {United States},
year = {2019},
month = {8}
}

Journal Article:
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https://doi.org/10.1149/2.0022001JES

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    Works referencing / citing this record:

    How Transition Metals Enable Electron Transfer through the SEI: Part II. Redox-Cycling Mechanism Model and Experiment
    journal, August 2019

    • Harris, Oliver C.; Leung, Kevin; Tang, Maureen H.
    • Journal of The Electrochemical Society, Vol. 167, Issue 1
    • DOI: 10.1149/2.0032001jes