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How Transition Metals Enable Electron Transfer through the SEI: Part II. Redox-Cycling Mechanism Model and Experiment
Journal article   Open access

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

Oliver C. Harris, Kevin Leung, Maureen H. Tang and Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Journal of the Electrochemical Society, v 167(1), p13503
26 Aug 2019
url
https://doi.org/10.1149/2.0032001jesView
Published, Version of Record (VoR)Maybe Open Access (Publisher Bronze) Open
url
https://doi.org/10.1149/2.0032001JESView
Published, Version of Record (VoR) Open

Abstract

Electrochemistry Materials Science Materials Science, Coatings & Films Physical Sciences Science & Technology Technology
At high operating voltages, metals like Mn, Ni, and Co dissolve from Li-ion cathodes, deposit at the anode, and interfere with the performance of the solid-electrolyte interphase (SEI) to cause constant Li loss. The mechanism by which these metals disrupt SEI processes at the anode remains poorly understood. Experiments from Part I of this work demonstrate that Mn, Ni, and Co all affect the electronic properties of the SEI much more than the morphology, and that Mn is the most aggressively disruptive of the three metals. In this work we determine how a proposed electrocatalytic mechanism can explain why Mn contamination is uniquely detrimental to SEI passivation. We develop a microkinetic model of the redox cycling mechanism and apply it to experiments from Part I. The results show that the thermodynamicmetal reduction potential does not explain why Mn is the most active of the three metals. Instead, kinetic differences between the three metals are more likely to govern their reactivity in the SEI. Our results emphasize the importance of local coordination environment and proximity to the anode within the SEI for controlling electron transfer and resulting capacity fade. (C) The Author(s) 2019. Published by ECS.

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Collaboration types
Domestic collaboration
Web of Science research areas
Electrochemistry
Materials Science, Coatings & Films
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