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Title: Solvent oligomerization pathways facilitated by electrolyte additives during solid-electrolyte interphase formation

Abstract

The solid–electrolyte interphase (SEI) layer formation is known to play an important role in determining the lifetime of lithium-ion batteries. A thin, stable SEI layer is linked to overall improved battery performance and longevity, however, the factors and mechanisms that lead to optimal SEI morphology and composition are not well understood. Inclusion of electrolyte additives (fluoroethylene carbonate, FEC; and vinylene carbonate, VC) is often necessary for improving SEI characteristics. To understand how these electrolyte additives impact SEI formation, we employed molecular dynamics (MD) and density functional theory (DFT) simulations to study the reaction networks and oligomerization pathways, respectively, for three systems containing ethylene carbonate (EC), a lithium ion, and FEC or VC. MD simulations suggest radical oligomerization pathways analogous to traditional oligomerization with nucleophilic alkoxide species via SN1 reaction mechanisms. Both SN1 and SN2 mechanisms were studied for all three systems using DFT. Oligomerization reactions were studied with both a standard alkoxide species and a ring-opened EC radical as the nucleophiles and EC, FEC, and VC as the electrophiles. For all cases, FEC and VC exhibited lower free energy barriers and more stable adducts when compared with EC. We conclude that one of the role of additives is to modifymore » the oligomerization process of EC by introducing branching points (FEC) or termination points (VC).« less

Authors:
ORCiD logo [1]; ORCiD logo [2]
+ Show Author Affiliations
  1. Univ. of Washington, Seattle, WA (United States)
  2. Univ. of Washington, Seattle, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1776852
Alternate Identifier(s):
OSTI ID: 1664493
Grant/Contract Number:  
SC0019483; DGE-1633216
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 22; Journal Issue: 37; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; solid-electrolyte interphase; molecular simulation

Citation Formats

Gibson, Luke D., and Pfaendtner, Jim. Solvent oligomerization pathways facilitated by electrolyte additives during solid-electrolyte interphase formation. United States: N. p., 2020. Web. doi:10.1039/d0cp03286g.
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Gibson, Luke D., & Pfaendtner, Jim. Solvent oligomerization pathways facilitated by electrolyte additives during solid-electrolyte interphase formation. United States. https://doi.org/10.1039/d0cp03286g
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Gibson, Luke D., and Pfaendtner, Jim. Tue . "Solvent oligomerization pathways facilitated by electrolyte additives during solid-electrolyte interphase formation". United States. https://doi.org/10.1039/d0cp03286g. https://www.osti.gov/servlets/purl/1776852.
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@article{osti_1776852,
title = {Solvent oligomerization pathways facilitated by electrolyte additives during solid-electrolyte interphase formation},
author = {Gibson, Luke D. and Pfaendtner, Jim},
abstractNote = {The solid–electrolyte interphase (SEI) layer formation is known to play an important role in determining the lifetime of lithium-ion batteries. A thin, stable SEI layer is linked to overall improved battery performance and longevity, however, the factors and mechanisms that lead to optimal SEI morphology and composition are not well understood. Inclusion of electrolyte additives (fluoroethylene carbonate, FEC; and vinylene carbonate, VC) is often necessary for improving SEI characteristics. To understand how these electrolyte additives impact SEI formation, we employed molecular dynamics (MD) and density functional theory (DFT) simulations to study the reaction networks and oligomerization pathways, respectively, for three systems containing ethylene carbonate (EC), a lithium ion, and FEC or VC. MD simulations suggest radical oligomerization pathways analogous to traditional oligomerization with nucleophilic alkoxide species via SN1 reaction mechanisms. Both SN1 and SN2 mechanisms were studied for all three systems using DFT. Oligomerization reactions were studied with both a standard alkoxide species and a ring-opened EC radical as the nucleophiles and EC, FEC, and VC as the electrophiles. For all cases, FEC and VC exhibited lower free energy barriers and more stable adducts when compared with EC. We conclude that one of the role of additives is to modify the oligomerization process of EC by introducing branching points (FEC) or termination points (VC).},
doi = {10.1039/d0cp03286g},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 37,
volume = 22,
place = {United States},
year = {Tue Sep 01 00:00:00 EDT 2020},
month = {Tue Sep 01 00:00:00 EDT 2020}
}
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