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Title: Elucidating electrolyte decomposition under electron-rich environments at the lithium-metal anode

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/c7cp06485c· OSTI ID:1430638
ORCiD logo [1]; ORCiD logo [2]
  1. Texas A & M Univ., College Station, TX (United States). Department of Chemical Engineering
  2. Texas A & M Univ., College Station, TX (United States). Department of Chemical Engineering, Department of Materials Science and Engineering, and Department of Chemistry
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The lithium metal anode is one of the key components of the lithium–sulfur (Li–S) batteries, which are considered one of the most promising candidates for the next generation of battery systems. However, one of the main challenges that have prevented Li-metal anodes from becoming feasible to be used in commercial batteries is the continuous decomposition of the electrolyte due to its high reactivity, which leads to the formation of solid–electrolyte interphase (SEI) layers. The properties of the SEI can dramatically affect the performance of the batteries. Thus, a rigorous understanding of the electrolyte decomposition is crucial to elucidate improvements in performance of the Li–S technology. Here, in this work, using density functional theory (DFT) and ab initio molecular dynamics simulations (AIMD), we investigate the effect of electron-rich environments on the decomposition mechanism of electrolyte species in pure 1,2-dimethoxyethane (DME) solvent and 1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI) salt solutions. It is found that systems with pure DME require an average environment of at least ~0.9 |e| per molecule for a DME to decompose into CH3O- and C2H42-via a 4-electron transfer. In the case of mixtures, the salts are very prone to react with any excess of electrons. In addition, DME dehydrogenation due to reactions with fragments coming from the salt decompositions was detected. Formation of oligomer anionic species from DME and salt fragments were also identified from the AIMD simulations. Finally, the thermodynamics and kinetics of the most relevant electrolyte decomposition reactions were characterized. DME decomposition reactions predicted from the AIMD simulations were found to be thermodynamically favorable under exposure to Li atoms and/or by reactions with salt fragments. Lastly, in most cases, these reactions were shown to have low to moderate activation barriers.

Research Organization:
Texas A&M, College Station, TX (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office. Batteries for Advanced Transportation Technologies (BATT) Program
Grant/Contract Number:
EE0007766
OSTI ID:
1430638
Alternate ID(s):
OSTI ID: 1868487
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Vol. 19, Issue 45; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 53 works
Citation information provided by
Web of Science

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Cited By (4)

Anode Interface Engineering and Architecture Design for High‐Performance Lithium–Sulfur Batteries journal January 2019
Multifunctional Silanization Interface for High‐Energy and Low‐Gassing Lithium Metal Pouch Cells journal December 2019
Localized high concentration electrolyte behavior near a lithium–metal anode surface journal January 2019
First-principles study on thermodynamic stability of the hybrid interfacial structure of LiMn 2 O 4 cathode and carbonate electrolyte in Li-ion batteries journal January 2018

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