Effects of High and Low Salt Concentration in Electrolytes at Lithium–Metal Anode Surfaces

Camacho-Forero, Luis E.; Smith, Taylor W.; Balbuena, Perla B.

doi:10.1021/acs.jpcc.6b10774

Effects of High and Low Salt Concentration in Electrolytes at Lithium–Metal Anode Surfaces

Journal Article · Thu Dec 15 23:00:00 EST 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b10774· OSTI ID:1430634

Camacho-Forero, Luis E. ^[1]; Smith, Taylor W. ^[2]; ^[3]

Texas A & M Univ., College Station, TX (United States). Department of Chemical Engineering; Texas A&M University
Texas A & M Univ., College Station, TX (United States). Department of Chemical Engineering and Department of Materials Science and Engineering
Texas A & M Univ., College Station, TX (United States). Department of Chemical Engineering, Department of Materials Science and Engineering and Department of Chemistry

The use of high concentration salts in electrolyte solutions of lithium-sulfur (Li-S) batteries has been shown beneficial for mitigating some effects such as polysulfide shuttle and dendrite growth at the Li metal anode. Such complex solutions have structural, dynamical, and reactivity associated issues that need to be analyzed for a better understanding of the reasons behind such beneficial effects. A passivation interfacial layer known as solid-electrolyte interphase (SEI) is generated during battery cycling as a result of electron transfer from the metal anode causing electrolyte decomposition. Here in this work, we investigate using density functional theory and ab initio molecular dynamics simulations the salt decomposition, solvation effects, interactions among intermediate products and other species, and potential components of the SEI layer as a function of chemical nature and concentration of the salt, for lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI) at 1M and 4M concentrations in dimethoxyethane. It is found that LiTFSI undergoes a less complete reduction and facilitates charge transfer from the anode, whereas LiFSI shows a more complete decomposition forming LiF as one of the main SEI products. In addition, the specific decomposition mechanisms of each salt clearly point to the initial SEI components and the potential main products derived from them. Finally, very complex networks are found among the salt and solvent molecules in their attempt to maximize Li ion solvation that is quantified through the determination of coordination numbers.

View Accepted Manuscript (DOE)

Research Organization:: Texas A&M Engineering Experiment Station, College Station, TX (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

Grant/Contract Number:: EE0006832

OSTI ID:: 1430634

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 1 Vol. 121; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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