Localized high concentration electrolytes decomposition under electron-rich environments

Zheng, Yu; Balbuena, Perla B.

doi:10.1063/5.0042896

Localized high concentration electrolytes decomposition under electron-rich environments

Journal Article · Mon Mar 08 00:00:00 EST 2021 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0042896· OSTI ID:1838936

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Texas A & M Univ., College Station, TX (United States); Texas A&M University
Texas A & M Univ., College Station, TX (United States)

Localized high concentration electrolytes have been proposed as an effective route to construct stable solid–electrolyte interphase (SEI) layers near Li-metal anodes. However, there is still a limited understanding of decomposition mechanisms of electrolyte components during SEI formation. In this work, we investigate reactivities of lithium bis(fluorosulfonyl)imide (LiFSI, salt), 1,2-dimethoxyethane (DME, solvent) and tris(2,2,2-trifluoroethyl)orthoformate (TFEO, diluent) species in DME+TFEO mixed solvents and 1M LiFSI/DME/TFEO solutions. By supplying excess of electrons into the simulation cell, LiFSI is initially reduced via a 4-electron charge transferring reaction yielding F^- and N(SO₂)₂^3-. The local solvation environment has little effect on the subsequent TFEO reaction, which typically requires 6 |e| to decompose into F^-, HCOO^-, CH2CF and ^-OCH₂CF₃. Besides, TFEO dehydrogenation reaction mechanism under the attack of anions is also identified. Unlike salt and diluent, DME shows good stability with any excess of electrons. Here, the energetics of most relevant reactions are characterized. Most reactions are thermodynamically favorable with low activation barriers.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: EE0008210

OSTI ID:: 1838936

Alternate ID(s):: OSTI ID: 1769530

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 10 Vol. 154; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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