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Fluoroethylene Carbonate and Vinylene Carbonate Reduction: Understanding Lithium-Ion Battery Electrolyte Additives and Solid Electrolyte Interphase Formation

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Michan, Alison L., Parimalam, Bharathy. S., Leskes, Michal, Kerber, Rachel N., Yoon, Taeho, Grey, Clare P., Lucht, Brett L.·2016·Chemistry of Materials
DOI 10.1021/acs.chemmater.6b02282
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Abstract

We have synthesized the products of fluoroethylene carbonate (FEC) and vinylene carbonate (VC) via lithium naphthalenide reduction. By analyzing the resulting solid precipitates and gas evolution, our results confirm that both FEC and VC decomposition products include HCO 2 Li, Li 2 C 2 O 4, Li 2 CO 3, and polymerized VC. For FEC, our experimental data supports a reduction mechanism where FEC reduces to form VC and LiF, followed by subsequent VC reduction. In the FEC reduction product, HCO 2 Li, Li 2 C 2 O 4, and Li 2 CO 3 were found in smaller quantities than in the VC reduction product, with no additional fluorine environments being detected by solid-state nuclear magnetic resonance or X-ray photoelectron spectroscopy analysis. With these additives being practically used in higher (FEC) and lower (VC) concentrations in the base electrolytes of lithium-ion batteries, our results suggest that the different relative ratios of the inorganic and organic reduction products formed by their decomposition may be relevant to the chemical composition and morphology of the solid electrolyte interphase formed in their presence.

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  • FEC is a widely used and extensively studied additive in LIB and LMA systems because it can participate in SEI formation due to its higher reduction potential compared to nonfluorinated carbonates, enhancing its capability to form a LiF-rich SEI that protects graphite and LMA and improves cycling stability and capacity retention at room temperature.

    “FEC is a widely used and extensively studied additive in LIB and LMA systems, as it can participate in SEI formation due to its higher reduction potential compared to nonfluorinated carbonates, enhancing its capability in forming a LiF-rich SEI to protect graphite and LMA, which in turn improves the cycling stability and capacity retention at RT [123,124].”

    From Review on Low-Temperature Electrolytes for Lithium-Ion and Lithium Metal Batteries (2023) · cites this paper as [123]

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Cited by

Sorted by citations

Authors
Michan, A. L., Parimalam, B. S., Leskes, M., Kerber, R. N., Yoon, T., Grey, C. P., & Lucht, B. L.
Affiliations
  • University of Cambridge (GB)
  • University of Rhode Island (US)
Corresponding author
Lucht, Brett L.
ORCID
Venue
Chemistry of Materials
Publisher
American Chemical Society (ACS)
Published
2016-11-03
Volume
28
Issue
22
Pages
8149-8159
ISSN
  • 0897-4756 (ISSN-L)
  • 1520-5002
DOI
10.1021/acs.chemmater.6b02282
OpenAlex
W2537935631
Cited by
541
References
5
Citations by year
2026: 57 · 2025: 76 · 2024: 67 · 2023: 54 · 2022: 58 · 2021: 65 · 2020: 45 · 2019: 56 · 2018: 37 · 2017: 25
FWCI
18.14
Type
journal article
Language
en
Open access
Locations
  • Chemistry of Materials (publishedVersion)
  • OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
  • Journal of Media Literacy Education (submittedVersion, cc-by)
  • Apollo (University of Cambridge) (submittedVersion)
  • Apollo
Funders
  • Weizmann Institute of Science
  • Vehicle Technologies Program (DE-AC02-05CH11231)
  • U.S. Department of Energy (DE-SC0007074)
  • Directorate-General for Research and Innovation
Topics
  • Physical Sciences › Engineering › Electrical and Electronic Engineering › Advancements in Battery Materials
  • Physical Sciences › Engineering › Electrical and Electronic Engineering › Advanced Battery Materials and Technologies
  • Physical Sciences › Engineering › Automotive Engineering › Advanced Battery Technologies Research
Keywords
fluoroethylene carbonate, vinylene carbonate, electrolyte additives, lithium-ion batteries, solid electrolyte interphase, electrolyte decomposition, lithium oxalate, lithium carbonate, reduction mechanism

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