A study of perfluorocarboxylate ester solvents for lithium ion battery electrolytes

Tyler M. Fears; Robert L. Sacci; Jeffrey G. Winiarz; Helmut Kaiser; Haskell Taub; Gabriel M. Veith

doi:10.1016/j.jpowsour.2015.08.098

A study of perfluorocarboxylate ester solvents for lithium ion battery electrolytes

Tyler M. Fears, Robert L. Sacci, Jeffrey G. Winiarz, Helmut Kaiser, Haskell Taub, Gabriel M. Veith

Energy Storage & Conversion

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

Several high-purity methyl perfluorocarboxylates were prepared (>99.5% purity by mole) and investigated as potential fluorine-rich electrolyte solvents in Li-ion batteries. The most conductive electrolyte, 0.1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in dimethyl perfluoroglutarate (PF5M₂) (ionic conductivity = 1.87 × 10^-2 mS cm^-1), is investigated in Si thin-film half-cells. The solid-electrolyte-interphase (SEI) formed by the PF5M₂ electrolyte is composed of similar organic and inorganic moieties and at comparable concentrations as those formed by ethylene carbonate/dimethyl carbonate electrolytes containing LiPF₆ and LiTFSI salts. However, the SEI formed by the PF5M₂ electrolyte undergoes reversible electrochemical defluorination, contributing to the reversible capacity of the cell and compensating in part for capacity fade in the Si electrode. While far from ideal these electrolytes provide an opportunity to further develop predictions of suitable fluorinated molecules for use in battery solvents.

Original language	English
Pages (from-to)	434-442
Number of pages	9
Journal	Journal of Power Sources
Volume	299
DOIs	https://doi.org/10.1016/j.jpowsour.2015.08.098
State	Published - Dec 20 2015

Funding

Student support and materials for ester synthesis were provided by the U.S. National Science Foundation under Grant No. DGE-1069091 . Student support for the electrochemical, XPS, and ATR-IR studies performed at Oak Ridge National Laboratory provided by the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program. The SCGSR program is administered by the Oak Ridge Institute for Science and Education for the DOE under contract number DE-AC05-06OR23100 . The equipment, materials and technical guidance at ORNL was supported by the Materials Sciences and Engineering Division, Office of Basic Energy Sciences, U.S. Department of Energy under contract with UT-Battelle, LLC (GMV – XPS, ATR-IR, electrochemical) and the Fluid Interface Reactions, Structures, and Transport (FIRST) Center, an Energy Frontier Research Center funded by the Office of Science, Office of Basic Energy Sciences (RLS – Conductivity, ATR-IR). T.M.F. would also like to thank Dr. C. Sotiriou-Leventis for help in formulating the perfluorocarboxylate ester synthesis.

Funders	Funder number
Office of Science Graduate Student Research
SCGSR
National Science Foundation	DGE-1069091
National Science Foundation
U.S. Department of Energy	DE-AC05-06OR23100
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Workforce Development for Teachers and Scientists
Oak Ridge National Laboratory
Oak Ridge Institute for Science and Education
Division of Materials Sciences and Engineering

Keywords

Fluorinated electrolyte
LiTFSI
SEI
Silicon thin-film

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1016/j.jpowsour.2015.08.098

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title = "A study of perfluorocarboxylate ester solvents for lithium ion battery electrolytes",

abstract = "Several high-purity methyl perfluorocarboxylates were prepared (>99.5% purity by mole) and investigated as potential fluorine-rich electrolyte solvents in Li-ion batteries. The most conductive electrolyte, 0.1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in dimethyl perfluoroglutarate (PF5M2) (ionic conductivity = 1.87 × 10-2 mS cm-1), is investigated in Si thin-film half-cells. The solid-electrolyte-interphase (SEI) formed by the PF5M2 electrolyte is composed of similar organic and inorganic moieties and at comparable concentrations as those formed by ethylene carbonate/dimethyl carbonate electrolytes containing LiPF6 and LiTFSI salts. However, the SEI formed by the PF5M2 electrolyte undergoes reversible electrochemical defluorination, contributing to the reversible capacity of the cell and compensating in part for capacity fade in the Si electrode. While far from ideal these electrolytes provide an opportunity to further develop predictions of suitable fluorinated molecules for use in battery solvents.",

keywords = "Fluorinated electrolyte, LiTFSI, SEI, Silicon thin-film",

author = "Fears, {Tyler M.} and Sacci, {Robert L.} and Winiarz, {Jeffrey G.} and Helmut Kaiser and Haskell Taub and Veith, {Gabriel M.}",

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doi = "10.1016/j.jpowsour.2015.08.098",

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AU - Fears, Tyler M.

AU - Sacci, Robert L.

AU - Winiarz, Jeffrey G.

AU - Kaiser, Helmut

AU - Taub, Haskell

AU - Veith, Gabriel M.

PY - 2015/12/20

Y1 - 2015/12/20

N2 - Several high-purity methyl perfluorocarboxylates were prepared (>99.5% purity by mole) and investigated as potential fluorine-rich electrolyte solvents in Li-ion batteries. The most conductive electrolyte, 0.1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in dimethyl perfluoroglutarate (PF5M2) (ionic conductivity = 1.87 × 10-2 mS cm-1), is investigated in Si thin-film half-cells. The solid-electrolyte-interphase (SEI) formed by the PF5M2 electrolyte is composed of similar organic and inorganic moieties and at comparable concentrations as those formed by ethylene carbonate/dimethyl carbonate electrolytes containing LiPF6 and LiTFSI salts. However, the SEI formed by the PF5M2 electrolyte undergoes reversible electrochemical defluorination, contributing to the reversible capacity of the cell and compensating in part for capacity fade in the Si electrode. While far from ideal these electrolytes provide an opportunity to further develop predictions of suitable fluorinated molecules for use in battery solvents.

AB - Several high-purity methyl perfluorocarboxylates were prepared (>99.5% purity by mole) and investigated as potential fluorine-rich electrolyte solvents in Li-ion batteries. The most conductive electrolyte, 0.1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in dimethyl perfluoroglutarate (PF5M2) (ionic conductivity = 1.87 × 10-2 mS cm-1), is investigated in Si thin-film half-cells. The solid-electrolyte-interphase (SEI) formed by the PF5M2 electrolyte is composed of similar organic and inorganic moieties and at comparable concentrations as those formed by ethylene carbonate/dimethyl carbonate electrolytes containing LiPF6 and LiTFSI salts. However, the SEI formed by the PF5M2 electrolyte undergoes reversible electrochemical defluorination, contributing to the reversible capacity of the cell and compensating in part for capacity fade in the Si electrode. While far from ideal these electrolytes provide an opportunity to further develop predictions of suitable fluorinated molecules for use in battery solvents.

KW - Fluorinated electrolyte

KW - LiTFSI

KW - SEI

KW - Silicon thin-film

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JO - Journal of Power Sources

JF - Journal of Power Sources

ER -

A study of perfluorocarboxylate ester solvents for lithium ion battery electrolytes

Abstract

Funding

Keywords

UN SDGs

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