Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: A study of perfluorocarboxylate ester solvents for lithium ion battery electrolytes

Abstract

We prepared several high-purity methyl perfluorocarboxylates (>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-electrolyteinterphase (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. But, 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. These electrolytes, though far from ideal, provide an opportunity to further develop predictions of suitable fluorinated molecules for use in battery solvents.

Authors:
 [1];  [2];  [3];  [4];  [4];  [2]
+ Show Author Affiliations
  1. Missouri Univ. of Science and Technology, Rolla, MO (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Missouri Univ. of Science and Technology, Rolla, MO (United States)
  4. Univ. of Missouri, Columbia, MO (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1265852
Alternate Identifier(s):
OSTI ID: 1253198
Grant/Contract Number:  
AC05-00OR22725; DGE-1069091; AC05-06OR23100
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Power Sources
Additional Journal Information:
Journal Volume: 299; Journal Issue: C; Journal ID: ISSN 0378-7753
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; SEI; LiTFSI; silicon thin-film; fluorinated electrolyte

Citation Formats

Fears, Tyler M., Sacci, Robert L., Winiarz, Jeffrey G., Kaiser, Helmut, Taub, Haskell, and Veith, Gabriel M. A study of perfluorocarboxylate ester solvents for lithium ion battery electrolytes. United States: N. p., 2015. Web. doi:10.1016/j.jpowsour.2015.08.098.
Copy to clipboard
Fears, Tyler M., Sacci, Robert L., Winiarz, Jeffrey G., Kaiser, Helmut, Taub, Haskell, & Veith, Gabriel M. A study of perfluorocarboxylate ester solvents for lithium ion battery electrolytes. United States. https://doi.org/10.1016/j.jpowsour.2015.08.098
Copy to clipboard
Fears, Tyler M., Sacci, Robert L., Winiarz, Jeffrey G., Kaiser, Helmut, Taub, Haskell, and Veith, Gabriel M. Fri . "A study of perfluorocarboxylate ester solvents for lithium ion battery electrolytes". United States. https://doi.org/10.1016/j.jpowsour.2015.08.098. https://www.osti.gov/servlets/purl/1265852.
Copy to clipboard
@article{osti_1265852,
title = {A study of perfluorocarboxylate ester solvents for lithium ion battery electrolytes},
author = {Fears, Tyler M. and Sacci, Robert L. and Winiarz, Jeffrey G. and Kaiser, Helmut and Taub, Haskell and Veith, Gabriel M.},
abstractNote = {We prepared several high-purity methyl perfluorocarboxylates (>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-electrolyteinterphase (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. But, 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. These electrolytes, though far from ideal, provide an opportunity to further develop predictions of suitable fluorinated molecules for use in battery solvents.},
doi = {10.1016/j.jpowsour.2015.08.098},
journal = {Journal of Power Sources},
number = C,
volume = 299,
place = {United States},
year = {Fri Sep 18 00:00:00 EDT 2015},
month = {Fri Sep 18 00:00:00 EDT 2015}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1016/j.jpowsour.2015.08.098
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Fluorinated electrolytes for 5 V lithium-ion battery chemistry
journal, January 2013

  • Zhang, Zhengcheng; Hu, Libo; Wu, Huiming
  • Energy & Environmental Science, Vol. 6, Issue 6
  • DOI: 10.1039/c3ee24414h

Fluorinated Electrolytes for 5-V Li-Ion Chemistry: Synthesis and Evaluation of an Additive for High-Voltage LiNi 0.5 Mn 1.5 O 4 /Graphite Cell
journal, January 2014

  • Hu, Libo; Xue, Zheng; Amine, Khalil
  • Journal of The Electrochemical Society, Vol. 161, Issue 12
  • DOI: 10.1149/2.0141412jes

Syntheses of novel delocalized cations and fluorinated anions, new fluorinated solvents and additives for lithium ion batteries
journal, December 2014

Reduction Mechanism of Fluoroethylene Carbonate for Stable Solid-Electrolyte Interphase Film on Silicon Anode
journal, November 2013

Performance Enhancement of 4.8 V Li 1.2 Mn 0.525 Ni 0.175 Co 0.1 O 2 Battery Cathode Using Fluorinated Linear Carbonate as a High-Voltage Additive
journal, January 2014

  • Pham, Hieu Quang; Nam, Kyoung-Mo; Hwang, Eui-Hyung
  • Journal of The Electrochemical Society, Vol. 161, Issue 14
  • DOI: 10.1149/2.1141412jes

Electrolytes and Interphases in Li-Ion Batteries and Beyond
journal, October 2014

A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries
journal, September 2010

A high-rate germanium-particle slurry cast Li-ion anode with high Coulombic efficiency and long cycle life
journal, September 2013

Surface chemistry and morphology of the solid electrolyte interphase on silicon nanowire lithium-ion battery anodes
journal, April 2009

Role of the LiPF 6 Salt for the Long-Term Stability of Silicon Electrodes in Li-Ion Batteries – A Photoelectron Spectroscopy Study
journal, January 2013

  • Philippe, Bertrand; Dedryvère, Rémi; Gorgoi, Mihaela
  • Chemistry of Materials, Vol. 25, Issue 3
  • DOI: 10.1021/cm303399v

Silicon nanowire anode: Improved battery life with capacity-limited cycling
journal, May 2012

Electrochemical reductive carbonization of polymers derived from hexafluoropropene
journal, November 1991

Carbonization of Highly Oriented Poly(tetrafluoroethylene)
journal, February 1999

  • Kavan, Ladislav; Dousek, František P.; Janda, Pavel
  • Chemistry of Materials, Vol. 11, Issue 2
  • DOI: 10.1021/cm9807438

Nonflammable perfluoropolyether-based electrolytes for lithium batteries
journal, February 2014

  • Wong, Dominica H. C.; Thelen, Jacob L.; Fu, Yanbao
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 9
  • DOI: 10.1073/pnas.1314615111

Structural evolution in LiFePO4-based battery materials: In-situ and ex-situ time-of-flight neutron diffraction study
journal, July 2014

Understanding structural changes in NMC Li-ion cells by in situ neutron diffraction
journal, June 2014

Chemical Reactions followed by in situ Neutron Powder Diffraction: Chemical Reactions followed by in situ Neutron Powder Diffraction
journal, October 2014

  • Hansen, Thomas C.; Kohlmann, Holger
  • Zeitschrift für anorganische und allgemeine Chemie, Vol. 640, Issue 15
  • DOI: 10.1002/zaac.201400359

Design of a new lithium ion battery test cell for in-situ neutron diffraction measurements
journal, March 2013

In Situ Determination of the Liquid/Solid Interface Thickness and Composition for the Li Ion Cathode LiMn 1.5 Ni 0.5 O 4
journal, October 2014

  • Browning, James F.; Baggetto, Loïc; Jungjohann, Katherine L.
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 21
  • DOI: 10.1021/am5032055

Neutron reflectometry studies on the lithiation of amorphous silicon electrodes in lithium-ion batteries
journal, January 2013

  • Jerliu, B.; Dörrer, L.; Hüger, E.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 20
  • DOI: 10.1039/c3cp44438d

Solid Electrolyte Interphase in Li-Ion Batteries: Evolving Structures Measured In situ by Neutron Reflectometry
journal, May 2012

  • Owejan, Jeanette E.; Owejan, Jon P.; DeCaluwe, Steven C.
  • Chemistry of Materials, Vol. 24, Issue 11
  • DOI: 10.1021/cm3006887

Direct measurement of the chemical reactivity of silicon electrodes with LiPF6-based battery electrolytes
journal, January 2014

  • Veith, Gabriel M.; Baggetto, Loïc; Sacci, Robert L.
  • Chemical Communications, Vol. 50, Issue 23
  • DOI: 10.1039/c3cc49269a

Improving the Stability of Nanostructured Silicon Thin Film Lithium-Ion Battery Anodes through Their Controlled Oxidation
journal, February 2012

  • Abel, Paul R.; Lin, Yong-Mao; Celio, Hugo
  • ACS Nano, Vol. 6, Issue 3
  • DOI: 10.1021/nn204896n

High-performance lithium battery anodes using silicon nanowires
journal, December 2007

  • Chan, Candace K.; Peng, Hailin; Liu, Gao
  • Nature Nanotechnology, Vol. 3, Issue 1, p. 31-35
  • DOI: 10.1038/nnano.2007.411

The failure mechanism of nano-sized Si-based negative electrodes for lithium ion batteries
journal, January 2011

  • Oumellal, Y.; Delpuech, N.; Mazouzi, D.
  • Journal of Materials Chemistry, Vol. 21, Issue 17
  • DOI: 10.1039/c1jm10213c

Nanosilicon Electrodes for Lithium-Ion Batteries: Interfacial Mechanisms Studied by Hard and Soft X-ray Photoelectron Spectroscopy
journal, February 2012

  • Philippe, Bertrand; Dedryvère, Rémi; Allouche, Joachim
  • Chemistry of Materials, Vol. 24, Issue 6
  • DOI: 10.1021/cm2034195

13C Solid State NMR Suggests Unusual Breakdown Products in SEI Formation on Lithium Ion Electrodes
journal, January 2011

  • Leifer, N.; Smart, M. C.; Prakash, G. K. S.
  • Journal of The Electrochemical Society, Vol. 158, Issue 5
  • DOI: 10.1149/1.3559551

Bis(2,2,2-trifluoroethyl) Ether As an Electrolyte Co-solvent for Mitigating Self-Discharge in Lithium–Sulfur Batteries
journal, May 2014

  • Gordin, Mikhail L.; Dai, Fang; Chen, Shuru
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 11
  • DOI: 10.1021/am501665s

Enabling LiTFSI-based Electrolytes for Safer Lithium-Ion Batteries by Using Linear Fluorinated Carbonates as (Co)Solvent
journal, August 2014

    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Evaluating the solid electrolyte interphase formed on silicon electrodes: a comparison of ex situ X-ray photoelectron spectroscopy and in situ neutron reflectometry
    journal, January 2016

    • Fears, T. M.; Doucet, M.; Browning, J. F.
    • Physical Chemistry Chemical Physics, Vol. 18, Issue 20
    • DOI: 10.1039/c6cp00978f
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: