Effect of Anion Size on Conductivity and Transference Number of Perfluoroether Electrolytes with Lithium Salts
Abstract
Mixtures of perfluoropolyethers (PFPE) and lithium salts with fluorinated anions are a new class of electrolytes for lithium batteries. Unlike conventional electrolytes wherein electron-donating oxygen groups interact primarily with the lithium cations, the properties of PFPE-based electrolytes appear to be dependent on interactions between the fluorinated anions and the fluorinated backbones. We study these interactions by examining a family of lithium salts wherein the size of the fluorinated anion is systematically increased: lithium bis(fluorosulfonyl)imide (LiFSI), bis(trifluoromethanesulfonyl)imide (LiTFSI) salts and lithium bis(pentafluoroethanesulfonyl)imide (LiBETI). Two short chain perfluoroethers (PFE), one with three repeat units, C6-DMC, and another with four repeat units, C8-DMC were studied; both systems have dimethyl carbonate end groups.We find that LiFSI provides the highest conductivity in both C6-DMC and C8-DMC. These systems also present the lowest interfacial resistance against lithium metal electrodes. The steady-state transference number (t+ss) was above 0.6 for all of the electrolytes and was an increasing function of anion size. The product of conductivity and the steady-state transference number, a convenient measure of the efficacy of the electrolytes for lithium battery applications, exhibited a maximum at about 20 wt% salt in all electrolytes. Finally, amongst the systems studied, LiFSI/PFE mixtures were the most efficacious electrolytes.
- Authors:
-
- Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division
- Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
- Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Technologies Division
- Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Technologies Division
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1476456
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the Electrochemical Society
- Additional Journal Information:
- Journal Volume: 164; Journal Issue: 14; Journal ID: ISSN 0013-4651
- Publisher:
- The Electrochemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Li ion transport; Perfluoropolyether; transference number
Citation Formats
Shah, Deep B., Olson, Kevin R., Karny, Adar, Mecham, Sue J., DeSimone, Joseph M., and Balsara, Nitash P. Effect of Anion Size on Conductivity and Transference Number of Perfluoroether Electrolytes with Lithium Salts. United States: N. p., 2017.
Web. doi:10.1149/2.0301714jes.
Shah, Deep B., Olson, Kevin R., Karny, Adar, Mecham, Sue J., DeSimone, Joseph M., & Balsara, Nitash P. Effect of Anion Size on Conductivity and Transference Number of Perfluoroether Electrolytes with Lithium Salts. United States. https://doi.org/10.1149/2.0301714jes
Shah, Deep B., Olson, Kevin R., Karny, Adar, Mecham, Sue J., DeSimone, Joseph M., and Balsara, Nitash P. Wed .
"Effect of Anion Size on Conductivity and Transference Number of Perfluoroether Electrolytes with Lithium Salts". United States. https://doi.org/10.1149/2.0301714jes. https://www.osti.gov/servlets/purl/1476456.
@article{osti_1476456,
title = {Effect of Anion Size on Conductivity and Transference Number of Perfluoroether Electrolytes with Lithium Salts},
author = {Shah, Deep B. and Olson, Kevin R. and Karny, Adar and Mecham, Sue J. and DeSimone, Joseph M. and Balsara, Nitash P.},
abstractNote = {Mixtures of perfluoropolyethers (PFPE) and lithium salts with fluorinated anions are a new class of electrolytes for lithium batteries. Unlike conventional electrolytes wherein electron-donating oxygen groups interact primarily with the lithium cations, the properties of PFPE-based electrolytes appear to be dependent on interactions between the fluorinated anions and the fluorinated backbones. We study these interactions by examining a family of lithium salts wherein the size of the fluorinated anion is systematically increased: lithium bis(fluorosulfonyl)imide (LiFSI), bis(trifluoromethanesulfonyl)imide (LiTFSI) salts and lithium bis(pentafluoroethanesulfonyl)imide (LiBETI). Two short chain perfluoroethers (PFE), one with three repeat units, C6-DMC, and another with four repeat units, C8-DMC were studied; both systems have dimethyl carbonate end groups.We find that LiFSI provides the highest conductivity in both C6-DMC and C8-DMC. These systems also present the lowest interfacial resistance against lithium metal electrodes. The steady-state transference number (t+ss) was above 0.6 for all of the electrolytes and was an increasing function of anion size. The product of conductivity and the steady-state transference number, a convenient measure of the efficacy of the electrolytes for lithium battery applications, exhibited a maximum at about 20 wt% salt in all electrolytes. Finally, amongst the systems studied, LiFSI/PFE mixtures were the most efficacious electrolytes.},
doi = {10.1149/2.0301714jes},
journal = {Journal of the Electrochemical Society},
number = 14,
volume = 164,
place = {United States},
year = {2017},
month = {11}
}
Web of Science
Works referenced in this record:
A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries
journal, September 2010
- Verma, Pallavi; Maire, Pascal; Novák, Petr
- Electrochimica Acta, Vol. 55, Issue 22, p. 6332-6341
Mechanism of ion transport in perfluoropolyether electrolytes with a lithium salt
journal, January 2017
- Timachova, Ksenia; Chintapalli, Mahati; Olson, Kevin R.
- Soft Matter, Vol. 13, Issue 32
Challenges for Rechargeable Li Batteries
journal, February 2010
- Goodenough, John B.; Kim, Youngsik
- Chemistry of Materials, Vol. 22, Issue 3, p. 587-603
Highly-fluorous pyrazolide-based lithium salt in PVDF-HFP as solid polymer electrolyte
journal, September 2016
- Cznotka, Eva; Jeschke, Steffen; Grünebaum, Mariano
- Solid State Ionics, Vol. 292
IONIC CONDUCTIVITY AND LITHIUM TRANSFERENCE NUMBER OF POLY(ETHYLENE OXIDE):LiTFSI SYSTEM
journal, February 2017
- Pożyczka, K.; Marzantowicz, M.; Dygas, J. R.
- Electrochimica Acta, Vol. 227
Relationship between Conductivity, Ion Diffusion, and Transference Number in Perfluoropolyether Electrolytes
journal, April 2016
- Chintapalli, Mahati; Timachova, Ksenia; Olson, Kevin R.
- Macromolecules, Vol. 49, Issue 9
Analysis of Transference Number Measurements Based on the Potentiostatic Polarization of Solid Polymer Electrolytes
journal, January 1995
- Doyle, Marc
- Journal of The Electrochemical Society, Vol. 142, Issue 10
XPS analysis of the SEI formed on carbonaceous materials
journal, May 2004
- Eshkenazi, V.; Peled, E.; Burstein, L.
- Solid State Ionics, Vol. 170, Issue 1-2
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
Comparative study of poly(ethylene oxide) electrolytes made with LiN(CF3SO2)2, LiCF3SO3 and LiClO4: Thermal properties and conductivity behaviour
journal, January 1992
- Vallée, A.; Besner, S.; Prud'Homme, J.
- Electrochimica Acta, Vol. 37, Issue 9
A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions
journal, June 2002
- Aurbach, D.
- Solid State Ionics, Vol. 148, Issue 3-4
Relationship between Steady-State Current in Symmetric Cells and Transference Number of Electrolytes Comprising Univalent and Multivalent Ions
journal, January 2015
- Balsara, Nitash P.; Newman, John
- Journal of The Electrochemical Society, Vol. 162, Issue 14
Liquid perfluoropolyether electrolytes with enhanced ionic conductivity for lithium battery applications
journal, September 2016
- Olson, Kevin R.; Wong, Dominica H. C.; Chintapalli, Mahati
- Polymer, Vol. 100
Lithium bis(fluorosulfonyl)imide/poly(ethylene oxide) polymer electrolyte
journal, July 2014
- Zhang, Heng; Liu, Chengyong; Zheng, Liping
- Electrochimica Acta, Vol. 133
Electrolyte Reactions with the Surface of High Voltage LiNi[sub 0.5]Mn[sub 1.5]O[sub 4] Cathodes for Lithium-Ion Batteries
journal, January 2010
- Yang, Li; Ravdel, Boris; Lucht, Brett L.
- Electrochemical and Solid-State Letters, Vol. 13, Issue 8
Electrochemical measurement of transference numbers in polymer electrolytes
journal, December 1987
- Evans, James; Vincent, Colin A.; Bruce, Peter G.
- Polymer, Vol. 28, Issue 13
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
Phase Diagrams and Conductivity Behavior of Poly(ethylene oxide)-Molten Salt Rubbery Electrolytes
journal, December 1994
- Lascaud, S.; Perrier, M.; Vallee, A.
- Macromolecules, Vol. 27, Issue 25
Steady state current flow in solid binary electrolyte cells
journal, June 1987
- Bruce, Peter G.; Vincent, Colin A.
- Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 225, Issue 1-2
Estimation of Li+ transport number in polymer electrolytes by the combination of complex impedance and potentiostatic polarization measurements
journal, September 1988
- Watanabe, M.
- Solid State Ionics, Vol. 28-30
Physical properties of solid polymer electrolyte PEO(LiTFSI) complexes
journal, August 1995
- Gorecki, W.; Jeannin, M.; Belorizky, E.
- Journal of Physics: Condensed Matter, Vol. 7, Issue 34
Mechanism of ion transport in PEO/LiTFSI complexes: Effect of temperature, molecular weight and end groups
journal, October 2012
- Devaux, D.; Bouchet, R.; Glé, D.
- Solid State Ionics, Vol. 227
Interface layer formation in solid polymer electrolyte lithium batteries: an XPS study
journal, January 2014
- Xu, Chao; Sun, Bing; Gustafsson, Torbjörn
- J. Mater. Chem. A, Vol. 2, Issue 20
Cation Transport in Polymer Electrolytes: A Microscopic Approach
journal, May 2007
- Maitra, A.; Heuer, A.
- Physical Review Letters, Vol. 98, Issue 22
Organic fluorine compounds: a great opportunity for enhanced materials properties
journal, January 2011
- Berger, Ricarda; Resnati, Giuseppe; Metrangolo, Pierangelo
- Chemical Society Reviews, Vol. 40, Issue 7
Ionic conductivity of composite electrolytes based on oligo(ethylene oxide) and fumed oxides
journal, January 2004
- Zhou, J.
- Solid State Ionics, Vol. 166, Issue 3-4
Phase Behavior and Electrochemical Characterization of Blends of Perfluoropolyether, Poly(ethylene glycol), and a Lithium Salt
journal, January 2015
- Wong, Dominica H. C.; Vitale, Alessandra; Devaux, Didier
- Chemistry of Materials, Vol. 27, Issue 2
Poly(ethylene oxide)-LiN(SO[sub 2]CF[sub 2]CF[sub 3])[sub 2] Polymer Electrolytes
journal, January 2002
- Appetecchi, G. B.; Passerini, S.
- Journal of The Electrochemical Society, Vol. 149, Issue 7
Higher, Stronger, Better…︁ A Review of 5 Volt Cathode Materials for Advanced Lithium-Ion Batteries
journal, June 2012
- Kraytsberg, Alexander; Ein-Eli, Yair
- Advanced Energy Materials, Vol. 2, Issue 8
Effect of molecular weight on conductivity of polymer electrolytes
journal, November 2011
- Teran, Alexander A.; Tang, Maureen H.; Mullin, Scott A.
- Solid State Ionics, Vol. 203, Issue 1
The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems—The Solid Electrolyte Interphase Model
journal, January 1979
- Peled, E.
- Journal of The Electrochemical Society, Vol. 126, Issue 12
Understanding organofluorine chemistry. An introduction to the C–F bond
journal, January 2008
- O'Hagan, David
- Chem. Soc. Rev., Vol. 37, Issue 2
Works referencing / citing this record:
Fluor und Lithium: Ideale Partner für Elektrolyte in wiederaufladbaren Hochleistungsbatterien
journal, July 2019
- Aspern, N.; Röschenthaler, G. ‐V.; Winter, M.
- Angewandte Chemie, Vol. 131, Issue 45
Fluorine and Lithium: Ideal Partners for High‐Performance Rechargeable Battery Electrolytes
journal, November 2019
- Aspern, N.; Röschenthaler, G. ‐V.; Winter, M.
- Angewandte Chemie International Edition, Vol. 58, Issue 45
Morphological effects on polymeric mixed ionic/electronic conductors
journal, January 2019
- Onorato, Jonathan W.; Luscombe, Christine K.
- Molecular Systems Design & Engineering, Vol. 4, Issue 2
Multivalent ion conduction in solid polymer systems
journal, January 2019
- Schauser, Nicole S.; Seshadri, Ram; Segalman, Rachel A.
- Molecular Systems Design & Engineering, Vol. 4, Issue 2
Difference between approximate and rigorously measured transference numbers in fluorinated electrolytes
journal, January 2019
- Shah, Deep B.; Nguyen, Hien Q.; Grundy, Lorena S.
- Physical Chemistry Chemical Physics, Vol. 21, Issue 15
Ohm’s law for ion conduction in lithium and beyond-lithium battery electrolytes
journal, July 2019
- Galluzzo, Michael D.; Maslyn, Jacqueline A.; Shah, Deep B.
- The Journal of Chemical Physics, Vol. 151, Issue 2