Effect of Anion Size on Conductivity and Transference Number of Perfluoroether Electrolytes with Lithium Salts

Shah, Deep B.; Olson, Kevin R.; Karny, Adar; Mecham, Sue J.; DeSimone, Joseph M.; Balsara, Nitash P.

doi:10.1149/2.0301714jes

Title: Effect of Anion Size on Conductivity and Transference Number of Perfluoroether Electrolytes with Lithium Salts

Journal Article · Wed Nov 15 00:00:00 EST 2017 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/2.0301714jes· OSTI ID:1476456

^[1]; Olson, Kevin R. ^[2]; Karny, Adar ^[1]; Mecham, Sue J. ^[2]; DeSimone, Joseph M. ^[3]; Balsara, Nitash P. ^[4]

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

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.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1476456

Journal Information:: Journal of the Electrochemical Society, Vol. 164, Issue 14; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 30 works

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References (32)

A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries Verma, Pallavi; Maire, Pascal; Novák, Petr Electrochimica Acta, Vol. 55, Issue 22, p. 6332-6341 https://doi.org/10.1016/j.electacta.2010.05.072	journal	September 2010
Mechanism of ion transport in perfluoropolyether electrolytes with a lithium salt Timachova, Ksenia; Chintapalli, Mahati; Olson, Kevin R. Soft Matter, Vol. 13, Issue 32 https://doi.org/10.1039/C7SM00794A	journal	January 2017
Challenges for Rechargeable Li Batteries Goodenough, John B.; Kim, Youngsik Chemistry of Materials, Vol. 22, Issue 3, p. 587-603 https://doi.org/10.1021/cm901452z	journal	February 2010
Highly-fluorous pyrazolide-based lithium salt in PVDF-HFP as solid polymer electrolyte Cznotka, Eva; Jeschke, Steffen; Grünebaum, Mariano Solid State Ionics, Vol. 292 https://doi.org/10.1016/j.ssi.2016.05.007	journal	September 2016
IONIC CONDUCTIVITY AND LITHIUM TRANSFERENCE NUMBER OF POLY(ETHYLENE OXIDE):LiTFSI SYSTEM Pożyczka, K.; Marzantowicz, M.; Dygas, J. R. Electrochimica Acta, Vol. 227 https://doi.org/10.1016/j.electacta.2016.12.172	journal	February 2017
Relationship between Conductivity, Ion Diffusion, and Transference Number in Perfluoropolyether Electrolytes Chintapalli, Mahati; Timachova, Ksenia; Olson, Kevin R. Macromolecules, Vol. 49, Issue 9 https://doi.org/10.1021/acs.macromol.6b00412	journal	April 2016
Analysis of Transference Number Measurements Based on the Potentiostatic Polarization of Solid Polymer Electrolytes Doyle, Marc Journal of The Electrochemical Society, Vol. 142, Issue 10 https://doi.org/10.1149/1.2050005	journal	January 1995
XPS analysis of the SEI formed on carbonaceous materials Eshkenazi, V.; Peled, E.; Burstein, L. Solid State Ionics, Vol. 170, Issue 1-2 https://doi.org/10.1016/S0167-2738(03)00107-3	journal	May 2004
Nonflammable perfluoropolyether-based electrolytes for lithium batteries Wong, Dominica H. C.; Thelen, Jacob L.; Fu, Yanbao Proceedings of the National Academy of Sciences, Vol. 111, Issue 9 https://doi.org/10.1073/pnas.1314615111	journal	February 2014
Comparative study of poly(ethylene oxide) electrolytes made with LiN(CF3SO2)2, LiCF3SO3 and LiClO4: Thermal properties and conductivity behaviour Vallée, A.; Besner, S.; Prud'Homme, J. Electrochimica Acta, Vol. 37, Issue 9 https://doi.org/10.1016/0013-4686(92)80115-3	journal	January 1992
A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions Aurbach, D. Solid State Ionics, Vol. 148, Issue 3-4 https://doi.org/10.1016/S0167-2738(02)00080-2	journal	June 2002
Relationship between Steady-State Current in Symmetric Cells and Transference Number of Electrolytes Comprising Univalent and Multivalent Ions Balsara, Nitash P.; Newman, John Journal of The Electrochemical Society, Vol. 162, Issue 14 https://doi.org/10.1149/2.0651514jes	journal	January 2015
Liquid perfluoropolyether electrolytes with enhanced ionic conductivity for lithium battery applications Olson, Kevin R.; Wong, Dominica H. C.; Chintapalli, Mahati Polymer, Vol. 100 https://doi.org/10.1016/j.polymer.2016.08.020	journal	September 2016
Lithium bis(fluorosulfonyl)imide/poly(ethylene oxide) polymer electrolyte Zhang, Heng; Liu, Chengyong; Zheng, Liping Electrochimica Acta, Vol. 133 https://doi.org/10.1016/j.electacta.2014.04.099	journal	July 2014
Electrolyte Reactions with the Surface of High Voltage LiNi[sub 0.5]Mn[sub 1.5]O[sub 4] Cathodes for Lithium-Ion Batteries Yang, Li; Ravdel, Boris; Lucht, Brett L. Electrochemical and Solid-State Letters, Vol. 13, Issue 8 https://doi.org/10.1149/1.3428515	journal	January 2010
Electrochemical measurement of transference numbers in polymer electrolytes Evans, James; Vincent, Colin A.; Bruce, Peter G. Polymer, Vol. 28, Issue 13 https://doi.org/10.1016/0032-3861(87)90394-6	journal	December 1987
Fluorinated electrolytes for 5 V lithium-ion battery chemistry Zhang, Zhengcheng; Hu, Libo; Wu, Huiming Energy & Environmental Science, Vol. 6, Issue 6 https://doi.org/10.1039/c3ee24414h	journal	January 2013
Phase Diagrams and Conductivity Behavior of Poly(ethylene oxide)-Molten Salt Rubbery Electrolytes Lascaud, S.; Perrier, M.; Vallee, A. Macromolecules, Vol. 27, Issue 25 https://doi.org/10.1021/ma00103a034	journal	December 1994
Steady state current flow in solid binary electrolyte cells Bruce, Peter G.; Vincent, Colin A. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 225, Issue 1-2 https://doi.org/10.1016/0022-0728(87)80001-3	journal	June 1987
Estimation of Li+ transport number in polymer electrolytes by the combination of complex impedance and potentiostatic polarization measurements Watanabe, M. Solid State Ionics, Vol. 28-30 https://doi.org/10.1016/0167-2738(88)90303-7	journal	September 1988
Physical properties of solid polymer electrolyte PEO(LiTFSI) complexes Gorecki, W.; Jeannin, M.; Belorizky, E. Journal of Physics: Condensed Matter, Vol. 7, Issue 34 https://doi.org/10.1088/0953-8984/7/34/007	journal	August 1995
Mechanism of ion transport in PEO/LiTFSI complexes: Effect of temperature, molecular weight and end groups Devaux, D.; Bouchet, R.; Glé, D. Solid State Ionics, Vol. 227 https://doi.org/10.1016/j.ssi.2012.09.020	journal	October 2012
Interface layer formation in solid polymer electrolyte lithium batteries: an XPS study Xu, Chao; Sun, Bing; Gustafsson, Torbjörn J. Mater. Chem. A, Vol. 2, Issue 20 https://doi.org/10.1039/C4TA00214H	journal	January 2014
Cation Transport in Polymer Electrolytes: A Microscopic Approach Maitra, A.; Heuer, A. Physical Review Letters, Vol. 98, Issue 22 https://doi.org/10.1103/PhysRevLett.98.227802	journal	May 2007
Organic fluorine compounds: a great opportunity for enhanced materials properties Berger, Ricarda; Resnati, Giuseppe; Metrangolo, Pierangelo Chemical Society Reviews, Vol. 40, Issue 7 https://doi.org/10.1039/c0cs00221f	journal	January 2011
Ionic conductivity of composite electrolytes based on oligo(ethylene oxide) and fumed oxides Zhou, J. Solid State Ionics, Vol. 166, Issue 3-4 https://doi.org/10.1016/j.ssi.2003.11.017	journal	January 2004
Phase Behavior and Electrochemical Characterization of Blends of Perfluoropolyether, Poly(ethylene glycol), and a Lithium Salt Wong, Dominica H. C.; Vitale, Alessandra; Devaux, Didier Chemistry of Materials, Vol. 27, Issue 2 https://doi.org/10.1021/cm504228a	journal	January 2015
Poly(ethylene oxide)-LiN(SO[sub 2]CF[sub 2]CF[sub 3])[sub 2] Polymer Electrolytes Appetecchi, G. B.; Passerini, S. Journal of The Electrochemical Society, Vol. 149, Issue 7 https://doi.org/10.1149/1.1483098	journal	January 2002
Higher, Stronger, Better…︁ A Review of 5 Volt Cathode Materials for Advanced Lithium-Ion Batteries Kraytsberg, Alexander; Ein-Eli, Yair Advanced Energy Materials, Vol. 2, Issue 8 https://doi.org/10.1002/aenm.201200068	journal	June 2012
Effect of molecular weight on conductivity of polymer electrolytes Teran, Alexander A.; Tang, Maureen H.; Mullin, Scott A. Solid State Ionics, Vol. 203, Issue 1 https://doi.org/10.1016/j.ssi.2011.09.021	journal	November 2011
The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems—The Solid Electrolyte Interphase Model Peled, E. Journal of The Electrochemical Society, Vol. 126, Issue 12 https://doi.org/10.1149/1.2128859	journal	January 1979
Understanding organofluorine chemistry. An introduction to the C–F bond O'Hagan, David Chem. Soc. Rev., Vol. 37, Issue 2 https://doi.org/10.1039/B711844A	journal	January 2008

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Fluor und Lithium: Ideale Partner für Elektrolyte in wiederaufladbaren Hochleistungsbatterien Aspern, N.; Röschenthaler, G. ‐V.; Winter, M. Angewandte Chemie, Vol. 131, Issue 45 https://doi.org/10.1002/ange.201901381	journal	July 2019
Fluorine and Lithium: Ideal Partners for High‐Performance Rechargeable Battery Electrolytes Aspern, N.; Röschenthaler, G. ‐V.; Winter, M. Angewandte Chemie International Edition, Vol. 58, Issue 45 https://doi.org/10.1002/anie.201901381	journal	November 2019
Multivalent ion conduction in solid polymer systems Schauser, Nicole S.; Seshadri, Ram; Segalman, Rachel A. Molecular Systems Design & Engineering, Vol. 4, Issue 2 https://doi.org/10.1039/c8me00096d	journal	January 2019
Difference between approximate and rigorously measured transference numbers in fluorinated electrolytes Shah, Deep B.; Nguyen, Hien Q.; Grundy, Lorena S. Physical Chemistry Chemical Physics, Vol. 21, Issue 15 https://doi.org/10.1039/c9cp00216b	journal	January 2019
Ohm’s law for ion conduction in lithium and beyond-lithium battery electrolytes Galluzzo, Michael D.; Maslyn, Jacqueline A.; Shah, Deep B. The Journal of Chemical Physics, Vol. 151, Issue 2 https://doi.org/10.1063/1.5109684	journal	July 2019

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Title: Effect of Anion Size on Conductivity and Transference Number of Perfluoroether Electrolytes with Lithium Salts

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