Comparing Two Electrochemical Approaches for Measuring Transference Numbers in Concentrated Electrolytes
Abstract
We compare two experimental approaches for measuring the cation transference number in mixtures of polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt: the well-established current-interrupt method proposed by Ma et al. [J. Electrochem. Soc., 142, 1859 (1995)], and a more recent method based on measuring the steady-state current proposed by Balsara and Newman [J. Electrochem. Soc., 162, A2720 (2015)]. In electrolytes comprised of high molecular weight PEO, the data from the two techniques agree, highlighting the equivalence of these two approaches. However, in lower molecular weight PEO electrolytes the values of the two approaches diverge at low salt concentrations. We posit this is because the approach of Ma et al. requires measurements that are sensitive to the nature of the interface between the electrolyte and the electrode. The transference numbers measured by the approach of Balsara and Newman for both low and high molecular weight samples vary from 0.7 to -0.8 and are within experimental error throughout the entire salt concentration window.
- Authors:
- 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:
- 1471808
- Alternate Identifier(s):
- OSTI ID: 1605215
- Grant/Contract Number:
- AC02-05CH11231; AC02-06CH11357
- Resource Type:
- Published Article
- Journal Name:
- Journal of the Electrochemical Society
- Additional Journal Information:
- Journal Name: Journal of the Electrochemical Society Journal Volume: 165 Journal Issue: 13; Journal ID: ISSN 0013-4651
- Publisher:
- IOP Publishing - The Electrochemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Pesko, Danielle M., Sawhney, Simar, Newman, John, and Balsara, Nitash P. Comparing Two Electrochemical Approaches for Measuring Transference Numbers in Concentrated Electrolytes. United States: N. p., 2018.
Web. doi:10.1149/2.0231813jes.
Pesko, Danielle M., Sawhney, Simar, Newman, John, & Balsara, Nitash P. Comparing Two Electrochemical Approaches for Measuring Transference Numbers in Concentrated Electrolytes. United States. doi:10.1149/2.0231813jes.
Pesko, Danielle M., Sawhney, Simar, Newman, John, and Balsara, Nitash P. Fri .
"Comparing Two Electrochemical Approaches for Measuring Transference Numbers in Concentrated Electrolytes". United States. doi:10.1149/2.0231813jes.
@article{osti_1471808,
title = {Comparing Two Electrochemical Approaches for Measuring Transference Numbers in Concentrated Electrolytes},
author = {Pesko, Danielle M. and Sawhney, Simar and Newman, John and Balsara, Nitash P.},
abstractNote = {We compare two experimental approaches for measuring the cation transference number in mixtures of polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt: the well-established current-interrupt method proposed by Ma et al. [J. Electrochem. Soc., 142, 1859 (1995)], and a more recent method based on measuring the steady-state current proposed by Balsara and Newman [J. Electrochem. Soc., 162, A2720 (2015)]. In electrolytes comprised of high molecular weight PEO, the data from the two techniques agree, highlighting the equivalence of these two approaches. However, in lower molecular weight PEO electrolytes the values of the two approaches diverge at low salt concentrations. We posit this is because the approach of Ma et al. requires measurements that are sensitive to the nature of the interface between the electrolyte and the electrode. The transference numbers measured by the approach of Balsara and Newman for both low and high molecular weight samples vary from 0.7 to -0.8 and are within experimental error throughout the entire salt concentration window.},
doi = {10.1149/2.0231813jes},
journal = {Journal of the Electrochemical Society},
number = 13,
volume = 165,
place = {United States},
year = {2018},
month = {9}
}
DOI: 10.1149/2.0231813jes
Web of Science
Works referenced in this record:
Transport Property and Raman Spectroscopic Studies of the Polymer Electrolyte System P(EO)[sub n]-NaTFSI
journal, January 1998
- Ferry, Anders
- Journal of The Electrochemical Society, Vol. 145, Issue 5
Polymer solid electrolytes - an overview
journal, December 1983
- Armand, Michel
- Solid State Ionics, Vol. 9-10
The Measurement of a Complete Set of Transport Properties for a Concentrated Solid Polymer Electrolyte Solution
journal, January 1995
- Ma, Yanping
- Journal of The Electrochemical Society, Vol. 142, Issue 6
Universal Relationship between Conductivity and Solvation-Site Connectivity in Ether-Based Polymer Electrolytes
journal, July 2016
- Pesko, Danielle M.; Webb, Michael A.; Jung, Yukyung
- Macromolecules, Vol. 49, Issue 14
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
Determination of Transport Properties for Solid Electrolytes from the Impedance of Thin Layer Cells
journal, January 1989
- Pollard, Richard
- Journal of The Electrochemical Society, Vol. 136, Issue 12
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
Salt Diffusion Coefficients in Block Copolymer Electrolytes
journal, January 2011
- Mullin, Scott A.; Stone, Gregory M.; Panday, Ashoutosh
- Journal of The Electrochemical Society, Vol. 158, Issue 6
Transport Properties of LiPF[sub 6]-Based Li-Ion Battery Electrolytes
journal, January 2005
- Valo̸en, Lars Ole; Reimers, Jan N.
- Journal of The Electrochemical Society, Vol. 152, Issue 5
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
Ueber die Allotropie des Selens
journal, January 1851
- Hittorf,
- Annalen der Physik und Chemie, Vol. 160, Issue 10
Measurement of transference numbers for lithium ion electrolytes via four different methods, a comparative study
journal, April 2011
- Zugmann, S.; Fleischmann, M.; Amereller, M.
- Electrochimica Acta, Vol. 56, Issue 11
Polymer Electrolytes for Lithium-Ion Batteries
journal, April 1998
- Meyer, Wolfgang H.
- Advanced Materials, Vol. 10, Issue 6
Transport Properties of a High Molecular Weight Poly(propylene oxide)-LiCF[sub 3]SO[sub 3] System
journal, June 1999
- Doeff, Marca M.
- Journal of The Electrochemical Society, Vol. 146, Issue 6
Optimizing Ion Transport in Polyether-Based Electrolytes for Lithium Batteries
journal, April 2018
- Zheng, Qi; Pesko, Danielle M.; Savoie, Brett M.
- Macromolecules, Vol. 51, Issue 8
Poly(ethylene oxide) electrolytes for operation at near room temperature
journal, January 1985
- Kelly, I. E.; Owen, J. R.; Steele, B. C. H.
- Journal of Power Sources, Vol. 14, Issue 1-3
Electrochemical measurement of transference numbers in polymer electrolytes
journal, December 1987
- Evans, James; Vincent, Colin A.; Bruce, Peter G.
- Polymer, Vol. 28, Issue 13
Polymer Electrolytes: The Key to Lithium Polymer Batteries
journal, March 2000
- Scrosati, B.; Vincent, C. A.
- MRS Bulletin, Vol. 25, Issue 3
A Differential Moving Boundary Method for Transference Numbers
journal, September 1943
- Longsworth, L. G.
- Journal of the American Chemical Society, Vol. 65, Issue 9
7Li and 19F diffusion coefficients and thermal properties of non-aqueous electrolyte solutions for rechargeable lithium batteries
journal, September 1999
- Capiglia, C.; Saito, Y.; Kageyama, H.
- Journal of Power Sources, Vol. 81-82
Transport property measurements of polymer electrolytes
journal, April 1998
- Ferry, Anders; Doeff, Marca M.; DeJonghe, Lutgard C.
- Electrochimica Acta, Vol. 43, Issue 10-11
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
Electromotive Force of the Cell with Transference and Theory of Interdiffusion of Electrolytes
journal, October 1927
- Taylor, P. B.
- The Journal of Physical Chemistry, Vol. 31, Issue 10
Effect of monomer structure on ionic conductivity in a systematic set of polyester electrolytes
journal, June 2016
- Pesko, Danielle M.; Jung, Yukyung; Hasan, Alexandra L.
- Solid State Ionics, Vol. 289
Mechanism of Ion Transport in Amorphous Poly(ethylene oxide)/LiTFSI from Molecular Dynamics Simulations
journal, February 2006
- Borodin, Oleg; Smith, Grant D.
- Macromolecules, Vol. 39, Issue 4
Transport Properties of the Solid Polymer Electrolyte System P(EO) n LiTFSI
journal, April 2000
- Edman, Ludvig; Doeff, Marca M.; Ferry, Anders
- The Journal of Physical Chemistry B, Vol. 104, Issue 15
Systematic Computational and Experimental Investigation of Lithium-Ion Transport Mechanisms in Polyester-Based Polymer Electrolytes
journal, July 2015
- Webb, Michael A.; Jung, Yukyung; Pesko, Danielle M.
- ACS Central Science, Vol. 1, Issue 4
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
Negative Transference Numbers in Poly(ethylene oxide)-Based Electrolytes
journal, January 2017
- Pesko, Danielle M.; Timachova, Ksenia; Bhattacharya, Rajashree
- Journal of The Electrochemical Society, Vol. 164, Issue 11
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
Conductivity, charge transfer and transport number—an ac-investigation of the polymer electrolyte LiSCN-poly(ethyleneoxide)
journal, December 1982
- Ravn Sørensen, Poul; Jacobsen, Torben
- Electrochimica Acta, Vol. 27, Issue 12
Negative Stefan-Maxwell Diffusion Coefficients and Complete Electrochemical Transport Characterization of Homopolymer and Block Copolymer Electrolytes
journal, January 2018
- Villaluenga, Irune; Pesko, Danielle M.; Timachova, Ksenia
- Journal of The Electrochemical Society, Vol. 165, Issue 11
Infrared and Raman study of the PEO-LiTFSI polymer electrolyte
journal, April 1998
- Rey, I.; Lassègues, J. C.; Grondin, J.
- Electrochimica Acta, Vol. 43, Issue 10-11
Pulsed‐field gradient nuclear magnetic resonance as a tool for studying translational diffusion: Part 1. Basic theory
journal, January 1997
- Price, William S.
- Concepts in Magnetic Resonance, Vol. 9, Issue 5
Über Gemischte elektrische Leitung in einheitlichen festen Verbindungen
journal, February 1927
- Tubandt, C.; Reinhold, Hermann
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 160, Issue 1
Ion Association and Ion Solvation Effects at the Crystalline−Amorphous Phase Transition in PEO−LiTFSI
journal, August 2000
- Edman, Ludvig
- The Journal of Physical Chemistry B, Vol. 104, Issue 31
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
Works referencing / citing this record:
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
Comparing Experimental Measurements of Limiting Current in Polymer Electrolytes with Theoretical Predictions
journal, January 2019
- Gribble, Daniel A.; Frenck, Louise; Shah, Deep B.
- Journal of The Electrochemical Society, Vol. 166, Issue 14
Lithium Transference Numbers in PEO/LiTFSA Electrolytes Determined by Electrophoretic NMR
journal, January 2019
- Rosenwinkel, Mark P.; Schönhoff, Monika
- Journal of The Electrochemical Society, Vol. 166, Issue 10