Comparing Measurements of Limiting Current of Electrolytes with Theoretical Predictions up to the Solubility Limit
Abstract
Imposing a steady ionic current through an electrolyte results in the formation of salt concentration gradients that compromise battery performance. The limiting current is usually defined as the current at which the salt concentration at the cathode approaches zero. Higher currents cannot be imposed on the cell as larger concentration gradients are unsustainable. We study the limiting current in electrolytes comprising a perfluorinated oligomer, C8-DMC, and lithium bis(fluorosulfonyl)imide salt in symmetric lithium cells. The time-dependence of the potential, which increases as salt concentration gradients develop, was also measured. Both steady-state and transient behaviors are modeled using Newman's concentrated solution theory; transport and thermodynamic parameters needed to perform the calculations were measured independently. The limiting current is a nonmonotonic function of salt concentration in both theory and experiment. The model shows that at low salt concentrations (below 0.88 mol/kg solvent), the concentration at the cathode approaches zero at limiting current. In contrast, at high salt concentrations (above 0.88 mol/kg solvent), the concentration at the anode approaches the solubility limit (2.03 mol/kg solvent). In conclusion, the experimentally determined salt concentration at which the limiting current is maximized is in excellent agreement with theoretical predictions made without resorting to any adjustable parameters.
- Authors:
-
[1];
[1]
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research (JCESR)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Univ. of California, Berkeley, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research (JCESR); Argonne National Lab. (ANL), Lemont, IL (United States)
- 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:
- 1605257
- Grant/Contract Number:
- AC02-05CH11231; AC02-06CH11357; 1505669
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 123; Journal Issue: 39; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Salts; Electrical properties; Electrodes; Electrolytes; Lithium
Citation Formats
Shah, Deep B., Kim, Hong Keun, Nguyen, Hien Q., Srinivasan, Venkat, and Balsara, Nitash P. Comparing Measurements of Limiting Current of Electrolytes with Theoretical Predictions up to the Solubility Limit. United States: N. p., 2019.
Web. doi:10.1021/acs.jpcc.9b07121.
Shah, Deep B., Kim, Hong Keun, Nguyen, Hien Q., Srinivasan, Venkat, & Balsara, Nitash P. Comparing Measurements of Limiting Current of Electrolytes with Theoretical Predictions up to the Solubility Limit. United States. https://doi.org/10.1021/acs.jpcc.9b07121
Shah, Deep B., Kim, Hong Keun, Nguyen, Hien Q., Srinivasan, Venkat, and Balsara, Nitash P. Wed .
"Comparing Measurements of Limiting Current of Electrolytes with Theoretical Predictions up to the Solubility Limit". United States. https://doi.org/10.1021/acs.jpcc.9b07121. https://www.osti.gov/servlets/purl/1605257.
@article{osti_1605257,
title = {Comparing Measurements of Limiting Current of Electrolytes with Theoretical Predictions up to the Solubility Limit},
author = {Shah, Deep B. and Kim, Hong Keun and Nguyen, Hien Q. and Srinivasan, Venkat and Balsara, Nitash P.},
abstractNote = {Imposing a steady ionic current through an electrolyte results in the formation of salt concentration gradients that compromise battery performance. The limiting current is usually defined as the current at which the salt concentration at the cathode approaches zero. Higher currents cannot be imposed on the cell as larger concentration gradients are unsustainable. We study the limiting current in electrolytes comprising a perfluorinated oligomer, C8-DMC, and lithium bis(fluorosulfonyl)imide salt in symmetric lithium cells. The time-dependence of the potential, which increases as salt concentration gradients develop, was also measured. Both steady-state and transient behaviors are modeled using Newman's concentrated solution theory; transport and thermodynamic parameters needed to perform the calculations were measured independently. The limiting current is a nonmonotonic function of salt concentration in both theory and experiment. The model shows that at low salt concentrations (below 0.88 mol/kg solvent), the concentration at the cathode approaches zero at limiting current. In contrast, at high salt concentrations (above 0.88 mol/kg solvent), the concentration at the anode approaches the solubility limit (2.03 mol/kg solvent). In conclusion, the experimentally determined salt concentration at which the limiting current is maximized is in excellent agreement with theoretical predictions made without resorting to any adjustable parameters.},
doi = {10.1021/acs.jpcc.9b07121},
journal = {Journal of Physical Chemistry. C},
number = 39,
volume = 123,
place = {United States},
year = {Wed Sep 04 00:00:00 EDT 2019},
month = {Wed Sep 04 00:00:00 EDT 2019}
}
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