Analysis of thermocapacitive effects in electric double layers under a size modified mean field theory
Abstract
Thermodynamics of the electric double layer has received renewed interest for its potential applications in low-grade waste heat harvesting and reversible heating/cooling in supercapacitors. We apply a size-modified mean field theory to analytically capture the influence on the pseudo-Seebeck coefficient S = ∂φ0/∂T)σ of different factors, including the electrode potential φ0, asymmetry in ion sizes, and ion concentration, under a fixed electrode surface charge σ. The pseudo-Seebeck coefficient is predicted to scale as φ0/T at low electrode potentials, but it reaches limiting values when the electrode potential exceeds crossover values due to the steric effect. The qualitative behavior changes substantially, however, when the temperature dependence of the permittivity is taken into account. The pseudo-Seebeck coefficient S is then predicted to scale linearly with φ0 even at high electrode potentials, significantly over-predicting the experimental values. Lastly, this suggests a strong influence of phenomena not captured in the mean field theory, such as deviation of local effective permittivity from the bulk value, thermally facilitated adsorption or desorption of ions on electrode surfaces, and weakening of ionic associations with temperature.
- Authors:
-
- Univ. of California, Los Angeles, CA (United States)
- Publication Date:
- Research Org.:
- SRI International, Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Advanced Research Projects Agency - Energy (ARPA-E)
- OSTI Identifier:
- 1510953
- Alternate Identifier(s):
- OSTI ID: 1402112
- Grant/Contract Number:
- AR0000532
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Applied Physics Letters
- Additional Journal Information:
- Journal Volume: 111; Journal Issue: 17; Journal ID: ISSN 0003-6951
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 42 ENGINEERING
Citation Formats
Ju, Y. Sungtaek. Analysis of thermocapacitive effects in electric double layers under a size modified mean field theory. United States: N. p., 2017.
Web. doi:10.1063/1.5003362.
Ju, Y. Sungtaek. Analysis of thermocapacitive effects in electric double layers under a size modified mean field theory. United States. https://doi.org/10.1063/1.5003362
Ju, Y. Sungtaek. Mon .
"Analysis of thermocapacitive effects in electric double layers under a size modified mean field theory". United States. https://doi.org/10.1063/1.5003362. https://www.osti.gov/servlets/purl/1510953.
@article{osti_1510953,
title = {Analysis of thermocapacitive effects in electric double layers under a size modified mean field theory},
author = {Ju, Y. Sungtaek},
abstractNote = {Thermodynamics of the electric double layer has received renewed interest for its potential applications in low-grade waste heat harvesting and reversible heating/cooling in supercapacitors. We apply a size-modified mean field theory to analytically capture the influence on the pseudo-Seebeck coefficient S = ∂φ0/∂T)σ of different factors, including the electrode potential φ0, asymmetry in ion sizes, and ion concentration, under a fixed electrode surface charge σ. The pseudo-Seebeck coefficient is predicted to scale as φ0/T at low electrode potentials, but it reaches limiting values when the electrode potential exceeds crossover values due to the steric effect. The qualitative behavior changes substantially, however, when the temperature dependence of the permittivity is taken into account. The pseudo-Seebeck coefficient S is then predicted to scale linearly with φ0 even at high electrode potentials, significantly over-predicting the experimental values. Lastly, this suggests a strong influence of phenomena not captured in the mean field theory, such as deviation of local effective permittivity from the bulk value, thermally facilitated adsorption or desorption of ions on electrode surfaces, and weakening of ionic associations with temperature.},
doi = {10.1063/1.5003362},
journal = {Applied Physics Letters},
number = 17,
volume = 111,
place = {United States},
year = {2017},
month = {10}
}
Web of Science
Figures / Tables:

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