Marcus–Hush–Chidsey kinetics at electrode–electrolyte interfaces
Abstract
Electrochemical kinetics at electrode–electrolyte interfaces limit the performance of devices including fuel cells and batteries. While the importance of moving beyond Butler–Volmer kinetics and incorporating the effect of electronic density of states of the electrode has been recognized, a unified framework that incorporates these aspects directly into electrochemical performance models is still lacking. In this work, we explicitly account for the density functional theory-calculated density of states numerically in calculating electrochemical reaction rates for a variety of electrode–electrolyte interfaces. We first show the utility of this for two cases related to Li metal electrodeposition and stripping on a Li surface and a Cu surface (anode-free configuration). The deviation in reaction rates is minor for cases with flat densities of states such as Li, but is significant for Cu due to nondispersive d-bands creating large variation. Finally, we consider a semiconducting case of a solid-electrolyte interphase consisting of LiF and Li2CO3 and note the importance of the Fermi level at the interface pinned by the redox reaction occurring there. We identify the asymmetry in reaction rates as a function of discharge/charge naturally within this approach.
- Publication Date:
- Sponsoring Org.:
- USDOE Advanced Research Projects Agency - Energy (ARPA-E)
- OSTI Identifier:
- 1670822
- Grant/Contract Number:
- AR0001211
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Name: Journal of Chemical Physics Journal Volume: 153 Journal Issue: 13; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics
- Country of Publication:
- United States
- Language:
- English
Citation Formats
Kurchin, Rachel, and Viswanathan, Venkatasubramanian. Marcus–Hush–Chidsey kinetics at electrode–electrolyte interfaces. United States: N. p., 2020.
Web. doi:10.1063/5.0023611.
Kurchin, Rachel, & Viswanathan, Venkatasubramanian. Marcus–Hush–Chidsey kinetics at electrode–electrolyte interfaces. United States. https://doi.org/10.1063/5.0023611
Kurchin, Rachel, and Viswanathan, Venkatasubramanian. Wed .
"Marcus–Hush–Chidsey kinetics at electrode–electrolyte interfaces". United States. https://doi.org/10.1063/5.0023611.
@article{osti_1670822,
title = {Marcus–Hush–Chidsey kinetics at electrode–electrolyte interfaces},
author = {Kurchin, Rachel and Viswanathan, Venkatasubramanian},
abstractNote = {Electrochemical kinetics at electrode–electrolyte interfaces limit the performance of devices including fuel cells and batteries. While the importance of moving beyond Butler–Volmer kinetics and incorporating the effect of electronic density of states of the electrode has been recognized, a unified framework that incorporates these aspects directly into electrochemical performance models is still lacking. In this work, we explicitly account for the density functional theory-calculated density of states numerically in calculating electrochemical reaction rates for a variety of electrode–electrolyte interfaces. We first show the utility of this for two cases related to Li metal electrodeposition and stripping on a Li surface and a Cu surface (anode-free configuration). The deviation in reaction rates is minor for cases with flat densities of states such as Li, but is significant for Cu due to nondispersive d-bands creating large variation. Finally, we consider a semiconducting case of a solid-electrolyte interphase consisting of LiF and Li2CO3 and note the importance of the Fermi level at the interface pinned by the redox reaction occurring there. We identify the asymmetry in reaction rates as a function of discharge/charge naturally within this approach.},
doi = {10.1063/5.0023611},
journal = {Journal of Chemical Physics},
number = 13,
volume = 153,
place = {United States},
year = {Wed Oct 07 00:00:00 EDT 2020},
month = {Wed Oct 07 00:00:00 EDT 2020}
}
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