Marcus-Hush-Chidsey Kinetics at Electrode-Electrolyte Interfaces
| Autor: | Venkatasubramanian Viswanathan, Rachel C. Kurchin |
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| Rok vydání: | 2020 |
| Předmět: |
Chemical Physics (physics.chem-ph)
Work (thermodynamics) Materials science 010304 chemical physics Fermi level Electrochemical kinetics General Physics and Astronomy FOS: Physical sciences Electrolyte 010402 general chemistry Electrochemistry 01 natural sciences 0104 chemical sciences Reaction rate symbols.namesake Chemical physics Physics - Chemical Physics 0103 physical sciences Electrode symbols Density of states Physical and Theoretical Chemistry |
| DOI: | 10.48550/arxiv.2007.15756 |
| Popis: | Electrochemical kinetics at electrode-electrolyte interfaces limit 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 have 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 DFT-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 (SEI) consisting of LiF and Li$_2$CO$_3$ and note the importance of the Fermi level at the interface, pinned by the redox reaction occuring there. We identify the asymmetry in reaction rates as a function of discharge/charge naturally within this approach. The analysis code used in this work is available open-source on Github. Comment: 5 pages, 4 figures |
| Databáze: | OpenAIRE |
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