Marcus-Hush-Chidsey Kinetics at Electrode-Electrolyte Interfaces

Abstract

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.

arXiv comment5 pages, 4 figures

References in corpus (4)

• A real-space grid implementation of the Projector Augmented Wave method
• Charge Transfer Kinetics at the Solid-Solid Interface in Porous Electrodes
• Computational Screening of Current Collectors for Enabling Anode-free Lithium Metal Batteries
• Non-linearity of the solid-electrolyte-interphase overpotential

Cited by in corpus (4)

• Tunable electrochemistry with moiré flat bands and topological defects at twisted bilayer graphene
• Kinetics of lithium electrodeposition and stripping
• Bayesian Parameterization of Continuum Battery Models from Featurized Electrochemical Measurements Considering Noise
• Twisto-electrochemical activity volcanoes in Trilayer Graphene