First-Principles Modeling of Deposition Processes at Metal Anodes

Metal anodes in batteries of the rocking chair type promise to lead to high energy densities as they yield the lowest possible binding energy for the metal atoms and require no host material. On the other, they are often rather reactive causing the decomposition of many commonly used electrolyte components. This may lead to the formation of a passivation layer known as the solid electrolyte interphase (SEI). A better understanding of these reaction mechanisms can lead to an improved electrolyte and substrate design to achieve highly reversible metal anodes. In this contribution, recent purely computational [1] and joint theoretical-experimental [2.3] studies addressing the most likely decomposition products of electrolyte components at a number of alkaline metal anodes are presented. It will be demonstrated how the analysis of the first-principles electronic structure calculations based on density functional theory (DFT) allows to identify the crucial steps in the decomposition reactions.<br/><br/>In addition, metal anodes also play a crucial in batteries using anionic charge carriers such as chloride. Based on periodic DFT calculations, the initial steps in the conversion of a Mg anode to a magnesium chloride salt will be analyzed [4] which represents the driving force in the operation of such Cl-ion batteries.<br/><br/>[1] D. Stottmeister and A. Groß, Batterie Supercaps 2023, 6, e202300156.<br/>[2] K. Forster-Tonigold, F. Buchner, A. Groß, R.J. Behm, Batteries Supercaps, 2023, 6, e202300336.<br/>[3] D. Stottmeister, L. Wildersinn, J. Maibach, A. Hofmann, F. Jeschull, A. Groß, ChemSusChem (2023) e202300995.<br/>[4] K. Sarkar, D. Hübner, D. Stottmeister, Axel Groß, Phys. Rev. Mater., submitted.