Ab Initio Interfacial Electrochemistry Applied to Understanding, Tuning and Designing Battery Chemistry

Ab initio calculations are now standardly used to investigate interfacial reactivity in many different fields including catalysis, energy materials and corrosion. Nevertheless, electrochemical interfaces were not modeled for a long time due to the lack of a proper methodology that would simultaneously consider the electrode potential and the chemical environment. Few years ago, different electrification schemes and implicit solvation models were introduced allowing to model the whole interfacial electrochemical environment at a reasonable computational cost. These approaches can nowadays be used as efficient probes to investigate the complex chemistry occurring at electrode/electrolyte interfaces, in particular for battery materials. The purpose of this chapter is to give a brief description of the methodology that is commonly used to model biased interfaces and highlight how specific interfacial properties (e.g. potential of zero-charge, redox potential, capacitance…) can be extracted from these calculations. Specific tools that allow the investigation and understanding of electrochemical reactivity at interfaces will be presented and discussed. This methodology will then be applied to the understanding and tuning of electrodes interfaces in batteries focusing in particular on solvent degradation, solid electrolyte interphase (SEI) formation, dendrite growth and electrode surface protection by the use of artificial SEI layers.