Formation of the Solid Electrolyte Interphase at Constant Potentials: A Model Study on Highly Oriented Pyrolytic Graphite

The solid electrolyte interphase (SEI) on graphite anodes is a key enabler for rechargeable lithium-ion batteries (LIBs). It ensures that only Li+ ions and no damaging electrolyte components enter the anode and hinders electrolyte decomposition. Its growth should be confined to the initial SEI formation process and stop once the battery is in operation to avoid capacity/power loss. In technical LIB cells, the SEI is formed at constant current, with the potential of the graphite anode slowly drifting from higher to lower voltages. SEI formation rate, composition, and structure depend on the potential and on the chemical properties of the anode surface. Here, we characterize SEIs formed at constant potentials on the chemically inactive basal plane of highly oriented pyrolytic graphite (HOPG). X-ray photoemission spectroscopy (XPS) detects carbonate species only at lower formation potentials. Cyclic voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) with Fc/Fc(+) as an electrochemical probe demonstrate how the formation potential influences ion transport and electrochemical kinetics to and at the anode surface, respectively. Breaking the EIS data down to a Distribution of Relaxation Times (DRT) reveals distinct kinetics and transport related peaks with varying Arrhenius-type temperature dependencies. We discuss our findings in the context of previous electrochemical studies and existing SEI models and of SEI formation protocols suitable for industry.