Elucidating the Transport of Electrons and Molecules in a Solid Electrolyte Interphase Close to Battery Operation Potentials Using a Four-Electrode-Based Generator-Collector Setup.

In lithium-ion batteries, the solid electrolyte interphase (SEI) passivates the anode against reductive decomposition of the electrolyte but allows for electron transfer reactions between anode and redox shuttle molecules, which are added to the electrolyte as an internal overcharge protection. In order to elucidate the origin of these poorly understood passivation properties of the SEI with regard to different molecules, we used a four-electrode-based generator-collector setup to distinguish between electrolyte reduction current and the redox molecule (ferrocenium ion Fc + ) reduction current at an SEI-covered glassy carbon electrode. The experiments were carried out in situ during potentiostatic SEI formation close to battery operation potentials. The measured generator and collector currents were used to calculate passivation factors of the SEI with regard to electrolyte reduction and with regard to Fc + reduction. These passivation factors show huge differences in their absolute values and in their temporal evolution. By making simple assumptions about molecule transport, electron transport, and charge transfer reaction rates in the SEI, distinct passivation mechanisms are identified, strong indication is found for a transition during SEI growth from redox molecule reduction at the electrode | SEI interface to reduction at the SEI | electrolyte interface, and good estimates for the transport coefficients of both electrons and redox molecules are derived. The approach presented here is applicable to any type of electrochemical interphase and should thus also be of interest for interphase characterization in the fields of electrocatalysis and corrosion.