Monitoring the Behavior of Na Ions and Solid Electrolyte Interphase Formation at an Aluminum/Ionic Liquid Electrode/Electrolyte Interface via Operando Electrochemical X‑ray Photoelectron Spectroscopy

In electrochemical energy storage devices, the interface between the electrode and the electrolyte plays a crucial role. A solid electrolyte interphase (SEI) is formed on the electrode surface due to spontaneous decomposition of the electrolyte, which in turn controls the dynamics of ion migration during charge and discharge cycles. However, the dynamic nature of the SEI means that its chemical structure evolves over time and as a function of the applied bias; thus, a true operando study is extremely valuable. X-ray photoelectron spectroscopy (XPS) is a widely used technique to understand the surface electronic and chemical properties, but the use of ultrahigh vacuum in standard instruments is a major hurdle for their utilization in measuring wet electrochemical processes. Herein, we introduce a 3-electrode electrochemical cell to probe the behavior of Na ions and the formation of SEI at the interface of an ionic liquid (IL) electrolyte and an aluminum electrode under operando conditions. A system containing 0.5 molar NaTFSI dissolved in the IL [BMIM]­[TFSI] was investigated using an Al working electrode and Pt counter and reference electrodes. By optimizing the scan rate of both XPS and cyclic voltammetry (CV) techniques, we captured the formation and evolution of SEI chemistry using real-time spectra acquisition techniques. A CV scan rate of 2 mVs^–1 was coupled with XPS snapshot spectra collected at 10 s per core level. The technique demonstrated here provides a platform for the chemical analysis of materials beyond batteries.