Electrochemical Surface Plasmon Resonance Spectroscopy for Investigation of the Initial Process of Lithium Metal Deposition.

Abstract

The initial process of Li-metal electrodeposition on the negative electrode surface determines the charging performance of Li-metal secondary batteries. However, minute depositions or the early processes of nucleation and growth of Li metal are generally difficult to detect under operando conditions. In this study, we propose an optical diagnostic approach to address these challenges. Surface plasmon resonance (SPR) spectroscopy coupled with electrochemical operation is a promising technique that enables the ultrasensitive detection of the initial stage of Li-metal electrodeposition. The SPR is excited in a thin copper film deposited on a glass substrate, which also serves as a current collector enabling electrochemical Li-metal deposition. For a propylene carbonate (PC)-based Li-ion battery electrolyte, under both cyclic voltammetry and constant-current operation, Li-metal deposition is readily detected by changes in the SPR absorption dip in the reflectance spectrum. Electrochemical SPR is highly sensitive to metal deposition, with a demonstrated capability of detecting an average thickness of approximately 0.1 nm, corresponding to a few atomic layers of Li. To identify the growth mechanism, the SPR reflectance spectra of various possible Li-metal deposition processes were simulated. Comparison of the simulated spectra with the experimental data found good agreement with the well-known nucleation and growth model for Li-metal deposition from PC-based electrolytes. The demonstrated operando electrochemical SPR measurement should be a valuable tool for basic research on the initial Li-metal deposition process.