Interface Behavior of Electrolyte/Quinone Organic Active Material in Battery Operation by Operando Surface-Enhanced Raman Spectroscopy

To elucidate the microscopic charge/discharge (delithiation/lithiation) mechanism at the interface of the electrolyte and organic cathode active material in the lithium-ion battery, we prepared a self-assembled monolayer (SAM) electrode of 1,4-benzoquinone terminated dihexyl disulfide (BQ-C6) on Au(111). An electrochemical setup with the BQ-C6 SAM as a working electrode and 1 M lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI)/triethyleneglycol dimethylether (G3) as the electrolyte was used. We adopted the shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) method to obtain sufficient Raman signal of SAM for operando Raman spectroscopy measurements by the enhancement with ∼100 nm diameter Au particles coated with SiO₂ shell (average thickness = 2 nm). By this method, we succeeded in acquiring the Raman signal of the molecular monolayer on the model electrode simulating the interface between the electrolyte and the organic active material. In the cyclic voltammogram, two peaks were observed during the reduction reaction (lithiation), whereas only one peak was detected in the course of the oxidation process (delithiation). Simultaneous operando SHINERS showed a two-step spectral shape change in lithiation and coinciding (or simultaneous) one-step recovery during delithiation to match cyclic voltammetry behavior. The results indicate an asymmetric lithiation/delithiation mechanism.