Monitoring self-discharge in a dual-ion battery using in situ Raman spectro-electrochemistry

Abstract

A dual-ion battery employs two graphite electrodes to host cations and anions from the electrolyte. The high potential required to intercalate anions in graphite fully, typically > 5 V versus Li+/Li, triggers electrolyte decomposition and dissolution of the aluminium current collector. Such unwanted reactions significantly aggravate self-discharge, leading to low energy efficiency and shorter cycle life. This study investigates changes in graphite structure during the intercalation of bis(fluorosulfonyl)imide (FSI) anion in 4 M LiFSI in ethyl methyl carbonate (EMC) and evaluates the stability of the associated FSI-intercalated graphite compounds using in situ Raman spectroscopy. The results highlight the critical importance of the duration the GICs remain in contact with the electrolyte, before the acquisition of the Raman spectra. Accordingly, the GICs with high FSI anion content exhibited only short-term stability and lost anions during open-circuit potential relaxation; only dilute GIC phases (stages ≥ IV) were sufficiently stable in the presence of the concentrated electrolyte. Furthermore, the formation of gaseous products during the charge–discharge cycles was verified using a 3-electrode cell with a pressure sensor. Future studies can adopt the experimental strategy developed in this work to assess the efficacy of electrolyte additives in mitigating self-discharge in DIBs.