Comprehensive Insight into the Probability of Cyclotriphosphazene Derivatives as the Functional Electrolyte Additives in Lithium-Ion Batteries: Which Is Better and Why?

Enhancing the flame retardancy of electrolytes and the quality of interface films is of great significance to improve the safety performance of lithium-ion batteries (LIBs). In this work, the effects of (ethoxy)pentafluorocyclotriphosphazene (PFPN), hexafluorocyclotriphosphazene (FPPN), and pentafluoro(phenoxy)cyclotriphosphazene (HFPN) as flame-retardant additives in the functional electrolyte on the performances of LiNi0.6Mn0.2Co0.2O2 (NCM622)/graphite pouch cells are comprehensively investigated. It is indicated that the contents of PFPN, FPPN, and HFPN, respectively, reach 5, 8, and 8% to achieve the purpose of flame retardancy in the 1 M LiPF6/EC + EMC (EC/EMC = 1:2 in weight) system. When the cells without and with PFPN, FPPN, and HFPN additives are, respectively, charge–discharged in the voltage range of 3.0–4.4 V at 1C, their capacity retentions are 36.1, 60.7, 74.7, and 73.8% after 150 cycles. The interface analysis and theoretical calculation show that PFPN, FPPN, and HFPN can facilitate the formation of stable interface films on two electrodes and subsequently improve the battery performance. The addition of cyclotriphosphazene flame retardant in the electrolyte ultimately improves the safety of NCM622/graphite pouch cells without sacrificing electrochemical performance. The as-prepared additive-containing electrolyte exhibits promising prospects in the application, and the evaluation method is also useful to develop the functional electrolyte with flame retardant and film-forming properties.