RESUMO
Effective electrolyte compositions are of primary importance in raising the performance of lithium-ion batteries (LIBs). Recently, fluorinated cyclic phosphazenes in combination with fluoroethylene carbonate (FEC) have been introduced as promising electrolyte additives, which can decompose to form an effective dense, uniform, and thin protective layer on the surface of electrodes. Although the basic electrochemical aspects of cyclic fluorinated phosphazenes combined with FEC were introduced, it is still unclear how these two compounds interact constructively during operation. This study investigates the complementary effect of FEC and ethoxy(pentafluoro)cyclotriphosphazene (EtPFPN) in aprotic organic electrolyte in LiNi0.5 Co0.2 Mn0.3 O ⥠SiOx /C full cells. The formation mechanism of lithium ethyl methyl carbonate (LEMC)-EtPFPN interphasial intermediate products and the reaction mechanism of lithium alkoxide with EtPFPN are proposed and supported by Density Functional Theory calculations. A novel property of FEC is also discussed here, called molecular-cling-effect (MCE). To the best knowledge, the MCE has not been reported in the literature, although FEC belongs to one of the most investigated electrolyte additives. The beneficial MCE of FEC toward the sub-sufficient solid-electrolyte interphase forming additive compound EtPFPN is investigated via gas chromatography-mass spectrometry, gas chromatography high resolution-accurate mass spectrometry, in situ shell-isolated nanoparticle-enhanced Raman spectroscopy, and scanning electron microscopy.