Fluoroethylene Carbonate as Electrolyte Additive for Improving the electrochemical performances of High-Capacity Li_1.16[Mn_0.75Ni_0.25]_0.84O₂ Material

Graphical abstract: Display Omitted -- Highlights: •FEC is introduced as electrolyte additive in the lithium-rich layered oxide cathode system. •DFT calculation results indicate the preferential reaction of FEC on cathode surface during charging. •A more conductive and thermal stable SEI film can be formed on the cathode surface with FEC as additive. -- Abstract: The effects of a small amount of fluoroethylene carbonate (C₃H₃FO₃ or FEC) on the electrochemical performance of lithium-rich layered oxide cathode Li_1.16[Mn_0.75Ni_0.25]_0.84O₂ have been focused herein. When 1 vol.% or 2 vol.% FEC was introduced into the electrolyte, cycling performance and rate capability of Li_1.16[Mn_0.75Ni_0.25]_0.84O₂ have been improved, and the initial irreversible capacity (C_irr) loss has been lessened by suppressing the parasitic side reactions between cathode and electrolyte. However, excess FEC (5% in volume) will lead to the decreased lithium transference number (t_Li+), large concentration polarization and the reduced discharge capacity especially at high current. DFT calculations indicate that FEC enhances the anti-oxidation ability of the electrolyte system, and the preferential accumulation and reaction of FEC near cathode during charging due to the strong coordination between FEC and PF₆⁻ anion. The results from electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and differential scanning calorimetry (DSC) measures indicate that a more stable SEI film has been formed on the cathode surface with FEC as additive, which leads to the suppression of the electrolyte aggressive decomposition and the enhancement of thermal stability