Implications of the Thermal Stability of FEC-Based Electrolytes for Li-Ion Batteries

Fluoroethylene-carbonate (FEC) is a common co-solvent for high-voltage cathodes and for silicon-based anodes in lithium-ion batteries. However, FEC has a limited thermal stability when used with LiPF₆ as conductive salt, and its decomposition can trigger detrimental side reactions. Here, we will examine the reaction mechanism of FEC with LiPF₆, confirming that vinylene-carbonate (VC) and HF are produced at elevated temperatures. By full-cell cycling at 45 °C in a T-cell setup with a micro-reference electrode (μ-RE), we can show by electrochemical impedance spectroscopy that these side reactions not only lead to an impedance increase of the anode and the cathode, but also trigger transition metal dissolution. By comparison of FEC and ethylene-carbonate (EC) as cyclic carbonate, we demonstrate that FEC has no advantage at high-voltage operation compared to EC, when employing cathode materials or cathode potentials for which no lattice oxygen is evolved. Finally, we use multi-layer pouch-cells to analyze the gassing of an EC- and FEC-based electrolyte upon extended charge/discharge cycling at 45 °C, showing that the latter leads to cell bulging upon extended charge/discharge cycling at 45 °C due to the oxidation of the VC formed by the thermal decomposition of FEC above ≈4.4 − 4.5 V vs. Li⁺/Li.