Insight into the Contribution of the Electrolyte Additive LiBF4 in High-Voltage LiCoO2||SiO/C Pouch Cells

High-voltage pouch cells using an LiCoO2 cathode and SiO/C anode are regarded as promising energy storage devices due to their high energy densities. However, their failure is associated with the unstable, high-impedance cathode electrolyte interphase (CEI) film on the cathode and the solid electrolyte interphase (SEI) film on the anode surface, which hinder their practical use. Here, we report a novel approach to ameliorate the above challenges through the rational construction of a stable, low-impedance cathode and anode interface film. Such films are simultaneously formed on both electrodes via the participation of the traditional salt, lithium tetrafluoroborate (LiBF4), as electrolyte additive. The application of 1.0% LiBF4 enhances the capacity retention of the cell from 26.1 to 82.2% after 150 cycles between 3.0 and 4.4 V at 1 C. Besides, the low-temperature discharge performance is also improved by LiBF4 application: the discharge capacity of the cell with LiBF4 is 794 mAh compared with 637 mAh without LiBF4 at 1 C and -20 °C. The excellent electrochemical performance of pouch cells is ascribed to the contribution of LiBF4. Especially, the low binding energy of LiBF4 with the oxygen on the LiCoO2 surface leads to the enrichment of LiBF4 that forms the protective cathode interface, which fills the blanks of previous research.