Lithium-ion batteries (LIBs) are key solutions to clean energy. Their high energy densities have led to the dominance of LIBs in mobile devices and electric vehicles. However, traditional electrolyte limits their operation at high voltage and extreme environmental temperatures. Here, we designed a new multifunctional electrolyte, in which lithium bis(fluorosulfonyl)imide (LiFSI) is used as salt and fluorinated diethyl carbonate (DFDEC) is used as the major solvent. With this optimized electrolyte, the graphite||LiNi0.8Mn0.1Co0.1O2 (NMC811) full cells are capable of fast-charging and can deliver long-term cycling with a cutoff voltage as high as 4.5V. Specifically, the battery shows the capacity retention of 84.3% after 500 cycles with an average coulombic efficiency (CE) as high as 99.93%. Synchrotron-based characterization suggests the formation of anion derived, LiF-rich interphases on the surfaces of both graphite anode and NMC811 cathode. Thanks to the fast ion transport and stable interphase, the cell in the optimized electrolyte demonstrates stable cycling behavior within a wide operating temperature. At high temperature (60 ºC), the full cell delivers 88.8% of its initial capacity after 130 cycles at a high current density of 1C. At low temperature (-20 ºC), the optimized electrolyte enables a capacity retention of 90.9% after 100 cycles when charging and discharging at 0.2C.Acknowledgment: The work done at Brookhaven National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the U.S. DOE through Applied Battery Research for Transportation (ABRT) program under contract no. DE-SC0012704. The electrodes used in this study were produced at the U.S. Department of Energy’s (DOE) CAMP (Cell Analysis, Modeling and Prototyping) Facility, Argonne National Laboratory. The CAMP Facility is fully supported by the DOE Vehicle Technologies Office (VTO). This research used beamline 7-ID-2 (SST-2) of the National Synchrotron Light Source II, U.S. DOE Office of Science User Facilities, operated for the DOE Office of Science by Brookhaven National Laboratory under contract number DE-SC0012704. SEM measurements for this manuscript were performed at Center for Functional Nanomaterials, a U.S. DOE office of Science User Facility, at Brookhaven National Laboratory under the contract number DE-SC0012704.