The thermal and electrochemical stability, as well as compatibility with various bench mark cathode and anode materials of two new lithium fluoride salt (LiF) based electrolytes have been studied. These two new electrolytes are formed by using boron-based anion receptors, tris(pentafluorophenyl) borane (TPFPB), or tris(2H-hexafluoroisopropyl) borate (THFPB) as additives, which were designed and synthesized at Brookhaven National Laboratory (BNL), to dissolve the LiF salt in carbonate solvents. The transference number of Li+ for these electrolytes is as high as 0.7 and the room-temperature conductivity is around 2×10−3 Scm−1. The electrolytes containing propylene carbonate (PC) show superior low-temperature conductivity properties. The electrochemical window is approaching 5.0V. It was also found that the new electrolytes work well with LiCoO2 or LiMn2O4 cathodes. However, when PC containing electrolytes were used, PC co-intercalation is still a problem for graphite anodes. The formation of a stable solid electrolyte interface layer on the surface of anode in this type of electrolyte needs to be studied further.