A new asymmetric sulfonium-based ionic liquid, 1-butyldimethylsulfonium bis(trifluoromethylsulfonyl) imide (S114TFSI), was developed as electrolyte material for lithium secondary battery. Its cathodic potential was a little more positive against the Li/Li+, so vinylene carbonate (VC) was added into the LiTFSI/S114TFSI ionic liquid electrolyte to ensure the formation of a solid electrolyte interface (SEI), which effectively prevented the decomposition of the electrolyte. The properties of the Li/LiMn2O4 cell containing S114TFSI-based electrolyte were studied and the cycle performances were compared to those with a conventional organic electrolyte (1 mol/L LiPF6/DMC:EC=1:1(w/w)) at room temperature. Electrochemical impedance spectroscopy (EIS) and X-ray diffraction (XRD) were conducted to analyze the mechanisms affecting the cell performances at different temperatures. The lithium secondary battery system, using the above ionic liquid electrolyte material, shows good cycle performances and good safety at room temperature, and is worthwhile to further investigate so as to find out the potential application.