The high thermal conduction resistances of a lithium-ion battery (LIB) severely limit the effectiveness of a conventional external thermal management system (TMS). A method for a new thermal management system for lithium-ion batteries that utilizes a multi-functional electrolyte (MFE) to remove heat locally inside the cell by evaporating a volatile component of the MFE is disclosed. These new electrolyte mixtures comprise a high vapor pressure co-solvent. The characteristics of a previously unstudied high vapor pressure co-solvent HFE-7000 (65 kPa at 25° C.) in an MFE (1 M LiTFSI in 1:1 HFE-7000/EMC), and other possible MFE compositions that can be utilized in a custom electrolyte boiling facility, are disclosed.