The conventional electrolyte system has been compared with the ionic liquid (IL) additive containing electrolyte system at room temperature as well as elevated temperature. In this work, two types of monocationic ILs such as 1-butyl-3-methylpyrrolidinium hexafluorophosphate (Pyr IL) and 1-ethy1-3-methylimidazolium hexafluorophosphate (IMI IL) are added as an additive at two different weight ratios in 1.15 M LiPF6 (EC/EMC = 3/7 v/v) electrolyte solution, the structural, electrochemical and thermal characteristics of LiNi0.80Co0.15Al0.05O2 (NCA)/carbon full-cell in different electrolyte formulations have been reconnoitered. X-ray diffraction (XRD) studies have proved that IL as an electrolyte additive does not alter the structural stability of cathode materials after cycling. Under room temperature, Pyr IL additives at 1 wt% and 3 wt% deliver better cycleability than others, with the retention ratios of 93.62% and 92.8%, respectively. At elevated temperature, only 1 wt% Pyr IL additive is giving stable capacity retention ratio of 80.74%. Ionic conductivity and self-extinguishing time (SET) values are increasing with respect to the amount of additive added to the electrolyte. Thermal studies reveal that 3 wt%. Pyr IL is favorable regarding the safety of the battery as it shows shifting of peak to higher temperature of 272.10 degrees C. Among the IL additives evaluated in this study, addition of 1 wt% Pyr IL is the most desirable additive for achieving the best cycling performance as well as thermal behavior of Li-ion batteries. (C) 2014 Elsevier B.V. All rights reserved.