Li-ion batteries (LIB) are now widely used in various areas such as electric vehicle (EV) or mobile phone. However, there are some issues of LIB like high-cost, safety, and energy density. Therefore, battery that has higher energy density and high power density is strongly required. Dual carbon battery (DCB), which consists of graphitic carbon for both positive and negative electrodes, is attracting much interest because of superior rate property, low cost, and high discharge potential. In this battery, for charge process, Li ions intercalate into anodic graphite, and counter anions in electrolyte also intercalate into cathodic graphite, and for discharge process, de-intercalation is occurred in both electrodes. Therefore, charge and discharge scheme is similar with that of capacitor, however, by using intercalation reaction, much higher energy storage capacity is expected. In our previous study, we investigated dual carbon battery using LiPF6 and demonstrated that discharge is observed at potential from 4.0 to 5V with 90mAh/g-carbon on the full cell and by using the high concentration electrolyte of 3 M LiPF6 in DMC, energy density is also much increased. Since it is reported that intercalation potential increases with increasing ionic size of anion, we investigated electrochemical intercalation property of bis(trifluoromethanesulfonyl) imide (TFSI) anion in this study. Effects of electrolyte on intercalation of TFSI anion into graphitic carbon was investigated and it was found that intercalation of TFSI anion was observed in propylene carbonate (PC) based electrolyte at room temperature. Among the electrolytes examined, the largest intercalation capacity was achieved in PC-EMC(1:1). By using 3MLiTFSI/PC-EMC (1:1), discharge capacity of 110mAh/g was stably sustained over 50 cycles, however, coulombic efficiency is around 90%. Further detail study was performed on intercalated structure of TFSI anion. Comparing with PF6 anion, intercalation potential is almost the same, however, the capacity is larger (90 mAh/g for PF6, and 110 mAh/g for TFSI). Therefore, it was found that the intercalation of TFSI anion is also usable for cathodic reaction in dual carbon battery. Stage structure of intercalated TFSI- is also studied by using in-situ XRD and it was confirmed that the distance of (002) plane of graphitic carbon was expanded by increasing potential suggesting that electrochemical intercalation of TFSI anion is occurred. From the distance of (002) plane, stage 1 structure seems to be observed at 5.2V with 0.79 nm distance which is little larger than that of PF6- (0.77nm). Although expansion of electrode is little larger, TFSI anion is also promising anion for dual carbon battery from high potential plateau (5V) and large capacity (110mAh/g).