Insulated polymer host and lithium salt need to be separately dissolved into organic solvents prior to assembly of lithium batteries, implying a large usage of organic solvents and the consequent disadvantages of poor thermal stability, flammability, and explosibility of the end products. Herein, a new generation of thermotropic ionic liquid crystalline lithium salt (LiBIB) with potential bilayer fast ion-conductive tunnels, having functionalities of both lithium salt and polymer host or electrolyte, is successfully synthesized. Molecular structure, thermal stability, ionic conductivity, electrochemical stability, and ion- conductive mechanism of the LiBIB are extensively assessed. The obtained LiBIB shows typical behaviors of both ionic liquid and liquid crystal. Melt point at 43 degrees C, much lower than that of traditional lithium salts like LiClO4 and LiPF6, and clear point of the LiBIB at 83 degrees C are both detected. Solid LiBIB salt shows better ionic conductivity (3 x 10(-3) S cm(-1)) and electrochemical stability at room temperature in comparison with those of traditional lithium salts. Time-resolved and perturbation-correlation moving window 2D-COR FTIR results indicate that the high ionic conductivity of the LiBIB is mainly originated from the formation of fast ion-conductive tunnels, implying a promising application in solvent-free Li-ion batteries. (c) 2018 Elsevier Ltd. All rights reserved.