Triboelectric nanogenerators (TENGs) can capture the low-frequency, disordered, and fragmented high-entropy energy in the surrounding environment and convert it into electrical energy. However, at present, this main focuse is on increasing the cumulative amount of surface charge of friction materials, and there are shortcomings such as the inability to fully utilize the overall volume of the friction layer and the short enhancement cycle. Herein, fluoroelastomers (FKM) and polyimide (PI) were respectively used as matrix and interlayer of electronegative friction materials. The electrical output performance was significantly improved by uniformly adding high dielectric barium titanate nanoparticles (BT particles) to the matrix. The introduced PI interlayer serves as the charge capture layer and storage layer, which slows down the rate of charge escape from the trap while decreasing the probability of the escaped charge combining with the opposite charge on the electrode. Meanwhile, adding an appropriate amount of BT particles can increase the dielectric constant of the composite film and the surface charge density during working process of TENG. When the addition amount is 1.5% , the corresponding transfer charge density, short-circuit current density and output voltage are 66 μC/ m², 8 mA / m² and 275 V, respectively, which are increased by 164% , 208% and 175% , respectively, compared with those before the addition of BT particles. Based on the intrinsic capacitance characteristics of the corresponding TENG devices, the enhancement mechanism of BT dielectric particles on the electrical output performance was deeply analyzed. This work provides a new reference for the design and fabrication of high-performance electronegative friction materials.