context: Fig. 4d shows the comparison of the rate performances and coulombic efficiencies of the three types of cathodes under different current densities (0.1, 0.2, 0.5, 1.0, and 2.0C). All three cathodes show a coulombic efficiency over 98%, which could be due to the highly conductive CNF skeletons. And, with increasing the current density from 0.1C to 2.0C, the CNF@V2S3/S cathodes can retain a specific capacitance of 922 mA h g−1 (78.9% of the initial value), which is much higher than those of VS2-based LSBs. However, the CNF@VO0.9/S and CNF/S cathodes can retain 390 mA h g−1 (55.1%) and 592 mA h g−1 (68.8%). Here, to gain better understanding of the effect of V2S3 on the rate performances of cathodes, the in situ reaction resistances were first derived from the charge/discharge curves (see the ESI for details†). As shown in Fig. 4e, the reaction resistances of all three cathodes increase with the increasing specific capacity, which is caused by the low conductivity of intermediate LiPSs. Compared to the CNF@VO0.9/S and CNF/S cathodes, the CNF@V2S3/S ones show a much lower reaction resistance along the whole electrochemical processes. And similar results can also be obtained from Electrochemical Impedance Spectroscopy (EIS) spectra (Fig. S14†). This decrease in resistances often leads to fast redox kinetics on the CNF@V2S3/S cathodes. Besides, galvanostatic intermittent titration technique (GITT) tests were further carried out to further study the origins for fast transfer kinetics of CNF@V2S3/S cathodes (Fig. S15†). The diffusivities of Li ions between the cathode and electrolyte were estimated, as listed in Table S2.† The diffusion coefficient of Li+ ions in the CNF@V2S3/S/electrolyte system is 2.857 × 10−6 cm2 s−1, which is much higher than those of CNF@VO0.9/S and CNF/S ones (1.554 × 10−7 and 1.645 × 10−7 cm2 s−1) in this work. This greatly improved diffusivities of Li ions would result in the high specific capacity and the high rate capability of CNF@V2S3/S cathodes. Also, a similar conclusion can be obtained from EIS spectra in the low-frequency region (Fig. S14†). It can be seen that the curve slope of CNF@V2S3/S cathodes is much larger than those of the CNF@VO0.9/S and CNF/S ones (Table S3†).