Although the OCV profile predicts the nature of electrode materials, it is a known fact that the performance of a LIB, especially the charge-discharge rate depends upon the mobility of Li-ions through the electrodes. Thus, understanding the Li-diffusion barrier of the electrode material is very crucial. For this we performed CI-NEB calculations for the diffusion of Li from one adsorption site to adjacent sites. The results are presented in Figure and Figure (refer Supporting Information). Likewise for other adjacent W-sites in the WS 2 /graphene interface, the energy barrier is in the range of 0.24-0.28 eV. However, it is highly probable that Li can get adsorbed on the surface of WS 2 and graphene layer at higher Li concentration. Hence, it is essential to estimate the Li diffusion barriers on those sites. Considering this we have extended Li diffusion calculations for Li at WS 2 and Li at graphene sites as shown in Figure (refer Supporting Information). The results demonstrate that the barriers are 0.20 and 0.36 eV for Li above the top of WS 2 and graphene layer, respectively. Eventually from the Li diffusion calculations we concluded that the energy barrier for the migration of Li through the energetically favored site of this heterostructure is only 0.27 eV, which is even lower than many of the previously reported LIB anode materials. Thus the electrochemical properties of the WS 2 /graphene heterostructure clearly prove that this system could be a promising material for futuristic LIBs.