The commercialization of Li-S batteries is severely hindered by shuttle effect and sluggish redox reaction kinetics of LiPSs. Heterostructure can resolve the above shortcomings through the synergistic effect of adsorption and catalysis. However, long-chain LiPSs dissolving in electrolyte tend to cluster, resulting in low sulfur utilization and preventing kinetic conversion Thus, it is necessary to regulate the diffusion of Sn2− to achieve the directional diffusion from adsorbent to catalyst. Nevertheless, the design principle has not yet been clarified. W-W2C@C heterostructure with W of strong adsorption ability and high work function and W2C of excellent catalytic activity and low work function is designed by theoretical screening. Due to work function difference, this heterostructure controls the direction of the interface built-in electric field (BIEF), realizing the directional migration process of Sn2− from adsorptive W to catalytic W2C, thereby achieving a continuous “trapping-directional migration-conversion” reaction mechanism. The batteries have an excellent Li+ diffusion rate, high initial discharge specific capacity (1400.6 mAh/g at 0.2C), excellent rate capability (853.2 mAh/g at 2C), high reversible capacity (977.9 mAh/g after 150 cycles at 0.2C) and an extremely low capacity decay rate of 0.09 % per cycle after 300 cycles at 1C.