Built‐in Electric Field Within CoSe2‐FeSe2 Heterostructure for Enhanced Sulfur Reduction Reaction in Li‐S Batteries

Abstract The conversion of Li 2 S 4 to Li 2 S is the most important and slowest rate‐limiting step in the complex sulfur reduction reaction (SRR) for Li‐S batteries, the adjustment of which can effectively inhibit the notorious “shuttle effect”. Herein, a CoSe 2 ‐FeSe 2 heterostructure embedded in 3D N‐doped nanocage as a modified layer on commercial separator is designed (CoSe 2 ‐FeSe 2 @NC//PP). The CoSe 2 ‐FeSe 2 heterostructure forms a built‐in electric field at the two‐phase interface, which leads to the optimized adsorption force on polysulfides and the accelerated reaction kinetics for Li 2 S 4 ‐Li 2 S evolution. Density functional theory (DFT) calculations and experimental results combine to show that the liquid‐solid reaction (Li 2 S 4 ‐Li 2 S 2 /Li 2 S) is significantly enhanced in terms of thermodynamics and electrodynamics. Consequently, the batteries assembled with CoSe 2 ‐FeSe 2 @NC//PP delivered an excellent rate capability (606 mAh g −1 under 8.0 C) and a long cycling lifespan (only 0.056% at 1.0 C after 1000 cycles). In addition, the cells can provide high initial capacity of 887 mAh g −1 at sulfur loading of 5.8 mg cm −2 and 0.1 C. This work would provide valuable insights into binary metal selenide heterostructures for liquid‐solid conversion in Li‐S batteries.