Electrochemically Active MoO₃/TiN Sulfur Host Inducing Dynamically Reinforced Built‐in Electric Field for Advanced Lithium–Sulfur Batteries

Although various electrocatalysts have been developed to ameliorate the shuttle effect and sluggish Li-S conversion kinetics, their electrochemical inertness limits the sufficient performance improvement of lithium-sulfur batteries (LSBs). In this work, an electrochemically active MoO₃/TiN-based heterostructure (MOTN) is designed as an efficient sulfur host that can improve the overall electrochemical properties of LSBs via prominent lithiation behaviors. By accommodating Li ions into MoO₃ nanoplates, the MOTN host can contribute its own capacity. Furthermore, the Li intercalation process dynamically affects the electronic interaction between MoO₃ and TiN and thus significantly reinforces the built-in electric field, which further improves the comprehensive electrocatalytic abilities of the MOTN host. Because of these merits, the MOTN host-based sulfur cathode delivers an exceptional specific capacity of 2520 mA h g^-1 at 0.1 C. Furthermore, the cathode exhibits superior rate capability (564 mA h g^-1 at 5 C), excellent cycling stability (capacity fade rate of 0.034% per cycle for 1200 cycles at 2 C), and satisfactory areal capacity (6.6 mA h cm^-2) under a high sulfur loading of 8.3 mg cm^-2. This study provides a novel strategy to develop electrochemically active heterostructured electrocatalysts and rationally manipulate the built-in electric field for achieving high-performance LSBs.