Ionic‐Liquid‐Assisted Synthesis of FeSe–MnSe Heterointerfaces with Abundant Se Vacancies Embedded in N,B Co‐Doped Hollow Carbon Microspheres for Accelerating the Sulfur Reduction Reaction

Abstract Currently, extensive research efforts are being devoted to suppressing the shuttle effect of polysulfides. The uncontrollable deposition of insulating Li₂S onto the surface of sulfur host materials dramatically inhibits the continuous reduction of polysulfides in lithium–sulfur (Li–S) batteries. Herein, N,B co‐doped hollow carbon microspheres embedded with dense FeSe–MnSe heterostructures and abundant Se vacancies (FeSe–MnSe/NBC) are rationally designed and synthesized via a facile hydrothermal reaction using ionic liquids as dopants. The introduction of abundant heterostructures subtly guides Li₂S nucleation and deposition in 3D frameworks, thus avoiding the formation of the Li₂S passivation layer and allowing for continuous Li⁺ diffusion and subsequent nucleation of Li₂S. Owing to these beneficial features, Li–S batteries comprising an FeSe–MnSe/NBC electrode exhibit significantly improved performance, including a high initial capacity of 1334 mAh g⁻¹ at 0.2 C and ultralong cycle stability with a low capacity fading rate of 0.029% cycle⁻¹ over 1000 cycles at 1.0 C. Remarkably, the FeSe–MnSe/NBC pouch cell delivers a considerable areal capacity of 3.6 mAh cm⁻² at 0.1 C. This study provides valuable insight into heterostructures and Se vacancies for developing practical Li–S batteries.