Structural and Interfacial Manipulation of Multifunctional Skeletons Enabled Shuttling‐Free and Dendrite‐Free Li–S Full Batteries

Abstract

Li–S batteries are regarded as promising devices for energy storage systems owing to high energy density, low cost, and environmental friendliness. However, challenges of polysulfides shuttling in sulfur cathode and dendrite growth of lithium anode severely hinder the practical application. Developing advanced skeletons simultaneously regulating the cathode and anode is significant and challenging. Hence, a novel and scalable strategy combining spray drying and topological nitriding is proposed, and hierarchically assembled rGO hollow microspheres encapsulated highly porous nanospheres consisted of ultrafine Nb₄N₅‐Nb₂O₅ or Nb₄N₅ nanoparticles as multifunctional skeletons for S and Li are designed. In such unique architecture, a 3D highly porous structure provides abundant void space for loading of S and Li, and accommodates volume change during cycling. Moreover, Nb₄N₅‐Nb₂O₅ heterostructured interface promotes adsorption‐conversion process of polysulfides, while strong lithophilic Nb₄N₅ induces the selective infiltration of Li into the void of the skeleton and regulates the uniform deposition and growth. More interestingly, in situ generated Li₃N@Nb ion/electron conducting interfaces induced by the reaction of Nb₄N₅ and Li reduce the nucleation overpotential and induce selective deposition of Li into the cavity. Consequently, the Li–S full cell exhibits superior cycling stability and impressive rate performance with a low capacity ratio of negative/positive.