Dependence of Interlayer or Sulfur Host on Hollow Framework of Lithium–Sulfur Battery

Lithium–sulfur batteries are recognized as the next generation of high‐specific energy secondary batteries owing to their satisfactory theoretical specific capacity and energy density. However, their commercial application is greatly limited by a series of problems, including disordered migration behavior, sluggish redox kinetics, and the serious shuttle effect of lithium polysulfides. One of the most efficient approaches to physically limit the shuttle effect is the rational design of a hollow framework as sulfur host. However, the influence of the hollow structure on the interlayers has not been clearly reported. In this study, the Mo2C/C catalysts with hollow(H‐Mo2C/C) and solid(S‐Mo2C/C) frameworks are rationally designed to explore the dependence of the hollow structure on the interlayer or sulfur host. In contrast to the physical limitations of the hollow framework as host, the hollow structure of the interlayer inhibited lithium‐ion diffusion, resulting in poor electrochemical properties at high current densities. Based on the superiority of the various frameworks, the H‐Mo2C/C@S | S‐Mo2C/C@PP | Li cells are assembled and displayed excellent electrochemical performance. This work re‐examines the design requirements and principles of catalyst frameworks in different battery units. The Mo2C/C catalysts with hollow and solid frameworks are rationally designed to explore the dependence of the hollow structure on the interlayer or sulfur host. In contrast to the physical limitations of the hollow framework as host, the hollow structure of the interlayer inhibited the lithium‐ion diffusion.