Hollow Multi‐Shelled Structural TiO2−x with Multiple Spatial Confinement for Long‐Life Lithium–Sulfur Batteries

TiO2−x with well‐controlled hollow multi‐shelled structures (HoMSs) were designed and synthesized, via a sequential templating approach (STA), to act as sulfur carrier materials. They were explored as physico‐chemical encapsulation materials. Particularly, the sulfur cathode based on triple‐shelled TiO2−x HoMSs delivered a specific capacity of 903 mAh g−1 with a capacity retention of 79 % at 0.5 C and a Coulombic efficiency of 97.5 % over 1000 cycles. The outstanding electrochemical performance is attributed to better spatial confinement and integrated conductivity of the intact triple‐shell that combine the features of physico‐chemical adsorption, short charge transfer path along with mechanical strength. Three shells: A TiO2−x hollow multi‐shelled structure (HoMS) used as sulfur carrier can significantly improve the coulombic efficiency and cycling stability of Li–S batteries. The three separated layers not only trap polysulfide through physical confinement, but the interlayer voids can efficiently buffer the volume expansion.