Unlocking the Potential of Lithium–Sulfur Batteries with Hollow ZnS–SnO ₂ Cubic Heterostructures

The commercialization of lithium–sulfur (Li–S) batteries is hindered by challenges such as the polysulfide shuttle effect, sluggish conversion kinetics, and loss of active materials. Regarding the above issues, through a precisely controlled coprecipitation–hydrothermal–thermal treatment synthesis strategy, this study reports the first successful construction of ZnS–SnO 2 (ZSSO) heterojunction cubes with well-defined porous surfaces and internal hollow structures, which were specifically employed as sulfur host materials. This structure not only integrates the advantages of the individual components but also generates a synergistic enhancement effect through the interfacial built-in electric field. Both theoretical calculations and operando spectroscopic analyses confirm that the heterointerface significantly outperforms every single component in mediating polysulfide conversion, achieving clear cooperative effects. By combining systematic operando characterizations with first-principles calculations, we establish a complete evidence chain linking microscopic electronic structures to macroscopic electrochemical behaviors, offering deep insights and theoretical guidance for the rational design of heterostructure materials. Based on this innovative design, the S@ZSSO cathode exhibits breakthroughs in key electrochemical performance metrics compared with relevant literature reports from the past year, especially in high-rate capability and cycling stability, highlighting its strong potential for practical applications. Experimental results show that the S@ZSSO cathode delivers an initial discharge capacity of 1343.7 mAh g –1 at 0.1C and maintains 603.9 mAh g –1 even at a high rate of 5C. It also demonstrates outstanding cycling stability, retaining 405.8 mAh g –1 after 800 cycles at 0.5C with an extremely low-capacity decay of only 0.063% per cycle. This work provides a simple yet effective host-material design strategy for high-performance Li–S batteries.