Integrated d‐p Orbital Coupling Within High‐Entropy Oxide/Halloysite Accelerates Sulfur Reduction Kinetics in Sodium‐Sulfur Batteries

ABSTRACT The sodium polysulfides (NaPSs) shuttle effect remains a major obstacle to achieving the high theoretical capacity of room‐temperature sodium‐sulfur (RT Na–S) batteries. Herein, the high‐entropy oxide/halloysite nanotube hybrid host (HEO/HNT) is developed by integrating multicomponent catalytic sites with a naturally abundant 1D clay scaffold for efficient sulfur conversion. The hollow tubular structure of HNT enables uniform HEO anchoring and effective confinement of sulfur species, while the robust Si─O and Al─OH framework enhances cathode stability during long‐term cycling. Density functional theory calculations reveal that interfacial coupling between the metal 3d orbitals of HEO and the Al/Si 3p orbitals of HNT induces extended orbital delocalization, thereby strengthening NaPSs adsorption and lowering the free energy barriers for stepwise polysulfide conversion. In situ and ex situ characterizations further verify accelerated NaPSs reduction kinetics and suppressed shuttling. Benefiting from these synergistic effects, the S@HEO/HNT cathode delivers a high reversible capacity of 1225 mAh g −1 after 450 cycles at 1 C and maintains 478 mAh g −1 over 2500 cycles at 10 C, corresponding to an ultralow capacity fading of 0.008% per cycle. This study bridges high‐entropy oxide with naturally abundant clay substrates, offering a scalable route toward durable, high‐rate RT Na–S batteries.