Tailoring Polysulfide Interaction with Balanced d‐Band Center via In Situ Construction of Atomically Dispersed Zr–O_x Sites in Mn₂O₃/β‐MnO₂ Heterostructure for Li–S Batteries

Abstract Although noteworthy research focuses on heterostructured catalysts for efficient polysulfide adsorption in lithium–sulfur (Li–S) batteries, the strategy for maximized electrocatalytic activity is less investigated. Herein, Mn₂O₃/β‐MnO₂ heterostructure electrocatalyst is engineered via in situ regulation of atomically dispersed Zr⁴⁺ sites in the form of Zr–O_x coordinated‐structure as a highly stable freestanding cathode. The fine‐tuned Zr⁴⁺ sites can adjust polysulfide adsorption inducing reduced overpotential, improved Li⁺ mobility, and boosted redox kinetics. Their achievements are synergistically derived from the inhibition of polysulfide migration, utilization of 3D Li₂S nucleation mechanism, and modification of the d‐band center of electrocatalysts, resulting in crack‐free anode‐protection, diffusion‐favorable Li₂S deposition, and sustainable sulfur‐reactions. Eventually, the Zr0.1‐Mn₂O₃/β‐MnO₂@MWCNT cathode demonstrates a high initial capacity of 808 mAh g⁻¹ with a low average decay rate of 0.068% over 1000 cycles at 1 C, even along with an impressive cyclic stability at 5 C showing capacity up to 559.3 mAh g⁻¹ with a decay rate of only 0.170% over 200 cycles. Noteworthy, the electrocatalyst‐applied cell achieves high areal capacity for half‐/full‐cell (N/P: 2.86) up to 4.45/3.88 mAh cm⁻² with 61.7/70.1% retention for 110/50 cycles under 4.6/5.4 mg cm⁻² sulfur loading with electrolyte in 8 µL mg_sulfur ⁻¹. This strategy highlights a new perspective to design an efficient cathode electrocatalyst for high‐performance Li–S batteries.