Local Built‐In Field at the Sub‐nanometric Heterointerface Mediates Cascade Electrochemical Conversion of Lithium–sulfur Batteries

Abstract Heterogeneous catalytic mediators have been proposed to play a vital role in enhancing the multiorder reaction and nucleation kinetics in multielectron sulfur electrochemistry. However, the predictive design of heterogeneous catalysts is still challenging, owing to the lack of in‐depth understanding of interfacial electronic states and electron transfer on cascade reaction in Li–S batteries. Here, a heterogeneous catalytic mediator based on monodispersed titanium carbide sub‐nanoclusters embedded in titanium dioxide nanobelts is reported. The tunable catalytic and anchoring effects of the resulting catalyst are achieved by the redistribution of localized electrons caused by the abundant built‐in fields in heterointerfaces. Subsequently, the resulting sulfur cathodes deliver an areal capacity of 5.6 mAh cm⁻² and excellent stability at 1 C under sulfur loading of 8.0 mg cm⁻². The catalytic mechanism especially on enhancing the multiorder reaction kinetic of polysulfides is further demonstrated via operando time‐resolved Raman spectroscopy during the reduction process in conjunction with theoretical analysis.