Interfacial Charge Redistribution–Driven Two‐Electron Conversion in Ni _0.85 Se@Mo‐Doped NiCo‐LDH for High‐Power Electrochemical Energy Storage

ABSTRACT Rational structural engineering and electronic modulation are vital for advancing high‐performance electrochemical energy storage. Herein, we construct a hierarchical Ni _0.85 Se@Mo‐doped NiCo‐LDH heterostructure (NS@MNC‐LDH) directly on hydrophilic carbon cloth (HCC) to achieve uniform nucleation and strong interfacial coupling (NS@MNC‐LDH/HCC). The conductive Ni _0.85 Se core provides fast electron transport and mechanical robustness, while the Mo‐doped NiCo‐LDH shell introduces abundant oxygen vacancies and optimized electronic states to enrich redox‐active sites. Combined experiments and density functional theory calculations reveal pronounced interfacial charge redistribution that accelerates ion/electron transport and enables efficient multi‐electron transfer. Distribution of relaxation times analysis and in situ Raman spectroscopy further verify rapid charge‐transfer kinetics and highly reversible NiCo‐LDH/Ni(Co)OOH/Ni(Co)O ₂ conversions. Benefiting from these synergistic effects, NS@MNC‐LDH/HCC delivers an ultrahigh capacity of 540.8 mAh g ⁻¹ at 1 A g ⁻¹ , approaching a two‐electron transfer capacity, along with 81.8% retention at 32 A g ⁻¹ . The assembled hybrid supercapacitor achieves an energy density of 128.5 Wh kg ⁻¹ at 750 W kg ⁻¹ and maintains 83.8% of its capacity after 10 000 cycles. This work demonstrates that interfacial electronic coupling combined with defect‐regulated multi‐electron transfer provides a powerful and generalizable design principle for next‐generation high‐power energy storage materials.