Accelerating Near‐Electrode Li ⁺ Transport via High‐Electronegativity Substrates for Sustainable Fast‐Charging Lithium Metal Batteries

Abstract Electronegativity engineering offers a powerful yet underexplored paradigm for regulating interfacial ion transport in rechargeable lithium metal batteries (LMBs), where uncontrolled dendrite growth and unstable solid electrolyte interphases (SEIs) remain critical bottlenecks for fast‐charging and high‐energy applications. Here, an oxygen‐functionalized MXene (Ti 3 C 2 O x ) scaffold with expanded interlayer spacing and high surface electronegativity, enabling cationophilic confinement of Li + flux, is demonstrated. Density functional theory calculations and finite element simulations reveal that electronegative oxygen terminations induce a uniform interfacial Li + concentration field, reduce nucleation overpotential, and promote the in situ formation of a Li 2 O‐rich SEI with superior Li + conductivity. This architecture delivers a Coulombic efficiency of 99.41% over 1600 cycles and sustains 1600 h of stable operation in symmetric cells with an ultralow overpotential of 11 mV. Practical full‐cell tests confirm its robustness, with a 1 Ah Ti 3 C 2 O x @Li||LiFePO 4 pouch cell achieving an energy density of 238.06 Wh kg −1 at an electrolyte‐to‐capacity ratio of 2.5 g Ah −1 while retaining 93.72% of its capacity after 40 cycles. Beyond a material advance, this work establishes electronegativity‐tailored interfacial engineering as a universal design principle to harmonize electrochemical kinetics and mass transport, paving the way for dendrite‐free, high‐rate, and high‐loading lithium metal anodes.