Enhanced Li‐Ion Battery Performance with Hybrid MXene/GnR Electrodes: Heterojunctions and Engineered Architectures Supported by DFT Mechanistic Studies for Improved Rate Performance, Stability & Capacity

ABSTRACT Lithium‐ion batteries (LIBs) continue to underpin modern energy‐storage technologies, yet their performance is limited by sluggish ion transport, dendrite formation, and structural degradation during cycling. Here, we introduce a binder‐free hybrid electrode composed of Ti ₃ C ₂ T _x MXene and reduced graphene oxide nanoribbons (rGOnRs), engineered through a directional freeze‐casting process to create a porous, mechanically robust 3D architecture. This microstructured network prevents MXene restacking, lowers tortuosity for rapid ion transport, and enables uniform Li‐ion distribution during cycling. Subsequent chemical and thermal reductions convert GOnRs into highly conductive graphene nanoribbons (GnRs) while simultaneously modifying MXene terminal groups, forming conductive heterostructures that enhance electronic coupling and provide additional active sites for reversible Li ⁺ storage. The Ti ₃ C ₂ T _x /GnR electrode delivers a discharge capacity of 401 mAh/g at 0.2 A/g, corresponding to a Coulombic efficiency of ∼97%. After 200 cycles, the electrode retains 92% of its initial capacity, demonstrating excellent cycling stability. Even at 5 A/g, the electrode maintains a high capacity of 370 mAh/g, demonstrating exceptional rate capability and reversibility. Density functional theory (DFT) calculations further reveal favorable charge transfer and lowered Li ⁺ migration barriers at the Ti ₃ C ₂ T _x /GnR interface, supporting the experimentally observed enhancements. Together, the synergistic interplay between microstructuring, terminal‐group engineering, and heterostructure formation establishes a scalable and commercially viable pathway for high‐performance LIB anodes.