Hierarchical Architecture Engineering of Branch‐Leaf‐Shaped Cobalt Phosphosulfide Quantum Dots: Enabling Multi‐Dimensional Ion‐Transport Channels for High‐Efficiency Sodium Storage

New-fashioned electrode hosts for sodium-ion batteries (SIBs) are elaborately engineered to involve multifunctional active components that can synergistically conquer the critical issues of severe volume deformation and sluggish reaction kinetics of electrodes toward immensely enhanced battery performance. Herein, it is first reported that single-phase CoPS, a new metal phosphosulfide for SIBs, in the form of quantum dots, is successfully introduced into a leaf-shaped conductive carbon nanosheet, which can be further in situ anchored on a 3D interconnected branch-like N-doped carbon nanofiber (N-CNF) to construct a hierarchical branch-leaf-shaped CoPS@C@N-CNF architecture. Both double carbon decorations and ultrafine crystal of the CoPS in-this exquisite architecture hold many significant superiorities, such as favorable train-relaxation, fast interfacial ion-migration, multi-directional migration pathways, and sufficiently exposed Na+ -storage sites. In consequence, the CoPS@C@N-CNF affords remarkable long-cycle durability over 10 000 cycles at 20.0 A g-1 and superior rate capability. Meanwhile, the CoPS@C@N-CNF-based sodium-ion full cell renders the potential proof-of-feasibility for practical applications in consideration of its high durability over a long-term cyclic lifespan with remarkable reversible capacity. Moreover, the phase transformation mechanism of the CoPS@C@N-CNF and fundamental springhead of the enhanced performance are disclosed by in situ X-ray diffraction, ex situ high-resolution TEM, and theoretical calculations.