LAUSR

Currently, the construction of amorphous/crystalline (A/C) heterophase has become an advanced strategy to modulate electronic and/or ionic behaviors and promote structural stability due to their concerted advantages. However, their different kinetics limit the synergistic effect. Further, their interaction functions and underlying mechanisms remain unclear. Here, a unique engineered defect‐rich V2O3 heterophase structure (donated as A/C‐V2O3−x@C‐HMCS) composed of mesoporous oxygen‐deficient amorphous − hollow core (A‐V2O3−x/HMC) and lattice‐distorted crystalline shell (C‐V2O3/S) encapsulated by carbon is rationally designed via a facile approach. Comprehensive density functional theory (DFT) calculations disclose that the lattice distortion enlarges the porous channels for Na+ diffusion in the crystalline phase, thereby optimizing its kinetics to be compatible with the oxygen‐vacancy‐rich amorphous phase. This significantly reduces the high contrast of the kinetic properties between the crystalline and amorphous phases in A/C‐V2O3−x@C‐HMCS and induces the formation of highly dense A/C interfaces with a strong synergistic effect. As a result, the dense heterointerface effectively optimizes the Na+ adsorption energy and lowers the diffusion barrier, thus accelerating the overall kinetics of A/C‐V2O3−x@C‐HMCS. In contrast, the perfect heterophase (defects‐free) A/C‐V2O3@C‐HCS demonstrates sparse A/C interfacial sites with limited synergistic effect and sluggish kinetics. As expected, the A/C‐V2O3−x@C‐HMCS achieves a high rate and ultrastable performance (192 mAh g−1 over 6000 cycles at 10 A g−1) when employed for the first time as a cathode for sodium‐ion batteries (SIBs). This work provides general guidance for realizing dense heterophase cathode design for high‐performance SIBs and beyond.