Unit‐Compartmentalized and Ensemble Integrated Silicon Laminates for Dense, Fast, and Stable Lithium Storage

Abstract Surface coating is believed to be a requisite to solve the dilemma of high‐capacity but large‐volume‐change silicon. Yet, the advances always prescind from lowered tap density and increased surface area that are crucial for battery operation. Herein, a hierarchical encapsulation strategy is proposed for silicon without compromising tap density and surface area, and actualized by controlling the impregnation process with dissimilar coating precursors. In the design, the laminate structure holds stable building blocks with tap density close to that of intrinsic silicon particles; the internal coating prevents nanosheet agglomeration and provides charge transport pathways, the external coating supervises the granule interface and strengthens the integrity. The laminated silicon exhibits remarkably high volumetric capacity (≈2888 mAh cm −3 @ 0.2 A g −1 ), superior rate capability (≈1200 mAh cm −3 @ 5 A g −1 ), and extraordinary cycling (≈1378 mAh cm −3 @ 2 A g −1 over 500 cycles), opening an avenue for the development of industrially applicable high‐performance silicon technologies.