Interlayer Atomic Stitching in Multilevel Interlayer Spacings Superstructures Unlocks Ultrafast Na‐Ion Storage Over 90,000 Cycles

ABSTRACT Current electrode materials remain constrained by the trilemma among capacity, fast charging, and cycle life. Two‐dimensional material assemblies with multi‐scale integration features offer a route beyond these trade‐offs. Here, interlayer atomic‐scale junctions are introduced to stitch two‐dimensional building blocks into multilevel interlayer‐spacing superstructures for durable ultrafast Na‐ion storage. Metal‐ligand junction‐induced large interlayer spacing, strong interlayer metal‐ion coordination‐induced medium interlayer spacing, and van der Waals force‐induced small interlayer spacing simultaneously enable fast ion migration, superior structural stability, and sufficient ion storage. A series of superstructures were programmably assembled. For high‐performance energy storage, the superstructure with intricately balanced multilevel interlayer spacings exhibits a high specific capacity of 364 mAh g −1 and delivers ultrahigh stability at 30 A g −1 with 85.6% capacity retention over 90,000 cycles and an ultrafast charging time of around 11 s. In full cells, 10,000 cycles can be achieved at 42.5 C. Toward practical applications, full cells with high mass‐loading electrodes deliver a high areal capacity of 3.42 mAh cm −2 at 1.86 mA cm −2 and achieve a lifespan of 1000 cycles at 18.61 mA cm −2 with 79.9% capacity retention. Our work advances the assembly of two‐dimensional materials for high‐performance electrochemical energy storage.