Approaching the Lithiation Limit of MoS₂ While Maintaining Its Layered Crystalline Structure to Improve Lithium Storage

MoS 2 holds great promise as high‐rate electrode for lithium‐ion batteries since its large interlayer can allow fast lithium diffusion in 3.0–1.0 V. However, the low theoretical capacity (167 mAh g −1 ) limits its wide application. Here, by fine tuning the lithiation depth of MoS 2 , we demonstrate that its parent layered structure can be preserved with expanded interlayers while cycling in 3.0–0.6 V. The deeper lithiation and maintained crystalline structure endows commercially micrometer‐sized MoS 2 with a capacity of 232 mAh g −1 at 0.05 A g −1 and circa 92 % capacity retention after 1000 cycles at 1.0 A g −1 . Moreover, the enlarged interlayers enable MoS 2 to release a capacity of 165 mAh g −1 at 5.0 A g −1 , which is double the capacity obtained under 3.0–1.0 V at the same rate. Our strategy of controlling the lithiation depth of MoS 2 to avoid fracture ushers in new possibilities to enhance the lithium storage of layered transition‐metal dichalcogenides.