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

MoS₂ 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 MoS₂, 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 MoS₂ 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 MoS₂ 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 MoS₂ to avoid fracture ushers in new possibilities to enhance the lithium storage of layered transition‐metal dichalcogenides.