Molecular Engineering on MoS2 Enables Large Interlayers and Unlocked Basal Planes for High‐Performance Aqueous Zn‐Ion Storage

Aqueous Zn‐storage behaviors of MoS2‐based cathodes mainly rely on the ion‐(de)intercalation at edge sites but are limited by the inactive basal plane. Herein, an in‐situ molecular engineering strategy in terms of structure defects manufacturing and O‐doping is proposed for MoS2 (designated as D‐MoS2‐O) to unlock the inert basal plane, expand the interlayer spacing (from 6.2 to 9.6 Å), and produce abundant 1T‐phase. The tailored D‐MoS2‐O with excellent hydrophilicity and high conductivity allows the 3D Zn2+ transport along both the ab plane and c‐axis, thus achieving the exceptional high rate capability. Zn2+ diffusion through the basal plane is verified by DFT computations. As a proof of concept, the wearable quasi‐solid‐state rechargeable Zn battery employing the D‐MoS2‐O cathode operates stably even under severe bending conditions, showing great application prospects. This work opens a new window for designing high‐performance layered cathode materials for aqueous Zn‐ion batteries. In‐situ molecular engineering of structure defect manufacturing and O‐doping unlocks the MoS2 basal plane and simultaneously upgrades its interlayer spacing (from 6.2 to 9.6 Å), hydrophilicity, and electrical conductivity. These merits enable highly efficient 3D Zn‐ion transport in the MoS2 lattice along both the ab plane and c‐axis, thus leading to fast reaction kinetics and the exceptional rate performance in aqueous Zn‐ion batteries.