Mo3S13 Cluster-Based Cathodes for Rechargeable Magnesium Batteries: Reversible Magnesium Association/Dissociation at the Bridging Disulfur along with Sulfur–Sulfur Bond Break/Formation

Multivalent cation batteries are attracting increasing attention in energy-storage applications, but reversible storage of highly polarizing multivalent cations is a major difficulty for the electrode materials. In the present study, charge-delocalizing Mo₃S₁₃ cluster-based materials (crystalline (NH₄)₂Mo₃S₁₃ and amorphous MoS_x) are designed and investigated as cathodes for rechargeable magnesium batteries. Both of the cathodes show high magnesium storage capacities (296 and 302 mAh g^-1 at 100 mA g^-1) and superior rate performances (76 and 80 mAh g^-1 at 15 A g^-1). A high area loading of 3.0 mg cm^-2 could be achieved. These performances are of the highest level compared with those of reported magnesium storage materials. Further mechanism study and theoretical computation demonstrate the magnesium storage active sites are the bridging disulfur groups of the Mo₃S₁₃ cluster. The valence state of bridging disulfur decreases/increases largely during magnesiation/demagnesiation along with breaking/formation of the sulfur-sulfur bond, which makes the Mg-association/dissociation highly reversible. The sulfur-sulfur bond breaking and formation provides high reversible capacities. Prominently, the valence state increase and sulfur-sulfur bond formation of the bridging disulfur during charge weakens the bonding with Mg²⁺, significantly assisting the magnesium dissociation. The present study not only develops high-performance magnesium storage cathode materials but also demonstrates the importance of constructing favorable magnesium storage active sites in the high-performance cathode materials design. The findings presented herein are of great significance for the development of electrode materials for the storage of multivalent cations.