3D Tunnel Copper Tetrathiovanadate Nanocube Cathode Achieving Ultrafast Magnesium Storage Reactions through a Charge Delocalization and Displacement Mechanism

Rechargeable magnesium batteries are attractive candidates for large-scale energy storage applications because of the low cost and high safety, but the scarcity and inferior performance of the cathode materials are hindering the development. In the present study, a kind of copper tetrathiovanadate (Cu₃VS₄) cathode is designed and developed with a comprehensive consideration of the chemical and electronic structures. The vanadium and sulfur atoms form chemical bonds with high covalent proportion, facilitating electron delocalization via the vanadium-sulfur bonds. This reduces the interaction with the bivalent magnesium cation and induces the coredox of vanadium and sulfur. The crystal structure of Cu₃VS₄ has interlaced 3D tunnels for solid-state magnesium cation transport. The Cu₃VS₄ cathode shows a high capacity of 350 mA h g^-1 at 100 mA g^-1, an outstanding rate performance of 67 mA h g^-1 at 10 A g^-1, and stable cycling for 1000 cycles at 5 A g^-1 without obvious capacity fading. Prominently, a high areal mass load of 3.5 mg cm^-2 could be achieved without obvious rate capability decay, which is quite favorable to pair with the high-capacity magnesium metal anode in practical application. The mechanism investigation and theoretical computation demonstrate that Cu₃VS₄ undergoes first a magnesium intercalation and then a displacement reaction, during which the crystal structure is maintained, assisting the reaction reversibility and cycling stability. All the copper, vanadium, and sulfur elements experience redox and contribute to the high capacity. Moreover, the weakened interaction with magnesium cations, well-kept 3D cation transport tunnels, and high electronic conductivity result in the superior rate performance and high areal active material loading. The present study develops a high-performance cathode for rechargeable magnesium batteries and reveal the design principle based on both of chemical and electronic structures.