Structural characterization of an amorphous VS 4 and its lithiation/delithiation behavior studied by solid-state NMR spectroscopy.

Vanadium sulfide (VS 4 ) is one of the promising positive electrode materials for next-generation rechargeable lithium-ion batteries because of its high theoretical capacity (1196 mA h g -1 ). Crystalline VS 4 has a unique structure, in which the Peierls-distorted one-dimensional chains of V-V bonds along the c axis are loosely connected to each other through van der Waals interactions. In this study, an amorphous VS 4 is prepared by mechanical milling of the crystalline material, and its lithiation/delithiation behavior is investigated by solid-state nuclear magnetic resonance (NMR) spectroscopy. The amorphous VS 4 shows a chain structure similar to that of crystalline VS 4 . The amorphous host structure is found to change drastically during the lithiation process to form Li 3 VS 4 : the V ions become tetrahedrally coordinated by S ions, in which the valence states of V and S ions simultaneously change from V 4+ to V 5+ and S - to S 2- , respectively. When the Li insertion proceeds further, the valence state of V ions is reduced. After the 1 st cycle, the amorphous VS 4 recovers to the chain-like structure although it is highly disordered. No conversion to elemental V is observed, and a high capacity of 700 mA h g -1 is reversibly delivered between 1.5 and 2.6 V.