Graphical Abstract

Defect engineering as efficiency method to modulate the microstructure and electronic structure of cathode for rechargeable magnesium batteries (RMBs). Owing to rich sulfur (S)vacancies tunes the electronic structure of VS4 with rich S vacancies (VS-VS4), the lower oxidation state of V3+ is induced for achieving the V3+/V4+ and V4+/V5+ multi-electrons reaction for Mg2+ storage. Amorphous structure is also constructed in VS-VS4 by chemical vapor deposition (CVD) method under the high temperature for providing fast magnesium ions (Mg2+) diffusion channels and expanding inner stress release space to balance the structural stability of multi-electrons reaction process. The simple defect engineering realizes the stable multi-electrons reaction in VS-VS4 for enhancing its Mg2+ storage performance with higher specific capacity (158.6 mAh g–1 at 50 mA g–1), stable cycling performance (capacity retention ratio of 72.7% after 3600 cycles) and the superior rate capability. This work provides electrode designing guidance for achieving stable multi-electrons to fully utilize the bivalent property of multivalence metal batteries.