Endothermic Dehydrogenation-Driven Preventive Magnesiation of SiO for High-Performance Lithium Storage Materials

Silicon monoxide (SiO)-based materials have gained much attention as high-capacity lithium storage materials based on their high capacity and stable capacity retention. However, low initial Coulombic efficiency associated with the irreversible electrochemical reaction of the amorphous SiO₂ phase in SiO inhibits the wide usage of SiO-based anode materials for lithium-ion batteries. Magnesiation of SiO is one of the most promising solutions to improve the initial efficiency of SiO-based anode materials. Herein, we demonstrate that endothermic dehydrogenation-driven magnesiation of SiO employing MgH₂ enhanced the initial Coulombic efficiency of 89.5% with much improved long-term cycle performance over 300 cycles compared to the homologue prepared by magnesiation of SiO with Mg and pristine SiO. High-resolution transmission electron microscopy with thermogravimetry-differential scanning calorimetry revealed that the endothermic dehydrogenation of MgH₂ suppressed the sudden temperature rise during magnesiation of SiO, thereby inhibiting the coarsening of the active Si phase in the resulting Si/Mg₂SiO₄ nanocomposite.