Carbon-Free Conversion of SiO(2) to Si via Ultra-Rapid Alloy Formation: Toward the Sustainable Fabrication of Nanoporous Si for Lithium-Ion Batteries

[Image: see text] Silicon has the potential to improve lithium-ion battery (LIB) performance substantially by replacing graphite as an anode. The sustainability of such a transformation, however, depends on the source of silicon and the nature of the manufacturing process. Today’s silicon industry still overwhelmingly depends on the energy-intensive, high-temperature carbothermal reduction of silica—a process that adversely impacts the environment. Rather than use conventional thermoreduction alone to break Si–O bonds, we report the efficient conversion of SiO(2) directly to Mg(2)Si by a microwave-induced Mg plasma within 2.5 min at merely 200 W under vacuum. The underlying mechanism is proposed, wherein electrons with enhanced kinetics function readily as the reductant while the “bombardment” from Mg cations and electrons promotes the fast nucleation of Mg(2)Si. The 3D nanoporous (NP) Si is then fabricated by a facile thermal dealloying step. The resulting hierarchical NP Si anodes deliver stable, extended cycling with excellent rate capability in Li-ion half-cells, with capacities several times greater than graphite. The microwave-induced metal plasma (MIMP) concept can be applied just as efficiently to the synthesis of Mg(2)Si from Si, and the chemistry should be extendable to the reduction of multiple metal(loid) oxides via their respective Mg alloys.