Activating silicon for high hydrogen conversion and sustainable anode recovery

The hydrolysis/methanolysis of silicon has received considerable attention to achieve efficient and on-demand hydrogen conversion. However, the intense covalent network and highly localized electrons in pure Si impede its reactivity with water (H2O) or methanol (CH3OH), thereby hindering the hydrogen release. In this work, we report the synthesis of Zintl phase alkalis-Si alloys via simple ball-milling or sintering, showing eminent performance in enhancement of H2O/CH3OH dissociation. Experiments combined with DFT calculations have revealed that the obtained Zintl phase alloys exhibit discrete Si clusters containing well-defined unpaired electrons that efficiently facilitate the interaction between reductant and solvent molecules. Such an effect thereby reduces the activation barrier of H2O/CH3OH dissociation to yield active intermediates containing Si-H structure, which significantly promotes the hydrogen release with favorable kinetics and efficiency. The optimal Zintl Li21Si5 alloy achieves ultrahigh Si utilization rates of 86.9% in water and 98.1% in methanol at 25 °C, respectively. Remarkably, even at an extremely low temperature of −40 °C, a substantial hydrogen yield of 1.091 L g−1 in methanol is retained. Furthermore, the desirable Zintl phase-water reaction inspires an economic-friendly “charge-hydrolysis-separation” strategy, for effectively recovering the valuable lithium, graphite, Si and Cu resources from the degraded lithium-ion batteries.