Synthesis of Activated Ferrosilicon-based Microcomposites by Ball Milling and their Hydrogen Generation Properties

Ferrosilicon 75, a 50:50 mixture of silicon and iron disilicide, has been activated toward hydrogen generation by processing using ball milling, allowing a much lower concentration of sodium hydroxide (2 wt %) to be used to generate hydrogen from the silicon in ferrosilicon with a shorter induction time than has been reported previously. An activation energy of 62 kJ/mol was determined for the reaction of ball-milled ferrosilicon powder with sodium hydroxide solution, which is around 30 kJ/mol lower than that previously reported for unmilled ferrosilicon. A series of composite powders were also prepared by ball milling ferrosilicon with various additives in order to improve the hydrogen generation properties from ferrosilicon 75 and attempt to activate the silicon in the passivating FeSi2 component. Three different classes of additives were employed: salts, polymers and sugars. The effects of these additives on hydrogen generation from the reaction of ferrosilicon with 2 wt% aqueous sodium hydroxide were investigated. It was found that composites formed of ferrosilicon and sodium chloride, potassium chloride, sodium polyacrylate, sodium polystyrene sulfonate-co-maleic acid or fructose showed reduced induction times for hydrogen generation compared to that observed for ferrosilicon alone, and all but fructose also led to an increase in the maximum hydrogen generation rate. In light of its low cost and toxicity and beneficial effects, sodium chloride is considered to be the most effective of these additives for activating the silicon in ferrosilicon toward hydrogen generation. Materials characterisation showed that neither ball milling on its own nor use of additives was successful in activating the FeSi2 component of ferrosilicon for hydrogen generation and the improvement in rate and shortening of the induction period was attributed to the silicon component of the mixture alone The gravimetric storage capacity for hydrogen in ferrosilicon 75 is therefore maintained at only 3.5% rather than the 10.5% ideally expected for a material containing 75% silicon. In light of these results, ferrosilicon 75 does not appear a good candidate for hydrogen production in portable applications.