Slag Treatment Followed by Acid Leaching as a Route to Solar-Grade Silicon

Refining of metallurgical-grade silicon was studied using a process sequence of slag treatment, controlled cooling, and acid leaching. A slag of the Na2O-CaO-SiO2 system was used. The microstructure of grain boundaries in the treated silicon showed enhanced segregation of impurities, and the formation of CaSi2 and other Ca-rich phases. Boron and phosphorus were found in the grain boundary phases of silicon after the slag treatment and were successfully removed together with most of the metallic impurities by acid leaching. The interaction between silicon and slag and the distribution of impurities are discussed. A novel mechanism of the refining approach is proposed, based on the microstructure of silicon and the analysis of impurities at each refining step. Parallel processes of slag refining, segregation, and solvent refining were observed, which explains the relatively high efficiency of the proposed refining technology. The investigated combination of refining processes followed by acid leaching has great potential as an efficient and cost-saving route for upgrading metallurgical-grade to solar-grade silicon.Materials Innovation InstituteMechanical, Maritime and Materials Engineerin

The Role of Granule Size on the Kinetics of Electrochemical Reduction of SiO2 Granules in Molten CaCl2

As a fundamental study to develop a new process for producing solar-grade silicon, the effect of granule size on the kinetics of the electrochemical reduction of SiO2 granules in molten CaCl2 was investigated. SiO2 granules with different size ranges were electrolyzed in molten CaCl2 at 1123 K (850 °C). The reduction kinetics was evaluated on the basis of the growth rate of the reduced Si layer and the behavior of the current during electrolysis. The results indicated that finer SiO2 granules are more favorable for a high reduction rate because the contact resistance between the bottom Si plate and the reduced Si particles is small and the diffusion of O2− ions in CaCl2 inside the porous Si shell is easy. Electrolysis using SiO2 granules less than 0.1 mm in size maintained a current density of no less than 0.4 A cm−2 within 20 minutes, indicating that the electrochemical reduction of fine SiO2 granules in molten CaCl2 has the potential of becoming a high-yield production process for solar-grade silicon