冰晶石熔盐体系下电沉积硅及电化学行为研究 - 中国科技论文在线.pdf

中国科技论文在线 冰晶石熔盐体系下电沉积硅及电化学行为 # 研究 * 田忠良，贾明 （中南大学冶金科学与工程学院，长沙 410083 ） 摘要：在冰晶石体系下，系统研究了硅沉积的电化学行为及影响因素。在此基础上，分别研 究了固态阴极和液态合金阴极上沉积硅形貌及形成机理。研究结果表明：Si (Ⅳ) 的电化学还 原过程是分步的，在有单质硅存在的情况下，会有反应：Si (Ⅳ) + Si= 2 Si ( Ⅱ)；一般情况下 Al 的析出电位比Si 要负，但在电极表面Si 离子匮乏的情况下，Al 会与Si 一起共沉积；由 于合金的去极化作用，Si 的还原电位比采用固态电极时更正，在这种情况下Si 更容易析出； 恒流电解固态电极上沉积硅呈颗粒状并与电解质夹杂，通过分离可以获得单质硅，所获硅纯 度99% ，硼、磷含量较低；直接电解制备Cu-Si 合金过程稳定，电解后合金中硅含量明显 升高，电流效率为 60%左右。采用液态电极的方法，将直接电解与精炼结合，有望实现电 化学方法制备高纯硅。 关键词： 电化学；硅；熔盐；电解；液态电极 中图分类号：TF111.522 Electrochemical study of the deposition of silicon from Na3AlF6-K2SiF6/SiO2 melts TIAN Zhongliang, JIA Ming (School of metallurgical science and engineering,Central South University, Changsha 410083) Abstract: In order to develop a new production process for very pure silicon, a fundamental electrochemical study of Si in Na3AlF6-LiF-K2SiF6/SiO2 melts and electrolysis using a small-scale laboratory cell was conducted. Cyclic voltammograms (CVs) showed that the reduction of Si proceeds by two successive electron transfers and the presence of Si( Ⅱ) species in the melt has been confirmed. Consistent with the thermodynamical data, the reduction of the Si ion was easier than Na and Al ions in such melts. Galvanostatic electrolysis showed that deposited silicon crystal does not form any dense and massive layer at the graphite cathode as some metals do, but is generally dispersed in the deposit around the cathode. Besides, co-deposition of Al and Si is possible when the appl