基于LiCl-LiF熔盐中Li2CO3在钨电极上的电化学行为.docVIP

LiCl-LiF熔盐中Li2CO3在钨电极上的电化学行为 张保国，赫婷婷，李继东，王一雍 （辽宁科技大学 材料与冶金学院，辽宁鞍山 114051） 摘要：680 ℃、LiCl-LiF纯锂盐体系，以Li2CO3为原料熔盐电解法制备金属锂。采用电化学方法（循环伏安、计时电位法）分析了Li2CO3在钨丝工作电极上的电化学行为。金属锂在钨丝电极上的还原为一步得电子可逆反应过程，在氯气析出峰前的氧化峰为加入Li2CO3所致，Li2CO3在电场作用下分解成氧化锂和二氧化碳，氧离子在氯气析出峰前放电生成氧气。往LiCl-LiF熔盐体系加入1% Li2CO3使锂离子的扩散系数由1.98×10-8 cm2/s减到0.82×10-8 cm2/s，最小还原电流密度由0.28 A/cm2增加到0.59 A/cm2，且锂离子在钨丝电极上的电化学还原过程由扩散环节控制。 关键词：碳酸锂；电化学；纯锂盐体系；熔盐电解 中图分类号：TF111.52+2；TF826+.3 文献标志码：A 文章编号：1007-7545（2016）02-0000-00 Electrochemical Behavior of Li2CO3 on Tungsten Electrode in LiCl-LiF Molten Salt ZHANG Bao-guo, HE Ting-ting, LI Ji-dong, WANG Yi-yong (School of Materials and Metallurgy, University of Science and Technology Liaoning, Anshan 114051, Liaoning, China) Abstract: Li2CO3 was used as raw materials to prepare lithium metal in LiCl-LiF pure lithium salt system at 680 ℃ by molten salt electrolysis method. Electrochemical behavior of Li2CO3 on tungsten electrode was analyzed by electrochemical methods such as cyclic voltammetry and chronopotentiometry. The results show that lithium metal reduction on tungsten electrode is one step electron reversible reaction process. There is an oxidation peak before chlorine emission peak, which is caused by addition of Li2CO3 under electric field. Li2CO3 decomposes into lithium oxide and carbon dioxide. Oxygen ions are discharged to produce oxygen before chlorine emission peak. Diffusion coefficient of lithium ion drops from 1.98×10-8 cm2/s to 0.82×10-8 cm2/s after addition of 1%Li2CO3 to LiCl-LiF molten salt system, and the minimal reduction current density rises from 0.28 A/cm2 to 0.59 A/cm2. The electrochemical reduction process of lithium on tungsten electrode is controlled by diffusion. Key words: lithium carbonate; electrochemical; pure lithium salt system; molten salt electrolysis 金属锂在炼铝、陶瓷、润滑脂、石油等传统领域得到了广泛应用，随着在航空航天、能源电池、热核聚变、轻质合金、医药、纺织等新兴技术领域的不断拓展，近年来金属锂的生产规模和产量得到迅速提高[1-2]。 传统的生产金属锂的方法是电解氯化锂—氯化钾熔盐，电解过程中阳极放出大量氯气，对环境污染很严重，并且原料特别昂贵[3-4]，如今熔盐电解氧化物制备金属或者合金是熔盐电解的发展方向[5]。本课题组在过去