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Development of innovative process for producing metalic lithium by converting raw material

开发通过原材料转化生产金属锂的创新工艺

基本信息

批准号：
12555204
负责人：
SATO Yuzuru
金额：
$ 8.51万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2002
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12555204/
关键词：
molten salt lithium carbonate lithium electrolysis diaphragm LiCl-KCl eutectic salt preceding and following reaction rate determining step 律速段階溶解塩塩化リチウム

项目摘要

The goal of present project is to establish the process for producing metallic lithium, which is important material as a negative electrode of high performance battery, with low cost by using Li_2CO_3 in stead of LiCl as a raw material. Li_2CO_3 has many advantages such as low price, no hygroscopicity and high purity compared with LiCl. Furthermore, the decomposition potential of Li_2CO_3 is about 1.5V lower than LiCl by reacting carbon anode. However, it was difficult to use Li2CO3 dissolved in the electrolyte directly because it reacts with metallic lithium deposited on the cathode.Therefore, the project was performed based on the idea that the electrolyte is divided with ceramic diaphragm into catholyte and anolyte. Lithium deposits on the cathode dipped in the catholyte which consists of just LiCl-KCl eutectic melt. On the other hand, Li_2CO_3 is fed into the anolyte and reacts with graphite anode to evolve CO_2 which is easy disposable compared with Cl_2.At first, the electrolysis … More was carried out at 400C^0 by using just LiCl-KCl eutectic melt to study the current efficiency of lithium deposition on the cathode! It was confirmed that high current efficiency higher than 90% was obtained. Next, anodic potential was studied to study the reaction of CO_3^<2-> by feeding Li_2CO_3 into the LiCl-KCl anolyte under 500C^0. As the result, reaction rate was very slow although the potential change was found.Based on above results, further experiments were performed at higher temperatures up to 800C^0. The anodic potential was found to decrease drastically by increasing temperature. Namely, the reaction to consume CO_3^<2-> has very strong temperature dependence. The mechanism of the reaction on the anode was clear as follows; first stage is CI_2 evolution and second stage is the reaction of CO_3^<2-> with graphite and Cl_2. First stage reaction occurs easily. However, second stage reaction has high activation energy. Therefore, second stage becomes the rate determining step. It was clear that the temperature higher than 650C^0 was effective to consume CO_3^<2-> sufficiently. It is considered that the knowledge obtained in this project is very useful to realize the process to use Li_2CO_3 as the raw material for producing lithium. Less

本课题的目标是建立以Li_2CO_3代替LiCl为原料，以低成本生产高性能电池负极材料金属锂的工艺。Li_2CO_3与LiCl相比具有价格低廉、无吸湿性、纯度高等优点。此外，Li_2CO_3的分解电位比LiCl低1.5V左右。然而，由于Li 2CO 3会与沉积在阴极上的金属锂发生反应，难以直接使用溶解在电解液中的Li 2CO 3，因此本项目基于将电解液用陶瓷隔膜分为阴极电解液和阳极电解液的想法进行。锂沉积在浸入由LiCl-KCl共晶熔体组成的阴极电解液中的阴极上。另一方面，在阳极液中加入Li_2CO_3，与石墨阳极反应生成CO_2，与Cl_2相比，CO_2更易处理。 ...更多信息在400 C^0下仅使用LiCl-KCl低共熔熔体进行，以研究锂在阴极上沉积的电流效率！证实获得高于90%的高电流效率。其次，<2->在500 ℃下，通过向LiCl-KCl阳极液中加入Li_2CO_3，研究了CO_3的反应。结果表明，虽然发现了电位的变化，但反应速率很慢。在上述结果的基础上，在更高的温度下进行了进一步的实验，直到800C^0。阳极电位随温度的升高而急剧下降。也就是说，消耗CO_3的反应<2->具有很强的温度依赖性。阳极上的反应机理如下：第一阶段为Cl_2析出，第二阶段为CO_3<2->与石墨和Cl_2的反应。第一阶段反应容易发生。而第二阶段反应具有较高的活化能。因此，第二阶段成为速率确定步骤。温度高于650C^0有利于CO_3 ~（2+）的充分消耗<2->。认为本课题所获得的知识对实现以Li_2CO_3为原料生产锂的工艺具有重要意义。少