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Electrochemical behaviors of Ln3+ in LnF3-LiCl-KCl molten salt
- NUCLEAR TECHNIQUES Vol. 41, Issue 6, Article number: 060301(2018)
- 作者机构：
1.中国科学院上海应用物理研究所 嘉定园区 上海 201800
2.中国科学院大学 北京 100049
- 作者简介：
- 基金信息：Strategic Priority Program of Chinese Academy of Sciences;National Natural Science Foundation of China;Youth Innovation Promotion Association of Chinese Academy of Sciences
DOI：10.11889/j.0253-3219.2018.hjs.41.060301
CLC： TL426Received：16 June 2017，
Revised：20 October 2017，
Published：10 June 2018
- 稿件说明：
移动端阅览
Xianbin WANG, Dewu LONG, Tiejian ZHU, et al. Electrochemical behaviors of Ln3+ in LnF3-LiCl-KCl molten salt[J]. Nuclear techniques, 2018, 41(6): 060301
Xianbin WANG, Dewu LONG, Tiejian ZHU, et al. Electrochemical behaviors of Ln3+ in LnF3-LiCl-KCl molten salt[J]. Nuclear techniques, 2018, 41(6): 060301 DOI： 10.11889/j.0253-3219.2018.hjs.41.060301.
摘要
钍的分离和再利用是熔盐堆钍铀燃料循环的重要组成部分，钍与裂变产物特别是化学性质相似的镧系元素的分离是熔盐堆氟盐燃料处理的关键之一。利用循环伏安法和方波伏安法研究了773 K下多种镧系元素氟化物（
w
=3%）在LnF
3
-LiCl-KCl熔盐中的电化学行为。研究结果表明：Ce
3+
和Gd
3+
在惰性电极上均一步还原为金属，Nd
3+
则是通过两步反应还原为金属，而Sm
3+
和Eu
3+
只能还原为低价态的Sm
2+
和Eu
2+
；Th和Ln在惰性金属阴极上的析出电位差Δ
E
均大于0.19 V，在LiCl-KCl熔盐体系中实现Th与Ln的电化学分离在理论上是可行的；与纯氯盐体系相比，少量F
-
的引入不会改变Ln
3+
在惰性电极上的电极反应过程，F
-
的存在使得Ln
3+
在LiCl-KCl熔盐中的活度降低，从而导致扩散系数减小。此研究结果为了解Th
4+
和Ln
3+
在含F
-
氯盐体系中的电化学行为和建立可行的分离方法提供了基础实验依据。
Abstract
Background
2
The separation and cyclic utilization of thorium is an important part of thorium-uranium fuel cycle for molten salt reactor. Therefore
separation of thorium from fission products
especially lanthanides
is the key step to electrochemical separation of thorium in molten salt because of their similar chemical properties.
Purpose
2
The aim of this work is to explore the influence of fluorine ion (F
-
) on electrochemical properties of 5 lanthanides in LnF
3
-LiCl-KCl molten salt and to confirm the feasibility of electrochemical separation of thorium from lanthanides in chloride molten salt.
Methods
2
Transient electrochemical techniques such as cyclic voltammetry and square wave voltammetry were employed to investigate the reduction mechanism and diffusion coefficient of Ln ions on a tungsten inert electrode.
Results
2
In LnF
3
-LiCl-KCl molten salt
Ce
3+
and Gd
3+
were reduced into metal Ce and Gd according to a one-step process by exchanging 3 electrons; Nd
3+
was reduced into metal Nd through two steps; Sm
3+
and Eu
3+
couldn't be reduced into metal in tungsten electrode
and both of them were transformed into divalent state. The existence of F
-
would not change the electrode reaction process of Ln cations. The differences of deposition potential between Th and the 5 Lns on inert electrode were larger than 0.19 V
which demonstrated theoretically that it was feasible to separate Th from Lns in LiCl-KCl molten salt. Compared with pure chloride molten salt
the existence of F
-
decreased the activity of Ln
3+
resulting in the decrease of diffusion efficiency of all Ln ions.
Conclusion
2
The study provided experimental foundation for feasibility investigation of the separation of thorium fluoride from lanthanides fluoride in LiCl-KCl molten salt.
关键词
Keywords
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