物理化学学报 >> 2013, Vol. 29 >> Issue (08): 1698-1704.doi: 10.3866/PKU.WHXB201305102

电化学和新能源 上一篇    下一篇

MgCl2在LiCl-KCl熔盐中的电化学特性

唐浩1, 颜永得1,2, 张密林1, 薛云2, 张志俭2, 杜卫超1, 何辉3   

  1. 1 哈尔滨工程大学材料科学与化学工程学院, 超轻材料与表面技术教育部重点实验室, 哈尔滨 150001;
    2 哈尔滨工程大学核科学与技术学院, 哈尔滨 150001;
    3 中国原子能研究院, 北京102413
  • 收稿日期:2013-02-25 修回日期:2013-05-10 发布日期:2013-07-09
  • 通讯作者: 颜永得 E-mail:y5d2006@hrbeu.edu.cn
  • 基金资助:

    国家高技术研究发展计划(2011AA03A409); 国家自然科学基金(21103033, 21101040, 91226201); 中央高校基本科研业务经费(HEUCF201310012)和黑龙江省普通高等学校青年学术骨干支持计划项目(1253G016)资助

Electrochemistry of MgCl2 in LiCl-KCl Eutectic Melts

TANG Hao1, YAN Yong-De1,2, ZHANG Mi-Lin1, XUE Yun2, ZHANG Zhi-Jian2, DU Wei-Chao1, HE Hui3   

  1. 1 Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, P. R. China;
    2 Key Discipline Laboratory of Nuclear Safety and Simulation Technology, Harbin Engineering University, Harbin 150001, P. R. China;
    3 China Institute of Atomic Energy, Beijing 102413, P. R. China
  • Received:2013-02-25 Revised:2013-05-10 Published:2013-07-09
  • Contact: YAN Yong-De E-mail:y5d2006@hrbeu.edu.cn
  • Supported by:

    The project was supported by the High Technology Research and Development Program of China (2011AA03A409), National Natural Science Foundation of China (21103033, 21101040, 91226201), Fundamental Research Funds for the Central Universities, China (HEUCF201310012), and Foundation for University Key Teacher of Heilongjiang Province of China (1253G016).

摘要:

研究了温度范围在723-908 K的LiCl-KCl 熔盐体系中MgCl2的电化学行为和热力学性质. 循环伏安和方波伏安法研究表明镁离子的电化学还原过程为包含了两个电子转移的一步反应. 利用Berzins 和Delahay 方程计算了不同温度下的镁离子的扩散系数, 并通过Arrhenius 公式计算了镁离子在LiCl-KCl 熔盐体系中的扩散活化能. 采用开路计时电位法得到了不同温度下的Mg(II)/Mg(0)体系的平衡电位, 并结合电动势法计算了在LiCl-KCl 熔盐体系中Mg(II)/Mg(0)体系的标准形式电位. 根据不同温度下的标准形式电位, 计算得到了MgCl2在LiCl-KCl 熔盐体系中的熵变和焓变以及不同温度下的活度系数.

关键词: 氯化物熔盐, 热力学性质, MgCl2活度系数, 标准形式电位

Abstract:

The electrochemical behavior and thermodynamic properties of MgCl2 dissolved in LiCl-KCl eutectic melts in the temperature range of 723-908 K were investigated. Cyclic and square wave voltammetry experiments indicated that the reduction of Mg ions into Mg metal occurred in a single step and involved exchange of two electrons. The diffusion coefficient (D) of Mg(II) was determined by the Berzins-Delahay equation and the Arrhenius law was validated by plotting lgD versus T-1 for the reduction of Mg(II). Open circuit chronopotentiometry was used to determine the equilibrium potential of Mg(II)/Mg(0). The standard apparent potentials of the Mg(II)/Mg(0) system and the activity coefficients of Mg(II) in LiCl-KCl eutectic melts based on a pure supercool reference state were calculated at several temperatures.

Key words: Molten chloride, Thermodynamic property, Activity coefficient of MgCl2, Standard apparent potential

MSC2000: 

  • O646