Thermodynamic properties of calcium-magnesium alloys determined by emf measurements

被引:43
|
作者
Newhouse, Jocelyn M. [1 ]
Poizeau, Sophie [1 ]
Kim, Hojong [1 ]
Spatocco, Brian L. [1 ]
Sadoway, Donald R. [1 ]
机构
[1] MIT, Dept Mat Sci & Engn, Cambridge, MA 02139 USA
关键词
Calcium-magnesium alloys; Emf method; Thermodynamic properties; High temperature electrochemistry; Liquid metal battery; LIQUID ALLOYS; ASSOCIATION MODEL; SYSTEM; CA; TEMPERATURES; EQUILIBRIUM; HALIDES; METALS; ENERGY;
D O I
10.1016/j.electacta.2012.11.063
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
The thermodynamic properties of calcium-magnesium alloys were determined by electromotive force (emf) measurements using a Ca(in Bi)vertical bar CaF2 vertical bar Ca(in Mg) cell over the temperature range 713-1048 K. The activity and partial molar Gibbs free energy of calcium in magnesium were calculated for nine Ca-Mg alloys, calcium mole fractions varying from x(ca) = 0.01 to 0.80. Thermodynamic properties of magnesium in calcium and the molar Gibbs free energy of mixing were estimated using the Gibbs-Duhem relationship. In the all-liquid region at 1010 K, the activity of calcium in magnesium was found to range between 8.8 x 10(-4) and 0.94 versus pure calcium. The molecular interaction volume model (MIVM) was used to model the activity coefficient of Ca and Mg in Ca-Mg liquid alloys. Based on this work, Ca-Mg alloys show promise as the negative electrode of a liquid metal battery in which calcium is the itinerant species: alloying with Mg results in both a decrease in operating temperature and suppression of Ca metal solubility in the molten salt electrolyte. (C) 2012 Elsevier Ltd. All rights reserved.
引用
收藏
页码:293 / 301
页数:9
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