Effect of Mg, Ca, and Zn on stability of LiBH4 through computational thermodynamics

被引：25
作者：
Lee, Sung Hoon [1 ]
Manga, Venkateswara Rao [1 ]
Liu, Zi-Kui [1 ]
机构：
[1] Penn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USA
来源：
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY | 2010年 / 35卷 / 13期
基金：
美国国家科学基金会;
关键词：
Hydrogen storage; Complex metal hydride; LiBH4; First-principles calculations; Thermodynamic modeling; HYDROGEN-STORAGE; THERMAL-DECOMPOSITION; MAGNESIUM BOROHYDRIDE; CALCIUM BOROHYDRIDE; LITHIUM BOROHYDRIDE; CRYSTAL-STRUCTURES; PHASE; DIFFRACTION; MG(BH4)(2); 1ST-PRINCIPLES;
D O I：
10.1016/j.ijhydene.2010.04.014
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
The effect of divalent metal-dopants, Mg, Ca, and Zn, on the stability of LiBH4 is studied by using the first-principles calculations and CALPHAD (CALculation of PHAse Diagram) modeling. The ground states of Mg1/2BH4, Ca1/2BH4, and Zn1/2BH4 are shown to be I (4) over bar m2, F2dd, and I (4) over bar m2, respectively, through first-principles calculations. Positive enthalpy of mixing between Li and the alloying element is predicted, indicating unfavorable solubility of alloying elements in LiBH4 and thus offering possibility to decrease the stability of LiBH4. The ionic sublattice model of (Li+, M2+, Va)(1)(BH(4) over bar)(1) is adopted for the metal substituted LiBH4 phase. It is observed that the addition of Mg or Zn has limited effect as the decomposition temperature is between those of LiBH4 and M1/2BH4 for Mg and Zn substitutions. LiBH4 is destabilized with magnesium borides or LiZn4 formation but its decomposition temperature is higher than that of M1/2BH4. On the other hand, the addition of Ca significantly reduces the H-2 releasing temperature due to the formation of highly stable CaB6. (C) 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
引用
收藏
页码：6812 / 6821
页数：10
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