A first principles study of the thermal stability of A(m)(MH4)(n) light complex hydrides

doi:10.1088/0953-8984/22/17/175502

IMR OpenIR

	A first principles study of the thermal stability of A(m)(MH4)(n) light complex hydrides
	Wang, Yong-li 2; Liu, Shi 2; Rong, Li-jian 2; Wang, Yuan-ming 1
通讯作者	Wang, Yuan-ming(ymwang@imr.ac.cn)
	2010-05-05
发表期刊	JOURNAL OF PHYSICS-CONDENSED MATTER
ISSN	0953-8984
卷号	22 期号:17 页码:7
摘要	From the physical point of view, the cohesive energy of a reactant is preferable to its formation energy for characterizing its influence on the reaction processes from the reactants to the products. In fact it has been found that there is a certain correlation between the experimental hydrogen desorption temperature and the cohesive energy calculated by a first principles method for a series of A(m)(MH4)(n) (A = Li, Na, Mg; M = Be, B, Al) light complex hydrides (including Na2BeH4, Li2BeH4, NaAlH4, LiAlH4, Mg(AlH4)(2), LiBH4 and NaBH4), which suggests that cohesive energy may be a useful physical quantity for evaluating the hydrogen desorption ability of complex hydrides, especially in cases when dehydrogenation products have unknown crystal structures, or may even be unknown. To understand this correlation more deeply, the ionic interaction between A and the MH4 complex and the covalent interaction between M and H were calculated and their contributions to the cohesive energy evaluated quantitatively. The calculated results show that the covalent M-H interaction in the MH4 complex is the dominant part of the cohesive energy E-coh (up to more than 75%) and hardly changes during high-pressure structural transitions of A(m)(MH4)(n). It was also found that low electronegativity of M or high electronegativity of A is responsible for the weak covalent M-H interaction and finally leads to the low thermodynamic stability of A(m)(MH4)(n), suggesting that complex hydrides A(m)(MH4)(n) can be destabilized by partial substitution of M (A) with an element with electronegativity lower (higher) than Ms (As). This conclusion has been confirmed by lots of experimental results and may be a useful guideline for the future design of new complex hydrides of the type A(m)(MH4)(n).
资助者	National Natural Science Foundation of China
DOI	10.1088/0953-8984/22/17/175502
收录类别	SCI
语种	英语
资助项目	National Natural Science Foundation of China[50771095]
WOS研究方向	Physics
WOS类目	Physics, Condensed Matter
WOS记录号	WOS:000276547300012
出版者	IOP PUBLISHING LTD
引用统计	被引频次：7[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.imr.ac.cn/handle/321006/101788
专题	中国科学院金属研究所
通讯作者	Wang, Yuan-ming
作者单位	1.Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, Shenyang 110016, Peoples R China 2.Chinese Acad Sci, Inst Met Res, Mat Special Environm Dept, Shenyang 110016, Peoples R China
推荐引用方式 GB/T 7714	Wang, Yong-li,Liu, Shi,Rong, Li-jian,et al. A first principles study of the thermal stability of A(m)(MH4)(n) light complex hydrides[J]. JOURNAL OF PHYSICS-CONDENSED MATTER,2010,22(17):7.
APA	Wang, Yong-li,Liu, Shi,Rong, Li-jian,&Wang, Yuan-ming.(2010).A first principles study of the thermal stability of A(m)(MH4)(n) light complex hydrides.JOURNAL OF PHYSICS-CONDENSED MATTER,22(17),7.
MLA	Wang, Yong-li,et al."A first principles study of the thermal stability of A(m)(MH4)(n) light complex hydrides".JOURNAL OF PHYSICS-CONDENSED MATTER 22.17(2010):7.