物理化学学报 >> 2008, Vol. 24 >> Issue (04): 686-690.doi: 10.3866/PKU.WHXB20080424

研究论文 上一篇    下一篇

LiAlH4与Li3AlH6的成键特性及热力学稳定性

梁初; 黎光旭; 蓝志强; 刘奕新; 韦文楼; 郭进   

  1. 广西大学物理科学与工程技术学院, 教育部有色金属材料及其加工新技术重点实验室, 南宁 530004
  • 收稿日期:2007-10-17 修回日期:2007-11-07 发布日期:2008-04-07
  • 通讯作者: 郭进 E-mail:guojin@gxu.edu.cn

Bond Characters and Thermodynamic Stabilities of LiAlH4 and Li3AlH6

LIANG Chu; LI Guang-Xu; LAN Zhi-Qiang; LIU Yi-Xin; WEI Wen-Lou; GUO Jin   

  1. Key Laboratory of National Education Ministry for Nonferrous Metals and Materials Processing Technology, College of Physics Science and Technology, Guangxi University, Nanning 530004, P. R. China
  • Received:2007-10-17 Revised:2007-11-07 Published:2008-04-07
  • Contact: GUO Jin E-mail:guojin@gxu.edu.cn

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摘要： 采用基于密度泛函理论(DFT)的平面波赝势(PW-PP)方法, 计算了LiAlH4分解反应中各个产物的晶胞参数、电子结构、生成焓和分解反应的反应焓. 反应中各固态、气态物质的晶胞的结构优化后的晶格参数与相应的实验值均符合得较好. 对LiAlH4与Li3AlH6的电子结构分析均表明, 其中的Al—H键为共价键、Li—H键为离子键. 对各分解反应的反应焓计算结果表明, (1) LiAlH4→1/3Li3AlH6+2/3Al+H2,(2) 1/3Li3AlH6→LiH+1/3Al+1/2H2及(3) LiH+Al→LiAl+1/2H2均为吸热反应, 298 K时计算的反应焓分别为14.3、14.9 与50.9 kJ·mol-1, 与相应的实验值符合得较好.

关键词: Li-Al-H络合物, 电子结构, 成键特征, 热力学稳定性

Abstract: The electronic structures, formation enthalpies, and reaction enthalpies of Li-Al-H system complex were investigated using plane-wave pseudo-potential method based on density functional theory. Calculated cell parameters were in agreement with experiment. The interaction between Al and H atoms was strong covalent bond and the interaction between Li andHatoms was strong ionic bond in both LiAlH4 and Li3AlH6. The calculated reaction enthalpies for reactions (1) LiAlH4→1/3Li3AlH6+2/3Al+H2, (2) 1/3Li3AlH6→LiH+1/3Al+1/2H2, and (3) LiH+Al→LiAl+1/2H2 were 14.3, 14.9, and 50.9 kJ·mol-1 at 298 K, respectively, which were in agreement with experiment results.

Key words: Li-Al-H complex, Electronic structure, Bond character, Thermodynamic stability

MSC2000: 

  • O641