SIOC English
化学学报
高级检索

化学学报 >

2012 , Vol. 70 >Issue 01: 71 - 77

DOI: https://doi.org/10.6023/A1107041

研究论文

LiBH4-X(X＝O,F和Cl)体系解氢性能的第一原理计算

  • 李闯 ,
  • 周惦武 ,
  • 彭平 ,
  • 万隆
展开
  • a. 湖南大学汽车车身先进设计制造国家重点实验室, 长沙 410082;
    b. 湖南大学材料科学与工程学院, 长沙 410082

收稿日期: 2011-07-04

  修回日期: 2011-08-30

  网络出版日期: 2012-02-25

基金资助

国家自然科学基金(No.51071065)和湖南大学汽车车身先进设计制造国家重点实验室自主课题(No.71075003)资助项目.

收起

First-Principles Calculation on Dehydrogenating Properties of LiBH4-X(X＝O,F,Cl)Systems

  • LI Chuang ,
  • ZHOU Dian-Wu ,
  • PENG Ping ,
  • WAN Long
Expand
  • a. State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body, Hunan University, Changsha 410082;
    b. School of Materials Science and Engineering, Hunan University, Changsha 410082

Received date: 2011-07-04

  Revised date: 2011-08-30

  Online published: 2012-02-25

Supported by

Project supported by the National Natural Science Foundation of China(No.51071065)and the Autonomous Subject of State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body(No.71075003).

Fold

摘要

采用基于密度泛函理论的第一原理方法,计算了LiBH4-X(X＝O,F和Cl)体系的晶体与电子结构及解氢性能.生成热和H原子解离能的计算结果表明:O原子掺杂优先占据LiBH4间隙位,F置换氢原子位,而Cl则取代BH4单元;O,F和Cl掺杂的LiBH4体系结构稳定性发生变化,其中O提高体系解氢效果明显,而F和Cl掺杂受H原子区域环境的影响.态密度、Mulliken电子占据数和电子密度的分析结果表明:B—H之间较强的共价键是LiBH4结构稳定、解氢困难的电子结构根源,O,F和Cl对LiBH4解氢能力影响主要是掺杂改变了H的s态与B的sp态的杂化特性、以及BH4单元与Li的成键作用．

关键词： 第一原理计算; LiBH4; 解氢能力; 电子结构

本文引用格式

李闯 , 周惦武 , 彭平 , 万隆 . LiBH4-X(X＝O,F和Cl)体系解氢性能的第一原理计算[J]. 化学学报, 2012 , 70(01) : 71 -77 . DOI: 10.6023/A1107041

Abstract

Crystal structure,electronic structure and dehydrogenation properties of LiBH4-X(X＝O,F,Cl) system have been studied by first-principles calculation based on density functional theory(DFT).The re-sults of heat of formation and hydrogen removal energy showed that O atom prefers to occupy the interstitial site,F atom replaces for H atom,while Cl atom substitutes the BH4 unit.H atoms from the LiBH4-O system can be easily released compared with LiBH4 doped F and Cl atom.The dehydrogenation properties of LiBH4 doped F and Cl were affected by the H atoms regional environment.After analysising the densities of states (DOS),Mulliken populations and the charge distribution,it was found that the effect of O,F and Cl on the dehydrogenation properties of LiBH4 may attribute to the changes of the orbital hybridization of H s and B sp and the bond characteristics between BH4 unit and Li atom.

Key words： first-principles calculation; LiBH4; dehydrogenation property; electronic structure

参考文献

1 Schlapbach, L. ; Züttel, A. Nature 2001, 414, 353.   

2 Züttel, A. ; Wenger, P. ; Rentsch, S. ; Sudan, P. ; Mauron, P. ; Emmenegger, C. J. Power Sources 2003, 118, 1.   

3 Orimo, S. -I. ; Nakamori, Y. ; Kitahara, G. ; Miwa, K. ; Ohba, N. ; Towata, S. ; Züttel, A. J. Alloys Compd. 2005, 404～406, 427.   

4 Züttel, A. ; Borgschulte, A. ; Orimo, S. -I. Scr. Mater. 2007, 56, 823.   

5 Guo, W. W. ; Niu, J. P. Mater. Rev. 2009, 23, 299(in Chinese). (郭威威, 牛建平, 材料导报, 2009, 23, 299. )

6 Fang, Z. Z. ; Kang, X. D. ; Wang P. Prog. Chem. 2009, 21, 2212(in Chinese). (方占召, 康向东, 王平, 化学进展, 2009, 21, 2212. )

7 Yu, X. B. ; Grant, D. M. ; Walker, G. S. J. Phys. Chem. C 2009, 113, 17945.   

8 Au, M. ; Walters, R. T. Int. J. Hydrogen Energy 2010, 35, 10311.   

9 Au, M. ; Jurgensen, A. R. ; Spencer, W. A. ; Anton, D. L. ; Pinkerton, F. E. ; Hwang, S. -J. ; Kim, C. ; Robert, C. ; Bowman, J. J. Phys. Chem. C 2008, 112, 18661.

10 Filinchuk, Y. ; Chernyshov, D. ; Cerny, R. J. Phys. Chem. C 2008, 112, 10579.   

11 Segall, M. D. ; Lindan, P. J. D. ; Probert, M. J. ; Pickard, C. J. ; Hasnip, P. J. ; Clark, S. J. ; Payne, M. C. J. Phys. :Condens. Matter 2002, 14, 2717.   

12 Vanderbilt, D. Phys. Rev. B 1990, 41, 7892.   

13 Perdew, J. P. ; Wang, Y. Phys. Rev. B 1992, 45, 13244.   

14 Hammer, B. ; Hansen, L. B. ; N?rskov, J. K. Phys. Rev. B 1999, 59, 7413.   

15 Francis, G. P. ; Payne, M. C. J. Phys. :Condens. Matter 1990, 2, 4395.   

16 Fischer, T. H. ; Almlof, J. J. Phys. Chem. 1992, 96, 9768.   

17 Miwa, K. ; Ohba, N. ; Towata, S. -I. ; Nakamori, Y. ; Orimo, S. -I. Phys. Rev. B 2004, 69, 245120.

18 Frankcombe, T. J. ; Kroes, G. -J. ; Züttel, A. Chem. Phys. Lett. 2005, 405, 73.   

19 Li, S. F. ; Xue, X. ; Li, P. ; Li, X. ; Jia, Y. Phys. Lett. A 2006, 352, 526.   

20 Yin, L. C. ; Wang, P. ; Fang, Z. Z. ; Cheng, H. M. Chem. Phys. Lett. 2008, 450, 318.   

21 Li, S. ; Jena, P. ; Ahuja, R. Phys. Rev. B 2006, 73, 214107.   

22 Arnbjerg, L. M. ; Ravnsb?k, D. B. ; Filinchuk, Y. ; Vang, R. T. ; Cerenius, Y. ; Besenbacher, F. ; J?rgensen, J. -E. ; Jakobsen, H. J. ; Jensen, T. R. Chem. Mater. 2009, 21, 5772.   
Options
文章导航

/

〈 〉