Li-N-H储氢体系热力学性质的第一性原理研究

赵玉娜; 高涛; 吕金钟; 马俊刚

doi:10.7498/aps.62.143101

摘要

基于密度泛函理论的第一性原理方法, 系统地研究了Li-N-H储氢过程中各个化合物的晶胞参数、生成焓和化学反应焓. 结果发现优化后的晶格参数与先前的理论和实验研究符合得很好. 通过计算Li3N, LiH, LiNH2和Li2NH在298 K的生成焓分别为-168.7, -81.0, -173.0和-190.8 kJ/mol, 进而计算得到整个储氢反应过程在T=298 K时反应焓为78.5 kJ/mol H2, 这和他人计算得到T=300 K的结果75.67 kJ/mol H2非常接近. 最后, 给出了储氢两步反应过程分别在T=298 K时的反应焓, 这些结果都与实验和他人理论计算得到的数据符合较好.

关键词:

Abstract

According to the plane wave pseudo-potential method of the first-principles based on density functional theory, we systematically investigate the cell parameters, the formation heat and the reaction enthalpy in the Li-N-H hydrogen storage process. The calculated lattice parameters of these compounds are in good agreement with previous theoretical and experimental results. The values of formation heat at 298 K for (lithium nitride) Li3N, (lithium hydride) LiH, (lithium amide) LiNH2 and (lithium imide) Li2NH are estimated to be -168.7, -81.0, -173.0 and -190.8 kJ/mol, respectively. The reaction enthalpy of this system is calculated to be 78.5 kJ/mol H2 at T=298 K and this value accords with the experimental value of 75.67 kJ/mol H2 at T=300 K. As a result, the reaction enthalpies for the two-step reactions are very close to their calculation results respectively.

Keywords:

作者及机构信息

1.
北京交通大学海滨学院, 黄骅 061100;

2.
四川大学原子与分子物理研究所, 成都 610064

Authors and contacts

1.
Beijing Jiaotong University Haibin College, Huanghua 061100, China;

2.
Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610064, China

参考文献

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[28]	Ruff O, Goerges H 1910 Chem. Ber. 44 502
[29]	Chase Jr M W 1998 NIST-JANAF Themo-chemical Tables (4th Ed.) (J. Phys. Chem. Ref. Data, Monograph, Vol.9)
[30]	Chen P, Xiong Z, Luo J, Lin J, Tan K L 2002 Nature 420 302
[31]	Wang Q, Chen Y G, Zheng X, Niu G, Wu C L, Tao M D 2009 Physica B 404 3431
[32]	Akbarzadeh A R, Ozolinš V, Wolverton C 2007 Adv. Mater. 19 3233
[33]	Kojima Y, Kawai Y 2005 J. Alloys Compd. 395 236
[34]	Yu D L, Chen Y H, Cao Y J, Zhang C R 2010 Acta Phys. Sin. 59 1991 (in Chinese) [于大龙, 陈玉红, 曹一杰, 张材荣 2010 物理学报 59 1991]

施引文献

[1]	Ichikawa T, Isobe S, Hanada N, Fujii H 2004 J. Alloys Compd. 365 271
[2]	Meisner G P, Pinkerton F E, Meyer M S, Balogh M P, Kundrat M D 2005 J. Alloys Compd. 24 404
[3]	Chen P, Xiong Z, Luo J, Lin J, Tan K L 2003 J. Phys. Chem. B 107 10967
[4]	Noritake T, Nozaki H, Aoki M, Towata S, Kitahara G, Nakamori Y, Orimo S 2005 J. Alloys. Compd. 393 264
[5]	Ohoyama K, Nakamori Y, Orimo S, Yamada K 2005 J. Phys. Soc. Jpn. 74 483
[6]	Balogh M P, Jones C Y, Herbst J F, Hector Jr L G, Kundrat M 2006 J. Alloys Compd. 420 326
[7]	Kohn W, Sham L J 1965 Phy. Rev. 137 A 1697
[8]	Li Q, Huang D H, Cao Q L, Wang F H 2013 Chin. Phys. B 22 037101
[9]	Chen X, Chen W B, Shang X F, Tao X M, Dai J H, Tan M Q 2007 Acta. Phys. Chim. Sin. 23 861 (in Chinese) [陈鑫, 陈文斌, 尚学府, 陶向明, 戴建辉, 谭明秋 2007 物理化学学报 23 861]
[10]	Chen Z J, Xiao H Y, Zu X T 2005 Acta Phys. Sin. 54 5301 (in Chinese) [陈中钧, 肖海燕, 祖小涛 2005 物理学报 54 5301]
[11]	The ABINIT code is a common project of the Université Catholique de Louvain, and other contributors (URL http: //www.abinit.org)
[12]	Troullier N, Martins J L 1991 Phys. Rev. B 43 1993
[13]	Herbst J F, Hector L G 2005 Phys. Rev. B 72 125120
[14]	Miwa K, Ohba N, Towata S 2006 Phys. Rev. B 74 075110
[15]	Siegel Donald J, Wolverton C, Ozolinš V 2007 Phys. Rev. B 75 014101
[16]	David R 1986 CRC Handbook of Chemistry and Physics (Vol. 67) (Boca Raton: CRC Press) pF-159
[17]	Villars P, Calvert L D 1991 Pearson's Handbook of Crystallographic Data for Intermetallic Phases (2nd Ed.) (Metals Park, OH: American Society of Metals)
[18]	Smith D K, Leider H R 1968 J. Appl. Crystallogr. 1 246.
[19]	Rabenau A, Schulz H 1976 J. Less-Common Met. 50 155
[20]	Jacobs Von H, Juza R 1972 Z. Anorg. Allg. Chem. 391 271
[21]	Nagib M, Jacobs H 1973 Atomkernenergie 21 275
[22]	Magyari-Köpe B, Ozolinš V, Wolverton C 2006 Phys. Rev. B 73 220101(R)
[23]	Miwa K, Ohba N, Towata S I, Nakimori Y, Orimo S I 2005 Phys. Rev. B 71 195109
[24]	Hino S, Ichikawa T, Ogita N, Udagawa M, Kojima Y 2009 J. Appl. Phys. 105 023527
[25]	Hino S, Ichikawa T, Koijma Y 2010 J. Chem. Thermodynamics 42 140
[26]	Barin I 1995 Thermochemical Data of Pure Substances (3rd Ed.) (New York: VCH)
[27]	Song Y, Guo Z X 2006 Phys. Rev. B 74 195120
[28]	Ruff O, Goerges H 1910 Chem. Ber. 44 502
[29]	Chase Jr M W 1998 NIST-JANAF Themo-chemical Tables (4th Ed.) (J. Phys. Chem. Ref. Data, Monograph, Vol.9)
[30]	Chen P, Xiong Z, Luo J, Lin J, Tan K L 2002 Nature 420 302
[31]	Wang Q, Chen Y G, Zheng X, Niu G, Wu C L, Tao M D 2009 Physica B 404 3431
[32]	Akbarzadeh A R, Ozolinš V, Wolverton C 2007 Adv. Mater. 19 3233
[33]	Kojima Y, Kawai Y 2005 J. Alloys Compd. 395 236
[34]	Yu D L, Chen Y H, Cao Y J, Zhang C R 2010 Acta Phys. Sin. 59 1991 (in Chinese) [于大龙, 陈玉红, 曹一杰, 张材荣 2010 物理学报 59 1991]

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