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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.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.
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Keywords:
- first-principles study /
- thermodynamic properties /
- Li-N-H hydrogen storage /
- reaction enthalpy
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[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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[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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