Crystal Structure and Stability of LiAlH4 from First Principles

ZHANG Yilong CUI Man'ai LIU Yanhui

张艺龙, 崔慢爱, 刘艳辉. LiAlH4晶体结构及稳定性的第一性原理研究[J]. 高压物理学报, 2018, 32(2): 021103. doi: 10.11858/gywlxb.20170561
引用本文: 张艺龙, 崔慢爱, 刘艳辉. LiAlH4晶体结构及稳定性的第一性原理研究[J]. 高压物理学报, 2018, 32(2): 021103. doi: 10.11858/gywlxb.20170561
ZHANG Yilong, CUI Man'ai, LIU Yanhui. Crystal Structure and Stability of LiAlH4 from First Principles[J]. Chinese Journal of High Pressure Physics, 2018, 32(2): 021103. doi: 10.11858/gywlxb.20170561
Citation: ZHANG Yilong, CUI Man'ai, LIU Yanhui. Crystal Structure and Stability of LiAlH4 from First Principles[J]. Chinese Journal of High Pressure Physics, 2018, 32(2): 021103. doi: 10.11858/gywlxb.20170561

Crystal Structure and Stability of LiAlH4 from First Principles

doi: 10.11858/gywlxb.20170561
Funds: 

National Natural Science Foundation of China 11764043

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    Author Bio:

    ZHANG Yilong(1998—), male, undergraduate, major in computational physics under high pressure.E-mail:122696148@qq.com

    Corresponding authors: CUI Man'ai(1979—), female, master, lecturer, major in computational physics under high pressure.E-mail:macui@ybu.edu.cn LIU Yanhui(1971—), female, Ph.D, professor, major in computational physics under high pressure.E-mail:yhliu@ybu.edu.cn
  • 摘要: 基于密度泛函理论的第一性原理赝势平面波方法,研究高压下三元碱金属氢化物LiAlH4的相变行为,分析了LiAlH4高压相变的物理机制。研究表明,在1.6 GPa时LiAlH4发生了相变,从α-LiAlH4转变为空间群为I2/bβ-LiAlH4,相变时伴随18%的体积坍塌,即一级相变。通过分析声子色散曲线得出,相变与声子软化有关。Millikan布局分析表明,常压相(α-LiAlH4)是很有潜力的储氢材料。

     

  • Figure  1.  Volume vs. pressure curves of α-LiAlH4 and β-LiAlH4 phases (Enthalpy difference (per formula unit) between α-LiAlH4 and β-LiAlH4 as a function of pressure is shown in the insert.)

    Figure  2.  Phonon dispersion relations and density of state in high-symmetry directions for the α-LiAlH4 structure at 0 and 1.6 GPa

    Figure  3.  Calculated total and partial electronic densities of states for α-LiAlH4 structure at 0 GPa (a) and β-LiAlH4 structure at 1.6 GPa (b) respectively

    Table  1.   Optimized structural parameters, atomic position parameters for the α-LiAlH4 and the β-LiAlH4 structures

    Phase Unit-cell dimensions Atom coordinates
    α-LiAlH4
    (P21/c)
    a=0.485 1 nm(0.481 7 nm*)
    b=0.781 4 nm(0.780 2 nm*)
    c=0.773 2 nm(0.782 1 nm*)
    Li:(0.585, 0.459, 0.829), (0.560, 0.466, 0.827)*
    Al:(0.159, 0.204, 0.938), (0.139, 0.203, 0.930)*
    H1:(0.193, 0.102, 0.766), (0.183, 0.096, 0.763)*
    H2:(0.377, 0.371, 0.986), (0.352, 0.371, 0.975)*
    H3:(0.254, 0.082, 0.119), (0.243, 0.081, 0.115)*
    H4:(0.822, 0.268, 0.882), (0.799, 0.247, 0.872)*
    β-LiAlH4
    (I2/b)
    a=0.445 2 nm
    b=0.445 9 nm
    c=1.010 2 nm
    β=89.978°
    Li:(0, 0.250, 0.125)
    Al:(0, 0.250, 0.625)
    H1:(0.259, 0.425, 0.542)
    H2:(0.324, 0.508, 0.792)
    Note:"*" represents experimental data from Ref.[18].
    下载: 导出CSV

    Table  2.   Average net charges, bond length (L) and scaled bond overlap population (Ps) between H, Al, and Li atoms in the α-LiAlH4 (at 0 GPa) and the β-LiAlH4 (at 2.0 GPa) structures

    Phase Average net charge L/nm Ps
    H Al Li Al─H Li─H Al─H Li─H
    α-LiAlH4 -0.48 0.64 1.29 0.161 5 0.188 6 0.506 0.019
    β-LiAlH4 -0.46 0.55 1.28 0.162 8 0.206 7 0.534 -0.063
    下载: 导出CSV
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出版历程
  • 收稿日期:  2017-04-05
  • 修回日期:  2017-04-30

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