轻金属储氢材料的结构和电子性质的理论研究
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摘要
对清洁能源的大量需求引起了对新型储能材料的注意,而固态储氢已被认为是最有效的方法之一。为了提高这些材料的性能,就必须理解它们的基础性质,尤其是晶体结构、电子结构和弹性性质等。本课题应用从头计算方法,计算研究了Li-N-H, Li-Mg-N-H, y-AlH3等轻金属储氢体系。
(1)应用从头计算方法研究了储氢材料Li2NH和LiNH2的结构和电子性质。通过Mulliken分布和晶体轨道分布分析得出Li和N之间的具有较强的离子性,N和H之间有较强的共价性,LiNH2中N-H之间的共价性较Li2NH中的N-H之间的共价性弱。态密度分析Li2NH和LiNH2的价带都是主要由H的s轨道和N的sp轨道贡献。在Li2NH价带部分有一个小的带隙存在,而在LiNH2价带部分有两个小的带隙存在。
(2)应用从头计算方法研究了储氢材料a-Li2Mg(NH)2和(3-Li2Mg(NH)2两种构型的结构性质和电子性质。计算优化得到的晶胞参数和N-H键长符合实验得到的数据。通过Murnaghan状态方程得到了体积模量和零压力下的能量,计算结果表明a-Li2Mg(NH)2为基态构型。通过Mulliken分布分析说明α构型的N-Li/Mg的离子特性和N-H间的交互作用都弱于p构型。态密度分析结果表明,价带轨道主要由N原子的s轨道和p轨道占据,并与H原子的s轨道杂化。
(3)应用密度泛函理论方法研究γ-AlH3的晶体结构,电子性质和弹性性质。计算优化得到原子坐标,键长,键角与实验测定值相符。通过Mulliken分布和晶体轨道分布分析Al和H之间有强的离子性和弱的共价性。这些电荷性质在电荷差分密度图中得到了进一步的证明。态密度分析y-AlH3的价带主要由H的s轨道和Al的sp轨道贡献。在价带的-7.5--7.0eV之间还有一个小的带隙。本文还研究了γ-AlH3晶体的弹性常数和体积模量。弹性常数C11,C22和C33的值分别为102.3514,93.4176和135.3996GPa,体积模量为49.2746GPa。
The strong demand for new clean energy has attracted the notice in materials for energy storage. Hydrogen storage in solids has been recognized as one of the most practical approaches for so long. It is indispensable to understand the fundamental properties of hydrogen storage materials, especially the electronic structure and elastic properties in order to improve their performance. In the present study, we have presented the results of Li-N-H, Li-Mg-N-H and y-AlH3 by using ab initio calculations.
(1) The structural and electronic properties of Li2NH and LiNH2 have been investigated by ab initio calculations. The optimized coordinates of atom and the bond lengths and angles are in good agreement with the experimental data. By analyzing the overlap population and Mulliken population, we find that the interaction between N and H atom is strongly covalent characters, and the N-H interaction of LiNH2 is weaker than that of Li2NH. The valence bands in the density of stares are dominated by the presence of N sp and H s states. One and two band gaps were observed in the valence bands of Li2NH and LiNH2, respectively.
(2) The structural and electronic properties of Li2Mg(NH)2 for hydrogen storage have been studied by ab initio calculations. The optimal unit cell parameters and the distance of N-H are determined, which are in good agreement with the experimental data. The bulk modules and the energies of zero pressure are obtained by using Murnaghan equation of states. The results show that the a-Li2Mg(NH)2 is a ground state configuration. The overlap population analysis shows that the N-Li/Mg ionic characteristics and N-H interaction of a phase are weaker than those ofβphase. The valence band is dominated by the presence of N s and p states, hybridized with the H s state.
(3) The structural, elastic and electronic properties of y-AlH3 have been investigated by density functional theory. The optimized lattice constants, the coordinates of atom and the bond lengths and angles are in good agreement with the experimental data. By analyzing the overlap population and Mulliken population, we find that the interaction between Al and H atom is strongly ionic with weak covalent characters. The valence band in the DOS is dominated by the presence of H s and Al sp states. A small band gap is separated the valence band from-7.5 to-7.0 eV. The elastic constants and bulk modulus are calculated. The elastic constants C11, C22, and C33 are 102.3514,93.4176 and 135.3996 GPa, respectively. The bulk modulus of y-AlH3 is 49.2746 GPa.
(1)应用从头计算方法研究了储氢材料Li2NH和LiNH2的结构和电子性质。通过Mulliken分布和晶体轨道分布分析得出Li和N之间的具有较强的离子性,N和H之间有较强的共价性,LiNH2中N-H之间的共价性较Li2NH中的N-H之间的共价性弱。态密度分析Li2NH和LiNH2的价带都是主要由H的s轨道和N的sp轨道贡献。在Li2NH价带部分有一个小的带隙存在,而在LiNH2价带部分有两个小的带隙存在。
(2)应用从头计算方法研究了储氢材料a-Li2Mg(NH)2和(3-Li2Mg(NH)2两种构型的结构性质和电子性质。计算优化得到的晶胞参数和N-H键长符合实验得到的数据。通过Murnaghan状态方程得到了体积模量和零压力下的能量,计算结果表明a-Li2Mg(NH)2为基态构型。通过Mulliken分布分析说明α构型的N-Li/Mg的离子特性和N-H间的交互作用都弱于p构型。态密度分析结果表明,价带轨道主要由N原子的s轨道和p轨道占据,并与H原子的s轨道杂化。
(3)应用密度泛函理论方法研究γ-AlH3的晶体结构,电子性质和弹性性质。计算优化得到原子坐标,键长,键角与实验测定值相符。通过Mulliken分布和晶体轨道分布分析Al和H之间有强的离子性和弱的共价性。这些电荷性质在电荷差分密度图中得到了进一步的证明。态密度分析y-AlH3的价带主要由H的s轨道和Al的sp轨道贡献。在价带的-7.5--7.0eV之间还有一个小的带隙。本文还研究了γ-AlH3晶体的弹性常数和体积模量。弹性常数C11,C22和C33的值分别为102.3514,93.4176和135.3996GPa,体积模量为49.2746GPa。
The strong demand for new clean energy has attracted the notice in materials for energy storage. Hydrogen storage in solids has been recognized as one of the most practical approaches for so long. It is indispensable to understand the fundamental properties of hydrogen storage materials, especially the electronic structure and elastic properties in order to improve their performance. In the present study, we have presented the results of Li-N-H, Li-Mg-N-H and y-AlH3 by using ab initio calculations.
(1) The structural and electronic properties of Li2NH and LiNH2 have been investigated by ab initio calculations. The optimized coordinates of atom and the bond lengths and angles are in good agreement with the experimental data. By analyzing the overlap population and Mulliken population, we find that the interaction between N and H atom is strongly covalent characters, and the N-H interaction of LiNH2 is weaker than that of Li2NH. The valence bands in the density of stares are dominated by the presence of N sp and H s states. One and two band gaps were observed in the valence bands of Li2NH and LiNH2, respectively.
(2) The structural and electronic properties of Li2Mg(NH)2 for hydrogen storage have been studied by ab initio calculations. The optimal unit cell parameters and the distance of N-H are determined, which are in good agreement with the experimental data. The bulk modules and the energies of zero pressure are obtained by using Murnaghan equation of states. The results show that the a-Li2Mg(NH)2 is a ground state configuration. The overlap population analysis shows that the N-Li/Mg ionic characteristics and N-H interaction of a phase are weaker than those ofβphase. The valence band is dominated by the presence of N s and p states, hybridized with the H s state.
(3) The structural, elastic and electronic properties of y-AlH3 have been investigated by density functional theory. The optimized lattice constants, the coordinates of atom and the bond lengths and angles are in good agreement with the experimental data. By analyzing the overlap population and Mulliken population, we find that the interaction between Al and H atom is strongly ionic with weak covalent characters. The valence band in the DOS is dominated by the presence of H s and Al sp states. A small band gap is separated the valence band from-7.5 to-7.0 eV. The elastic constants and bulk modulus are calculated. The elastic constants C11, C22, and C33 are 102.3514,93.4176 and 135.3996 GPa, respectively. The bulk modulus of y-AlH3 is 49.2746 GPa.
引文
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