ANiN(A = Li, Na, Mg, Ca)的结构、热力学、弹性和电子性质的第一性原理研究

doi:10.13208/j.electrochem.210302

摘要/Abstract

摘要：

三元过渡金属氮化物ANiN (A = Li, Na, Mg, Ca)是潜在的可充放电池的电极材料。物理性质,比如热稳定性、电子能隙以及弹性稳定性等,对于这些材料的电池应用都是非常重要的。本文使用第一原理方法,对比研究了ANiN这些材料的结构、动力学、弹性和电子结构性质。对状态方程和声子谱的计算被用来确定体系的稳定结构。对最稳定结构的弹性常数的计算表明,这些稳定结构都满足 Born-Huang的稳定性判据,意味着它们的弹性稳定性。对体系电子结构的计算表明,LiNiN和CaNiN是半金属（half-metals）,MgNiN是磁性材料,而NaNiN是通常的金属。这些材料的磁学性质都通过Stoner理论进行了解释。最后,电荷密度的计算被用来很好地说明了这些材料中的Ni-N成键的特征,表明成键特点主要是离子性的,但明显地混合了共价性。

关键词: ANiN (A = Li, Na, Mg, Ca), 结构稳定性, 电子性质, 第一性原理计算

Abstract:

Ternary transition metal nitrides ANiN (A = Li, Na, Mg, Ca) are potential electrode materials for rechargeable batteries. The physical properties, such as the thermodynamic stability, the electronic band gap as well as the elastic stability, are important for their battery applications. Here, comparative studies are performed for the structural, dynamic, elastic and electronic properties of ANiN by the first-principles method. The calculations on the cohesive energy versus unit-cell volume and phonon spectra are employed to determine the most stable structures of ANiN. The calculated elastic constants of the most stable structures indicate that the Born-Huang criterion for the elastic stability can all be satisfied, showing the elastic stability of the materials. The electronic structures calculations suggest that LiNiN and CaNiN are half-metals, MgNiN is magnetic metal, while NaNiN is a common metal. The magnetization of the materials is understood by the Stoner theory. Furthermore, the charge density plots have been used to illustrate the bonding between Ni and N atoms, which is mainly ionic mixed with covalent.

Key words: ANiN (A = Li, Na, Mg, Ca), structural stability, electronic properties, first-principles calculations

黄夏敏, 张丽红, 吴顺情, 杨勇, 朱梓忠. ANiN(A = Li, Na, Mg, Ca)的结构、热力学、弹性和电子性质的第一性原理研究[J]. 电化学（中英文）, 2021, 27(3): 339-350.

Xia-Min Huang, Li-Hong Zhang, Shun-Qing Wu, Yong Yang, Zi-Zhong Zhu. Structural, Dynamic, Elastic and Electronic Properties of ANiN (A = Li, Na, Mg, Ca): First-Principles Calculations[J]. Journal of Electrochemistry, 2021, 27(3): 339-350.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.210302

https://electrochem.xmu.edu.cn/CN/Y2021/V27/I3/339

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	a/Å	c/Å	Vol/Å³	d_A-N/Å	C₁₁	C₁₂	C₁₃	C₃₃	C₄₄	C₆₆
sta-LiNiN	3.57	5.14	65.56	2.20	316	35	28	122	25	36
sta-NaNiN	3.39	7.40	84.95	2.51	54	28	13	564	13	26
una-MgNiN	3.11	3.57	34.61	2.20	214	49	44	520	41	60
sta-CaNiN	3.59	7.01	89.90	2.50	292	18	51	152	37	28

	B_V	B_R	B	G_V	G_R	G	E	ν
sta-LiNiN	104	85	95	61	39	50	128	0.276
sta-NaNiN	86	40	63	52	18	35	89	0.266
una-MgNiN	136	118	127	82	60	71	180	0.264
sta-CaNiN	108	102	105	61	47	54	138	0.280