石墨炔类结构储锂性能的第一性原理研究

doi:10.7503/cjcu20140317

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (8): 1731.doi: 10.7503/cjcu20140317

石墨炔类结构储锂性能的第一性原理研究

赵晗^1,², 周丽娜², 魏东山²(), 周新建¹, 史浩飞²

1. 华东交通大学机电工程学院, 南昌 330013
2. 中国科学院重庆绿色智能技术研究院, 跨尺度制造技术重点实验室, 重庆 400714

收稿日期:2014-04-04 出版日期:2014-08-10 发布日期:2019-08-01
作者简介:联系人简介: 魏东山, 男, 博士, 副研究员, 主要从事计算化学研究. Email: dswei@cigit.ac.cn
基金资助:
中国科学院“西部之光”项目(批准号: Y32Z030H10)和重庆市科技攻关项目(批准号: cstc2012ggC50002)资助

Lithium Storage on Extended Graphynes: Predicted by DFT Calculations^†

ZHAO Han^1,², ZHOU Lina², WEI Dongshan^2,^*(), ZHOU Xinjian¹, SHI Haofei²

1. College of Mechanical and Electrical Engineering, East China Jiaotong University, Nanchang 330013, China
2. Key Laboratory of Multi-scale Manufacturing Technology, Chongqing Institute of Green and Intelligent Technology, Chinese Academy of Sciences, Chongqing 400714, China

Received:2014-04-04 Online:2014-08-10 Published:2019-08-01
Contact: WEI Dongshan E-mail:dswei@cigit.ac.cn
Supported by:
Supported by the West Light Foundation of the Chinese Academy of Sciences(NoY32Z030H10) and the Key Scientific & Technological Projects of Chongqing, China(Nocstc2012ggC50002)

摘要/Abstract

摘要：

基于密度泛函理论的第一性原理的计算方法, 研究了石墨炔类结构的储锂性能, 结果表明, 石墨炔类体系是一种理想的储锂材料, 锂原子通过向衬底转移电荷而带正电, 彼此之间的库仑排斥作用避免了锂原子的团簇化. 通过比较石墨一炔到石墨五炔的储锂性能, 发现并不是炔键越多其储锂性能就越好, 还需考虑炔键的增多对结构稳定性的影响. 在保证石墨炔类结构稳定的前提下, 石墨二炔和石墨五炔达到LiC₃的最大储锂量.

关键词: 石墨炔, 储锂, 密度泛函理论, 吸附, 石墨n炔

Abstract:

Graphyne, which contains planar sheets equally occupied by sp² and sp carbon atoms, is a layered carbon allotrope. Since the length of the acetylene chains within graphyne can be variable by adjusting the number of acetylenic linkages(—C≡C—) between carbon hexagons, resulting in a family of graphyne-extended graphynes(i.e. graph-n-ynes). In this work, density functional theory(DFT) calculations were carried out to investigate the adsorption of lithium atoms on extended graphynes monolayers, and the results were compared to extrapolate the potential relationship between lithium storage capacity and the number of acetylenic linkages. The results show that further extending the acetylenic chains might not be helpful in achieving higher capacity. The longer acetylene chains result in the lower carbon atom density, as well as the lower stability of the carbon networks, which should be taken into consideration seriously. High-capacity Li storage as LiC₃ in graphdiyne and graph-5-yne, was achieved, and the preferred adsorption sites for Li were identified computationally. With high Li storage capacity and structural advantages, these porous carbon materials are expected to be applied in efficient lithium storage.

Key words: Graphyne, Lithium storage, Density functional theory, Adsorption, Graph-n-yne

中图分类号:

O647.3

TrendMD:

赵晗, 周丽娜, 魏东山, 周新建, 史浩飞. 石墨炔类结构储锂性能的第一性原理研究. 高等学校化学学报, 2014, 35(8): 1731.

ZHAO Han, ZHOU Lina, WEI Dongshan, ZHOU Xinjian, SHI Haofei. Lithium Storage on Extended Graphynes: Predicted by DFT Calculations^†. Chem. J. Chinese Universities, 2014, 35(8): 1731.

图/表 10

Fig.1 Optimized geometries of extended graphynes(n=1—5) and the calculated bond lengths(nm)

Fig.2 Schematic plots for the single-layer graphyne(A) and graphdiyne(B) in a 1×1 super cell and possible Li adsorption sites

Table 1 Adsorption energy and height of possible Li adsorption sites on graph-3-yne after fully optimized

Site	E_ads/eV	h/nm	Site	E_ads/eV	h/nm
h	-2.25	0.178	B	-1.97	0.002
H	-1.80	0.002	A	-2.79	0.005

Table 2 Calculated parameters of single Li atom adsorption on extended graphynes after optimized

n	a/nm	E_ads/eV	h/nm	n	a/nm	E_ads/eV	h/nm
1	0.689	-3.06	0.089	4	1.460	-2.74	0.009
2	0.946	-2.66	0.003	5	1.717	-2.82	0.004
3	1.203	-2.79	0.005

Fig.3 Schematic plots for the single-layer graph-3-yne in a 1×1 super cell and possible Li adsorption sites

Fig.4 Optimized geometries for the adsorption of Li atoms on graphyne and graphdiyne with maximum capacities (A) LiC6; (B) LiC3

Fig.5 Initial(A—C) and optimized(D—F) geometries and adsorption energies for the adsorption of Li atoms on graph-5-yne with different capacities (A), (D) LiC1.5, Eads=-1.83 eV; (B), (E) LiC2, Eads=-2.04 eV; (C), (F) LiC3, Eads=-2.05 eV.

Table 3 Calculated parameters for the adsorption of Li atoms on extended graphynes with respective maximum capacities after fully optimized

n	Li	LiC_x	E_ads/eV	h/nm	d_min(Li—Li)/nm
1	2	LiC₆	-2.62	0.092	0.398
2	6	LiC₃	-2.00	0.098	0.289
3	6	LiC₄	-2.31	0.000	0.413
4	6	LiC₅	-2.50	0.000	0.424
5	12	LiC₃	-2.05	0.000	0.417

Fig.6 Variations of bond length of graphdiyne(A, B) and graph-5-yne(C, D) before(A, C) and after(B, D) maximum Li adsorption

Table 4 Net charge of C and Li before and after adsorption from Bader charge analysis

Atom	Before adsorption/e	After adsorption/e	Difference/e	Atom	Before adsorption/e	After adsorption/e	Difference/e
C1	+0.25	+0.18	-0.07	C4	-0.12	-0.13	-0.01
C2	-0.12	-0.23	-0.11	Li	0.00	+0.90	+0.90
C3	+0.03	-0.36	-0.39

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石墨炔类结构储锂性能的第一性原理研究

Lithium Storage on Extended Graphynes: Predicted by DFT Calculations^†

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石墨炔类结构储锂性能的第一性原理研究

Lithium Storage on Extended Graphynes: Predicted by DFT Calculations†

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Lithium Storage on Extended Graphynes: Predicted by DFT Calculations^†