外电场对锂修饰氧化石墨烯结构储氢性能的影响

doi:10.7503/cjcu20150472

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (1): 100.doi: 10.7503/cjcu20150472

外电场对锂修饰氧化石墨烯结构储氢性能的影响

赵晗^1,², 周丽娜^1,³, 魏东山¹(), 周新建², 史浩飞¹

1. 中国科学院重庆绿色智能技术研究院, 跨尺度制造技术重庆市重点实验室, 重庆 400714
2. 华东交通大学机电工程学院, 南昌 330013
3. 河北大学化学与环境科学学院, 保定 071000

收稿日期:2015-06-16 出版日期:2016-01-10 发布日期:2015-12-20
基金资助:
中国科学院“西部之光”一般项目(批准号: Y32Z030H10)、重庆市科技攻关项目(批准号: cstc2012ggC50002, cstc2012ggC90003)和教育部留学回国人员科研启动基金资助

Effects of External Electric Field on Hydrogen Storage Performance of Li-decorated Graphene Oxide^†

ZHAO Han^1,², ZHOU Lina^1,³, WEI Dongshan^1,^*(), ZHOU Xinjian², SHI Haofei¹

1. Chongqing Key Laboratory of Multi-scale Manufacturing Technology, Chongqing Institute of Green and Intelligent Technology, Chinese Academy of Sciences, Chongqing 400714, China
2. College of Mechanical and Electrical Engineering, East China Jiaotong University, Nanchang 330013, China
3.College of Chemistry & Environmental Science, Hebei University, Baoding 071000, China

Received:2015-06-16 Online:2016-01-10 Published:2015-12-20
Contact: WEI Dongshan E-mail:dswei@cigit.ac.cn
Supported by:
† Supported by the West Light Foundation of the Chinese Academy of Sciences( No.Y32Z030H10 ) , the Key Scientific and Technological Projects of Chongqing, China(Nos.cstc2012ggC50002, cstc2012ggC90003) and the Scientific Research Foundation for the Returned Overseas Chinese Scholars, Ministry of Education, China

摘要/Abstract

摘要：

基于密度泛函理论(DFT)的第一性原理方法, 研究了外加电场对锂修饰氧化石墨烯结构(Li@GO)储氢性能的影响. 考察Li@GO结构的稳定性及其对外加电场的响应, 研究H₂-Li@GO结构的H₂分子吸附能、几何构型与外加电场的关系. 研究结果表明, 当外加电场方向垂直Li@GO平面向下(负电场)时, 随电场强度增加, H₂分子的吸附能逐渐降低, H₂分子逐渐接近Li原子; 当外加电场方向向上(正电场)时, 随电场强度增加, H₂分子的吸附能逐渐升高, H₂分子逐渐远离Li原子. 分波态密度(PDOS)分析表明: 与无外加电场体系的PDOS相比, 当对体系施加负电场时, H₂-Li的杂化峰向低能量方向位移, H₂分子与Li@GO结合更加紧密, 提升了储氢稳定性; 施加正电场时, H₂-Li的杂化峰向高能量方向位移, H₂分子与Li@GO作用减弱, 提升了氢气释放动力学性能. 进一步计算表明, 在无外加电场情况下, Li@GO结构最大储氢量在3.1%以上.

关键词: 氧化石墨烯, 储氢性能, 外电场, 密度泛函理论, 吸附能, 分波态密度

Abstract:

Hydrogen storage performance of Li decorated graphene oxide(GO) under an external electric field was investigated with the first-principle method based on the density functional theory(DFT) calculations. Firstly the stability of Li@GO structure due to the adsorption of Li atoms at different binding sites on GO structure was investigated. Then a stable Li@GO structure was obtained and dependences of the structural stability and H₂ adsorption of the Li@GO structure on the electric field were discussed. The results indicate that both the H₂ adsorption energy, E_ad, and the distance between H₂ and Li atom, d(Li-H₂), decrease with the increasing intensity of the downward electric field. While both E_ad and d(Li-H₂) increase with the increasing intensity of the upward electric field. From the partial density of state(PDOS) analysis, the H₂-Li hybridization peaks under a negative electric field shifted to the larger negative energy region compared to those without an electric field, which indicates the H₂-Li@GO system becomes more stable under the negative electric field. When the positive electric field was added, the H₂-Li hybridization peaks shifted to the smaller negative energy region, which indicates the interaction between H₂ and Li becomes weaker. It is therefore anticipated that the adsorption-desorption processes of H₂ on Li@GO structure can be easily controlled by adding an electric field with appropriate intensity and direction. Further calculation indicates the Li@GO structure has a maximum hydrogen storage capability of larger than 3.1% without the external electric field.

Key words: Graphene oxide, Hydrogen storage performance, Electric field, Density functional theory, Adsorption energy, Partial density of state

中图分类号:

O647.3

TrendMD:

赵晗, 周丽娜, 魏东山, 周新建, 史浩飞. 外电场对锂修饰氧化石墨烯结构储氢性能的影响. 高等学校化学学报, 2016, 37(1): 100.

ZHAO Han, ZHOU Lina, WEI Dongshan, ZHOU Xinjian, SHI Haofei. Effects of External Electric Field on Hydrogen Storage Performance of Li-decorated Graphene Oxide^†. Chem. J. Chinese Universities, 2016, 37(1): 100.

图/表 10

Fig.1 Top view(A) and side view(B) of model GO structure^The dashed line represents 2× supercell. A1, A2, B1, B2 and B3 represent the possible Li anchor sites(B1, B2 and B3 lie in the green dashed line).

Table 1 Binding energy, Li—O and Li—C distances of possible Li binding sites on GO after fully optimized

Site	E_b/eV	d(Li—O_E)/nm	d(Li—O_H)/nm	d(Li—C₁)/nm	d(Li—C₂)/nm
A1	-2.994	0.1810	0.2047	0.2552	0.2323
A2	-2.994	0.1808	0.2026	0.2546	0.2332
B1	-1.892	0.2126	0.1833	0.2525	0.2263
B2	-3.080	0.1889	0.2141	0.2675	0.2305
B3	-2.427	0.2202	0.2035	0.2701	0.2371

Fig.2 Top view(A) and side view(B) of optimized geometry of Li@GO(initial state: B2) structure^The dashed line represents the distance(nm) between different atoms.

Fig.3 Binding energy() of Li(A) and the length of C—O bond and the distance between Li and its neighboring atoms under different electric fields(B)^ a. d(CE—OE); b. d(CH—OH); c. d(Li—OE); d. d(Li—OH); e. d(Li—C1); f. d(Li—C2).

Table 2 Net charge of Li, O and C under different electric fields from Bader charge analysis

E-field/(V·nm^-1)	Net charge/e
E-field/(V·nm^-1)	Li	O_E	O_H	C₁	C₂	C_E	C_H
-6	+0.86	-1.13	-1.15	+0.46	-0.13	+0.55	+0.46
0	+0.88	-1.08	-1.13	+0.47	-0.01	+0.53	+0.43
6	+0.89	-1.10	-1.15	+0.46	-0.05	+0.51	+0.42

Fig.4 Partial density of states(PDOS) of Li atom(a) and GO(b) on Li@GO system with the electric field of 6 V/nm(A), 0 V/nm(B) and -6 V/nm(C)

Fig.5 Possible H2 adsorption sites(A1—A4) on Li@GO structure

Fig.6 Adsorption energy() of H2(A) and the length of C—O bond and the distance between Li and its neighboring atoms in the presence of an external electric field(B)^ Inset of (A) is the intensity-dependent distance between Li and H2. a. d(CE—OE); b. d(CH—OH); c. d(Li—OE); d. d(Li—OH); e. d(Li—C1); f. d(Li—C2).

Fig.7 PDOS of GO(a), Li atom(b), and hydrogen molecule(c) with the electric field of 6 V/nm(A), 0 V/nm(B) and -6 V/nm(C) to H2-Li@GO system

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外电场对锂修饰氧化石墨烯结构储氢性能的影响

Effects of External Electric Field on Hydrogen Storage Performance of Li-decorated Graphene Oxide^†

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外电场对锂修饰氧化石墨烯结构储氢性能的影响

Effects of External Electric Field on Hydrogen Storage Performance of Li-decorated Graphene Oxide†

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Effects of External Electric Field on Hydrogen Storage Performance of Li-decorated Graphene Oxide^†