First-principles study of structural stability and lithium storage property of Sin clusters (n ≤ 6) adsorbed on graphene

Shen Ding; Liu Yao-Han; Tang Shu-Wei; Dong Wei; Sun Wen; Wang Lai-Gui; Yang Shao-Bin

doi:10.7498/aps.70.20210521

Abstract

Silicon/carbon composite is one of the most potential high-capacity anode materials for lithium-ion batteries. The interface state between silicon and carbon of silicon/carbon composite is an important factor affecting its electrochemical performance. In this paper, Si_n (n ≤ 6) clusters with different numbers of Si atoms are constructed on graphene as a structural unit of carbon material. The geometric configuration, structure stability and electronic property of Si_n clusters adsorbed on graphene (Si_n/Gr) are studied by the first-principles method based on density functional theory (DFT). The results show that when the number of Si atoms n ≤ 4, the Si_n clusters are preferentially adsorbed on graphene in a two-dimensional configuration parallel to graphene. When n ≥ 5, the Si_n clusters are preferentially adsorbed on graphene in a three-dimensional configuration. With the increase of the number of Si atoms n, the thermodynamic stability of Si_n clusters on graphene decreases significantly, the interface binding strength between Si_n clusters and graphene decreases, and the charge transfer between Si_n clusters and graphene becomes less. At the same time, the storage capacity of Li atoms in Si_n/Gr complex is also studied. Li atoms are mainly stored on the graphene surface near Si_n clusters and around Si_n clusters. The complex synergistic effect of Si_n clusters and graphene enhances the thermodynamic stability of Li adsorption. When n ≤ 4, storing two Li atoms is beneficial to improving the thermodynamic stability of xLi-Si_n/Gr system, and the thermodynamic stability decreases with the increase of Li atom number. When n ≥ 5, the thermodynamic stability of xLi-Si_n/Gr system decreases with the increase of Li atom number. In the xLi-Si₅/Gr system, the C-C bond and Si-Si bond are mainly covalent bonds, while the Li-C bond and Li-Si bond are mainly ionic bonds with certain covalent properties.

Keywords:

Authors and contacts

1.
College of Materials Science and Engineering, Liaoning Technical University, Fuxin 123000, China
2.
School of Mechanics and Engineering, Liaoning Technical University, Fuxin 123000, China

Corresponding author: Yang Shao-Bin, lngdysb@163.com

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 51874167, 21808095, 51774175), the China Postdoctoral Science Foundation (Grant No. 2018M641707), and the Discipline Innovation Team of Liaoning Technical University, China (Grant No. LNTU20TD-09)

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References

[1]	王晓钰, 张渝, 马磊, 魏良明 2019 化学学报 77 24 Google Scholar Wang X Y, Zhang Y, Ma L, Wei L M 2019 Acta Chim. Sin. 77 24 Google Scholar
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Cited By

图 1 单个Si原子在石墨烯表面的吸附行为　(a)吸附能量ΔE_ab; (b) Si—C键长d_Si—C和C原子位移高度Δh

Figure 1. Adsorption behavior for a single Si atom on graphene: (a) Adsorption energy ΔE_ab; (b) length of Si—C d_Si—C and shift height Δh of C atom.

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图 2 石墨烯表面Si_n团簇的构型 (ΔE_rel为亚稳态与稳态构型的总能量之差)

Figure 2. Configuration for Si_n clusters on graphene (ΔE_rel is the difference of total energy between metastable and steady-state configurations).

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图 3 孤立Si_n团簇和Si_n/Gr复合材料的态密度图　(a) 孤立Si_n团簇的分波态密度; (b), (c) Si_n/Gr复合材料的分波态密度; (d) Si_n/Gr复合材料的总态密度

Figure 3. Density of states for isolated Si_n clusters and Si_n/Gr composites: (a) Partial density of states for isolated Si_n clusters; (b), (c) partial density of states for Si_n/Gr composites; (d) total density of states for Si_n/Gr composites.

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图 4 Si_n/Gr复合结构吸附不同Li原子数的稳态构型

Figure 4. Configuration for Si_n/Gr system with different Li atom numbers.

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图 5 稳态构型(xLi-Si_n/Gr)中Li原子数与平均吸附能ΔE_ab的关系

Figure 5. Relationship between the average adsorption energy ΔE_ab and the number of Li atoms in the steady-state configuration (xLi-Si_n/Gr).

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图 6 xLi-Si₅/Gr体系(x = 1, 3和6)稳态构型的电子结构分析(图中数据为Mulliken布局)

Figure 6. Electronic structure analysis of steady-state configuration of xLi-Si₅/Gr system (x = 1, 3 and 6) (The data in figure is Mulliken population).

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表 1 石墨烯表面Si_n团簇的平均吸附能、结构参数和Mulliken布局

Table 1. Average adsorption energy, structural parameters and Mulliken population for Si_n clusters on graphene.

n	ΔE_ab/eV	h/Å	Δh/Å	d_Si—C/Å	d_Si—Si/Å	Mulliken population/e
1	–1.216	2.168	0.078	2.093	—	0.50
2	–0.312	2.532	0.167	2.223	2.262	0.30
3	–0.116	3.365	0.007	3.456	2.187	–0.02
4	–0.152	3.235	0.010	3.246	2.335	–0.02
5	–0.088	3.314	0.005	3.403	2.316	0.02
6	–0.083	3.425	0.008	3.512	2.371	0.04

DownLoad: CSV

[1]	王晓钰, 张渝, 马磊, 魏良明 2019 化学学报 77 24 Google Scholar Wang X Y, Zhang Y, Ma L, Wei L M 2019 Acta Chim. Sin. 77 24 Google Scholar
[2]	Feng K, Li M, Liu W, Kashkooli A G, Chen Z 2018 Small 14 1702737 Google Scholar
[3]	魏剑, 秦葱敏, 苏欢, 王佳敏, 李雪婷 2020 新型炭材料 35 97 Wei J, Qin C M, Su H, Wang J M, Li X T 2020 New Carbon Materials 35 97
[4]	Zhao X Y, Lehto V P 2021 Nanotechnology 32 042002 Google Scholar
[5]	Gao H, Xiao L, Plümel I, Xu G L, Ren Y, Zuo X, Liu Y, Schulz C, Wiggers H, Amine K 2017 Nano Lett. 17 1512 Google Scholar
[6]	Liu J, Kopold P, Aken P A, Maier J, Yu Y 2015 Angew. Chem. Int. Ed. 54 9632 Google Scholar
[7]	Li X, Gu M, Hu S, Kennard R, Yan P, Chen X, Wang C, Sailor M J, Zhang J G, Liu J 2014 Nat. Commun. 5 4105 Google Scholar
[8]	Song H C, Wang H X, Lin Z X, et al. 2016 Adv. Funct. Mater. 26 524 Google Scholar
[9]	Su J M, Zhang C C, Chen X Liu S Y, Huang T, Yu A S 2018 J. Power Sources 381 66 Google Scholar
[10]	Zuo X X, Wang X Y, Xia Y G, Yin S S Ji Q, Yang Z H, Wang M M, Zheng X F, Qiu B, Liu Z P, Zhu J, Müller P, Cheng Y J 2019 J. Power Sources 412 93 Google Scholar
[11]	Shi J, Jiang X S, Sun J F, Ban B Y, Li J W, Chen J 2021 J. Colloid Interface Sci. 588 737 Google Scholar
[12]	Ko M, Chae S, Ma J, Kim N, Lee H W, Cui Y Cho J 2016 Nat. Energy 1 16113 Google Scholar
[13]	李昆儒, 胡省辉, 张正富, 郭玉忠, 黄瑞安 2021 无机材料学报 3 454 Li K R, Hu X H, Zhang Z F, Guo Y Z, Huang R A 2021 Journal of Inorganic Materials 3 454
[14]	刘振源, 刘烈凯, 金鑫, 汤昊, 孙润光 2019 复合材料学报 36 1568 Liu Z Y, Liu L K, Jin X, Tang H, Sun R G 2019 Acta Mater. Compos. Sin. 36 1568
[15]	Luo W, Wang Y X, Chou S L, Xu Y F, Li W, Kong B, Dou S X, Liu H K, Yang J P 2016 Nano Energy 27 255 Google Scholar
[16]	Cai W, Liu X, Zhu Y, Lan Y, Ma K, Qian Y 2016 Dalton Trans. 45 13667 Google Scholar
[17]	林伟国, 孙伟航, 曲宗凯, 冯晓磊, 荣峻峰, 陈旭, 杨文胜 2019 高等学校化学学报 40 1216 Google Scholar Lin W G, Sun W H, Qu Z K, Feng X L, Rong J F, Chen X, Yang W S 2019 Chem. J. Chin. Univ. 40 1216 Google Scholar
[18]	Zhu X, Choi S H, Tao R, Jia X L, Lu Y F 2019 J. Alloys Compd. 791 1105 Google Scholar
[19]	Yu Y, Li G, Zhou S, Chen X, Yang W 2017 Carbon 120 397 Google Scholar
[20]	Deiss E, Wokaun A, Barras J L, Daul C, Dufek P 1997 J. Electrochem. Soc. 144 3877 Google Scholar
[21]	Ullah A, Majid A, Rani N 2018 J. Energy Chem. 27 219
[22]	闫小童, 侯育花, 郑寿红, 黄有林, 陶小马 2019 物理学报 68 187101 Google Scholar Yan X Tong, Hou Y H, Zheng S H, Huang Y L, Tao X M 2019 Acta Phys. Sin. 68 187101 Google Scholar
[23]	张伟, 齐小鹏, 方升, 张健华, 史碧梦, 杨娟玉 2020 化学进展 32 454 Zhang W, Qing X P, Fang S, Zhang J H, Shi B M, Yang J Y 2020 Prog. Chem. 32 454
[24]	Li G C, Yang Z W, Yin Z L, Guo H J, Wang Z X, Yan G C, Liu Y, Li L J, Wang J X 2019 J. Mater. Chem. A 26 15541
[25]	Clark S J, Segall M D, Pickard C J, Hasnip P J, Probert M J, Refson K, Payne M C 2005 Z. Kristallogr. 220 567
[26]	Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865 Google Scholar
[27]	Grimme S 2006 J. Comput. Chem. 27 1787 Google Scholar
[28]	Vanderbilt D 1990 Phys. Rev. B 41 7892 Google Scholar
[29]	Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188 Google Scholar
[30]	Gao H, Jian Z, Lu M, Wei F, Chen Y 2010 J. Appl. Phys. 107 666
[31]	Aktuerk E, Ataca C, Ciraci S 2010 Appl. Phys. Lett. 96 123112 Google Scholar
[32]	Stockmeier M, Müller R, Sakwe S A, Wellmann P J, Magerl A 2009 J. Appl. Phys. 105 033511 Google Scholar
[33]	Tsirelson V, Stash A 2002 Chem. Phys. Lett. 351 142 Google Scholar
[34]	Zhang S, Wang Q, Kawazoe Y, Jena P 2013 J. Am. Chem. Soc. 135 18216 Google Scholar

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