Lithium Storage on Extended Graphynes: Predicted by DFT Calculations†

doi:10.7503/cjcu20140317

Abstract

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

CLC Number:

O647.3

TrendMD:

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

Figures/Tables 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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