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

doi:10.7503/cjcu20150472

Abstract

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

CLC Number:

O647.3

TrendMD:

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

Figures/Tables 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

References 37

[1]	Schlapbach L., Züttel A., Nature,2001, 414(6861), 353—358
[2]	Schlapbach L., Nature, 2009, 460(7257), 809—811
[3]	Wang Y., Meng Z., Liu Y., You D., Wu K., Lü J., Wang X., Deng K., Rao D., Lu R., Applied Physics Letters, 2015, 106(6), 063901
[4]	Fichtner M., Advanced Engineering Materials, 2005, 7(6), 443—455
[5]	Grochala W., Edwards P. P., Chemical Reviews, 2004, 104(3), 1283—1316
[6]	Eberle U., Felderhoff M., Schueth F., Angewandte Chemie International Edition, 2009, 48(36), 6608—6630
[7]	Chen P., Wu X., Lin J., Tan K., Science,1999, 285(5424), 91—93
[8]	Rosi N. L., Eckert J., Eddaoudi M., Vodak D. T., Kim J., O’Keeffe M., Yaghi O. M., Science,2003, 300(5622), 1127—1129
[9]	Yang W. J., Huang R. Z., Liu L., J. Mater. Sci. Eng., 2012, 30(3), 449—452
	(杨文静, 黄仁忠, 刘柳, 材料科学与工程学报,2012, 30(3), 449—452)
[10]	Wang L., Lee K., Sun Y. Y., Lucking M., Chen Z., Zhao J. J., Zhang S. B., ACS Nano, 2009, 3(10), 2995—3000
[11]	Burress J. W., Gadipelli S., Ford J., Simmons J. M., Zhou W., Yildirim T., Angewandte Chemie International Edition, 2010, 49(47), 8902—8904
[12]	Kostoglou N., Tzitzios V., Kontos A. G., Giannakopoulos K., Tampaxis C., Papavasiliou A., Charalambopoulou G., Steriotis T., Li Y., Liao K., International Journal of Hydrogen Energy,2015, 40(21), 6844—6852
[13]	Zhou H., Liu X., Zhang J., Yan X., Liu Y., Yuan A., International Journal of Hydrogen Energy,2014, 39(5), 2160—2167
[14]	Chen C., Zhang J., Zhang B., Duan H. M., J. Phys. Chem. C, 2013, 117(9), 4337—4344
[15]	Sun Q., Jena P., Wang Q., Marquez M., Journal of the American Chemical Society,2006, 128(30), 9741—9745
[16]	Guo Y., Jiang K., Xu B., Xia Y., Yin J., Liu Z., J. Phys. Chem. C, 2012, 116(26), 13837—13841
[17]	Liu W., Zhao Y., Li Y., Jiang Q., Lavernia E., J. Phys. Chem. C, 2009, 113(5), 2028—2033
[18]	Lu R., Rao D., Lu Z., Qian J., Li F., Wu H., Wang Y., Xiao C., Deng K., Kan E., J. Phys. Chem. C, 2012, 116(40), 21291—21296
[19]	Ao Z., Peeters F., Phys. Rev. B, 2010, 81(20), 205406
[20]	Zhou J., Wang Q., Sun Q., Jena P., Chen X. S., Proceedings of the National Academy of Science,2010, 107(7), 2801—2806
[21]	Zhang L., Zhang S., Wang P., Liu C., Huang S., Tian H., Computational & Theoretical Chemistry, 2014, 1035(9), 68—75
[22]	Kohn W., Sham L. J., Phys. Rev., 1965, 140(4A), A1133—A1138
[23]	Kresse G., Furthmüller J., Phys. Rev. B, 1996, 54(16), 11169—11186
[24]	Kresse G., Hafner J., Phys. Rev. B, 1993, 47(1), 558—561
[25]	Kresse G., Hafner J., Phys. Rev. B, 1994, 49(20), 14251—14269
[26]	Kresse G., Furthmüller J., Computational Materials Science, 1996, 6(1), 15—50
[27]	Kresse G., Joubert D., Phys. Rev. B, 1999, 59(3), 1758—1775
[28]	Perdew J. P., Chevary J., Vosko S., Jackson K. A., Pedersenm M., Singh D., Fiolhais C., Phys. Rev. B, 1992, 46(1), 6671—6687
[29]	Perdew J. P., Burke K., Ernzerhof M., Physical Review Letters, 1996, 77(18), 3865—3868
[30]	Jiang D. E., Sumpter B. G., Dai S., J. Chem. Phys., 2007, 126(13), 134701
[31]	Tkatchenko A., Scheffler M., Physical Review Letters, 2009, 102(7), 073005
[32]	Chan K. T., Neaton J. B., Cohen M. L., Phys. Rev. B, 2008, 77(23), 235430
[33]	Sun C., Searles D. J., J. Phys. Chem. C, 2012, 116(50), 26222—26226
[34]	Bellert D., Breckenridge W. H., J. Chem. Phys., 2001, 114(7), 2871—2874
[35]	Chen C., Kong W., Duan H., Zhang J., Physical Chemistry Chemical Physics, 2015, 17(20), 13654—13658
[36]	Wei D., Wang F., Surface Science, 2012, 606(3/4), 485—489
[37]	Henkelman G., Arnaldsson A., Jónsson H., Computational Materials Science, 2006, 36(3), 354—360