Abstract
Using the plane wave ultrasoft pseudopotential method based on the first-principles density functional theory (DFT), the influence on the electronic structure and dehydrogenation properties of VH2 doped with Zr, Cu and Zn has been studied. The results show that the negative heat of formation increases and the valence electron number at the Fermi level E F, N(E F) decreases in the Zr-doped model, indicating the higher stability of VH2 after Zr alloying. On the other hand, the negative heat of formation of VH2 decreases and the N(E F) increases in Cu- or Zn-doped systems, suggesting the lower stability of VH2 after Cu or Zn alloying. The calculated overlap populations and electron densities of the V-H bond demonstrate that the bonding is strengthened by Zr doping and weakened by Cu or Zn doping. The results predict that the maximum capacity to absorb and desorb hydrogen can be raised by the introduction of Zr and reduced by the introduction of Cu or Zn, while the dehydrogenation properties will be poorer in Zr-doped systems and enhanced in Cu- or Zn-doped systems. These predictions are consistent with the experimental results. Mulliken populations were also calculated and it was found that the Mulliken population of the V 3d orbitals decreased as a result of Zr doping, and increased after Cu or Zn doping.
Similar content being viewed by others
References
Itoh H, Arashima H, Kubo K, Kabutomori T, Ohnishi K. Improvement of cyclic durability of BCC structured Ti-Cr-V alloys. J Alloys Compd, 2005, 404: 417–420
Young K, Fetcenko MA, Li F, Ouchi T, Koch J. Effect of vanadium substitution in C14 Laves phase alloys for Ni-MH battery application. J Alloys Compd, 2009, 468: 482–492
Singh BK, Cho SW, Yoon HS, Kim CJ, Bartwal KS. Influence of Cu addition on structure and hydrogen desorption characteristics of Ti0.16Zr0.05Cr0.22V0.57 alloy. Mater Chem Phys, 2008, 112: 686–689
Pan HG, Li R, Liu YF, Gao MX, He M, Lei YQ, Wang QD. Structure and electrochemical properties of the Fe substituted Ti-V-based hydrogen storage alloys. J Alloys Compd, 2008, 463:189–195
Zhu YF, Liu YF, Hua F, Li LQ. Effect of rapid solidification on the structural and electrochemical properties of the Ti-V-based hydrogen storage electrode alloy. J Alloys Compd, 2008, 463: 528–532
Elanski D, Lim JW, Mimura K. Impurity removal from Fe, Cr, Ti, and V metals by hydrogen plasma arc melting and thermodynamic estimation of hydride and sulfide formation. J Alloys Compd, 2006, 421: 203–208
Li SC, Zhao MS, Wang LM, Liu Y, Wang YZ. Structures and electrochemical characteristics of Ti0.26Zr0.07V0.24Mn0.1Ni0.33Mox (x = 0–0.1) hydrogen storage alloys. Mater Sci Eng B, 2008, 150: 168–174
Basak S, Shashikala K, Sengupta P, Kulshreshtha SK. Hydrogen absorption properties of Ti-V-Fe alloys: Effect of Cr substitution. Int J Hydrogen Energy, 2007, 32: 4973–4977
Sung WC, Jeong HY, Gun S, Choong NP, Jeon C. Effects of B addition on the hydrogen absorption-desorption property of Ti0.32Cr0.43V0.25 alloy. Int J Hydrogen Energy, 2008, 33: 1700–1705
Jeong HY, Gun S, Sung WC, Choong NP. Effects of desorption temperature and substitution of Fe for Cr on the hydrogen storage properties of Ti0.32Cr0.43V0.25 alloy. Int J Hydrogen Energy, 2007, 32: 2977–2981
Tsukahara M, Takahashi K, Mishima T, Isomura A, Sakai T. Influence of various additives in vanadium-based alloys V3TiNi0.56 on secondary phase formation, hydrogen storage properties and electrode properties. J Alloys Compd, 1996, 245: 59–65
Chen LX, Li L, Wang XH, Dai FB, Zheng FP, Lei YQ. Phase structures and electrochemical properties of V2.1TiNi0.4Zrx (x = 0–0.06) hydrogen storage electrode alloys (in Chinese). Acta Phys-Chim Sin, 2006, 22: 523–527
Liu J, Chen LX, Zheng FP, Dai FB, Chen CP. Effect of Zr content on the microstructures and hydrogen storage properties of (Ti-Cr)45−x V55Zrx (x = 1–7) alloys (in Chinese). Rare Metal Mat Eng, 2005, 34: 1871–1874
Chen LX, Dai FB, Liu J, Zheng FP, Lei YQ. Influence of ball-milling with Cu powder on electrochemical properties of V-based solid solution type hydrogen storage alloys (in Chinese). Chin J Nonferr Meta, 2005, 15: 661–667
Li R, Zhou SQ, Liang GM, Luo XL. Theoretical investigation on the effect of exothermic alloying on storage hydrogen materials (in Chinese). Chin J Inorg Chem, 2007, 23: 584–590
Li R, Zhou SQ, Liang GM, Yun YY, Liu SP, Luo XL, Wan Y. Effect of addition of endothermic metals on the properties of vanadium-based storage hydrogen materials. Rare Metal Mat Eng, 2007, 36: 1592–1596
Li R, Zhou SQ, Chen CG, Liang GM. Quantum chemistry study on electronic structure of vanadium hydride. Acta Phys-Chim Sin, 2005, 21: 716–721
Matumura T, Yukawa H, Morinaga M. Alloying effects on the electronic structures of VH2 and V2H. J Alloys Compd, 1999, 284: 82–88
Segall MD, Lindan PLD, Probert MJ, Pickard CJ, Hasnip PJ, Clark SJ, Payne MC. First-principles simulation: Ideas, illustrations and the CASTEP code. J Phys: Condens Matter, 2002, 14: 2717–2743
Marlo M, Milman V. Density-functional study of bulk and surface properties of titanium nitride using different exchange-correlation functionals. Phys Rev B, 2000, 62: 2899–2907
Nakamura H, Nguyen MD, Pettifor DG. Electronic structure and energetics of LaNi5, α-La2Ni10H and β-La2Ni10H14. J Alloys Compd, 1998, 281: 81–91
Zhou DW, Liu JS, Peng P. First-principles calculation of dehydrogenating properties of MgH2-V systems (in Chinese). Sci China Ser E, 2006, 36: 1–8
Reilly JJ, Wiswall RH. Higher hydrides of vanadium and niobium. Inorg Chem, 1970, 9: 1678–1682
Zhao M, Song XP, Pei P, Zhang PL. Thermodynamics of V7.4Zr7.4Ti7.4Ni hydrogen storage alloy (in Chinese). Rare Metal Mat Eng, 2009, 38: 651–654
Hu ZL. Hydrogen Storage Materials (in Chinese). Beijing: Chemical Industry Press, 2002. 26–28
Zhang H, Qi KZ, Zhang GY, Wu D, Zhu SL. First-principles study on the influence of component element substitution on the dehydrogenation ability of LiNH2 hydrogen storage material (in Chinese). Acta Phys Sin, 2009, 58: 8077–8082
Zhao ZY, Liu QJ, Zhang J, Zhu ZQ. First-principles study of 3d transition metal-doped anatase (in Chinese). Acta Phys Sin, 2007, 56: 6592–6597
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Li, R., Luo, X., Liang, G. et al. A theoretical study of the influence of dopants on the dehydrogenation properties of VH2 . Sci. China Chem. 54, 1510–1517 (2011). https://doi.org/10.1007/s11426-011-4354-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11426-011-4354-3