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Wu 2008
Wu 2008
Synthetic paramontroseite VO2 has been successfully obtained Further, the paramontroseite phase shows a continuous DOS
using a simple chemical reaction route for the first time after starting from 0.93 eV and the Fermi level tangles with its
fifty years; the paramontroseite phase shows a conducting conducting bands for all the high-symmetry points (see ESI,w
property and good aqueous lithium ion battery performance. S2). Comparing these calculation results with those for rutile
and monoclinic VO2, it is found that the DOS of rutile VO2
In the 1950s, Mrose and Evans discovered a new mineral also possesses a continuous DOS around the Fermi level while
paramontroseite VO2 from the Colorado Plateaus region.1 the DOS of monoclinic VO2 has a 0.1 eV wide deep minimum
Paramontroseite vanadium dioxide (VO2) possesses a regular just above eF with a separated band.5 Therefore, the charac-
tunnel form, in which the VO6 octahedra are linked into teristics of DOS and energy bands for paramontroseite VO2
double chains and the double chains link corners with each are quite similar to those of the metallic rutile VO2 phase,
other in turn to form a framework having tunnels with rather than that of the semiconducting monoclinic VO2 phase.
rectangular-shaped cross sections that are 12 octahedra on This similarity of calculation results between the paramontro-
a side.2,3 For more than fifty years, efforts have been strongly seite VO2 and metallic rutile VO2 phase thus provides further
focused on the structural analysis of paramontroseite and the evidence for the metallic behavior of the paramontroseite VO2
transformation relationship between paramontroseite and structure.
montroseite, owing to its fascinating tunnelled structure.1–3 Moreover, as observed from the DOS and energy bands for
However, almost all of the experimental data for paramon- paramontroseite VO2 (see ESI,w S2), it can be seen that the one
troseite originated from investigation of mineral samples, and spin direction (spin up) behaves like a metal and the other
not synthetic samples. Here, we highlight an available pathway (spin down) is semiconducting, showing the half-metal prop-
to accomplish this challenge by a simple reaction of sodium erty with a complete polarization of electrons at the Fermi
orthovanadate (Na3VO412H2O) and thioacetamide (TAA). level. That is to say, paramontroseite VO2 in orthorhombic
The fascination for paramontroseite VO2 also arises from its structure is also amenable to spintronics and spin injection.6
structural analysis and calculation results, which indicate Our experimental results show that the paramontroseite
potentially conducting behavior. For the paramontroseite VO2 could be chemically synthesized by a simple reaction of
VO2 phase, due to the presence of infinite chains along the sodium orthovanadate (Na3VO412H2O) and thioacetamide
c-axis with nearest V–V distances of 0.293 nm, its d-orbital (TAA). Details of the experimental process can be described as
electrons would be shared by all of the metal V atoms along follows: first, 4 mmol Na3VO412H2O and 20 mmol thioace-
the paramontroseite c-axis similar to that in tetragonal rutile tamide (TAA) were dissolved in 50 ml distilled water to form a
VO2 4 (see ESI,w S1). Therefore, paramontroseite would homogeneous solution in a glass jar. This solution was then
appear to have promising electrical conducting properties at loaded into a 50 ml Teflon-lined autoclave, which was sealed
room temperature from the structural point of view. Here, and heated at 220 1C for 10 h. The system was then allowed to
first-principle calculations using the VASP program were also
performed to further understand the conducting behavior of
paramontroseite VO2, and the spin-dependent density of states
(DOS) and energy bands of paramontroseite VO2 are shown in
Fig. 1. In Fig. 1(b), the DOS resides across the Fermi level and
gives a certain local DOS value at the Fermi level, indicating
its metallic character. In more detail, the total DOS value of
paramontroseite VO2 around the Fermi level is mainly con-
tributed from the V 3d and O 2p orbitals as shown in Fig. 1(b).
This journal is
c The Royal Society of Chemistry 2008 Chem. Commun., 2008, 3891–3893 | 3891
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VO2/LiMn2O4 aqueous cell is 61.9 mAh g1, which is a highly 1 H. T. Evans, Jr and M. E. Mrose, Am. Mineral., 1955, 40, 861.
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previous reports,14–16 although it is still smaller than that in 3 L. Löffler and W. Mader, J. Am. Ceram. Soc., 2003, 86, 534.
the organic electrolytes (usually 4120 mA h g1).17 Further- 4 Ch. Leroux, G. Nihoul and G. Van Tendeloo, Phys. Rev. B:
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5 K. Hermann, A. Chakrabarti, A. Haras, M. Witko and B. Tepper,
range of 1.3–1.6 V, while the second average output voltage is Phys. Status Solidi A, 2001, 187, 137–149.
1.0–1.2 V. Here, the output voltage is again very impressive 6 S. Sanna, B. Hourahine, U. Gerstmann and Th. Frauenheim, Phys.
when compared with previous aqueous LIBs.14–16 Also, the Rev. B: Condens. Matter, 2007, 76, 155128–155140.
7 L. Löffler and W. Mader, J. Am. Ceram. Soc., 2003, 86, 534.
first output voltage for paramontroseite VO2/LiMn2O4 aqu- 8 G. Thomas, Nature, 1997, 389, 907.
eous LIB is higher than the output voltage of primary 9 H. Kawazoe, M. Yasukawa, H. Hyodo, M. Kurita, H. Yanagi and
Zn–MnO2, Ni–MH and Ni–Cd cell systems (ca. 1.2 V), while H. Hosono, Nature, 1997, 389, 939.
even the lowest output voltage approached 1.2 V. The rela- 10 F. Q. Huang, P. Brazis, C. R. Kannewurf and J. A. Ibers, J. Am.
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tively high output voltage and high discharge capacity value 11 X. Wang, X. Y. Chen, L. S. Gao, H. G. Zheng, Z. D. Zhang and Y.
infer that our aqueous LIB is the promising substitute candi- T. Qian, J. Phys. Chem. B, 2004, 108, 16401.
date for cells with higher energy density. 12 C. Z. Wu, Y. Xie, L. Y. Lei, S. Q. Hu and C. Z. Ouyang, Adv.
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Second, it is clear that the as-obtained paramontroseite VO2
13 A. N. Jansen, A. J. Kahaian, K. D. Kepler, P. A. Nelson, K.
electrode exhibits better cycling behavior than those in the Amine, D. W. Dees, D. R. Vissers and M. M. Thackeray, J. Power
previously reported aqueous LIBs.14–16 Fig. 4(b) (inset in (a)) Sources, 1999, 81–82, 902.
shows the cycling behavior at a current density of 60 mA g1 14 G. James, Science, 1994, 264, 1084.
15 J. Kohler, H. Makihara, H. Uegaito, H. Inoue and M. Toki,
between 0.5 and 1.7 V in aqueous electrolyte. It is found that Electrochim. Acta, 2000, 46, 59.
the discharge capacity after 50 cycles is 45.96 mAh g1, which 16 G. J. Wang, L. Fu, N. H. Zhao, L. C. Yang, Y. P. Wu and H. Q.
is approximately 74% of the first discharge capacity, while it Wu, Angew. Chem., Int. Ed., 2007, 46, 295; G. J. Wang, L. Fu, N.
shows good resistance to fading up to 50 cycles. Third, the H. Zhao, L. C. Yang, Y. P. Wu and H. Q. Wu, Angew. Chem.,
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paramontroseite VO2 electrode exhibits a good stability at 17 M. Okubo, E. Hosono, J. Kim, M. Enomoto, N. Kojima, T. Kudo,
high current density as shown in Fig. 4(c), showing the H. Zhou and I. Honma, J. Am. Chem. Soc., 2007, 129, 7444–7452.
This journal is
c The Royal Society of Chemistry 2008 Chem. Commun., 2008, 3891–3893 | 3893