Energy storage studies of bare and doped vanadium pentoxide, (V 1.95 M 0.05 )O 5 ,M ¼ Nb, Ta, for lithium ion batteries A. Sakunthala, ab M. V. Reddy, * a S. Selvasekarapandian, bc B. V. R. Chowdari * a and P. Christopher Selvin d Received 1st October 2010, Accepted 4th February 2011 DOI: 10.1039/c0ee00513d The bare V 2 O 5 and doped (V 1.95 M 0.05 )O 5 (M ¼ Nb, Ta) nano/submicron sized compounds were prepared by the simple polymer precursor method. The compounds were characterized by different physical and electroanalytical techniques. The effects of doping and different synthesis conditions on the energy storage performance of the V 2 O 5 compounds were discussed. All compounds delivered a discharge capacity (at the end of the 2 nd cycle) in the range 245 to 261 (3) mA h g 1 , except for the tantalum doped compound (V 1.95 Ta 0.05 )O 5 which exhibited a discharge capacity of 210 (3) mA h g 1 , cycled in the range 2.0–4.0 V at a current rate of 120 mA g 1 . An excellent cycling stability of 96% till twenty cycles was achieved for the compound V 2 O 5 prepared by the polymer precursor method. Electrochemical impedance spectroscopy studies at different voltages during discharge and charge cycles were discussed in detail. Introduction Lithium ion batteries are the preferable choices of power sources for electronic devices due to their higher energy density. 1–4 Owing to the drawbacks associated with the commercially used layered lithium cobalt oxide (LiCoO 2 ) such as low energy density, safety issues, relatively more toxic and expensive nature, interest has developed for alternative cathode materials. 1 Vanadium based cathode materials such as lithium trivanadate (LiV 3 O 8 ) and vanadium pentoxide (V 2 O 5 ) are considered as the attractive alternatives due to their unique advantages such as high energy density, low cost and relatively less toxic in nature. 5–7 They have a moderate working voltage (3 V), particularly suitable for the lithium polymer batteries, which will not degrade the polymer electrolyte even at high temperatures. 8 The compounds possess good chemical stability as well as excellent safety characteristics during overcharging due to the multiple oxidation states of vanadium atom. 5,9,10 LiV 3 O 8 is made up of V 3 O 8 layers stacked one above the other forming a monoclinic structure. 11 A reversible phase transition takes place during the discharge/ charge cycling, where the presence of lithium ions in the octa- hedral site between the layers acts like a pillar and gives an excellent stability to the structure. 12 Vanadium pentoxide (V 2 O 5 ) is made up of V 2 O 5 layers stacked along the c-axis of the orthorhombic structure. Each layer is in turn made up of VO 5 square pyramids sharing edges and corners (Fig. 1). 13 Unlike LiV 3 O 8 , which has a pillar like Li-ion in the octahedral site, the V 2 O 5 layers are held together only by the presence of weak van der Waals forces. So the compound easily undergoes different structural phase transitions such as a, 3, d, g and u phases a Department of Physics, National University of Singapore, Singapore 117542. E-mail: [email protected]; [email protected]; Fax: +65- 67776126; Tel: +65-651662605 b DRDO-BU, Centre for Life Sciences, Bharathiar University, Coimbatore, 641046, India c Kalasalingam University, Krishnankoil, Virudhunagar, 626190, Tamil Nadu, India d NGM College, Pollachi, Tamilnadu, India Broader context In recent years, lithium ion batteries are one of the major power sources for any kind of portable electronic devices. This is mainly due to its advantage in terms of higher energy density along with long cycle life over any other type of batteries. Among the popular cathode materials such as LiCoO 2 , LiFePO 4 , LiMn 2 O 4 , etc., vanadium based cathode V 2 O 5 could enhance the energy density of the lithium batteries more than twice (vs. Li) as high as the other cathode materials. But the cycle life of the battery with V 2 O 5 as the cathode is very poor and could be enhanced by different approaches such as proper preparation methods and conditions, doping metal ions or conductive coating. In this paper, we report submicron sized particles of V 2 O 5 synthesized using simple methods, electrochemical studies were found to give better cycling stability. We also studied the effect of doping of tantalum or niobium ions on V 2 O 5 and reported its energy storage properties. 1712 | Energy Environ. Sci., 2011, 4, 1712–1725 This journal is ª The Royal Society of Chemistry 2011 Dynamic Article Links C < Energy & Environmental Science Cite this: Energy Environ. Sci., 2011, 4, 1712 www.rsc.org/ees PAPER Downloaded by National University of Singapore on 02 May 2011 Published on 22 March 2011 on http://pubs.rsc.org | doi:10.1039/C0EE00513D View Online
14
Embed
Bare Ta-doped V2O5 Energy & Environmetal Science 2011
This document is posted to help you gain knowledge. Please leave a comment to let me know what you think about it! Share it to your friends and learn new things together.
Energy storage studies of bare and doped vanadium pentoxide,(V1.95M0.05)O5, M ¼ Nb, Ta, for lithium ion batteries
A. Sakunthala,ab M. V. Reddy,*a S. Selvasekarapandian,bc B. V. R. Chowdari*a and P. Christopher Selvind
Received 1st October 2010, Accepted 4th February 2011
DOI: 10.1039/c0ee00513d
The bare V2O5 and doped (V1.95M0.05)O5 (M ¼ Nb, Ta) nano/submicron sized compounds were
prepared by the simple polymer precursor method. The compounds were characterized by different
physical and electroanalytical techniques. The effects of doping and different synthesis conditions on
the energy storage performance of the V2O5 compounds were discussed. All compounds delivered
a discharge capacity (at the end of the 2nd cycle) in the range 245 to 261 (�3) mA h g�1, except for the
tantalum doped compound (V1.95Ta0.05)O5 which exhibited a discharge capacity of 210 (�3) mA h g�1,
cycled in the range 2.0–4.0 V at a current rate of 120 mA g�1. An excellent cycling stability of 96% till
twenty cycles was achieved for the compound V2O5 prepared by the polymer precursor method.
Electrochemical impedance spectroscopy studies at different voltages during discharge and charge
cycles were discussed in detail.
Introduction
Lithium ion batteries are the preferable choices of power sources
for electronic devices due to their higher energy density.1–4 Owing
to the drawbacks associated with the commercially used layered
lithium cobalt oxide (LiCoO2) such as low energy density, safety
issues, relatively more toxic and expensive nature, interest has
developed for alternative cathode materials.1 Vanadium based
cathode materials such as lithium trivanadate (LiV3O8) and
vanadium pentoxide (V2O5) are considered as the attractive
alternatives due to their unique advantages such as high energy
aDepartment of Physics, National University of Singapore, Singapore117542. E-mail: [email protected]; [email protected]; Fax: +65-67776126; Tel: +65-651662605bDRDO-BU, Centre for Life Sciences, Bharathiar University, Coimbatore,641046, IndiacKalasalingam University, Krishnankoil, Virudhunagar, 626190, TamilNadu, IndiadNGM College, Pollachi, Tamilnadu, India
Broader context
In recent years, lithium ion batteries are one of the major power so
due to its advantage in terms of higher energy density along with lon
cathode materials such as LiCoO2, LiFePO4, LiMn2O4, etc., vanadi
lithium batteries more than twice (vs. Li) as high as the other catho
cathode is very poor and could be enhanced by different approach
metal ions or conductive coating. In this paper, we report submic
electrochemical studies were found to give better cycling stability. W
on V2O5 and reported its energy storage properties.
1712 | Energy Environ. Sci., 2011, 4, 1712–1725
density, low cost and relatively less toxic in nature.5–7 They have
a moderate working voltage (�3 V), particularly suitable for the
lithium polymer batteries, which will not degrade the polymer
electrolyte even at high temperatures.8 The compounds possess
good chemical stability as well as excellent safety characteristics
during overcharging due to the multiple oxidation states of
vanadium atom.5,9,10 LiV3O8 is made up of V3O8 layers stacked
one above the other forming a monoclinic structure.11 A
reversible phase transition takes place during the discharge/
charge cycling, where the presence of lithium ions in the octa-
hedral site between the layers acts like a pillar and gives an
excellent stability to the structure.12 Vanadium pentoxide (V2O5)
is made up of V2O5 layers stacked along the c-axis of the
orthorhombic structure. Each layer is in turn made up of VO5
square pyramids sharing edges and corners (Fig. 1).13 Unlike
LiV3O8, which has a pillar like Li-ion in the octahedral site, the
V2O5 layers are held together only by the presence of weak van
der Waals forces. So the compound easily undergoes different
structural phase transitions such as a, 3, d, g and u phases
urces for any kind of portable electronic devices. This is mainly
g cycle life over any other type of batteries. Among the popular
um based cathode V2O5 could enhance the energy density of the
de materials. But the cycle life of the battery with V2O5 as the
es such as proper preparation methods and conditions, doping
ron sized particles of V2O5 synthesized using simple methods,
e also studied the effect of doping of tantalum or niobium ions
This journal is ª The Royal Society of Chemistry 2011
Fig. 11 The capacity vs. cycle number plots of the compounds:
(a) V2O5-B (symbol: P), V2O5-WP (symbol: O) and (V1.95M0.05)O5
(M ¼ Nb or Ta) (symbols: ,, B) (b) V2O5-H (symbols: ,) and V2O5-S
(symbol: B). Current density: 120 mA g�1; voltage range: 2.0-4.0 V.
Closed symbols: charge capacity. Open symbols: discharge capacity.
Table 2 Galvanostatic cycling data of the bare and doped compoundV2O5 prepared under different preparation conditions; current density:120 mA g�1; voltage range: 2.0 to 4.0 V
CompositionCapacity/(�3) mA h g�1
(cycle number)
Capacity retention (%)(2nd to 20th cycle);(2nd to 60th cycle)
60th cycles was more or less the same and much higher than the
2nd cycle. The impedance values are noted in Table 3, which
indicated an abrupt increase in impedance with increase in cycle
number. At 2.2 V (discharge), the Rsf+ct value observed was less
than 200 U at 1st cycle. But, the value was found to be more than
double its value in the case of 20th cycle. Only a single high
frequency semicircle corresponding to surface film + charge
transfer resistance was observed in the case of 20th cycle, but it
was seen well separated for the 60th cycle (Fig. 14(b)). The
impedance analysis indicated that after 20 cycles there was an
abrupt increase in impedance in the voltage region below 2.8 V
than in the voltage region above 2.8 V. Long term cycling
resulted in the clear appearance of surface film resistance and
similar behaviour was noted in literature.47
Conclusions
We studied the effect of different preparation methods and
doping of niobium and tantalum ions on V2O5 compound. The
compounds were characterized using X-ray diffraction, XANES,
SEM, TEM, density and BET surface area, cyclic voltammetry,
galvanostatic cycling and impedance techniques. The submicron
sized V2O5 compound (V2O5-B) synthesized by the polymer
precursor method was found to give a good stability of 96% till
twenty cycles. After 15 cycles, the capacity fading was noted
irrespective of the preparation method or doping. This may be
due to the intrinsic nature of the material or non-suppression of
structural transformations.
Acknowledgements
Authors thank Prof. G. V. Subba Rao, Dept. of Physics, NUS
for his helpful discussions. Authors thank Dr Aga Banas, SSLS,
for her help with XAS data collection. A. Sakunthala thanks the
Defence Research and Development Organisation (DRDO),
India, for grant of Senior Research Fellowship. Dr M. V. Reddy
and Prof. B. V. R. Chowdari thank to Ministry of education
(MOE) (Grant no. R-284-000-076-112) and National Research
Foundation (NRF), Singapore.
References
1 High Energy Density Lithium Batteries: Materials, Engineering,Applications, ed. K. E. Alifantis, S. A. Hackney and R. Vasantkumar, Wiley VCH, 2010.
2 (a) M. Wakihara, Mater. Sci. Eng., R, 2001, 33, 109; (b) J. L. Tirado,Mater. Sci. Eng., R, 2003, 40, 103; (c) M. Armand and J. M. Tarascon,Nature, 2008, 451, 652; (d) B. Scrosati and J. Garche, J. PowerSources, 2010, 195, 2419–2430; (e) J. Cabana, L. Monconduit,D. Larcher and M. R. Palacin, Adv. Mater., 2010, 22, E170; (f)M. V. Reddy, G. V. Subba Rao and B. V. R. Chowdari, J. Mater.Chem., 2010, invited review, submitted.
3 (a) A. Manthiram, A. V. Murugan, A. Sarkar and T. Muraliganth,Energy Environ. Sci., 2008, 1, 621; (b) D. Deng, M. G. Kim,J. Y. Lee and J. Cho, Energy Environ. Sci., 2009, 2, 818; (c)K. Saravanan, P. Balaya, M. V. Reddy, B. V. R. Chowdari andJ. J. Vittal, Energy Environ. Sci., 2010, 3, 457; (d) L. W. Ji andX. W. Zhang, Energy Environ. Sci., 2010, 3, 124; (e) K. S. Tan,M. V. Reddy, G. V. Subba Rao and B. Chowdari, J. PowerSources, 2005, 147, 241; (f) M. V. Reddy, G. V. Subba Rao andB. V. R. Chowdari, J. Power Sources, 2006, 159, 263; (g)M. V. Reddy, G. V. Subba Rao and B. V. R. Chowdari, J. PowerSources, 2006, 160, 1369.
1724 | Energy Environ. Sci., 2011, 4, 1712–1725
4 M. V. Reddy, G. V. Subba Rao and B. V. R. Chowdari, Solid StateIonics: Fundamental Researches and Technological Applications, inProceedings of the 12th Asian Conf. on Solid State Ionics, ed. B. V.R. Chowdari, et al.,Wuhan Univ. of Tech. Press, Wuhan, China,2010, pp. 497–508.
5 A. M. Kannan and A. Manthiram, J. Electrochem. Soc., 2003, 150,A990.
6 D. Liu, S. Zhan, G. Chen, W. Pan, C. Wang and Y. Wei, Mater. Lett.,2008, 62, 4210.
7 Q. Y. Liu, H. W. Liu, X. W. Zhou, C. J. Cong and K. L. Zhang, SolidState Ionics, 2005, 176, 1549.
8 S. Y. Chew, J. Z. Sun, J. Z. Wang, H. K. Liu, M. Forsyth andD. R. MacFarlane, Electrochim. Acta, 2008, 53, 6460.
9 A. M. Kannan and A. Manthiram, J. Power Sources, 2006, 159, 1405.10 (a) E. Potiron, A. L. La Salle, A. Verbaere, Y. Piffard and
D. Guyomard, Electrochim. Acta, 1999, 45, 197; (b) Y. J. Wei,C. W. Ryu and K. B. Kim, J. Power Sources, 2007, 165, 386; (c)F. Leroux, B. E. Koene and L. F. Nazar, J. Electrochem. Soc.,1996, 143, L181.
11 A. D. Wadsley, Acta Crystallogr., 1957, 10, 261.12 J. Kawakita, H. Mori, T. Miura and T. Kishi, Solid State Ionics, 2000,
131, 229.13 C. Delmas, H. C. Auradou, J. M. Cocciantelli, M. Menetrier and
J. P. Doumerc, Solid State Ionics, 1994, 69, 257.14 (a) S. Y. Zhan, C. Z. Wang, K. Nikolowski, H. Ehrenberg, G. Chen
and Y. J. Wei, Solid State Ionics, 2009, 180, 1198; (b) A. Gies,B. Pecquenard, A. Benayad, H. Martinez, D. Gonbeau, H. Fuessand A. Levasseur, Thin Solid Films, 2008, 516, 7271–7281; (c)F. Coustier, J. Hill, B. B. Owens, S. Passerini and W. H. Smyrl, J.Electrochem. Soc., 1999, 146, 1355.
15 J. M. Cocciantelli, M. Menetrier, C. Delmas, J. P. Doumerc,M. Pouchard, M. Broussely and J. Labat, Solid StateIonics, 1995, 78, 143.
16 C. Q. Feng, S. Y. Wang, R. Zeng, Z. P. Guo, K. Konstantinov andH. K. Liu, J. Power Sources, 2008, 184, 485.
17 N. A. Chernova, M. Roppolo, A. C. Dillon and M. S. Whittingham,J. Mater. Chem., 2009, 19, 2526.
18 K. Takahashi, S. J. Limmer, Y. Wang and G. Cao, J. Phys. Chem. B,2004, 108, 9795.
19 I. Khan and M. Zulfequar, Phys. B, 2010, 405, 579.20 C. O. Avellaneda, Mater. Sci. Eng., B, 2007, 138, 118.21 C. O. Avellaneda, Sol. Energy Mater. Sol. Cells, 2006, 90, 444.22 Y. Iida and Y. Kanno, J. Mater. Process. Technol., 2009, 209, 2421.23 G. T. Chandrappa, N. Steunou and J. Livage, Nature, 2002, 416, 702.24 Q. Tang, X. Huang, Y. Chen, T. Liu and Y. Yang, J. Mol. Catal. A:
Chem., 2009, 301, 24.25 S. H. Lim, N. Phonthammachai, T. Liu and T. J. White, J. Appl.
Crystallogr., 2008, 41, 1009.26 P. Chaurand, J. Rose, V. Briois, M. Salome, O. Proux, V. Nassif,
L. Olivi, J. Susini, J. L. Hazemann and J. Y. Bottero, J. Phys.Chem. C, 2007, 111, 5101.
27 M. Kaneko, S. Matsuno, T. Miki, M. Nakayama, H. Ikuta,Y. Uchimoto, M. Wakihara and K. Kawamura, J. Phys. Chem. B,2003, 107, 1727.
28 W. Avansi, Jr, C. Ribeiro, E. R. Leite and V. R. Mastelaro, Cryst.Growth Des., 2009, 9, 3626.
29 J. L. Bronkema and A. T. Bell, J. Phys. Chem. C, 2008, 112, 6404.30 T. Yamamoto, X-Ray Spectrom., 2008, 37, 572.31 M. Giorgetti, M. Berrettoni and W. H. Smyrl, Chem. Mater., 2007,
19, 5991.32 S. Passerini, W. H. Smyrl, M. Berrettoni, R. Tossici, M. Rosolen,
R. Marassia and F. Decker, Solid State Ionics, 1996, 90, 5.33 L. Agasi, F. J. Berry, M. Carbucicchio, J. F. Marco, M. Mortimer and
F. F. F. Vetel, J. Mater. Chem., 2002, 12, 3034.34 L. Q. Mai, L. Xu, C. H. Han, Y. Z. Luo, S. Y. Zhao and Y. L. Zhao,
Nano Lett., 2010, 10, 4750.35 D. Zhu, H. Liu, L. Lv, Y. D. Yao and W. Z. Yang, Scr. Mater., 2008,
59, 642.36 P. Ragupathy, S. Shivakumara, H. N. Vasan and
N. Munichandraiah, J. Phys. Chem. C, 2008, 112, 16700.37 S. H. Ng, S. Y. Chew, J. Wang, D. Wexler, Y. Tournayre,
K. Konstantinov and H. K. Liu, J. Power Sources, 2007, 174, 1032.38 M. D. Levi, G. Salitra, B. Markovsky, H. Teller, D. Aurbach,
U. Heider and L. Heiderb, J. Electrochem. Soc., 1999, 146, 1279.39 D. Aurbach, M. D. Levi, E. Levi, H. Telier, B. Markovsky and
G. Salitra, J. Electrochem. Soc., 1998, 9, 3024.
This journal is ª The Royal Society of Chemistry 2011