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Effects of heat-treatment on the spectroscopic and electrochemical properties of a mixed manganese/vanadium oxide film prepared by electrodeposition

Published online by Cambridge University Press:  03 March 2011

Masaharu Nakayama*
Affiliation:
Faculty of Engineering, Department of Applied Chemistry, Yamaguchi University, 2-16-1 Tokiwadai, Ube 755-8611, Japan
Akihiro Tanaka
Affiliation:
Faculty of Engineering, Department of Applied Chemistry, Yamaguchi University, 2-16-1 Tokiwadai, Ube 755-8611, Japan
Sayaka Konishi
Affiliation:
Faculty of Engineering, Department of Applied Chemistry, Yamaguchi University, 2-16-1 Tokiwadai, Ube 755-8611, Japan
Kotaro Ogura
Affiliation:
Faculty of Engineering, Department of Applied Chemistry, Yamaguchi University, 2-16-1 Tokiwadai, Ube 755-8611, Japan
*
a) Address all correspondence to this author. e-mail: nkymm@yamaguchi-u.ac.jp
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Abstract

Thin films of mixed manganese (mainly 4+) and vanadium (5+) oxides deposited electrochemically on a platinum substrate have been heat-treated under vacuum at various temperatures between 25 and 400 °C. Electron spin resonance and x-ray photoelectron spectroscopy revealed that the reductive formation of Mn2+ occurs at 300 °C only in the presence of vanadium within the film. This phenomenon can be regarded as a result of electron transfer from V4+ ions generated thermally to neighboring Mn sites. Voltammetric response of the heat-treated Mn/V oxide film in borate solution was enhanced with increasing the number of potential cycles, and the steady-state current was much larger than that of pure manganese oxide. Vanadate ions were diffused from the film to maintain the charge balance during the repetition cycles. The resultant porous structure can allow easier mass transport of protons to electrically conductive Mn oxide surface, offering the improved charge–discharge performance of the electrode.

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Articles
Copyright
Copyright © Materials Research Society 2004

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References

REFERENCES

1Gummow, R.J., de Kock, A. and Thackeray, M.M., Improved capacity retention in rechargeable 4 V lithium/lithium manganese oxide (spinel) cells. Solid State Ionics 69, 59 (1994).CrossRefGoogle Scholar
2Tarascon, J.M. and Guyomard, D., The lithium manganese oxide (Li1+xMn2O4)/carbon rocking-chair system. Electrochim Acta 38, 1221 (1993).CrossRefGoogle Scholar
3Lee, H.Y. and Goodenough, J.B., Supercapacitor behavior with KCl electrolyte. J. Solid State Chem. 144, 220 (1999).CrossRefGoogle Scholar
4Lee, H.Y., Kim, S.W. and Lee, H.Y., Expansion of active site area and improvement of kinetic reversibility in electrochemical pseudocapacitor electrode. Electrochem. Solid-State Lett. 4 A19 (2001).CrossRefGoogle Scholar
5Xu, J.J., Yang, J. and Jain, G., Effect of copper doping on intercalation properties of amorphous manganese oxides prepared by oxidation of Mn(II) precursors. Electrochem. Solid-State Lett. 5 A223 (2002).CrossRefGoogle Scholar
6Franger, S., Bach, S., Pereira-Ramos, J-P. and Baffier, N., Chemistry and electrochemistry of low-temperature manganese oxides as lithium intercalation compounds. J. Electrochem. Soc. 147, 3226 (2000).CrossRefGoogle Scholar
7Kim, H. and Popov, B.N., Synthesis and characterization of MnO2-based mixed oxides as supercapacitors. J. Electrochem. Soc. 150 D56 (2003).CrossRefGoogle Scholar
8Nakayama, M., Nishio, M. and Ogura, K., Electron spin resonance and x-ray photoelectron spectroscopic studies on an electrochemically deposited film of mixed manganese/vanadium oxides. J. Mater. Res. 18, 2364 (2003).CrossRefGoogle Scholar
9Hausen, L.D. Frederickson Jr.and D.M., Infrared spectra-structure correlation study of V-O compounds. Anal. Chem. 35, 818 (1963).Google Scholar
10Maruyama, T. and Osaki, Y., Electrochromic properties of manganese oxide thin films prepared by chemical vapor deposition. J. Electrochem. Soc. 142, 3137 (1995).CrossRefGoogle Scholar
11Bellamy, L.J. in The Infra-red Spectra of Complex Molecules , 3rd ed. (Chapman and Hall, London, 1975) p. 263.CrossRefGoogle Scholar
12Andrukaitis, E., Reversible lithium intercalation in alkali metal vanadium bronzes. J. Power Sources 54, 470 (1995).CrossRefGoogle Scholar
13Hashemi, T. and Brinkman, A.W., X-ray photoelectron spectroscopy of nickel manganese oxide thermistors. J. Mater. Res. 7, 1278 (1992).CrossRefGoogle Scholar
14Aronson, B.J., Blanford, C.F. and Stein, A., Synthesis, characterization, and ion-exchange properties of zinc and magnesium manganese oxides confined within MCM-41 channels. J. Phys. Chem. B 104, 449 (2000).CrossRefGoogle Scholar
15Kozyrev, B.M., Paramagnetic resonance in solutions of electrolytes. Disc. Faraday Soc. 19, 135 (1955).CrossRefGoogle Scholar
16Kijlstra, W.S., Poels, E.K., Bliek, A., Weckhuysen, B.M. and Schoonheydt, R.A., Characterization of Al2O3-supported manganese oxides by electron spin resonance and diffuse reflectance spectroscopy. J. Phys. Chem. B 101, 309 (1997).CrossRefGoogle Scholar
17Védrine, J.C. in Characterization of Homogeneous Catalysts , edited by Delanay, F. (Dekker,New York, 1984), p. 161.Google Scholar
18Cachet-Vivier, C., Bach, S. and Pereira-Ramos, J., Electrochemical proton insertion in manganese spinel oxides from aqueous borate solution. Electrochim. Acta 44, 2705 (1999).CrossRefGoogle Scholar
19Chigane, M. and Ishikawa, M., Manganese oxide thin film preparation by potentiostatic electrolyses and electrochromism. J. Electrochem. Soc. 147, 2246 (2000).CrossRefGoogle Scholar
20Lee, S-H., Liu, P., Seong, M.J., Cheong, H.M., Tracy, C.E. and Deb, S.K., Electrochemical supercapacitors for optical modulation. Electrochem. Solid-State Lett. 6 A40 (2003).CrossRefGoogle Scholar
21Kubec, F. and Šroubek, Z., Paramagnetic resonance of interstitial V4+ in TiO2. J. Chem. Phys. 57, 1660 (1972).CrossRefGoogle Scholar
22de Torresi, S.I. Cordoba and Gorenstein, A., Electrochromic behavior of manganese dioxide electrodes in slightly alkaline solutions. Electrochim. Acta 37, 2015 (1992).CrossRefGoogle Scholar
23Kumagai, N., Fujiwara, T., Tanno, K. and Horiba, T., Preparation and electrochemical characteristics of new MnO2-V2O5 systems as positive materials for rechargeable lithium batteries. Electrochim. Acta 37, 1039 (1992).CrossRefGoogle Scholar
24Casella, I.G. and Gatta, M., Electrochemical and XPS characterization of composite modified electrodes obtained by nickel deposition on noble metals. Anal. Chem. 72, 2969 (2000).CrossRefGoogle ScholarPubMed