Nanostructured Manganese Dioxide Thin Films prepared by a Novel Self-Assembly Process

Authors

  • Pang Suh Cem
  • Wee Boon Hong
  • Chin Suk Fun

DOI:

https://doi.org/10.33736/bjrst.250.2013

Keywords:

Manganese dioxide, nanoparticles, self-assembly, thin films, electrochemical capacitors

Abstract

We have reported herein a novel self-assembly horizontal submersion process for the deposition of
nanostructured manganese dioxide thin films on metalized plastic supporting substrates at ambient temperature
and pressure. Uniform manganese dioxide thin films were deposited directly onto metallized plastic supporting
substrate via the spontaneous assembly of preformed manganese dioxide nanoparticles in the form of stable
colloidal suspension. This process affords a facile approach for the deposition of manganese dioxide thin films
by simply repeating the submersion process after the prior deposited layer had been air-dried completely. Thinfilm
deposition process initially occurred through the spontaneous adsorption of manganese dioxide
nanoparticles onto specific surface sites of the metalized substrate. Subsequent events of particle growth,
clusters formation, and aggregation or self-organization of particle clusters eventually led to the deposition of
nanostructured thin films which were nanoparticulate and highly porous in nature. The surface morphological
characteristics of deposited thin films were observed to be significantly affected by the duration of submersion
and the post-deposition calcination temperature. By modulating and optimizing these parameters, thin films of
tailored microstructure could therefore be prepared. Optimized manganese dioxide thin films were observed to
exhibit excellent capacitive behavior as evidenced by the almost perfectly rectangular shape of cyclic
voltamograms within the potential range of 0.0 to 1.0 V (versus SCE) in mild aqueous Na2SO4 electrolyte. The
cycling stability and reversibility of these films were evaluated by prolonged charge-discharge cycling and no
substantial deterioration of performance in terms of charge capacity and capacitive behaviors were observed
after 1000 cycles. We speculate that the high capacitance value exhibited by self-assembled manganese dioxide
thin films in mild aqueous electrolyte could be attributed to reversible and homogenous intercalation and
deintercalation of protons during the charge and discharge cycling. The potential utility of self-assembled
manganese dioxide thin films for the fabrication of electrochemical devices, in particular thin-film
electrochemical capacitors is therefore envisaged.

References

Brousse, T., Toupin, M., Dugas, R., Athouel. L., Crosnier, O., & Bèlanger, D. (2006). Crystalline MnO2 as Possible Alternatives to Amorphous Compounds in Electrochemical Supercapacitors. Journal of the Electrochemical Society, 153 (12): A2171 - A2180.

https://doi.org/10.1149/1.2352197

Chin, S. F. Pang S. C., & Anderson M.A. (2002). Material and Electrochemical Characterization of Tetrapropylammonium Manganese Oxide Thin Film as Novel Electrode Materials for Electrochemical Capacitors. Journal of Electrochemical Society, 149(4): A379 - 384.

https://doi.org/10.1149/1.1453406

Dai, Y., Wang, K., Zhao, J. C., & Xie, J. Y. (2006). Manganese oxide film electrodes prepared by electrostatic spray deposition for electrochemical capacitors from the KMnO4 solution. Journal of Power Sources, 161: 737 - 742.

https://doi.org/10.1016/j.jpowsour.2006.04.098

Lee, H. Y., Manivannan, V., & Goodenough, J. B. (1999). Electrochemical capacitors with KCl electrolyte. Comptes Rendus de l'Académie des Sciences - Series IIC - Chemistry, 565 - 577.

https://doi.org/10.1016/S1387-1609(00)88567-9

Liu, E. H., Meng, X. Y., Ding, R., Zhou, J. C., & Tan, S. T. (2007). Potentiodynamical codeposited manganese oxide/carbon composite for high capacitance electrochemical capacitors. Materials Letters, 61: 3486 - 3489.

https://doi.org/10.1016/j.matlet.2006.11.091

Mochizuki, N., Ueno, H., & Kaneko, M. (2004). Solid medium for conventional electrochemical measurements. Electrochimica Acta, 49: 4143 - 4148.

https://doi.org/10.1016/j.electacta.2004.04.008

Nagarajan, N., Humadi, H., & Zhitomirsky, I. (2006). Cathodic electrodeposition of MnOx films for electrochemical supercapacitors. Electrochimica Acta, 51: 3039 - 3045.

https://doi.org/10.1016/j.electacta.2005.08.042

Qu, D. Y. (2006). Investigation of the porosity of electrolytic manganese dioxide and its performance as alkaline cathode material. Journal of Power Sources, 156: 692 - 699.

https://doi.org/10.1016/j.jpowsour.2005.06.013

Pang S. C., Anderson, M. A. & Chapman, T. W. (2000) Novel Electrode Materials for Thin-Film Ultracapacitors: I. Comparison of Electrochemical Properties of Sol-Gel-Derived and Electrodeposited Manganese Dioxide. Journal of Electrochemical Society, 147(2): 444-450.

https://doi.org/10.1149/1.1393216

Perez-Benito, J. F., Arias, C. & Amat, E. (1996). A kinetic study of the reduction of colloidal manganese dioxide by oxalic acid. Journal of Colloid and Interface Science, 177: 288-297.

https://doi.org/10.1006/jcis.1996.0034

Wen S., Lee, J. W., Yeo, I. H., Park, J. M., & Mho, S. I. (2004). The role of cations of the electrolyte for the pseudocapacitive behavior of metal oxide electrodes, MnO2 and RuO2. Electrochimica Acta, 50: 849 - 855.

https://doi.org/10.1016/j.electacta.2004.02.056

Yagi, H., Ichikawa, T., Hirano, A., Imanishi, N., Ogawa, S., & Takeda, Y. (2002). Electrode characteristics of manganese oxides prepared by reduction method. Solid State Ionics, 154 -155: 273 - 278.

https://doi.org/10.1016/S0167-2738(02)00443-5

Zolfaghari, A., Ataherian, F., Ghaemi, M., & Gholami, A. (2007). Capacitive behavior of nanostructured MnO2 prepared by sonochemistry method. Electrochimica Acta, 52: 2806 - 2814.

https://doi.org/10.1016/j.electacta.2006.10.035

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How to Cite

Cem, P. S., Hong, W. B., & Fun, C. S. (2016). Nanostructured Manganese Dioxide Thin Films prepared by a Novel Self-Assembly Process. Borneo Journal of Resource Science and Technology, 3(1), 1–13. https://doi.org/10.33736/bjrst.250.2013

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