Influence of the exchange current density and overpotential for hydrogen evolution reaction on the shape of electrolytically produced disperse forms - Review

  • Nebojša D. Nikolić ICTM-Department of ElectrochemistryNjegoÅ¡eva 12, 11000 Belgrade
Keywords: Electrolysis, metal, morphology, powder particles, SEM

Abstract

In this study, comprehensive survey of formation of disperse forms by the electrolysis from aqueous electrolytes and molten salt electrolysis has been presented. The shape of electrolitically formed disperse forms primarily depends on the nature of metals, determined by the exchange current density (j0) and overpotential for hydrogen evolution reaction as a parallel reaction to metal electrolysis. The decrease of the j0 value leads to a change of shape of dendrites from the needle-like and the 2D fern-like dendrites (metals characterized by high j0 values) to the 3D pine-like dendrites (metals characterized by medium j0 values). The appearing of a strong hydrogen evolution leads to formation of cauliflower-like and spongy-like forms (metals characterized by medium and low j0 values). The other disperse forms, such as regular and irregular crystals, granules, cobweb-like, filaments, mossy and boulders, usually feature metals characterized by the high j0 values. The globules and the carrot-like forms are a characteristic of metals with the medium j0 values. The very long needles were a product of molten salt electrolysis of magnesium nitrate hexahydrate. Depending on the shape of the disperse forms, i.e. whether they are formed without and with vigorous hydrogen evolution, formation of all disperse forms can be explained by either application of the general theory of disperse deposits formation or the concept of "effective overpotential". With the decrease of j0 value, the preferred orientation of the disperse forms changed from the strong (111) in the needle-like and the fern-like dendrites to randomly oriented crystallites in the 3D pine-like dendrites and the cauliflower-like and the spongy-like forms.

Downloads

Download data is not yet available.

References

K. I. Popov, S. S. Djokić, B. N. Grgur, Fundamental aspects of electrometallurgy, New York, Kluwer Academic/Plenum Publishers, New York, USA, 2002, p.p. 1–305.

K. I.Popov, S. S.Djokić, N. D.Nikolić, V. D. Jović, Morphology of Electrochemically and Chemically Deposited Metals, Springer, Switzerland, 2016, p.p. 1–368.

R. Winand, Electrochimica Acta 39 (1994) 1091–1105.

N. D. Nikolić, P.M. Živković, G. Branković, M.G. Pavlović, Journal of the Serbian Chemical Society 82 (2017) 539–550.

K. Fetter, Electrochemical Kinetics, Moscow, Khimiya, 1967 (in Russian).

N. D. Nikolić, P. M. Živković, J. D. Lović, G. Branković, Journal of Electroanalytical Chemistry 785 (2017) 65–74.

J. O’M. Bockris, Z. Nagy, A. Damjanović, Journal of The Electrochemical Society 119 (1972) 285–295.

K. I. Popov, N .V. Krstajić, S. R. Popov, Surface Technology 20 (1983) 203–208.

K .I. Popov, B. N. Grgur, E. R. Stojilković, M. G. Pavlović, N. D. Nikolić, Journal of the Serbian Chemical Society 62 (1997) 433–442.

N. D. Nikolić, K. I. Popov, P. M. Živković, G. Branković, Journal of Electroanalytical Chemistry 691 (2013) 66–76.

N. D. Nikolić, P. M. Živković, S. I. Stevanović, G. Branković, Journal of the Serbian Chemical Society 81 (2016) 553–566.

N. D. Nikolić, Dj. Dj. Vaštag, P. M. Živković, B. Jokić, G. Branković, Advanced Powder Technology 24 (2013) 674–682.

N. D. Nikolić, Dj. Dj. Vaštag, V. M. Maksimović, G. Branković, Transactions of Nonferrous Metals Society of China 24 (2014) 884−892.

N. D. Nikolić, K. I. Popov, A New Approach to the Understanding of the Mechanism of Lead Electrodeposition, in Electrodeposition and Surface Finishing, Series: Modern Aspects of Electrochemistry, S.S. Djokić, Ed., vol. 57, Springer, 2014, pp. 85 – 132.

G. Wranglen, Electrochimica Acta 2 (1960) 130–146.

H. M. Liaw, J. W. Faust Jr, Journal of Crystal Growth 18 (1973) 250–256.

N. D. Nikolić, E. R. Ivanović, G. Branković, U. Č. Lačnjevac, S. I. Stevanović, J. S. Stevanović, M. G. Pavlović, Metallurgical and Materials Transactions. B: Process Metallurgy and Materials 46 (2015) 1760–1774.

N. D. Nikolić, S. I. Stevanović, G. Branković, Transactions of Nonferrous Metals Society of China 26 (2016) 3274–3282.

N. D. Nikolić, V. M. Maksimović, G. Branković, RSC Advances 3 (2013) 7466–7471.

N. D. Nikolić, V. M. Maksimović, G. Branković, P. M. Živković, M. G. Pavlović, Journal of the Serbian Chemical Society 78 (2013) 1387–1395.

R. Sivasubramanian, M. V. Sangaranarayanan, CrystEngComm 15 (2013) 2052–2056.

Y. Xia, Y. Xiong, B. Lim, S. E. Skrabalak, Angewandte Chemie International Edition 48 (2009) 60–103.

J. O`M. Bockris, A. K. N. Reddy, M. Gamboa-Aldeco, Modern Electrochemistry 2A, Fundamentals of Electrodics, Kluwer Academic/Plenum Publishers, New York, USA, 2000, p. 1333.

Lj. Avramović, E. R. Ivanović, V. M. Maksimović, M. M. Pavlović, M. Vuković, J. S. Stevanović, N. D. Nikolić, Transactions of Nonferrous Metals Society of China 28 (2018) 1903–1912.

Lj. Avramović, M. Bugarin, D. Milanović, V. Conić, M. M. Pavlović, M. Vuković, N. D. Nikolić, Journal of Mining and Metallurgy, Section B: Metallurgy 54 B (2018) 291–300.

N. D. Nikolić, P. M. Živković, B. Jokić, M. G. Pavlović, J. S. Stevanović, Macedonian Journal of Chemistry and Chemical Engineering 33 (2014) 169–180.

N. D. Nikolić, G. Branković, M. G. Pavlović, K. I. Popov, Journal of Electroanalytical Chemistry 621 (2008) 13–21.

K. I. Popov, P. M. Živković, B. Jokić, N. D. Nikolić, Journal of the Serbian Chemical Society 81 (2016) 291–306.

N. D. Nikolić, K. I. Popov, Lj. J. Pavlović, M. G. Pavlović, Journal of Electroanalytical Chemistry 588 (2006) 88–98.

N. D. Nikolić, K. I. Popov, Lj. J. Pavlović, M. G. Pavlović, Sensors 7 (2007) 1–15.

N. D. Nikolić, Lj. Avramović, E. R. Ivanović, V. M. Maksimović, Z. Baščarević, N. Ignjatović, Transactions of Nonferrous Metals Society of China 29 (2019) 1275–1284.

V. D. Jović, B. M. Jović, M. G. Pavlović, Electrochimica Acta 51 (2006) 5468–5477.

V. D. Jović, N. D. Nikolić, U. Č. Lačnjevac, B. M. Jović, K. I. Popov, Morphology of Different Electrodeposited Pure Metal Powders, in Electrochemical Production of Metal Powders, Series: Modern Aspects of Electrochemistry, S.S. Djokić, Ed., vol. 54. Springer, New York, USA, 2012, p.p. 63–123.

V. D. Jović, V. M. Maksimović, M. G. Pavlović, K. I. Popov, Journal of Solid State Electrochemistry 10 (2006) 373–379.

V. D. Jović, B. M. Jović, V. Maksimović, M. G. Pavlović, Electrochimica Acta 52 (2007) 4254–4263.

N. D. Nikolić, V. M. Maksimović, G. Branković, P. M. Živković, M. G. Pavlović, Materials Protection 59 (2018) 256–264.

V. M. Maksimović, N. D. Nikolić, V. B. Kusigerski, J. L. Blanuša, Journal of the Serbian Chemical Society 80 (2015) 197–207.

Lj. J. Pavlović, M. M. Pavlović, M. G. Pavlović, N. D. Nikolić, M. V. Tomić, International Journal of Electrochemical Science 5 (2010) 1898–1910.

V. S . Cvetković, N. M. Vukićević, N.D . Nikolić, G. Branković, T. S. Barudžija, J. N . Jovićević, Electrochimica Acta 268 (2018) 494–502.

V.S . Cvetković, N. M. Vukićević, N. D. Nikolić, Z. Baščarević, T. S. Barudžija, J. N. Jovićević, Journal of Electroanalytical Chemistry 842 (2019) 168–175.

K. I. Popov, N. V. Krstajić, M. I. Čekerevac, The mechanism of formation of coarse and disperse electrodeposits, in Modern Aspects of Electrochemistry, R. E. White, B. E. Conway, J. O'M. Bockris, Eds., vol. 30, Plenum Press, New York, USA, 1996, p.p. 261–312.

A. R. Despić, K. I. Popov, Transport controlled deposition and dissolution of metals, in Modern Aspects of Electrochemistry, B. E. Conway, J. O`M. Bockris, Eds., vol. 7, Plenum Press, New York, USA, 1972, p.p. 199–313.

J. W. Diggle, A. R. Despić, J. O` M. Bockris, Journal of The Electrochemical Society 116 (1969) 1503–1514.

K. I. Popov, N. D. Nikolić, General Theory of Disperse Metal Electrodeposits Formation, in Electrochemical Production of Metal Powders, Series: Modern Aspects of Electrochemistry, S.S. Djokić, Ed., vol. 54, Springer, 2012, p.p. 1–62.

N. D. Nikolić, K. I. Popov, E. R. Ivanović, G. Branković, S. I. Stevanović, P. M. Živković, Journal of Electroanalytical Chemistry 739 (2015) 137–148.

Published
09-03-2020
Section
7th RSE SEE & 8th Kurt Schwabe symposium Special Issue