Comparative analysis of the polarization and morphological characteristics of electrochemically produced powder forms of the intermediate metals

Nebojsa D. Nikolic, Predrag M. Zivkovic, Bojan Jokic, Miomir G. Pavlovic, Jasmina S. Stevanovic


The polarization and morphological characteristics of powder forms of the group of the intermediate metals were examined by the analysis of silver and copper electrodeposition processes at high overpotentials. The pine-like dendrites constructed from the corncob-like forms, very similar to each others, were obtained by electrodeposition of these metals at the overpotential belonging to the plateaus of the limiting diffusion current density. The completely different situation was observed by electrodeposition of silver and copper at the overpotential outside the plateaus of the limiting diffusion current density in the zone of the fast increase of the current density with the overpotential. The silver dendrites, very similar to silver and copper dendrites obtained inside the plateaus of the limiting diffusion current density, were obtained at the overpotential outside the plateau. Due to the lower overpotential for hydrogen evolution for copper, hydrogen produced during copper electrodeposition process strongly affected the surface morphology of copper. The same shape of the polarization curves with the completely different surface morphology of Cu and Ag electrodeposited at overpotentials after the inflection point clearly indicates on the importance of morphological analysis in the investigation of polarization characteristics of the electrodeposition systems. Role of hydrogen as crucial parameter in the continuous change of copper surface morphology from dendrites to the honeycomb-like structures was investigated in detail. On the basis of this analysis, the transitional character of the intermediate metals between the normal and inert metals was considered. The typical powder forms characterizing electrodeposition of the intermediate metals were also defined and systematized.


electrodeposition; copper; silver; dendrite; hydrogen; pores; cauliflower-like forms

Full Text:



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

R.Winand, Electrodeposition of metals and alloys – new results and perspectives, Electrochim. Acta, 39, 1091–1105 (1994).

V. M. Kozlov, L. Peraldo Bicelli, Influence of the nature of metals on the formation of the deposit's polycry¬stalline structure during electrocrystallization, J. Cryst. Growth, 203, 255–260 (1999).

G. Orhan, G. Hapci, Effect of electrolysis parameters on the morphologies of copper powder obtained in a rotating cylinder electrode cell, Powder Technol., 201, 57–63 (2010).

G. Orhan, G. G. Gezgin, Effect of electrolysis para-meters on the morphologies of copper powder obtained at high current densities, J. Serb. Chem. Soc., 77, 651–665 (2012).

N. D. Nikolić, G. Branković, M. G. Pavlović, Correlate between morphology of powder particles obtained by the different regimes of electrolysis and the quantity of evolved hydrogen, Powder Technol., 221, 271–277 (2012).

Y. Ni, Y. Zhang, L. Zhang, J. Hong, Mass synthesis of dendritic Bi nanostructures by a facile electrodeposition route and influencing factors. CrystEngComm, 13, 794–799 (2011).

M. Yang, Fern-shaped bismuth dendrites electro-deposited at hydrogen evolution potentials, J. Mater. Chem., 21, 3119–3124 (2011).

C. Ding, C. Tian, R. Krupke, J. Fang, Growth of non-branching Ag nanowires via ion migrational-transport controlled 3D electrodeposition, CrystEngComm, 14, 875–879 (2012).

T-H. Lin, C-W. Lin, H-H. Liu, J-T. Sheu, W-H. Hung, Potential controlled electrodeposition of gold dendrites in the presence of cysteine, Chem. Commun., 47, 2044–2046 (2011).

J. Han, J. Liu, Electrodeposition of Crystalline Dendritic Silver in 12-Tungstosilicate Acid System, J. Nanoeng. Nanomanuf., 2, 171–174 (2012).

M. V. Mandke, S-H. Han, H. M. Pathan, Growth of silver dendritic nanostructures via electrochemical route, CrystEngComm, 14, 86–89 (2012).

J. Wang, L. Wei, L. Zhang, Y. Zhang, C. Jiang, Electro¬lytic approach towards the controllable synthesis of symmetric, hierarchical, and highly ordered nickel dendritic crystals, CrystEngComm, 14, 1629–1636 (2012).

N. D. Nikolić, H. Wang, H. Cheng, C. Guerrero, E. V. Ponizovskaya, G. Pan, N. Garcia, Magnetoresistance Controls Arboreous Bead-Dendritic Growth of Magnetic Electrodeposits: Experimental and Theoretical Results, J. Electrochem. Soc., 151, C577–C584 (2004).

V. D. Jović, B. M. Jović, V. M. Maksimović, M. G. Pavlović, Electrodeposition and morphology of Ni, Co and Ni–Co alloy powders: Part II. Ammonium chloride supporting electrolyte, Electrochim. Acta, 52, 4254–4263 (2007).

V. D. Jović, V. M. Maksimović, M. G. Pavlović, K. I. Popov, Morphology, internal structure and growth mechanism of electrodeposited Ni and Co powders, J. Solid State Electrochem., 10, 373–379 (2006).

H. Shin, J. Dong, M. Liu, Nanoporous Structures Prepared by an Electrochemical Deposition Process, Adv. Mater., 15, 1610–1614 (2003).

Y. Li, W Jia, Y. Song, X. H. Xia, Superhydrophobicity of 3D porous copper films prepared using the hydrogen bubble dynamic template, Chem. Mater., 19, 5758–5764 (2007).

N. D. Nikolić, K. I. Popov, Lj. J. Pavlović, M. G. Pavlović, The effect of hydrogen codeposition on the morphology of copper electrodeposits. I. The concept of effective overpotential, J. Electroanal. Chem., 588, 88–98 (2006).

N. D. Nikolić, Lj. J. Pavlović, M. G. Pavlović, K. I. Popov, Formation of dish-like holes and a channel structure in electrodeposition of copper under hydrogen co-deposition, Electrochim. Acta, 52, 8096–8104 (2007).

N. D. Nikolić, G. Branković, M. G. Pavlović, K. I. Popov, The effects of the pause to pulse ratio in the regime of pulsating overpotential on the formation of honeycomb-like structures, Electrochem. Commun., 11, 421–424 (2009).

N. D. Nikolić, G. Branković, Effect of parameters of square-wave pulsating current on copper electro-deposition in the hydrogen co-deposition range, Electrochem. Commun., 12, 740–744 (2010).

S. Cherevko, X. Xing, C-H. Chung, Electrodeposition of three-dimensional porous silver foams, Electrochem. Commun., 12, 467–470 (2010).

S. Cherevko, C. Chung, Impact of key deposition parameters on the morphology of silver foams prepared by dynamic hydrogen template deposition, Electrochim. Acta, 55, 6383–6390 (2010).

S. Cherevko, C. Chung, Direct electrodeposition of nanoporous gold with controlled multimodal pore size distribution, Electrochem. Commun., 13, 16–19 (2011).

R. Sivasubramanian, M. V. Sangaranarayanan, Electro¬deposition of silver nanostructures: from polygons to dendrites, CrystEngComm, 15, 2052–2056 (2013).

M. Rosso, E. Chassaing, V. Fleury, J-N. Chazalviel, Shape evolution of metals electrodeposited from binary electrolytes, J. Electroanal. Chem., 559, 165–173 (2003).

K. I. Popov, N. V. Krstajić, S. R. Popov, Fundamental aspects of plating technology. II. Morphological aspects of metal electrodeposition from complex salt solutions, Surf. Technol., 20, 203–208 (1983).

S. Trasatti, Work function, electronegativity, and electrochemical behaviour of metals: III. Electrolytic hydrogen evolution in acid solutions, J. Electroanal. Chem., 39, 163–184 (1972).

N. D. Nikolić, Lj. J. Pavlović, M. G. Pavlović, K. I. Popov, Morphologies of electrochemically formed copper powder particles and their dependence on the quantity of evolved hydrogen, Powder Technol., 185, 195–201 (2008).

G. Wranglen, Dendrites and growth layers in the electrocrystallization of metals. Electrochim. Acta, 2, 130–146 (1960).

J. W. Diggle, A. R. Despić, J.O’M. Bockris, The mechanism of the dendritic electrocrystallization of zinc, J. Electrochem. Soc., 116, 1503–1514 (1969).

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, 1972, pp 199–313.

N. D. Nikolić, K. I. Popov, P. M. Živković, G. Branković, A new insight into the mechanism of lead electrodeposition: ohmic–diffusion control of the electrodeposition process, J. Electroanal. Chem., 691, 66–76 (2013).

Z-Y. Lv, A-Q. Li, Y. Fei, Z. Li, J-R. Chen, A-J. Wang, J-J. Feng, Facile and controlled electrochemical route to three-dimensional hierarchical dendritic gold nano-structures, Electrochim. Acta, 109, 136–144 (2013).

N. D. Nikolić, G. Branković, V. M. Maksimović, Effect of the anodic current density on copper electrodeposition in the hydrogen co-deposition range by the reversing current (RC) regime, J. Electroanal. Chem., 661, 309–316 (2011).

N. D. Nikolić, G. Branković, K. I. Popov, Optimization of electrolytic process of formation of open and porous copper electrodes by the pulsating current (PC) regime, Mater. Chem. Phys., 125, 587–594 (2011).

N. D. Nikolić, G. Branković, M. G. Pavlović, Effect of the electrolysis regime on the structural characteristics of honeycomb-like electrodes, Maced. J. Chem. Chem. Eng., 32, 79–87 (2013).

H. Shin, M. Liu, Copper Foam Structures with Highly Porous Nanostructured Walls, Chem. Mater., 16, 5460–5464 (2004).

J.-H. Kim, R.-H. Kim, H.-Sang Kwon, Preparation of copper foam with 3-dimensionally interconnected spherical pore network by electrodeposition, Electro-chem. Commun., 10, 1148–1151 (2008).

N. D. Nikolić, V. M. Maksimović, G. Branković, Morphological and crystallographic characteristics of electrodeposited lead from the concentrated electrolyte, RSC Adv., 3, 7466–7471 (2013).

N. D. Nikolić, Dj. Dj. Vaštag, P. M. Živković, B. Jokić, G. Branković, Influence of the complex formation on the morphology of lead powder particles produced by the electrodeposition processes, Adv. Powder Technol., 24, 674–682 (2013).

V. D. Jović, B. M. Jović, M. G. Pavlović, Electro-deposition of Ni, Co and Ni–Co alloy powders, Electrochim. Acta, 51, 5468–5477 (2006).

C. A. Marozzi, A. C. Chialvo, Development of electrode morphologies of interest in electrocatalysis. Part 1: Electrodeposited porous nickel electrodes, Electrochim. Acta, 45, 2111–2120 (2000).



  • There are currently no refbacks.

Copyright (c) 2016 Nebojsa D. Nikolic, Predrag M. Zivkovic, Bojan Jokic, Miomir G. Pavlovic, Jasmina S. Stevanovic

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.