metals

Editorial
Advances in Understanding Metal Electrolysis Process
Bernd Friedrich 1, * , Jovan N. Jovićević 2, * , Dominic Feldhaus 1 and Vesna S. Cvetković 2

1 IME Process Metallurgy and Metal Recycling, Institute of RWTH Aachen University, 52056 Aachen, Germany
2 Department of Electrochemistry, Institute of Chemistry, Technology and Metallurgy, University of Belgrade,
11000 Belgrade, Serbia
* Correspondence: bfriedrich@metallurgie.rwth-aachen.de (B.F.); jovicevic@ihtm.bg.ac.rs (J.N.J.)

1. Introduction
Advancements in technologies related to the electrorefining and electrodeposition
of metals—as important manufacturing process steps—continue to receive significant
attention. Specifically, novel ideas that focus on the development of new approaches
to the electrochemical synthesis of alloys and composites are important for advancing
technologies that can promote increased supply sustainability in the future. This Special
Issue, “Advances in understanding metal electrolysis process”, aims at the fundamental
level of research with respect to novel approaches in areas of electrolysis and electrochemical
mechanisms as well as their impact on the efficiency and quality of metal deposition. It
consists of ten papers addressing various issues and their possible solutions around the
electrolysis/-deposition of aluminum, copper, indium, rare earth metals, and their alloys,
including Zn-Co coatings. One review paper provides an overview of the structure of metal
powders produced by electrochemical methods.

2. Contributions
Rare earth elements (REEs) and their alloys are an increasingly important group of mate-
rials, considering their ongoing and potential future applications in everyday and advanced
technologies. A combination of rapidly growing global demand for (REEs), the generation
of large volumes of solid waste as the byproducts of primary production, and limitations in
current technologies call for technological advancements in the increase of REEs available.
In particular, the recycling, substitution, and efficient use of REEs is critical for developing a
strategy towards a “green RE economy” and supplementing current supply channels. Exam-
Citation: Friedrich, B.; Jovićević, J.N.;
ples of recent research focusing on several of these aspects are discussed in three papers: [1–3].
Feldhaus, D.; Cvetković, V.S.
Articles [1,3] are focused on neodymium and praseodymium deposition, including the com-
Advances in Understanding Metal
Electrolysis Process. Metals 2023, 13,
plete electroreduction mechanism of both metals, to enable better control over the process,
307. https://doi.org/10.3390/
greenhouse gas emission reduction during electrolysis, and better deposition efficiency. The
met13020307 key objective was to simultaneously deposit neodymium and praseodymium from a fluo-
ride molten bath containing their oxides, as an alloy, by reducing the ecological footprint
Received: 11 December 2022
of the process. The environmentally improved process for neodymium and praseodymium
Accepted: 9 January 2023
co-deposition is performed in these studies under relatively small praseodymium deposition
Published: 2 February 2023
overpotentials on inert Mo and W cathodes resulting in very low levels of carbon oxide, fluo-
rine, and fluorocarbon gas emissions due to the low anodic overpotentials. The application
of the Nd and Pr co-deposition in a potentiostatic mode is a highly promising approach for
Copyright: © 2023 by the authors.
recycling REEs from neodymium iron boron magnets if initially separated from the magnet in
Licensee MDPI, Basel, Switzerland. the oxide form [1,3]. The conditions for an anode effect during neodymium and didymium
This article is an open access article oxide electrowinning were discussed in paper [2]. The influence of decisive parameters on
distributed under the terms and the anodic process (high current densities, low neodymium or didymium oxide content, high
conditions of the Creative Commons viscosity, electrolyte composition) was discussed and a mechanism proposed for the anode
Attribution (CC BY) license (https:// effect based on models used in aluminum electrolysis. Moreover, a mathematical model was
creativecommons.org/licenses/by/ proposed to estimate the neodymium and didymium electrochemical cell voltage in an elec-
4.0/). trolytic cell with vertical electrodes [2]. The recycling route for materials containing precious

Metals 2023, 13, 307. https://doi.org/10.3390/met13020307 https://www.mdpi.com/journal/metals

metals, such as ruthenium (e.g., used catalysts from the chemical industry), is covered in
paper [4]. A systematic study was conducted to address the oxidation behavior of ruthenium
in copper electrowinning. Ruthenium is not directly electrochemically oxidized to ruthenium
tetroxide at the anode. On the anode parallel to the oxygen evolution, the oxidants are formed;
they oxidize ruthenium compounds to highly volatile ruthenium tetroxide through chemical
reactions. The main variables influencing the rate of ruthenium oxidation were addressed,
and suggestions for avoiding the emission of toxic ruthenium tetroxide were derived [4].
Materials scientists working with aluminum alloys may find interesting results for
controlled vanadium and aluminum co-deposition from low-temperature chloroaluminate
molten salts containing vanadium ions [5]. Intermetallic alloys were synthetized during
aluminum underpotential deposition onto a vanadium metal that was previously deposited
on the glassy carbon electrode. As a result of solid-state interdiffusion between the initially
deposited vanadium and the subsequently deposited aluminum, Al3 V and AlV3 alloys
were formed. Not only did this provide a general introduction to the Al-V alloy generation,
but addressed the influence of the vanadium ion concentration in the electrolyte on the
deposition rate. This innovative research provides a solid foundation for the development
of a controllable electrochemical synthesis of vanadium trialuminide (Al3 V) and A15 alloy
(AlV3 ) intermetallics [5]. Contributing to the fundamental understanding of primary
aluminum production, the electrochemical behavior of aluminum in the LiF–AlF3 melt
and the presence of the spent catalyst at 740–800 ◦ C was presented in [6]. Experimental
data obtained the optimal process parameters for aluminum reduction during the spent
catalyst treatment and primary production, as well as key parameters; the effect of the
catalyst content, temperature, and electrolyte composition was outlined. The mechanism
of aluminum reduction in the LiF–AlF3 melts appears as a diffusion-controlled two-step
process. Both one-electron and two-electron steps occur simultaneously at close (or the
same) potentials, which affect the cyclic voltammograms. The diffusion coefficients of
electroactive species for the one-electron and two-electron processes were presented in [6].
Readers interested in composite materials may learn much from the investigation of
electrochemically synthetized ceria-doped Zn-Co composite coatings. Some recent advances
on the topic are well presented in study [7]. The morphology and corrosion resistance of the
electrolytically synthesized novel ceria-doped Zn-Co composite coatings were examined and
compared with pure Zn-Co coatings obtained under the same conditions. The effect of two
ceria sources, powder and homemade sol, was investigated. Zn-Co, doped with ceria particles
originating from ceria sol, exhibited superior corrosion resistance compared to Zn-Co-CeO2
(powder) coatings. The application of ceria sol caused an increase in the ceria content within
the resultant coating and favored the refinement from a cauliflower-like morphology (Zn-Co)
to a uniform and compact coral-like structure (Zn-Co-CeO2 sol) [7].
Another increasingly important field in electrolysis is metal coating electrodeposition,
and one paper investigates advances in the electrochemical synthesis of Cu coatings. The
influence of various electrolysis parameters, such as the type of cathode, composition of
the electrolyte, and electrolysis time, on the morphology, structure, and hardness of Cu
coatings is reviewed [8]. The critical relative indentation depth (RID), independent of
electrolysis parameters, was established for all types of Cu coatings. This value separated
the zone where the composite hardness could be equal to the coating hardness and the
zone requiring an application of the Chicot–Lesage (C-L) composite hardness model to
determine the absolute hardness of the Cu coatings [8].
A fundamental understanding of the electrochemical deposition process of indium
and indium gold alloys formed from 0.1 mol/L InCl3 in 1-butyl-1-methylpyrrolidinium
bis(trifluoromethylsulfonyl)amide ([Py1,4 ]TFSI) was presented in [9]. Using the potentio-
static mode of electrolysis, compact and dense indium deposits composed of indium and
an AuIn2 alloy were obtained. Several processes preceding the formation of the Au-In alloy
were involved, including the reduction of In(III) to In(I) and In(I) to In(0) [9].
The review article in this issue focuses exclusively on the morphology of electrolytically
synthesized metal powder particles that are correlated to their crystal structure [10]. Metals
Metals 2023, 13, 307 3 of 3

belonging to a face-centered cubic (fcc) type of crystal lattice, such as Pb, Ag, Cu, and Ni,
were analyzed. The shape of the powder particles depended on kinetic parameters, such
as the exchange in current density and overpotential for hydrogen evolution reactions,
strongly influencing the crystal structure of the particles. With the decrease in the exchange
current density value, the crystal structure of the powder particles changed from the strong
(111) preferred orientation obtained for the needle-like (Ag) and the 2D (Pb) dendrites to
randomly orientated crystallites in particles with spherical morphology (the 3D dendrites,
the cauliflower-like, and the spongy-like particles) [10].

3. Conclusions
This Special Issue, “Advances in Understanding Metal Electrolysis Processes”, covers
research articles regarding advanced approaches to metal electrolysis processes.
The Guest Editors Professor dr Bernd Friedrich and Professor dr Jovan Jovićević expect
this collection of papers to be a helpful reference for researchers working in this field.

Acknowledgments: The guest editors would like to thank all who have contributed directly and
indirectly to the successful development of this Special Issue. The guest Editors thank all the authors
for their contribution and all reviewers for their efforts to ensure high-quality publications. Credit
should also be given to the Editors of Metals for their continuous help, and to the Metals Editorial
Assistants. The Guest Editors would like to take this special opportunity to thank Vesna Cvetković,
ICTM-University of Belgrade and Dominic Feldhaus, IME-Institute of RWTH Aachen University, for
their valuable help in editing this issue.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Cvetković, V.S.; Feldhaus, D.; Vukićević, N.M.; Milicevic-Neumann, K.; Barudžija, T.S.; Friedrich, B.; Jovićević, J.N. Influence of
Rare Earth Oxide Concentration on Electrochemical Co-Deposition of Nd and Pr from NdF3 -PrF3 -LiF Based Melts. Metals 2022,
12, 1204. [CrossRef]
2. da Silva, A.L.N.; dos Santos, C.A.L.; de Melo Riberio de Araújo, R.; Feldhaus, D.; Friedrich, B.; Landgraf, F.J.G.; Guardani, R.
Model and Mechanism of Anode Effect of an Electrochemical Cell for Nd or (Nd, Pr) Reduction. Metals 2022, 12, 498. [CrossRef]
3. Cvetković, V.S.; Feldhaus, D.; Vukićević, N.M.; Barudžija, T.S.; Friedrich, B.; Jovićević, J.N. Electrochemical Study of Nd and Pr
Co-Deposition onto Mo and W from Molten Oxyfluorides. Metals 2021, 11, 1494. [CrossRef]
4. Thiere, A.; Bombach, H.; Stelter, M. The Behavior of Ruthenium in Copper Electrowinning. Metals 2022, 12, 1260. [CrossRef]
5. Cvetković, V.S.; Vukićević, N.M.; Feldhaus, D.; Milicevic-Neumann, K.; Barudžija, T.S.; Friedrich, B.; Jovićević, J.N. Electrodeposi-
tion of Aluminium-Vanadium Alloys from Chloroaluminate Based Molten Salt Containing Vanadium Ions. Metals 2021, 11, 123.
[CrossRef]
6. Yasinskiy, A.; Padamata, S.K.; Stopic, S.; Feldhaus, D.; Varyukhin, D.; Friedrich, B.; Polyakov, P. Towards Understanding the
Cathode Process Mechanism and Kinetics in Molten LiF–AlF3 during the Treatment of Spent Pt/Al2 O3 Catalysts. Metals 2021,
11, 1431. [CrossRef]
7. Rid̄ošić, M.; Nikolić, N.D.; Salicio-Paz, A.; García-Lecina, E.; Živković, L.S.; Bajat, J.B. Zn-Co-CeO2 vs. Zn-Co Coatings: Effect
of CeO2 Sol in the Enhancement of the Corrosion Performance of Electrodeposited Composite Coatings. Metals 2021, 11, 704.
[CrossRef]
8. Mladenović, I.O.; Lamovec, J.S.; Vasiljević-Radović, D.G.; Vasilić, R.; Radojević, V.J.; Nikolić, N.D. Implementation of the
Chicot–Lesage Composite Hardness Model in a Determination of Absolute Hardness of Copper Coatings Obtained by the
Electrodeposition Processes. Metals 2021, 11, 1807. [CrossRef]
9. Liu, Z.; Cheng, J.; Höfft, O.; Endres, F. Electrodeposition of Indium from an Ionic Liquid Investigated by In Situ Electrochemical
XPS. Metals 2021, 12, 59. [CrossRef]
10. Nikolić, N.D.; Maksimović, V.M.; Avramović, L. Correlation of Morphology and Crystal Structure of Metal Powders Produced by
Electrolysis Processes. Metals 2021, 11, 859. [CrossRef]

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