Journal of Electroanalytical Chemistry 865 (2020) 114143

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Journal of Electroanalytical Chemistry

journal homepage: www.elsevier.com/locate/jelechem

Edge electrodeposition effect of cobalt under an external magnetic field

⁎∗
Yaomeng Zhang a, Boyu Yuan a, , Liang Li b, Chao Wang b,
⁎
a
Jiangsu Key Laboratory of Advanced Laser Materials and Devices, School of Physics and Electronic Engineering, Jiangsu Normal University, Xuzhou 221116, China
b
School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou 221116, China

A R T I C L E I N F O A B S T R A C T

Article history: The dynamic changes in the concentration and diffusion layer at the Ni/CoCl2 solution interface were studied by dig-
Received 12 December 2019 ital holography during the electrodeposition of cobalt on a nickel electrode in 0.15 M CoCl2 with and without an ex-
Received in revised form 31 March 2020 ternal magnetic field. Edge electrodeposition was observed under the condition of a non-uniform magnetic field on
Accepted 8 April 2020
the electrode. The concentration distribution at the interface was consistent with the intensity of the magnetic field
Available online 14 April 2020
distribution. However, there was no “edge electrodeposition” during the electrodeposition of cobalt on copper elec-
Keywords:
trodes under magnetic field conditions. It was proposed that the edge electrodeposition of cobalt on a nickel electrode
Cobalt under magnetic field conditions was mainly caused by the magnetic gradient force and the Lorentz force around the
Electrodeposition edges of the magnetised electrode.
Non-uniform magnetic field
Digital holography © 2020 Published by Elsevier B.V.

1. Introduction
Over the last few years, increased interest has been seen in the electro-
deposition of cobalt and cobalt alloys. Materials obtained by this method
are applicable for broad application prospects [1], solid oxide fuel cells
[2–8], energy storage systems [4–8], and magnetic data carriers [9]. Prop-
erties such as hardness, corrosion resistance and thermal stability of electro-
deposited cobalt have prompted researchers to study the kinetics and the
mechanism of electrodeposited cobalt [10–12]. However, the current effi-
ciency of electrodeposition of cobalt is low, the electrode reaction speed
is slow, and hydrogen evolution is obvious. In order to improve the deposi-
tion efficiency and quality, pulse electrodeposition [13], jet electrodeposi-
tion [14], electrolyte additive [15], magneto electrodeposition and other
methods are often used [16].
The magnetic field (MF) can be applied during electrodeposition to in-
crease the deposition rate and induce turbulence. Therefore, magnetic
electroplating is an attractive interdisciplinary area with good opportuni-
ties for producing novel materials and nanostructures [17–21]. There are
different views regarding the magnetic field effects on electrodeposition
processes. Krause et al. suggested that the Lorentz force promoted electro-
deposition of Co2+ ions, but the paramagnetic force hindered the electrode-
position of Co2+ ions [22]. Similarly, Yu et al. found that the paramagnetic
force also hindered the electrodeposition of Co2+ ions [23]. Zieliński re-
ported that the Lorentz force promoted the electrodeposition of Co2+ ions
[24]. Many studies have discussed the effect of magnetohydrodynamics
(MHD) caused by the Lorentz force on ions electrodeposition [25–32].
!
Some studies suggested that the magnetic gradient forces F B play a domi-
nant role in heterogeneous magnetic fields [33,34]. White et al. reported
that magnetised microferromagnetic electrodes can generate magnetic gra-
dient forces across depleted layers [35,36]. Coey et al. believed that mag-
netic gradient forces increase mass transfer and change the reaction speed
[26,37,38]. Mutschke et al. studied the effect of magnetic field gradient
on electrodeposition by means of simulation [39,40]. In addition, Waskaas
considered that the concentration gradient of paramagnetic ions led to a
susceptibility gradient of the solution on the electrode surface in a ferro-
magnetic electrode/paramagnetic ion system [41]. And there are also
some researchers believing that the paramagnetic force does not exist
[42,43].
This paper aims to validate the effects of the non-uniform magnetic field
on the electrodeposition of cobalt. The dynamic concentration changes dur-
ing the electrodeposition processes were mapped by use of the digital ho-
lography and edge electrodeposition was observed under the condition of
a non-uniform magnetic field on the electrode.
2. Experimental
The electrochemical experiments were carried out in a traditional three-
electrode cell (Fig. S1) that consisted of a nickel or copper working elec-
trode (Johnson Matthey Company, 99.98% and 99.9%, respectively), a
large sheet of Pt that served as the counter electrode and a saturated calo-
mel electrode (SCE) that served as the reference electrode. The working

⁎ Corresponding authors.
E-mail addresses: yuanby@jsnu.edu.cn, (B. Yuan), wangc@jsnu.edu.cn. (C. Wang).

http://dx.doi.org/10.1016/j.jelechem.2020.114143
1572-6657/© 2020 Published by Elsevier B.V.
Y. Zhang et al. Journal of Electroanalytical Chemistry 865 (2020) 114143

electrode (diameter of 2 mm) was sealed with epoxy resin then placed in a
glass tube, with one end tightly welded to a Cu wire and the other end ex-
posed to the solutions. Before each experiment, the electrode was mechan-
ically abraded with #600 and #1200 emery papers to a mirrorlike surface
and then cleaned by alcohol and triply distilled water in an ultrasonic bath.
A renewed electrode surface (both for nickel and copper) was used in each
experiment. Separate nickel electrodes were used for the experiments with
and without MF, respectively, considering their ferromagnetic property.
For the convenience of the holographic recording, a pair of small NdFeB
magnets (AIM Magnet Shenzhen Co., Ltd.) with a diameter of 30 mm was
used. The electrode located at the center of the two magnets. MF was ap-
plied parallel to the surface of the electrode, the strength of which could
be adjustable by changing the distance between the two permanent
magnets.
The in-line digital holography experimental setup is described in [44].
Holography is based on the development of the refractive index gradients
that give rise to the interference fringes. The change in the phase of the ob-
ject beam is caused by the change in the refractive index inside the cell,
which is associated with the concentration changes of the soluble species
in solution. The relationship between the phase difference (ΔΦ) and the
change in solution refractive index (Δn) can be formulated as [44–47],

Δn ¼ ðλ=2πdÞΔϕ ð1Þ

where λ is the wavelength of the laser light and d represents the geometrical
path length where the refractive index variation exists. Therefore, Δn and
Fig. 1. Top: the j-t curves of nickel in 0.15 M CoCl2 solutions without and with MF at
ΔC were average variations along the object beam trajectory in the electro-
E = −0.85 V vs. SCE. Bottom: concentration distributions corresponding to points
chemical cell. Then, the relationship between the concentration change and
(A–C) in the j-t curves without (a1–c1) and with (a2–c2) MF.
phase difference was obtained as

ΔC ¼ k 1 Δn ¼ ðk1 λ=2πdÞΔϕ ð2Þ

diffusion layer became thicker with time (Fig. 1(b1)). Finally, the diffusion
layer was relatively steady and uniform when the current density was stable
where k1 is the concentrative refractivity. As such, this method can be
(Fig. 1(c1)). In the presence of MF, there was no observable difference in
employed to measure the thickness of the diffusion layer and obtain quan-
the concentration maps at the initial of the reaction (Point A), although
titative information about concentration changes at the electrode/solution
the concentration diffusion layer became increasingly more different as
interface.
the reaction proceeded further (Points B and C). There was almost no con-
The electrochemical experiments were carried out with a CHI660E elec-
centration change at both edges of the electrode, but the concentration de-
trochemical instrument. Chronoamperometry methods were used, and the
creased sharply, and a thick diffusion layer formed in the middle of the
working electrodes were kept at −0.85 V vs. SCE. The electrolyte was
electrode, as shown in Fig. 1b2 and c2. This meant that there was an inho-
0.15 mol·dm−3 CoCl2 solution. The electrochemical experiments were con-
mogeneous deposition phenomenon of “edge electrodeposition” under the
ducted at room temperature (25 ± 2 °C). After the electrochemical mea-
influence of the external MF. From the concentration maps, the applied MF
surement, the electrode was washed in an ultrasonic bath with distilled
had a significant effect on the evolution of the electrodeposition process of
water and ethanol, and then its surface morphology was observed with
cobalt on the nickel electrode. Fig. 2 shows the SEM images before (a, aa)
SEM.
and after (b, bb1 and bb2) the electrodeposition of Co2+ on the surface of
the nickel electrode with MF. Fig. 2bb1 and bb2 were imaged at the center
3. Results and discussion
and near the edges of Fig. 2b with high magnification, respectively. Com-
pared with the sites in the center (bb2), there were fewer scratches at the
3.1. The electrodeposition of cobalt in a non-uniform magnetic field
sites near the edges (bb1), indicating that there was more cobalt deposition
near the edges of the nickel surface. It was further confirmed that there was
Fig. 1 (top) presents the i-t curves of the nickel in 0.15 mol·dm−3 CoCl2
edge electrodeposition effect with MF.
solution at −0.85 V vs. SCE with and without MF. The curves exhibited ob-
The non-uniform distribution of magnetic field intensity will be gener-
servable differences showing that the deposition current density was higher
ated near the ferromagnetic metal electrode due to the magnetization of
in the presence of MF than in the absence of it. It was indicated that the
the electrode itself under the external magnetic field. The distribution of
presence of the magnetic field promoted deposition rate. It should be
magnetic induction intensity around the nickel electrode was simulated
noted that the current density with MF increased rapidly at the initial
by finite element software (Ansoft Maxwell 16, Ansoft), as shown in
stage and then turned stable soon afterwards.
Fig. 3a. The magnetic field intensity and its gradient along the electrode/
Fig. 1 (bottom) presents the quantitative concentration maps obtained
electrolyte interface were obtained, as shown in Fig. 3b. The magnetic in-
at the given time points (A–C) in the current density curves. The images ex-
tensity distribution at the surface gradually decreased from the edge to
hibited the distribution of the concentration changes at the respective times
the center of the electrode, which was similar to the concentration distribu-
with reference to the starting of the reactions. In each concentration map,
tion in Fig. 1(c2). Therefore, it was reasonable to believe that the “edge
the left was the electrode, the right was the solution part, and the space
electrodeposition” was closely related to the magnetic field distribution.
in between was the interface. It was evident that the concentration varia-
Generally, three main sources of body forces have been taken into ac-
tion appeared only at the interface, where turning blue meant a decrease.
count when electrochemical reactions are carried out in a magnetic field:
As shown in Figs. 1(a1–c1) without MF, the concentration at the interface ! !
decreased gradually with time. A concentration gradient from the electrode the magnetic gradient force ( F B ), the paramagnetic force ( F p ) and the
!
surface to the bulk solution was established, and the concentration MHD force F MHD [48]. In the magnetic field gradient environment

2
Y. Zhang et al.
Fig. 2. SEM images before (a, aa) and after (b, bb1 and bb2) the electrodeposition of
the nickel electrode with MF. Fig. 2aa is a magnified; bb1 and bb2 are imaged at the
center and edge of panel b with high magnification, respectively. Panel c is the
diagrammatic sketch of the edge and the center of the nickel surface.
Fig. 3. a: The magnetic induction distribution at the nickel/solution interface. b: the
magnetic induction gradient at the interface.
3
Journal of Electroanalytical Chemistry 865 (2020) 114143
shown in Fig. 3, the first force to be considered is the magnetic field gradi-
!
ent force ( F B ) [27], which can be expressed by the equation below:
! cB !
F B ¼ χm ∇ B ð3Þ
μ0
where μ0 is the permeability of free space, χm is the molar susceptibility, B is
!
the field strength and ∇ B is the gradient of B. During the electrodeposition
2+
process, Co ions were driven by a magnetic gradient force towards the in-
creased direction of MF and accumulated at the edges of the electrode,
where the MF intensity was the greatest under the magnetization of the
nickel. Fujiwara [49] investigated the movement of paramagnetic ions in
an inhomogeneous magnetic field and concluded that the motion of para-
magnetic ions was related to the susceptibility of ions. Therefore, it was pro-
posed that the magnetic gradient force on Co2+ ions was remarkable
during the electrodeposition process under MF. It is worth mentioning
that the concentration at the top of the diffusion layer is less than that at
the bottom in the concentration maps since Co2+ ions partially transport
along the direction of gravity (opposite y-axis) during electrodeposition
processes.
Waskaas and Khartkats [41] showed that a magnetic driving force oc-
curred if a gradient in the concentration of paramagnetic ions led to a gra-
dient in the magnetic susceptibility. After the electrodeposition reaction
occurred, the concentration of CoCl2 at the interface became reductive,
and a concentration gradient was formed in the diffusion layer. The concen-
tration gradient of paramagnetic cobalt ions induces a magnetic driving
force in the magnetic field [50], which can be expressed as:
! B2 !
F p ¼ χm ∇C ð4Þ
2μ0
!
where ∇ C is the concentration gradient. This force was oriented in the di-
!
rection of ∇ C and was independent of the field orientation (because of B2).
This meant that the Co2+ ions at the interface migrated towards the bulk
!
solution at a relatively high concentration by the paramagnetic force F p
!
in Eq. (4). If F p were dominant in the MF effects, the electrodeposition pro-
cess would probably be inhibited since the concentration polarization
would be enhanced by the paramagnetic force. But MF accumulates the
electrodeposition, as shown in the current density curves in Fig. 1. There-
!
fore, F p was not obvious in the MF effects. Coey et al. have also suggested
!
that the effect of the paramagnetic force F p on mass transport is negligible
in aqueous solutions in electrochemistry [43].
The electrodeposition of cobalt led to a concentration polarization of
CoCl2 perpendicular to the direction of the electrode surface (Fig. 1(a1–
!
c1)). Since the magnetic field gradient force ( F B ) was proportional to the
gradient of MF, it led to the concentration depolarization at the edge of
the nickel electrode where the MF gradient was high enough (Fig. 3b).
Then, the concentration distribution shown in Fig. 1(b2) was formed.
Low concentration of Co2+ at the center of the electrode (Fig. 1(b2)and
c2) resulted in the low electrodeposition rate, which was consistent with
!
the SEM image (Fig. 2 bb2). The magnetic field gradient force ( F B ) in-
creased the concentration gradient from the electrode center to its edge par-
allel to the electrode surface, resulting in the edge electrodeposition effect
of cobalt on a nickel electrode under an external magnetic field.
3.2. The enhanced HER electrocatalytic activity of non-uniform deposits
The electrocatalytic activity of the hydrogen evolution reaction (HER)
of the cobalt deposits obtained under different conditions was investigated
to examine the differences provoked by MF further. As shown in Fig. 4a, the
polarization curves of two deposited electrodes with and without MF were
measured in 1 M KOH solution with a scan rate of 2 mV s−1. It is found that
the cobalt deposits under the magnetic field has a lower overpotential. It
has been proved that the thicker and rougher deposits can be obtained in
Y. Zhang et al.
Fig. 4. a: HER electrocatalytic activities of cobalt deposits without (electrode 1) and
with (electrode 2) MF, the direction of magnetic field and the position of nickel
electrode 2 during electrodeposition corresponding to panel aa. b: HER
electrocatalytic activities of cobalt deposits under different magnetic gradient, the
direction of magnetic field and the position of nickel electrodes 3 and 4 during
electrodeposition corresponding to panel bb. Both polarization curves were
obtained in 1 M KOH with a scan rate of 2 mV s−1.
the MF conditions, resulting in the enhanced electrocatalytic activity to-
wards hydrogen evolution [51].
Moreover, two deposited electrodes with different magnetic field gradi-
ent were measured in the same condition, as shown in Fig. 4b. It is found
that the electrode 4 in large magnetic field gradient (Fig. 4bb) has lower
overpotential than the electrode 3 in small gradient. We simulated the dis-
tribution of magnetic density on the surface of the two electrodes, as shown
in Fig. 5. It can be seen evidently that the electrode 4 were electrodeposited
under higher magnetic field gradient than the electrode 3. Therefore, we
can infer that the deposits in high magnetic field gradient has larger surface
area and more active sites leading to a lower overpotential. High magnetic
field gradient would improve the HER electrocatalytic activity of the cobalt
!
deposits. It is further confirmed that the magnetic field gradient force F B
plays a significant role during the electrodeposition processes.
Fig. 5. Simulated surface magnetic density distribution. Electrode 4 is near
permanent magnet while electrode 3 is in the middle, as shown in Fig. 4d.
4
Journal of Electroanalytical Chemistry 865 (2020) 114143
3.3. The MHD effect on the electrodeposition of cobalt
Fig. 6 (top) presents the potentiostatic polarization curves of copper in
0.15 mol.dm−3 CoCl2 solution at −0.85 V vs. SCE with and without MF.
The curves also showed that MF increased the deposition rate and the cur-
rent increase Δj between two curves was relatively stable. The electrodepo-
sition current on copper was higher than that on nickel (Fig. 1) without MF
due to its property, especially its surface electrochemical activity. During
the electrodeposition on copper, Δj was almost stable since it was only
caused by the Lorenz force. During the electrodeposition on nickel with
MF, the current density increased rapidly at initially and then tended stable
soon afterwards, which was due to the fact that Δj was caused by the Lorenz
force and the magnetic field gradient force.
Fig. 6 (bottom) presents the quantitative concentration maps obtained
at the given time points (A–C) in the current density curves. The diffusion
layer gradually tended to be uniform and stable without a magnetic field,
as shown in Fig. 6(a1–c1). In the presence of MF, there was a flow from
the solution to the center of the electrode (Fig. 6 b2–c2), which then
moved downwards and evolved into a vortex flow [25]. In our previous
study [48], this kind of magnetic field-driven cyclotron flow was called
“MHD flow” and mainly arose from the Lorentz force:
! ! !
FL ¼ J  B ð5Þ
! !
where J is the local net flux of current carrying species in solution and B is
the externally applied MF. A uniform magnetic field was formed on the sur-
face of the copper electrode due to the application of MF. The MHD flow
was attributed to the Lorenz force on the cobalt ions crossing the lines of
the magnetic flux in the mass transport. The MHD flow enhanced the
mass transport rate, which resulted in the great increase of the current den-
sity in the plateau region. It was evident that only the vortex appeared at
the interface but not “edge electrodeposition”. The “edge
Fig. 6. Top: the j-t curves of copper in 0.15 M CoCl2 solutions without and with MF
at E = −0.85 V vs. SCE. Bottom: concentration distributions corresponding to
points (A–C) in the j-t curves without (a1–c1) and with (a2–c2) MF.
Y. Zhang et al.
electrodeposition” phenomenon appeared under the non-uniform magnetic
field from the magnetization of the ferromagnetic metal electrode.
During the electrodeposition on nickel, the MF intensity was low on
most part of the nickel surface (Fig. 3b) and the Lorenz force was relatively
! [5] S. Zuluaga, S. Stolbov, Factors controlling the energetics of the oxygen reduction reac-
weak according to Eq. (5). However, the Lorentz force F L cannot be ig-
nored particularly near the edges of the magnetised electrode. In these re-
gions, it accelerated the mass transport of cobalt ions from bulk solution
to the interface, which was beneficial to the edge electrodeposition. There
is still much to probe into before precise quantification of the MF effects
on electrodeposition can be realized due to the complexity of the various
magnetic forces. However, it is doubtless that the external magnetic field
can enhance the electrodeposition rate in high magnetic gradient regions,
resulting in non-uniform electrodeposition on magnetised ferromagnetic
electrode surfaces.
4. Conclusions
In this study, digital holography was used to observe the dynamic pro-
cesses during the electrodeposition of cobalt on nickel and copper elec-
trodes with the application of a magnetic field. The conclusions can be
drawn as follows.
(1) The applied magnetic field can change the electrodeposition behaviour
of Co2+ on the nickel electrode and lead to “edge electrodeposition”.
According to the analysis, it was mainly caused by the magnetic gradi-
! !
ent force F B and the high Lorentz force F L around the edges of the
magnetised electrode.
(2) During the electrodeposition of cobalt ions on copper electrodes, the
“vortex” rather than the “edge electrodeposition” occurred at the inter-
face. It was further verified that the electrodeposition of Co2+ ions on
nickel electrodeposition was mainly caused by the non-uniform mag-
netic field from the magnetization of the ferromagnetic metal
electrode.
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jelechem.2020.114143.
CRediT authorship contribution statement
Yaomeng Zhang:Data curation, Formal analysis, Investigation, Valida-
tion.Boyu Yuan:Conceptualization, Formal analysis, Supervision, Writing -
original draft.Liang Li:Investigation, Formal analysis, Validation, Writing -
review & editing.Chao Wang:Conceptualization, Supervision, Writing - re-
view & editing, Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial inter-
ests or personal relationships that could have appeared to influence the
work reported in this paper.
Acknowledgements
This study was supported by the National Natural Science Foundation of
China (No. 21972059, 51401094, and 21473081) and project-funded by
the Priority Academic Program Development of Jiangsu Higher Education
Institutions.
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