Journal of Environmental Chemical Engineering 7 (2019) 103010

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Journal of Environmental Chemical Engineering

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

Pulse current electrodeposition of manganese metal from sulfate solution T

a,⁎ a b,⁎ b a
Xingran Zhang , Xiaoyu Zhang , Zuohua Liu , Changyuan Tao , Xuejun Quan
a
School of Chemistry and Chemical Engineering, Chongqing University of Technology, Chongqing 400054, China
b
School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China

A R T I C LE I N FO A B S T R A C T

Keywords: In this study, pulse current (PC) electrodeposition method was successfully introduced to the process of man-
Manganese ganese electrodeposition. The results showed that, due to the transient high current density, pulse electrolysis
Pulse current electrodeposition can rise cathode overpotential (larger 90–100 mV than the direct current (DC)) at the same current density. And
Hydrogen evolution high cathode overpotential can significantly suppress the hydrogen evolution and improve the reaction rate of
Current efficiency
manganese deposit. At the same time, the higher cathode potential promotes crystal nucleus formation, which
tends to get smooth manganese metal product surface. Through electrolysis experiment, it was found that when
the pulse frequency was 500Hz, the duty ratio was 0.5, the average current density was 300A/m2, after elec-
trolysis for 2h under the condition, the current efficiency can reach 88.3%, being improved by 8.72% and anode
slime was 0.49g, being reduced by 55.5% compare to 300A/m2 of DC electrodeposition. In addition, PC elec-
trodeposition method may have a certain significance to the development of electrolytic manganese industry.

1. Introduction [7]. Hydrogen evolution reaction reduces the current efficiency of

manganese electrodeposition while the oxidation of Mn(II) to MnO2
Metal manganese is not only an important raw material in the consumes manganese ions [6,8], these two processes directly relate to
production of stainless steel, high strength alloy steel and copper, alu- the production and economic benefits of electrodeposition of manga-
minum and other non-ferrous metal alloys, but also a widely applied nese. Correspondingly, current efficiency loss of hydrogen evolution is
material in the field of medicine and chemical industry [1,2]. Manga- higher than 98.5% [3]. Hydrogen evolution is the major, the most
nese is mainly produced by the electrometallurgical method [3–5]. serious and competitive secondary reaction. The key to enhance the
Currently, almost all of the world’s metal manganese is produced by current efficiency in manganese electrodeposition process is to under-
traditional direct current (DC) electrodeposition. In a typical cell, there stand the characteristics of H2 evolution and inhibit the hydrogen
are two competing reactions (hydrogen evolution and manganese de- evolution reaction.
posit) on the cathode. And on the anode, the formation of oxygen and As manganese is plated, manganese deposits become rougher, and
the oxidation of Mn(II) occurred [1,6]. nodules grow up and outward from the electrode surface to the solu-
Cathode: tion, forming a cauliflower-like structure or even tree-like dendrites [9],
resulting in trapping of electrolyte, difficulty in stripping of manganese
MnSO4 + 2e− → Mn + SO42 − (1)
deposits, short circuit between electrodes, and even difficulty in re-
2H2 O + 2e− → ¼ H2 + 2OH− (2) moval of cathodes from cells [6]. Which is also one of the main factors
that reduce current efficiency and production [8].
Anode:
For decades, to elucidate the related mechanism [10], the condi-
H2 O → 2H+ + 1/2O2 + 2e− (3) tions that influence the reaction process were investigated [6,7,11,12].
And to improve the current efficiency, various methods including ad-
MnSO4 + 2H2 O = MnO2 + H2 SO4 + 2 H+ (4)
ditives and electrolytes were developed [7,13–16]. However, research
Hydrogen evolution reaction always accompanies the manganese on the new electrodeposition methods remains insufficient. An attempt
electrodeposition in aqueous electrolyte system, because the standard was therefore made to set up a new electrodeposition method using
potential of manganese is more negative (E0 = −1.18 V (vs. saturated pulse current (PC) electrodeposition method.
calomel electrode (SHE))) than the standard hydrogen electrode(HER) PC electrodeposition method could reduce diffusion layer thickness

⁎
Corresponding authors.
E-mail addresses: [email protected] (X. Zhang), [email protected] (Z. Liu).

https://doi.org/10.1016/j.jece.2019.103010
Received 14 December 2018; Received in revised form 7 March 2019; Accepted 8 March 2019
Available online 09 March 2019
2213-3437/ © 2019 Elsevier Ltd. All rights reserved.
X. Zhang, et al. Journal of Environmental Chemical Engineering 7 (2019) 103010

by changing the current waveform, and eliminate concentration po- 2.3. Electrochemical testing
larization by adjusting the duty ratios [17]. Moreover, it plays relatively
significant roles in improving cathode current density [18], suppressing Voltammetric studies were carried out on a CHI660D electro-
side reaction, reducing impurity content and enhancing current dis- chemical workstation (Shanghai Chenhua, China). A three-electrode
tribution [19,20]. In recent years, therefore, pulse current(PC) have system was used, including the reference electrode (RE), a saturated
been applied in the electrodeposition of metals, and have achieved good calomel electrode (SCE), the working electrode (WE) (area = 98.5
results in controlling the metal surface morphology and particle sizes, mm2, Ф = 11.2 mm), made of stainless steel(304 L) and commonly used
improving coating corrosion resistance, and reducing the dosage of in the electrolytic metallic manganese industry, and the counter elec-
electrolytic additive [19,21–26]. trode (CE) (area = 249 mm2, Ф = 17.8 mm), made of
In this study, PC electrodeposition method was introduced to the PbSn0.4Ag0.014Sb0.014 alloy. To prevent fluctuation of the electrode area
process of manganese electrodeposition. The impact of PC on the in- during stirring besides the effective area of the electrode, the rest was
hibition of hydrogen evolution reaction, electrodeposition manganese sealed by an insulating polymer. The scanning speed of the cyclic vol-
cathode potential, current efficiency and surface morphology were in- tammetry was 10 mV/s.
vestigated. Cathode potential experiments were carried out on a CHI660D
electrochemical workstation (Shanghai Chenhua, China).
Chronopotentiometry technique was employed to measure the over-
2. Materials and methods
potential during manganese electrodeposition. The reference electrode
(RE), which was a saturated calomel electrode (SCE). The working
2.1. Materials
electrode (WE) was the cathode, and the counter electrode was the
anode.
The manganese sulfate (MnSO4), ammonium sulfate ((NH4)2SO4)
and selenium dioxide (SeO2) were analytical grade and purchased from
Chongqing Boyi Chemical Reagent Co., Ltd., China. Purified water used 2.4. Morphology analytical methods
in the experiment was provided by the Water Purification System
(HMC-WS10). The concentrations of Mn2+, (NH4)2SO4 and SeO2 in Surface morphology of the manganese deposits were analyzed via
electrolyte were constantly maintained at 30 g/L, 120 g/L and 0.03 g/L, scanning electron microscopy (SEM) (VEGA II LMV, Tescan Co., LTD.,
respectively. The pH value (measured by PHSJ-3 F, Lei-Ci Shanghai) of Czech) and the metallurgical microscope (MIT300, Ao Te Optical
the solution was adjusted to 7.0 by adding ammonia or H2SO4. Instruments Co., LTD., Chongqing, China).

3. Results and discussion

2.2. Manganese electrodeposition
3.1. Voltammetric test of manganese electrolyte
Fig. 1 shows that the schematic of the electrolysis system used in
this work. It consisted of a plexi glass tank, a cathode plate, two anode To study the behavior of the electrolyte during the electrolytic
plates and a fiber diaphragm bag used to wrap the cathode region. The process, cyclic voltammetric technique was used. Fig.2 shows that the
cathode was made of stainless-steel plate with 1.5 mm thickness cyclic voltammograms curve of the stainless steel electrode in an
(measured by HIOS AF-4500, Mitutoyo, Japan). The anode was made of electrolyte of 30 g/L Mn2+, 120 g/L (NH4)2SO4, 0.03 g/L SeO2 at
PbSn0.4Ag0.014Sb0.014 alloy. The temperature was controlled at 40 ± °C pH = 7.0, 40℃. At about −0.85 V the reductive of H+ started and in-
using a heating mantle and temperature controller during the electro- creased gradually along with the sweeping the potential towards the
deposition process. The electrolyte cycle replenishment with a digital cathode. The peak at −1.18 V indicated that manganese precipitation
constant-flow pump (HL-2B, Shanghai, Huxi, China). Numerical control occurred. After the new precipitate of manganese cover stainless steel
double pulse plating power supply (SMD-30, Da Shun Plating Equip- electrode, the precipitation overpotential of hydrogen on the manga-
ment Co., LTD., Handan, China) was used as the power supply for nese metal was higher than stainless steel electrode [27]. With potential
electrodeposition. shifted to cathode direction, the cathodic current increased rapidly. The
Current efficiency was calculated by Faraday's Law according to the peak at −1.46 V indicated that hydrogen reduction on new precipitate
quantity change of plate before and after manganese electrodeposition manganese, and the Mn2+ large reduction into metal manganese po-
[11], that is, tential is 1.54 V. In addition, a resistance current loop emerged between
m −1.65 V˜ −1.52 V was the formation of crystal nucleus in the man-
η= × 100%
qIt (5) ganese electrodeposition [28].

Where η is the current efficiency expressed in percentage (%), m is the

quantity of cathode product in kilograms (Kg), I is the current intensity
in amperes(A), t is the electrodeposited time in hours(H), and q is the
electrochemical equivalent in grams per ampere per hour (1.025 g/
(A·h)) [14].

Fig. 1. Schematic of the electrolysis system(1-catholyte, 2-anolyte, 3- digital

constant-flow pump, 4- electrolysis tank, 5-anode, 6- fiber diaphragm bag, 7- Fig. 2. Cyclic voltammograms (10 mV/s) at steel disc electrode from solution
cathode, 8- double pulse plating power device). containing 30 g/L Mn2++120 g/L (NH4)2SO4+0.0 3 g/L SeO2, pH = 7.0, 40℃.

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X. Zhang, et al. Journal of Environmental Chemical Engineering 7 (2019) 103010

According to the dynamics equation of ploy-electronic electrode

reaction (Eq. (6)) [27],

aF βF
jc = j 0 [exp( η ) − exp(− η )]
RT c RT c (6)
0
where, jc is the cathode current density; j is the exchange current
density; ηc denotes cathode overpotential; α and β are reaction transfer
coefficients. When cathode polarization (ηc) increased, the reaction rate
(jc) was larger. Thus, when the cathodic polarization reached a certain
value, manganese precipitation accelerated, and also accompanied by
the precipitation of hydrogen.

3.2. Analysis of the hydrogen evolution reaction inhibition of the PC

Fig. 3. Cathode potential of DC electrodeposition.

Based on Tafel Eq. (7), the relationship of overpotential and current
density of hydrogen in metal material are as follows:
3.3. Comparison of cathodic overpotential between PC and DC
ηc = a + b lgjc (7) electrodeposition
where, ηc is the cathode overpotential, a and b are called the Tafel
constants, jc is the current density. Thereby, increasing current density Electrode potential have great effects on the rate of the electrode
can increase the hydrogen evolution overpotential and suppress the reaction. Under the same conditions of electrodeposition, the speed of
hydrogen evolution. High current density however was not conducive the electrode reaction could be increased only by increasing the elec-
to effectively electrodeposition of meatal manganese. When the current trode potential [26].
density was high (jc > > j0), electrode process was jointly controlled In the process of DC electrodeposition manganese, cathode potential
by electron transfer steps and diffusion steps [27]. Thus, the influence changes slightly over time due to the current was a constant value, as
of concentration polarization (electrode surface manganese ion con- shown in Fig. 3. When the average current density was 250 A/m2,
centration) should be considered in the Eq. (6), as shown in the Eq. (8) cathode potential was −1.595 V. With the increase of current density
below: cathode potential shifts to negative direction gradually. When the
average current density was 600A/m2, cathode potential was −1.66 V.
cs aF cs βF c s 2+ αF Fig. 4 shows that the change of manganese electrodeposition
Mn2 +
jc = j 0 [ exp( ηc ) − Mn exp( ηc )] ≈ j 0 Mn exp( η)
c 0 2+ RT 0
cMn RT c 0 2+ RT c (8) cathode potential over time when pulse frequency (f) was 500 Hz, and
Mn Mn
the duty ratio (r) was 0.5. The cathode potential presented cyclical
where fluctuations with the cyclical change of pulse current. In Fig. 4, the
maximum value of potential represented the cathode potential corre-
jc
s
cMn 2 + = cc
0 (1 − ) sponded by pulse peak current. Fig. 5 shows that comparison of the
Mn2 + jd (9) peak potential of PC and DC electrodeposition at different current
density. When the current density was 300˜600 A/m2, the cathode po-
and
tential of DC electrodeposition was −1.61 V˜−1.66 V, and pulse
nFDc0 cathodic peak potential was −1.70 V˜ −1.77 V, namely, the cathodic
jd = , jd>jc
δ (10) overpotential using pulse electrodeposition was (90 mV–110 mV)
greater than DC. The increase of cathode overpotential can significantly
so
suppress the hydrogen evolution and improve the reaction rate of
jc aF manganese deposit. Furthermore, according the nuclei formation rate
jc = (1 − ) j 0 exp( η) formula (Eq. (13)), it can be inferred that the high cathode over-
jd RT c (11)
potential makes deposits crystallization finer [17,25], and helps to
or smooth the surface of manganese [17].

RT jj −K
ηc = ( c d − lnj 0 ) υ = K1 exp ⎜⎛ 2 ⎟⎞
aF jd − jc (12) ⎝ η ⎠ (13)

In the Eq. (10), jd denotes limiting diffusion current density; n is ion where, υ is nuclei formation rate, K1 is proportionality constant, K2 is
charge number; D denotes ion diffusion coefficient; δ is diffusion layer the amount of energy needed for nucleation and is the crystallization
thickness; c0 denotes ion concentration of bulk solution. overpotential.
According to the Eq. (12), with the increase of cathodic current
density, cathodic polarization (ηc) increases in the DC electrodepostion. 3.4. Microstructure analysis of pulse electrodeposition Manganese
Then the deposition of manganese ions in the cathode surface accel-
erates and manganese ion concentration on the surface of the cathode In Fig. 6a–c, spherical particles on the surface of manganese after
reduces. At last, diffusion layer thickness δ gradually increases (jd de- electrolysis for 5 min were observed. When the metal ions were ad-
creases); manganese deposition rate is gradually controlled by ion dif- sorbed in the cathode surface, electron transferred and then formed
fusion steps (jc < jd), that is not conducive to manganese deposition. deposit layer, which was also accompanied by hydrogen adsorption
In the process of PC electrodeposition, within the period of off-time [18]. The newly-generated hydrogen bubble on the surface of electrode
of pulse current electrodeposition, manganese ion in the solution had quite high surface energy [29,30], so metal crystal nucleus were
transferred to near the cathode surface by diffusion, and insufficient more likely to form in the active position, and metal crystal grown
manganese ion on the cathode surface can be timely supplemented by along the surface of the overall bubble. After long time of electro-
the bulk solution [17]. Thus, the diffusion layer thickness (δ) could be deposition, the spherical “dendrite” was formed. At the pulse current
reduced, which is suitable for high current density electrodeposition. condition, however, with the decrease of the pulse duty ratio, the peak

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X. Zhang, et al. Journal of Environmental Chemical Engineering 7 (2019) 103010

Fig. 4. Cathode potential responses of PC electrodeposition, r = 0.5, f = 500 Hz.

current density increased, and the hydrogen evolution reaction re-

duced. The electrode surface bubbles decreased, which reduced the
formation of surface spherical dendrite. Furthermore, long period of off-
time was conducive to the stripping of the adsorbed hydrogen, and
reduced the spherical particles.
As shown in Fig. 7, after 2 h of electrodeposition, the manganese
surface after PC electrodeposition was more uniform and finer than the
manganese surface after DC electrodeposition, with the particle size
decreased as the decrease of duty cycle. When duty ratio was 20%, the
sediment particle size was about a third of that after the DC electro-
deposition. Under the same current density, smaller duty ratio means
higher peak current density, which could effectively increase cathodic
overpotential, improve manganese nucleation rate, tend to form smaller
amounts of crystal nucleus, and enhance the quality of the sediment
Fig. 5. Cathode potential comparison of DC and PC electrodeposition. layer.

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X. Zhang, et al. Journal of Environmental Chemical Engineering 7 (2019) 103010

Fig. 6. Metallurgical microscope image of manganese deposits after electrolysis for 5 min, (A) direct current (r = 100%), (B) f = 500 Hz, r = 50%, (C) f = 500 Hz,
r = 20%.

3.5. Effect of pulse parameters on the electrodeposition of the manganese

3.5.1. DC electrolytic experiment

To contrast with the subsequent experiments, the electrolytic cur-
rent efficiency and the amount of anode slime as the current density
range from 250 A/m2 to 450 A/m2 were investigated, the results were
shown in Fig. 8. The current efficiency first increased with the increase
of current density then decreased because high current density was
harmful to manganese deposit. When the current density was 300 A/
m2, the current efficiency was 79.58%, the anode slime quantity was
1.2 g. When the current density was 350 A/m2, the largest current ef-
ficiency reached at 82.39%, anode slime was 1.1 g.

3.5.2. Effect of the pulse frequency

Fig. 8. Effect of the DC current density on the current efficiency and the anode
To understand the effect of pulse frequency on the manganese slime quantity.
electrowinning, sequential pulse frequency ranges from 100 to 1250 Hz
were carried out in all experiments. In Fig. 9, the increase of pulse
frequency caused an improvement in the current efficiency when the
frequency was less than 500 Hz. At 500 Hz, the highest current effi-
ciency was obtained as 86% and the anode slime was relatively low of
0.8 g. When frequency was greater than 500 Hz, the current efficiency
decreased slightly with further increase of frequency.

3.5.3. Effect of duty ratio

Duty ratio of the pulse current was a very important parameter at
pulse electrodeposition process. Fig.10 shows that the effect of duty
ratio on the electrowinning. When duty ratio was 0.2, current efficiency
was 79.79%, the amount of anode slime was 0.7 g. When duty ratio was
0.3, the current efficiency was decreased (77.41%) and the amount of
anode slime was increased (0.8 g). With the increasing of duty ratio (0.3
to 0.5) the current efficiency was increased, and the maximum current
efficiency 86.0% was obtained at duty ratio of 0.5, at this time of anode
Fig. 9. Influence of pulse frequency on the current efficiency and the anode
slime was relatively less. When the duty cycle was greater than 0.5 (0.5
slime quantity, ja = 400 A/m2, r = 50%, t = 2 h.
to 0.8), and the current efficiency was decreased along with the in-
creasing of duty ratio, the anode slime production was increased. When
the duty ratio was 1 (DC condition), anode slime quantity was 1.21 g, at

Fig. 7. SEM images of manganese deposits at current for 2 h, (A) direct current, (B) f = 500 Hz, r = 50%, (C) f = 500 Hz, r = 20%.

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X. Zhang, et al. Journal of Environmental Chemical Engineering 7 (2019) 103010

3.5.4. Effect of the pulse current density

To understand the effect of current density on the pulse electro-
deposition process, a series of runs with varying current density from
200 to 500 A/m2 were performed. In Fig. 11, the current efficiency
increased from 76.71% to 88.3% steadily and significantly when the
current density increased from 200 A/m2 to 300 A/m2, and it decreased
when the current density was greater than 300 A/m2. Meanwhile, the
amount anode slime first decreased and the minimum was gained as
0.49 g when the current density was 300 A/m2. However, the amount
anode slime increased with the increase of current density when the
current density was greater than 300 A/m2. The increase of the average
current density was conductive to the deposition of manganese in the
beginning. When the density further increased, manganese could be
deposited more quickly, but the concentration polarization would
occur. Accordingly, the hydrogen evolution reaction would be ac-
Fig. 10. Influence of pulse duty ratio on the current efficiency and the anode celerated, and lead to lower current efficiency. According Fig.12, under
slime, ja = 400 A/m2, f = 500 Hz, t = 2 h.
the condition of the pulse frequency was 500 Hz, the duty ratio was 0.5,
the average current density was 300 A/m2, the metal manganese was α-
Mn.

4. Conclusions

Pulse electrodeposition method can be successfully applied to the

metal manganese electrodeposition and has good effect. Due to the
transient high current density, pulse electrolysis can rise cathode
overpotential (larger 90–100 mV than the DC) at the same current
density to inhibit the action of the hydrogen precipitation, which in
turn improves the cathode current efficiency. At the same time, the
higher cathode potential promotes crystal nucleus formation, which
tend to get smooth manganese metal product surface. Through elec-
trolysis experiment, it was found that when the pulse frequency was
500 Hz, the duty ratio was 0.5, the average current density was 300A/
m2, after electrolysis for 2 h under the condition, the current efficiency
Fig. 11. Influence of pulse current density on the current efficiency and the can reach 88.3%, and anode slime was 0.49 g. The current efficiency
anode slime quantity, r = 0.5, f = 500 Hz. being improved by 8.72% and anode slime quantity being reduced by
55.5% relative to 300A/m2 of DC electrodeposition. In addition, PC
electrodeposition method may have a certain significance to the de-
velopment of electrolytic manganese industry.

Acknowledgment

This project was financially supported by the Scientific Research

Project of Chongqing University of Technology (No. 2017ZD46).

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