Manganese Electrodeposition - A Literature Review

Jianming Lu, David Dreisinger, Thomas Glück

PII: S0304-386X(13)00218-1
DOI: doi: 10.1016/j.hydromet.2013.11.002
Reference: HYDROM 3795

To appear in: Hydrometallurgy

Received date: 21 June 2013

Revised date: 23 September 2013
Accepted date: 1 November 2013

Please cite this article as: Lu, Jianming, Dreisinger, David, Glück, Thomas,
Manganese Electrodeposition - A Literature Review, Hydrometallurgy (2013), doi:
10.1016/j.hydromet.2013.11.002

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 ACCEPTED MANUSCRIPT

Manganese Electrodeposition - A Literature Review

Jianming Lu1 David Dreisinger1 and Thomas Glück2

1
Department of Materials Engineering, University of British Columbia,

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309-6350 Stores Road, Vancouver, BC, Canada, V6T 1Z4
2
Baja Mining Corporation,
Suite 1430-800 West Pender St., Vancouver, BC, Canada, V6C 2V6

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Abstract
Electrolytic manganese metal has been used in a wide range of applications such as
production of steel and aluminum alloys. However, manganese electrowinning is

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technically and commercially challenging due to a low current efficiency and high cell
voltage. Rigorous purification and the use of additives are required for commercial
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manganese electrowinning. Some effective additives, such as selenium compounds,
contaminate the metal and have negative environmental impacts. This literature review
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summarizes the background information on hydrogen evolution on manganese,

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manganese electrodeposition and its polarization behavior, effects of impurities, and the
effects of additives such as selenium compounds, and their mechanisms in order to
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provide guidelines for development of cleaner and more efficient manganese

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electrodeposition conditions.

Electrolytic manganese is conventionally produced from ammonium sulfate media in a

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diaphragm cell. Hydrogen evolution on manganese in Mn-free electrolyte is very slow

compared to manganese deposition. However, it is catalyzed by manganese deposition.
With increasing polarization, the manganese deposit structure changes from -Mn to -
Mn. Heavy metal impurities (e.g. Ni and Co) are co-deposited with manganese and
catalyze the dissolution of manganese and then hydrogen evolution thorough the
formation of galvanic micro-cells, resulting in a low manganese current efficiency. With
increasing deposition time, the manganese deposit gradually becomes rougher and more
dendritic, resulting in an increase in the rate of manganese dissolution. Smooth and
compact deposition reduces the harmful effect of impurities and increases manganese


Corresponding author. Tel.: + 604 822 1357; fax: +1 604 822 3619.
E-mail address: Jianming.Lu@ubc.ca (J. Lu).

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current efficiency. Various additives (typically sulfite and selenite) have been used to
counteract the harmful effects of impurities and improve manganese deposit quality. The
addition of selenite (or selenate) and sulfite inhibits hydrogen evolution, increases the
overpotential of manganese deposition in the low polarization region and decreases the

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overpotential of manganese deposition in the high polarization region, facilitates the
crystallization of stable -manganese, improves the leveling effects of the electrolyte,

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and finally increases the manganese current efficiency. The formation of insoluble

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selenides and sulfides with impurities eliminates or suppresses the generation of galvanic
micro-cells and then contributes to an increase in the current efficiency of manganese

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deposition. Alternative additives should inhibit hydrogen evolution significantly, but
manganese deposition to an appropriate degree, promote the formation of α-Mn, function
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as a leveling agent, have a minimum contamination of the manganese deposit and
reducing capacity to stabilize the electrolyte.

Key words: Manganese electrodeposition, additives, selenite, selenate, sulfite

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1. Introduction

Manganese is an important industrial metal used as an additive for production of

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various steels, non-ferrous alloys, electronic components and special chemicals. The
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manganese ore use is as follows: 38% for silicomanganese, 38% for carbon
ferromanganese, 13% for slag, 8% for other alloys, 9% of electrolytic manganese and 2%
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for electrolytic manganese dioxide (Virga et al., 2013). Electrolytic manganese is mainly
used for production of stainless steel, nonferrous alloys, electronics and specialty
chemicals. The annual electrolytic manganese production increased from 180,000 to
1,700,000 tons between 2000 and 2012 mainly due to the rapid growth in the Chinese
electrolytic manganese capacity tied to their robust demand. It is forecast that the annual
demand for electrolytic manganese may grow by 83% from 2012 to 2021 (Virga et al.,
2013). The development of technology for electrolytic manganese production has
consistently sought more cost effective performance.

The standard reduction potential for Mn2+/Mn is –1.18 V vs. SHE. Manganese is the
least noble metal that can be electrodeposited from aqueous solutions on a technical
scale. Manganese electrodeposition from ammonium sulfate and chloride media has been

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most well studied. Electrolytic manganese is conventionally produced from ammonium

sulfate media due to some limitations of chloride media such as the removal of chlorine
from the anolyte and consumption of ammonia. Chloride systems have several
advantages such as a lower energy consumption resulting from a lower cell voltage and a

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higher current efficiency, the ability to operate at a higher current density and the higher
solubility of metals in the process solutions.

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The current efficiency, deposit morphology and the crystal structure of the electro-

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deposited manganese are influenced by the impurities in the electrolyte, the current
density and temperature. In carefully prepared and purified solution, coarse grained -

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manganese was deposited with a current efficiency of over 90% (Znamenskii et al., 1961;
Gamali and Stender, 1962a). However the presence of heavy metal impurities
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significantly decreases the manganese deposition current efficiency. Manganese,
together with many impurities, is usually leached into aqueous solution from manganese
ore. These impurities must be removed before electrowinning. Aluminum and iron can
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be removed by hydroxide precipitation through neutralization to pH~ 6.5. Molybdenum,

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arsenic and silica are removed by co-precipitation. Copper, zinc, nickel and cobalt are
removed by addition of ammonium sulfide. However, the current efficiency of
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manganese deposition from such purified leaching solution is very low and the quality of
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manganese deposit is poor. This indicates that trace amounts of impurities affect the
manganese deposition process. Further purification of manganese electrolyte is very
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expensive. Appropriate additives have to be used in the industrial production of

electrolytic manganese to counteract harmful effects of impurities

Even without any impurity in solution, additives such as sulfite are required to
improve the quality of manganese deposits. As manganese is electrodeposited,
manganese deposits gradually become rougher, and nodules grow up and outward,
forming cauliflower-like dendritic structures or even “trees”, resulting in trapping of
electrolyte in electrolytic manganese, difficulty stripping of manganese deposits from
cathodes, and even difficulty in removing cathodes from cells. In addition, nodules tend
to be broken off and lost during handling, thus decreasing metal recovery. As manganese
deposits become more dendritic, the local real current density deviates more from the

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ideal current density that corresponds to the maximum manganese current efficiency. In
extreme cases, manganese re-dissolves in some local areas due to the loss of cathodic
protection. Therefore the manganese current efficiency decreases with increasing
deposition time. To limit these effects shorter plating cycle of manganese are used in

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comparison to copper, cobalt, zinc and nickel. This requires frequently harvesting of
cathodes and a large circulating inventory of cathodes in the stripping and preparation

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processes. In addition, the catholyte pH is generally maintained at 7 and above by

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operating with a diaphragm cell. Mn(II) is gradually oxidized by oxygen from air to form
MnOOH, affecting manganese deposition and even plugging the porous diaphragm.

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Some additives have to be used to level manganese deposits and stabilize the catholyte.
The use of additives is a key to produce dense high-quality manganese metal at a high
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current efficiency.

Allmand and Campbell (1924a, 1924b) produced electrolytic manganese from

ammonium media in a divided cell in the early 1920s. However, the commercial
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production of electrolytic manganese from ammonium sulfate systems in a diaphragm

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cell began in the late1930s after some additives were used (Dean, 1952).
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The addition of a certain amount of S, Se and Te compounds into the electrolyte can
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significantly improve manganese electrodeposition (Jacobs and Churchward, 1948;

Shulgina and Polukarov, 1966a; Polukarov and Shulgina, 1969). SeO32- is the most
effective among these additives. The manganese deposition current efficiency can reach
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as high as 96% in the presence of SeO32- (Shulgina and Polukarov, 1966a; Polukarov and
Shulgina, 1969). However the addition of these additives (especially SeO32-) results in
the contamination of manganese and may lead to environmental issues at the plant and
the product use sites. An alternative additive is needed to improve manganese deposition
without contamination of manganese product.

The objective of this review was to collect and analyze the information regarding
manganese electrodeposition, the effects of additives and how these improve the
manganese current efficiency in order to provide background information for the
development of new additives. The review focuses on the fundamental aspects of

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hydrogen evolution, manganese electrodeposition and the effects of additives in

manganese electrowinning.

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2. Manganese Electrowinning from Sulfate Media

2.1. Operation Conditions

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Manganese electrowinning has to be conducted in a diaphragm cell so that manganese

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can be electrodeposited from the catholyte. The operation conditions vary for different
manganese electrowinning processes. For example, with the use of SeO32-, the cell

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operates in the pH range 7.0-7.5 and high manganese concentrations can be used (Rao et
al., 1966) while with the use of SO2, the pH is generally above 8.0 and with lower
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manganese concentrations. The effects of the operation conditions (the catholyte
composition, current density, temperature and pH) on the manganese electrodeposition
from sulfate media with SO2 have been discussed by Jacob et al. (1946), Louis and
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Martin (1976) and Araujo et al. (2006). The manganese concentration significantly
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affects manganese electrodeposition and its optimum value is determined by the other
operation conditions. The typical optimum catholyte manganese concentration is around
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12 g/L (Araujo et al., 2006; Harris et al., 1977; Jacob et al., 1946). A lower manganese
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concentration results in a lower current efficiency. A higher manganese concentration

(above 15 g/L) results in precipitation of manganese hydroxide and dendrite formation.
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Ammonium sulfate plays two important roles. The first is to increase the solution
conductivity, and hence decrease the cell voltage and reduce the energy consumption.
The second role is its capabilities of pH buffering and the formation of manganese-
ammonia complexes to prevent the precipitation of manganese hydroxides and oxides at
the cathode surface in a neutral or weak alkaline solution according to the following
reactions:

Buffering role: NH4+  NH3 + H+ (1)

or NH4+ + OH-  NH3 + H2O (1a)

Complexation role: [Mn(NH3)(n-1)]2++ NH3  [Mn(NH3)n]2+ (1  n 4) (2)

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The stability constants for formation of the manganese ammines in 2 M NH4NO3

solution at 40 C are 8.1, 24.0, 38.0, 33.9 for n = 1, 2, 3, 4 respectively (Isaev, 1990).
The complexation of manganese with ammonia not only reduces the free manganese
concentration, but also plays a buffering role. Therefore, MnSO4-(NH4)2SO4 solution has

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a higher buffering capacity than (NH4)2SO4 solution as reported by Dean (1952) and
Tilak et al. (1962). The buffering effect of MnSO4-(NH4)2SO4 solution occurs at a lower

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pH than that of (NH4)2SO4 solution as expected from Reactions 1 and 2.

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Since the stability constants of the Mn(II)-NH3 complexes are not large, the
ammonium sulfate concentration needs to be sufficiently high to stabilize manganese ions

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in the solution. A minimum ammonium sulfate concentration suggested by Jacobs et al.
(1946) is 125 g/L to prevent the precipitation of manganese ions. For stable operation,
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ammonium concentrations of 130 to 135 g/L were used. The current efficiency at a
current density of 484 A/m2 continuously decreased from 64.6 to 60.2 to 55.9 to 52.8%
with increasing ammonium sulfate concentration from 125 to 150 to 175 to 200 g/L.
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Similar results were obtained by Araujo et al. (2006). Commercial operations are
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characterized by effective ammonium sulfate concentration ranges from 130 to 150 g/L in
the catholyte which is 20 to 30 g/L higher than that in the anolyte or in the feed. This is
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due to pH related equilibria and the diffusion and migration of ions in the divided cell.
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The temperature significantly affects the manganese deposition. The optimum

temperature reported varies from 30 to 40 C for different authors (Araujo, 2006; Jacob et
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al., 1946; Louis and Martin, 1976) since it is related to the current density, deposit
quality, catholyte cooling efficiency and energy consumption. At a temperature below 35
C, the manganese deposit is light gray, smooth and fined-grained while at a temperature
above 35C, the manganese deposit becomes nodular and dendritic with increasing
temperature (Jacob et al., 1946). At a temperature above 45 C, “trees” form readily and
manganese re-dissolution takes places at the base of these structures. However a
temperature slightly higher than 40 C is used in some industrial plants for a higher
production efficiency and a lower energy consumption.

With increasing current density, the manganese current efficiency first increases with
increasing density, reaches a maximum value and then decreases. The current efficiency

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or relative rate of manganese to hydrogen evolution as a function of current density is

related to the other operation conditions such as temperature and deposition time (Araujo
et al., 2006; Jacobs et al., 1946). The highest current efficiency was found to be 67% at
540 A/m2 and 24 hours of deposition (Jacobs et al., 1946), 65% at 600 A/m2 (Louis and

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Martin, 1976) and 63.5% at 484 A/m2 and 24 hours of deposition (Araujo et al., 2006).
The optimum current density should be not only determined by the current efficiency, but

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also by the deposit quality and deposition time. With increasing deposition time, the

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manganese current efficiency decreases and the deposit becomes more dendritic. A short
deposition time may be used at a high current density while a long deposition time

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should be used at a low current density. The optimum manganese deposit time is
determined by the sensitivity of current efficiency relative to current density, cell house
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current supply capacity and cathode harvesting capacity.

With increasing pH, the manganese current efficiency first increases, then reaches a
maximum value and finally decreases when the manganese starts precipitating in the
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catholyte. pH 8.1 to 8.5 was recommended by Jacob et al., (1946) which is controlled by
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diaphragm cloth selection and other parameters. Louis and Martin (1976) reported that
the current efficiency continuously increased with increasing pH from 7.2 to 9.2.
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However at a high pH, manganese hydroxide may be precipitated at the cathode,

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decreasing the current efficiency. At a higher pH, manganous ions are more easily
oxidized to MnOOH by oxygen from air and the loss of NH3 becomes more significant.
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2.2. Practical Aspects of Manganese Electrowinning

Besides the factors (pH, temperature, current density, manganese and ammonium
sulfate concentrations and deposition time) discussed in the previous section, cell design,
anode and cathode materials, cathode treatment, and diaphragm are also important
factors. The successful manganese electrowinning is dependent on a combination of these
factors. Nearly all of these factors depend on the others, and the limits of one factor
cannot be specified without defining the other conditions. The operation conditions for
two electrolytic manganese plants are summarized in Table 1.

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A diaphragm cell has to be used to maintain a neutral or slightly alkaline electrolyte

for manganese electrodeposition. An ideal diaphragm should have an appropriate
porosity to control the diffusion of the acid formed at anodes into the catholyte and allow
the cell to be operated at a low cell voltage. The electrical resistance across the

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diaphragm is important not only to save electrical energy, but also to prevent overheating
a cell. Polyester and polypropylene filter cloths are now widely used as diaphragm

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materials.

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Table 1 Operational conditions for manganese electrowinning
Plants Delta Manganese (Harris et Union Carbide and carbon
al., 1977) Co. (Carosella, 1956)

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Feed
Mn / g L-1 30-34 34-36
-1
(NH4)2SO4 / g L 120-130 125-145
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SO2 / g L-1 0.2-0.4 > 0.1
pH 6.7-7.2
Catholyte
Mn / g L-1 12 10-12
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pH 8.2-8.8
(NH4)2SO4 / g L-1
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- 145-165
Temperature / C 36-38
Anolyte
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Mn / g L-1 - 10-12
-1
(NH4)2SO4 / g L - 125-145
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H2SO4 / g L-1 - 39-46

Cathode 316 stainless steel Stainless steel
Cathode size /mm 980 x 680 1016 x 559
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-2
Cathode current / Am 430-540 485
Anode 99% Pb and 1% Ag 99% Pb and 1% Ag
-2
Anode current / Am 970-1500 1500
Mn current efficiency / % 68 65
Mn(II) oxidation < 1.5% of Mn input -
Cell voltage / V 5.5
Cooling Internal cooling -

A significant amount of manganese dioxide is precipitated at anodes and anode

compartments can quickly be filled with anode sludge. Therefore the anode compartment
should have enough extra space for anode sludge to allow a cell to operate for a
sufficiently long time. Several types of cells were first proposed by Jacobs et al. (1946) to
solve the problem resulting from anode sludge. False-bottom-type and clamp-type

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electrode frame cells are typical ones. In a false-bottom-type cell, an anode is placed in
the upper part of an anode compartment while anode sludge is collected in the lower part
of the anode compartment (or a false bottom of the cell). The cathodes are suspended
freely in the catholyte compartment while the anodes are each surrounded by a

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diaphragm. Rising hydrogen bubbles streams induce the catholyte circulation, providing
exchange solution between the plating and cooling zones and mixing the catholyte with

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fresh feed for uniformity of catholyte composition.

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In a clamp-type electrode frame cell, all of the cathode and anode frames are bolted
together into one solid block. Rectangular compartments in the bottom of the frames fit

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together to form an anode sludge chamber. The anode frames are open into this chamber
and the cathode frames are closed from it. Hydrogen generated at cathodes acts as a gas-
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lift to draw the common catholyte into each cathode compartment through the holes
drilled in the lower part of the cathode frame sides and eject the catholyte into the
common catholyte chamber through the holes drilled in the upper part of the cathode
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frame sides. This results in a uniform Mn concentration, pH and temperature in all

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cathode compartments. Feed solution is added into the common catholyte chamber. The
entire frame assembly can be lifted out and replaced by another assembly. Many
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commercial cells are modified or improved from false-bottom-type and clamp-type frame
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cells or their combination (Araujo et al., 2006; Carosella and Fowler, 1957; Harris et al,
1977). The modified clamp-type frame cells are still used in Manganese Metal Company.
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In another type of cell, cathodes are in separate compartments while the anodes hang
freely in the open. Each cathode compartment is fed with a small tube from a header line
along the cells (Dean, 1952). The anolyte overflows at the end of the cell.

The formation of manganese dioxide is dependent on the anode material and current
density. The selection of anode materials is based on the rate of Mn(II) oxidation to
MnO2 and corrosion resistance. The essential feature of a suitable anode is the formation
of a porous adherent self-limiting coating. A coating should build on the anode, remain
porous and adherent until a thickness is reached to reduce manganese dioxide formation
to the desire amount and then sloughs off as formed. Alloys like lead-silver and lead-
silver-arsenic enable the anode to hold the coating firmly as the lead itself is oxidized.

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99% Pb and 1% Ag alloy is a typical anode material used for manganese electrowinning.
A thicker coating is formed at a higher current density and less manganese is oxidized to
MnO2. Therefore, the anode current density is normally two to three times the cathode
current density.

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Cathodes for manganese electrowinning should have the following properties: (1)

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stable in catholyte and dilute sulfuric acid solution used for cleaning, (2) a low electrical
resistance, (3) good flexibility, (4) a high hydrogen overpotential, (5) the appropriate

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adhesion between the cathodes and manganese deposits. Stainless steel (typically Type
316), titanium and Hastelloy alloy have been used as cathode materials for manganese

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deposition (Dean, 1952, Carosella and Fowler, 1957; Harris et al, 1977). Different
materials need different surface treatments to maintain the proper adhesion of manganese
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deposits to the cathode so that manganese deposit can be easily stripped, but don’t fall off
the cathode before stripping. For example, stainless steel cathodes are first thoroughly
cleaned, then polished, and finally treated with sodium silicate solution. After such a
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treatment, a thin sodium silicate film on the cathodes prevents the manganese deposit
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from adhering too tightly to the cathode surface.

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The manganese and ammonium sulfate electrolyte has a relatively high electrical
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resistance. Therefore a significant amount of heat is generated in the cell. The electrolyte
has to be cooled to maintain an optimized temperature. The electrolyte is cooled either
internally or externally. For internal cooling, stainless steel cooling coils are placed in the
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common catholye chamber and the catholyte is self-circulated. For external cooling, the
electrolyte is circulated out for cooling and concentration control. The advantage for
external cooling is: (1) better temperature and solution composition control and (2)
elimination or reduction of solid precipitate (e.g. calcium and manganese sulfate) in the
cathode compartment. The forced catholyte circulation with an external heat exchanger
was employed by Kerr-McGee Chemical Co.

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3. Kinetics of Hydrogen Evolution and Manganese Electrodeposition

3.1. Hydrogen Evolution on Manganese from Mn-Free Electrolyte

The kinetics of hydrogen evolution and manganese electrodeposition in various

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chloride and sulfate solutions has been investigated by different authors (Agladze et al.,
1974; Belanger and Vijh, 1974; Gamali and Stender, 1962a; Hurlen and Valand, 1964a,

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1964b; Ilea et al., 1997b, 2000) and the results differ to some extent.

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Hydrogen evolution is generally accepted to proceed via three steps. The initial
proton discharge in acidic solution or water discharge in neutral/ alkaline solution

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(Reaction 3) is followed by the combination of the adsorbed hydrogen-catalytic
desorption (Reaction 4) or electrochemical desorption of adsorbed hydrogen (Reaction
5).
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H3O+ (or H2O) + e  Hads + H2O (or OH-) (3)

Tafel slope = 2.303RT/F (0.118 V at 25 C and =0.5) (3a)

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2 Hads  H2 (4)

Tafel slope = 2.303RT/2F (0.0295 V at 25 C) (4a)

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H3O+ (or H2O) + Hads + e  H2 + H2O (or OH-)

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(5)

Tafel slope = 2.303RT/(1+)F (0.0393 V at 25 C and =0.5) (5a)

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where  is the charge transfer coefficient, F the Faraday constant, R the molar gas
constant and T the absolute temperature.

Gamali and Stender (1962a) studied the overpotential of hydrogen evolution on

manganese in very pure weakly acidic/alkaline ammonium sulfate and sodium sulfate
solutions. The most essential requirement in the study of hydrogen overpotential on
manganese is the purity of electrolyte. The contradictory results obtained by different
authors may be attributed to the differences in these effects. The impurities that affect the
manganese electrodeposition cannot always be detected by standard analytical methods.
Such impurities also include minute amounts of organic substances.

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In the initial polarization region, the slope of the polarization curve was very low and
the hydrogen evolution was accompanied by the dissolution of manganese. With
increasing polarization, the Tafel line appeared in the moderate current density range.
The Tafel slopes for both sulfuric acid and sodium sulfate solutions were 0.12 V per

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decade while the Tafel slopes for ammonium sulfate are 0.16-0.18 V per decade.

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The overpotential of hydrogen evolution on manganese was nearly independent of
ammonium salt concentration (0.125-2.6 M (NH4)2SO4). In ammonium sulfate solution,

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NH4+ can be discharged at a sufficiently low potential:

NH4+ + e = NH3 + Hads (6)

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The favorable effect of ammonium salts in the electrodeposition of manganese is that
ammonia produced at the cathode dissolves manganese hydroxide through complexation.
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Hurlen and Valand (1964a, 1964b) investigated hydrogen evolution on manganese
from HCl-KCl /H2SO4-K2SO4 solution. In the manganese corrosion potential region, the
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hydrogen evolution reaction was under proton diffusion control in acidic solution. At a
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more negative potential, a pH-independent Tafel slope of 22.303RT/F was observed for
the discharge of water as the rate-determining step.
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Belanger and Vijh (1974) reported steady-state potentiostatic Tafel plots for hydrogen
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evolution on manganese in 0.05 N H2SO4 and 1 M Na2SO4 solution. At a low cathodic

polarization, no Tafel line was observed because of the vigorous open-circuit corrosion
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reaction. With increasing cathodic polarization, a long Tafel line appeared and was
associated with the hydrogen evolution by the discharge of water as the rate-determining
step.
Agladze et al. (1974) studied hydrogen evolution on manganese in various solutions
over the pH range from 1 to 14. At a pH below 3, in the low cathodic polarization region,
the Tafel slope was only 0.01-0.02 V per decade due to the reduction of protons by
manganese. With increasing cathodic polarization, the Tafel slope increased to 0.14 V
per decade. In the pH range from 1.68 to 14, the potential was independent of pH at a
constant current while the Tafel slope was 0.14-0.15 V per decade. The overpotential of
hydrogen evolution linearly decreased with increasing pH. This relationship between the

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overpotential and pH is quite different from that on mercury, i.e. with increasing pH, the
overpotential first increases to a peak value around pH 7 and then decreases.

Ilea et al. (1997b, 2000) reported that the Tafel slopes of hydrogen evolution on
manganese in 1 M (NH4)2SO4 solution were 0.124 V per decade in the current range 1-

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200 mA cm-2 while the Tafel slopes of hydrogen evolution on manganese in 1 M Na2SO4
solution 0.301 V per decade in the current range 6-127 mA cm-2.

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The Tafel coefficients (a and b) for the Tafel equation (overpotential:  = a + b logi)

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are summarized in Table 2. All these data indicate that the discharge of hydrogen donors
on manganese is the rate-determining step.

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Table 2 Summary for Tafel coefficients from the literature.
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a / V b/V Electrolyte References
1.19 0.18 0.5 M (NH4)2SO4, pH 7.5 and 25 C Gamali and Stender, 1962a
0.12 0.5 M Na2SO4, pH 10 and 25 C Gamali and Stender, 1962a
1.31 0.12 0.025 M Na2SO4, pH 10 and 25 C Gamali and Stender, 1962a
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22.303RT/F HCl-KCl /H2SO4-K2SO4 Hurlen and Valand, 1964a,

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1.60 0.14 0.05M H2SO4 + 1 M Na2SO4, 25 C Belanger and Vijh, 1974

* 0.14-0.15 pH 1.68-14, 25 C Agladze et al., 1974
0.933 0.124 1 M (NH4)2SO4, pH 7.8 Ilea et al., 1997b, 2000
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1.364 0.301 1 M Na2SO4, pH 7.8 Ilea et al., 1997b, 2000

* a = constant – 0.059 pH, i.e. at a constant current, the potential is independent of pH.
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3.2. Hydrogen evolution and Manganese deposition from Mn-Containing Solution

Galushko and Loshkarev (Galushko and Loshkarev, 1962; Loshkarev, 1963) found
that the Tafel slopes for the discharge of H+ and Mn2+ are 0.033 and 0.025 V per decade
respectively. The low Tafel slope for hydrogen evolution in the presence of manganese
was attributed to a catalytic mechanism such as:

Mn2+ + ne = Mn(2-n)+ (7)

Mn(2-n)+ + nH+ = Mn2+ + n/2H2 (8)

where n = 1 or 2. The similarity of the Tafel slopes for the manganese deposition and the
hydrogen evolution suggested that the rate of the catalytic evolution of hydrogen is

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determined by the stage of the electron addition to manganese or by the formation of an

active complex such as H2O-Mn2+-e.

Hurlen and Valand (1964a, 1964b) found that the steady-state dissolution and
deposition of manganese obeyed mutually symmetrical and pH-independent Tafel lines

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with a slope of 2.303RT/2F.

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Heusler and Bergmann (1970) reported that a pH-independent Tafel slope for
manganese deposition from MnSO4-(NH4)2SO4 and MnCl2-NH4Cl solutions was 0.029 V

SC
per decade at 25 C and a reaction order of 1.5 with respect to Mn2+ was obtained. This
unusual reaction order was explained by assuming that the charge transfer reaction took

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place only at specific sites on the manganese surface, the surface activity of which
depended on overpotential. However, the reaction order was obtained by the plot of
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current against the total Mn concentration. Mn2+ does not exist in one form of species and
not all Mn2+ species are electrochemically active in the potential range studied. Probably
only one Mn2+ species was discharged on the electrode. The concentration of that Mn2+
D

species discharged may not be proportional to the total Mn2+ concentration. Therefore
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the reaction order obtained was probably apparent and may not reflect the real reaction
P

mechanism. A pH-independent Tafel slope of 0.12 V per decade for hydrogen evolution
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was observed for the discharge of water.

Agladze et al. (2000) investigated the kinetics of manganese electrodeposition from

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MnSO4 - (NH4)2SO4 solution and gave results similar to that by Heusler and Bergmann
(1970). The purity of the electrolyte significantly affected the polarization behavior of
manganese electrodeposition and the current of manganese electrodeposition from the
purified electrolyte was about 10 times higher than that from the unpurified electrolyte
due to the catalytic effect of impurities on hydrogen evolution. The electrolyte was
prepared using double crystallized reagents and it was subject to 20 hours of pre-
electrolysis for kinetic studies. The current efficiency of manganese deposition from such
an electrolyte can reach 90%.

The polarization curves of manganese deposition from ammonium sulfate solutions

are shown in Figure 1. In the low polarization region (Region A), the Tafel slope was
about 2.303 RT/2F (0.0295 mV per decade at 25 C), which was independent of

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manganese and ammonia concentrations, and pH. The reaction order with respect to
Mn2+ was 1.6, which was obtained using the same method as by Heusler and Bergmann
(1970), i.e. the plot of the current of manganese deposition against the total Mn2+
concentration. The current of Mn(II) discharge should be higher than the current of

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manganese deposition (crystallization) since some of discharged manganese was re-
dissolved. Therefore it was an apparent reaction order. The reaction rate is described by

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the following equation:

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i = k (CMn(II))1.6 exp(-2FE/RT) (9)

where i is the current density, E the potential and k the rate constant.

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-1.50
D
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9.06 g/L Mn(II)
-1.45 27.2 g/L Mn(II)
82.4 g/L Mn(II)
Potential vs. SHE / V

110 g/L Mn(II)

D

-1.40
TE

-1.35 B
P

A
CE

-1.30

-1.25
AC

-3.0 -2.5 -2.0 -1.5 -1.0

-2
Log (i / A cm )

Figure 1 Polarization curves of Mn deposition in solutions with 70 g/L (NH4)2SO4 and

different manganese concentrations (Replotted from Agladze et al., 2000).

In the medium overpotential range (Region B), a first limiting current was observed
and increased with increasing MnSO4 concentration. With further increasing
ovepotential, a second Tafel line appeared in Region C, but it was not well-defined. In
the high overpotential range (Region D), a second limiting current appeared. Contrary to
the first limiting current, the second limiting current was nearly independent of Mn(II)
concentration. The rate of manganese deposition was not sensitive to the rotational speed

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of manganese disc electrode, indicating that the manganese deposition was kinetically
limited by the electrode surface reaction.

The investigation of manganese corrosion indicated that manganese reacts with water,
resulting in hydrogen evolution and formation of surface manganese oxide or hydroxide

PT
(MnO or Mn(OH)2):

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Mn + H2O  MnO + H2 (10)

SC
or

Mn+ 2H2O  Mn(OH)2 + H2 (11)

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In the presence of H+ or NH4+, the formation of surface oxide can be suppressed
according to the following reactions:
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MnO + 2 H3O+  Mn2+ + 3 H2O (12)

MnO + 2 NH4+  Mn(NH3)22+ + H2O (13)

D

The formation of oxide/hydroxide layers leads to an increase in the overpotential of

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Mn(II) discharge. The overall kinetics of the deposition reaction is determined by the
P

balance between rates of manganese oxidation and activation reactions. Since the
CE

removal of the oxide/hydroxide layer is probably the slowest and is a potential-

independent reaction, an unfavorable balance between inhibition and activation reactions
at sufficiently negative potentials may result in kinetic limitation of the overall rate of
AC

deposition reaction. An additional factor affecting the inhibition/activation balance may

be due to electrochemical reaction of hydrogen evolution. At a low overpotential, water
is discharged while at a high overpotential, the discharge of ammonium ion becomes
more favorable. This is in agreement with the findings reported by Suliakas et al. (1984).

Around the corrosion potential of manganese, the rate of manganese dissolution was
almost independent of potential and increased with decreasing pH and increasing
ammonium sulfate concentration. Even under cathodic protection, the dissolution of
manganese was observed. For manganese dissolution, the reaction orders with respect to
both H+ and NH4+ are 2.

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Contrary to that discussed in the above, Radhakrishnamurthy and Reddy (1974) found
that the Tafel slope of manganese deposition from MnSO4-(NH4)2SO4 solution was 0.12
V per decade at pH 2-7 and the reaction order with respect to Mn(II) was 1. They
proposed the following mechanism:

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Mn2+ + e  Mn+ (14)

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Mn+ + e  Mn (15)

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Reaction 14 was the rate-determining step. However the Tafel slope was obtained in
a narrow range of current densities (less than one decade). The Tafel slope obtained is in

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doubt.

Gamali and his coworkers (Bondar, et al. 1967, 1970; Gamali et al., 1974; Gamali
MA
and Vorozhko, 1980a, 1980b; Trofimenko and Gamali, 1970) conducted a series of
studies in concentrated ammonia-ammonium chloride solution and proposed that not all
of the adsorbed atoms or mono-valent manganese ions formed pass into the metallic
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phase. Some ions experience hindrances during entry into the crystal lattice and interact
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with solution. The result of such an interaction is the liberation of hydrogen (secondary
mechanism). For manganese deposition process, the following reactions should be
P

considered:
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Mn2+ + 2 e  Mn(crystal) (icr) (16)

2H2O (NH4+) + 2 e  H2 + 2 OH- (NH3)

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( id H2) (17)

Mn2+ + 2 e  Mn0 (Mn is discharged, but oxidized by solution) (18)

Mn0 + 2 H2O (NH4+)  H2 + Mn2+ + 2 OH- (NH3) (iH2 sec) (19)

The rate of Mn(II) discharge is the sum of the rates of crystallization (Reaction 16)
and secondary liberation of hydrogen (Reaction 19), i.e. id Mn = icr + iH2sec while the total
rate of hydrogen evolution is the sum of hydrogen evolution (Reaction 17) due to the
discharge of hydrogen donors and secondary liberation of hydrogen (Reaction 19), i.e. iH2
= idH2 + iH2sec. The total current is the sum of the currents for manganese crystallization
and hydrogen evolution, i.e. id = icr + iH2.

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 ACCEPTED MANUSCRIPT

As shown in Figure 2, in the initial polarization region, the hydrogen evolution was
mainly due to the discharge of H2O or NH4+. The Tafel slopes for hydrogen evolution
and manganese electrodeposition were 0.11-0.14 V per decade and 0.03 V per decade
respectively. With decreasing potential, the Tafel slope for hydrogen evolution decreased

PT
to around 0.030 V per decade due to secondary liberation of hydrogen. With further
decreasing potential, there was a limiting current for manganese deposition (the sharp

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change in the slopes of the polarization curve for Mn crystallization icr). Finally the

SC
slopes of the polarization curves for hydrogen evolution (iH2), manganese deposition
(crystallization rate icr) and Mn(II) discharge (id) shifted to 0.09-0.10 V per decade. It

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was speculated that the initial Tafel slope (b = 0.03 V) corresponded to the discharge of
hydrated manganese while the second slope (b = 0.09-0.10 V) corresponded to the
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discharge of complex ions. With increasing current density, the hydrogen evolution rate
increased, and hence the pH at the cathode surface rose, resulting in a higher ammonia
concentration. The distribution of manganese species at the cathode surface shifted from
D

hydrated manganese ions to ammonia–manganese complexes with increasing current

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density (Gamali et al., 1981) as indicated by Reaction 2. The ammonia-manganese

complexes were discharged at a lower potential than hydrated manganese ions. The
P

limiting current corresponded to the discharge of the hydrated manganese ions and
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resulted from the transition of the discharged species from hydrated manganese ions to
ammonia-manganese complexes.
AC

With decreasing potential, the deposited manganese shifted from -phase to -phase
(Figure 3). The total manganese current efficiency first increased, reached a peak value
and then decreased.

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 ACCEPTED MANUSCRIPT

PT
RI
SC
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MA
Figure 2 Kinetics curves of Mn crystallization (icr), Mn (II) discharge (id), hydrogen
evolution due to the discharge of H2O or NH4+ (idH2), secondary liberation of hydrogen
(iH2 sec) and the total hydrogen evolution (iH2) (Replotted from Gamali and
D

Vorozhko,1980a). Electrolyte: 0.5 M MnCl2, 4 M NH4Cl, 0.5 g/L NH4OHHCl and pH

8.75 (2.5 M NH3).
P TE
CE
AC

Figure 3 Potential vs. current efficiency for the deposition of -Mn, - Mn and total
manganese (α+γ) (Replotted from Gamali and Vorozhko, 1980a). Electrolyte: 0.25 M
MnCl2, 4 M NH4Cl and pH 6.15.

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From the above discussions, the Tafel slope for manganese electrodeposition is about
2.303RT/2F at a low cathodic polarization while it varies for different authors at a high
cathodic polarization due to the use of different solution compositions, purities and
conditions. For example, manganese ions were stabilized in a concentrated ammonia-

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ammonium chloride solution due to the strong complexation of manganese with ammonia
and chloride and a high pH buffering capacity. The manganese hydroxide was not

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precipitated, causing the passivation of the cathode surface. Chloride ions probably also

SC
played an activation role for manganese deposition. Therefore there was a well-defined
second Tafel line (Figure 2). Manganese ions were not well stabilized in the ammonia-

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ammonium sulfate solution because of weak complexation of manganese with ammonia
and a low pH buffering capacity. Manganese was readily precipitated as hydroxide,
MA
resulting in the passivation of the cathode surface. The manganese deposition was
limited by the cathode surface conditions. Therefore there was no well-defined second
Tafel line (Figure 1).
D
P TE

4. Effects of Impurities
CE

The effects of metal impurities on manganese electrodeposition and hydrogen

AC

evolution have been studied by several researchers (Agladze and Gofman, 1957a, 1957b;
Gamali and Stender, 1962b; Janickis et al. 1978; Kuodyte et al., 1977a., 1977b; Shvab,
1971, 1972, 1975; Shvab et al., 1971; Zosimovich et al. 1967). Shvab (1975) divided the
impurities into two groups. One hinders the conversion of metastable -Mn to stable -
Mn while another does not retard or favor the conversion of -Mn to stable -Mn. The
first group consists of Ga, Zn, Co, Ni and Cu while the second group consists of Cd, Pb,
Se and S.
Shvab et al. (Shvab, 1971, 1972, 1975; Shvab et al., 1971; Zosimovich et al. 1967)
pointed out that the impurities (e.g. Cu, Co and Ni) with low H2 overpotential co-deposit
with manganese, resulting in a localized galvanic cell. The initiation of a galvanic cell is
caused by the non-uniform distribution of current density on the cathode surface during

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electrodeposition. In the impurity-rich area, the H2 evolution is dominant, leading to an

increase in pH and consequently a non-uniform distribution of pH on the surface. The
presence of galvanic pair causes an intense dissolution of the freshly deposited
manganese, resulting in a low current efficiency.

PT
With the use of a rotating disk electrode, the harmful effects of impurities on

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manganese deposition were significantly suppressed (Zosimovich et al. 1967). From
Figure 4, with increasing impurity concentration, the manganese current efficiency

SC
decreased quickly for a stationary electrode, but slowly for a rotating disk. The contents
of Co, Ni and Cu were proportional to their concentrations in the electrolyte, indicating

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they were deposited at limiting currents. Since the rotation speed was high enough to
efficiently remove hydrogen bubbles, the screening effect of bubbles, which significantly
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causes manganese corrosion, was eliminated. It should be pointed out that the non-
uniform deposition of impurities is mainly due to the screening effect of hydrogen
bubbles adhering to the cathode surface. The screening effect of bubbles retards the
D

electrodeposition of manganese, but not that of impurities that have higher deposition
TE

potentials, resulting in impurity-rich areas.

The presence of impurities can significantly affects hydrogen evolution
P

characteristics on manganese. Trace amounts (0.005 mg/L) of Cu and Ni can decrease

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the overpotential of hydrogen evolution while Pb increases the overpotential.

The hydrogen overpotential on zinc is greater than that on manganese and the zinc
AC

ions also increase the overpotential. A small amount of zinc (several ppm) can increase
the current efficiency while increasing Zn concentration to 110 mg/L resulted in a zero
current efficiency of manganese deposition from the electrolyte with 40-42 g/L Mn as
MnSO4 and 135-145 g/L (NH4)2SO4 (Shvab et al. 1971).

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80

Current efficiency / %
60

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40

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Co (Stationary)
Ni (Stationary)
Cu (Stationary)

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20 Co (rotating disk)
Ni (rotating disk)
Cu (rotating disk)

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0
0 10 20 30 40
-1
Impurity concentration / mg L
MA
Figure 4 Effects of Co, Ni and Cu concentrations on manganese current efficiency at
stationary and rotating disk electrodes (900 rpm) (Replotted from Zosimovich et al.
1967). Electrolyte: 40-42 g/L Mn as MnSO4, 135-145 g/L (NH4)2SO4 and pH 5-6.
D

Conditions: 3 hours of electrolysis, 500 A m-2 and 18-22 C.

TE

The maximum tolerable concentrations of impurities vary for different solution

P

qualities and operating conditions (e.g. 0.35 to 5 mg/L Ni, 0.3 to 5 mg/L Co, 5 to 20
CE

mg/L Cu, 10 to 20 mg/L Fe, and 1-2 mg/L Mo (Louis, 1976)). Harmful impurities such
as Ni, Co Cu. Fe, Mo, As and Sb often have deleterious synergetic effects on manganese
AC

electrodeposition. The tolerance of one impurity is dependent on the concentrations of

the other impurities. The maximum tolerable concentration of one impurity can be
allowed to be higher if the other impurity concentrations are lower. The harmful effects
of impurities become more significant for longer manganese deposition time. Therefore
the maximum tolerable concentration should be lower for a longer plating cycle. Other
operating conditions such as temperature, current density, pH, solution composition, and
additive dosages also affect the tolerance of impurities. Therefore, each manganese
producer has its own standard for impurity limits. The reported impurity concentrations
in the catholyte from Electrolytic Metal Co. (now Manganese Metal Company) were 0.7
mg/L Fe, 0.4 mg/L Ni, 0.3 mg/L Co and <0.1 mg/L Cu (Louis, 1976).

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5. Effects of Additives on Mn Electrodeposition

Group VI element (S, Se and Te) compounds have similar beneficial effects on
manganese electrodeposition and therefore discussed together.

PT
5.1. Effects of Se, S and Te Compounds

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Dean (1952) reported that the addition of sulfite facilitates the deposition of more
stable -manganese, prevents the precipitation of MnOOH, and stabilizes the catholyte

SC
because of its reducing power. In an alkaline catholyte, Mn(II) can readily be oxidized to
MnOOH, causing many problems (bad quality deposit and plugging diaphragm). The

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addition of 0.1 g/L SO2 is sufficient to maintain a good manganese current efficiency.
Tilak et al. (1964a, 1964b) found that the manganese deposits were black and powdery,
MA
and the manganese current efficiency was less than 10% at a SO2 dosage below 0.015 g/L
due to Ni and Co-enhanced corrosion of manganese (hydrogen evolution) while the
manganese deposit became white and compact, and the manganese current efficiency
D

reached as high as 67% at a SO2 dosage above 0.1 g/L due to the inhibiting effect of SO2
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on manganese corrosion or hydrogen evolution. The manganese current efficiency

increased with increasing SO2 concentration and then practically did not increase at a SO2
P

concentration above 0.1 g/L.

CE

Yanistskii and his coworkers conducted a significant amount of work on the effect of
selenium compounds on manganese electrodeposition (Janickis et al., 1966a, 1966b;
AC

Klungeviciute et al., 1966; Kuodyte et al., 1975; Suliakas et al. 1974; Suliakas et al.,
1976a, 1976b; 1978; Viskelis et al, 1984; Yanitskii et al., 1961, 1984; Yanitskii and
Stul'pinas, 1957, 1958). The authors first studied the effect of the addition of H2SeO3 on
manganese electrodeposition. The addition of 0.1-0.2 g/L H2SeO3 to the electrolyte with
63-125 g/L MnSO4, 75 g/L (NH4)2SO4 and pH 7.0-7.5 increased the manganese current
efficiency from 50-60 to 90% at 200-500 A m-2 and 18-25 C, and resulted in fine
grained and smooth deposits containing 0.2-0.5% Se mainly as MnSe (Yanitskii and
Stul’pinas, 1957). This deposit had a higher corrosion-resistance than that obtained from
the electrolyte without H2SeO3. With increasing concentration of H2SeO3, the current
efficiency first increased to a maximum value (90-94%) at 0.2-0.4 g/L H2SeO3 and then
decreased. The addition of 0.1 g/L H2SeO3 shifted the polarization curve in a negative

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direction significantly (Yanitskii et al., 1961), indicating that the overpotentials of both
hydrogen evolution and manganese deposition were increased.
The content of selenium in the manganese deposit linearly increased from 0.2% to
1.7% at 450 Am-2 with increasing concentration of H2SeO3 from 0.1 to 0.8 g/L (Yanitskii

PT
and Stul’pinas, 1958). The manganese deposit produced from the electrolyte containing
0.5 g/L H2SeO3 was mirror-like. Selenite functioned as both a leveling and brightening

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agent and should inhibit manganese deposition according to Winand (1984).

SC
The addition of selenium increased the hydrogen overpotential on both manganese
and impurities (e.g. Ni (Suliakas, et al. 1974)) and suppressed the harmful effects of

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impurities possibly due to the formation of selenides with impurities (Yanitskii et al.,
1961). The selenides formed are not metallic electro-conductive. Therefore the corrosion
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due to the galvanic micro-cells was eliminated or impeded.

In an acidic electrolyte, the decomposition of H2SeO3 results in the formation of

D

colloidal selenium. (NH4)2SeO4 is more stable and therefore more effective in an acidic
electrolyte (Janickis et al., 1966b; Klungeviciute et al., 1966). A current efficiency of
TE

90% for manganese deposition from the electrolyte with pH 2.5 and 0.5-5.0 g/L
(NH4)2SeO4 was obtained at 1000 A m-2. The addition of (NH4)2SeO4 also resulted in a
P
CE

lower selenium content in the manganese deposit than that of H2SeO3.

The addition of sulfite or selenite or selenate resulted in the conversion of -Mn to -

AC

Mn (Janickis, 1966a). The introduction of selenite and selenate significantly decreased

the dissolution of γ-manganese (Suliakas et al., 1976a, 1976b). This inhibiting behavior
resulted from the protective properties of their reduction products.

In the presence of silver, Ag2Se was found in the manganese deposit with the addition
of H2SeO3 while with the addition of (NH4)2SeO4, Ag and Ag2Se were found in the
manganese deposit (Suliakas et al., 1976a, 1976b). In the presence of Cu, SeO42- is more
effective than SeO32-. CuSe was detected in the manganese deposit (Kuodyte et al.,
1975).

Selenite is reduced to elemental selenium by an electrochemical mechanism.

Selenide in the manganese deposit is formed by a secondary chemical reduction. SeO42-
is chemically reduced by manganese to manganese selenide and H2Se (Suliakas et al.,

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1978). Selenate is not reduced electrochemically and therefore selenium occlusions in the
cathodic layer were less than those in the case of selenite (Suliakas et al., 1978; Yanitskii
et al., 1984). The dissolution of pure manganese in the electrolyte containing selenite and
selenate was accompanied by the reduction of SeO42- to H2Se, which led to the formation

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of MnSe. In the case of H2SeO3, elemental selenium was found.

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Viskelis et al. (1984) reported that in the pH range 2 to 9.5, both selenite and selenate
significantly suppressed the hydrogen evolution. Beyond that region, selenite and

SC
selenate had a little effect on hydrogen evolution. The Se-containing additives did not
retard the discharge of hydroxonium ions, but significantly inhibited the discharge of

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H2O or possibly NH4+. At a pH above 9.5, the reduction products of selenite or selenate
were less effective to suppress the hydrogen evolution probably due to the change in the
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reduction products or the shift in their speciation distribution with increasing pH.
Gamali and his coworkers (Gamali and Stender, 1962b, 1967; Gamali et al., 1975;
Rybalskaya et al. 1974) conducted systematic studies on the effect of selenium and sulfur
D

compounds on manganese deposition. They first investigated the effect of O2, SO32-,
TE

SeO32- and TeO32- on the hydrogen evolution from ultra-pure (NH4)2SO4 solution. The
order of the effect on increasing hydrogen overpotential is as follows: O2 < SO32- <
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SeO32- < TeO32- (Figure 5). With increasing the concentrations of the additives, the
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hydrogen overpotential first increased, then reached a maximum value around 0.03 mM
and finally decreased. They found that manganese displaced sulfur, selenium and
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tellurium from the solution containing SO32-, SeO32- and TeO32- and the surface was
coated with a white, red or black film. Hydrogen evolution ceased at the coated regions.
The reduction products of sulfur, selenium and tellurium were adsorbed on the electrode
and poisoned its active points for hydrogen evolution.

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1.3
H2 atmosphere
Air
1.2 0.04 mM SO3‫־‬²

H 2 overpotetential / V
0.04 mM SeO3‫־‬²
0.04 mM TeO3‫־‬²

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1.1

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1.0

SC
0.9

0.8

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-3.0 -2.5 -2.0 -1.5 -1.0 -0.5
-2
Log (i / A cm )
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Figure 5 Hydrogen overpotential vs. log (current density) on manganese at 25 C in the
presence of O2, SO32-, SeO32- and TeO32-. Electrolyte: 0.5 M (NH4)2SO4 and pH 7.5
(Replotted from Gamali and Stender, 1962b).
D
TE

SO32- and SeO32- suppressed the harmful effects of certain organic compounds such as
fish glue and polyacrylamide on the manganese deposition (Gamali and Stender, 1967).
P

Fish glue and polyacrylamide significantly decreased the manganese current efficiency.
CE

The harmful effect diminished with addition of 0.4 g/L or less H2SeO3 and H2SO3 or
colloidal S. In the presence of these additives, the deposition of -Mn was predominant.
AC

The addition of fish glue or polyacrylamide virtually did not affect the polarization
behavior (maximum potential difference at a constant current: 5-8 mV) whether or not
sulfite and selenite was added into the electrolyte. This small shift of potential cannot be
the cause of such a significant decrease in the manganese current efficiency because the
decrease in the Mn(II) concentration in the pure electrolyte from 40 to 14 g/L shifts the
potential of manganese deposition by 25-30 mV while the manganese current efficiency
is decreased slightly (4%). The organic additives were probably adsorbed on the cathode
and hindered the crystallization of the manganese atoms, thus enhancing manganese
dissolution and hydrogen evolution. The reduction products of selenite and sulfite –
colloidal Se and S were also adsorbed on the cathode, inhibiting the discharge of Mn(II)
and shifting the potential to more negative values where the crystal lattice of -Mn is

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easily formed, thus eliminating the deleterious effect of the organic additives. A
simultaneous replacement of the adsorbed organic additives on the electrode surface by
colloidal Se and S or a screening effect on the organic additives was also possible.
The effects of sulfite and selenite on manganese electrodeposition from

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ethylenediamine electrolyte were studied by Rybalskaya et al. (1974). Like the
deposition from ammonia-ammonium electrolyte, in the presence of SO32- and SeO32-, -

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manganese was deposited. However a high current efficiency for the manganese

SC
deposition from ethylenediamine electrolyte was not obtained in the presence of SO32-
and SeO32- like that from ammonia-ammonium electrolyte, indicating ammonia or

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ammonium plays an important role to facilitate manganese deposition.

With addition of selenate, there was no limiting current like that without additive
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(Figures 6) (Gamali et al., 1975). Without addition of selenate, coarsely crystalline -Mn,
whose lattice had a high degree of perfection, was formed in the low polarization region.
The manganese crystallization proceeded without significant hindrance, and hydrogen
D

was evolved through electrochemical reduction of hydrogen donors (Reaction 17). As

TE

the current density increased, the limiting current appeared. The coherent scattering of
the -Mn deposits decreased significantly, micro-stresses arose, and the lattice parameters
P

changed, which indicates that the regularity of the lattice structure was disturbed and
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gave rise to the hindrance of the crystallization and then the increase in the surface
concentration of adsorbed manganese atoms. Therefore the rate of hydrogen evolution
AC

by Reaction 19 (secondary liberation of hydrogen) increased.

With addition of selenate, the overpotential for hydrogen evolution increased by 40-
50 mV in the whole potential range. In the low polarization region, the addition of
selenate inhibited the deposition of γ-Mn and facilitated the deposition of -Mn. The
overall effect of selenate is the inhibition of manganese deposition as indicated from the
increase in the overpotential of manganese deposition. Because only -Mn was
deposited, the surface condition did not change with increasing cathodic polarization as
significantly as that without addition of selenate. Therefore in the high polarization
region, the overpotential decreased as the manganese crystallization was not hindered
significantly. Besides, the addition of selenate probably facilitated the discharge of one

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manganese species. Therefore there was only one well-defined Tafel line. A high
manganese current efficiency resulted from the facilitation of the crystallization of
manganese because it resulted in a lower surface concentration of adsorbed manganese
and then suppressed the secondary liberation of hydrogen. These effects of the additives

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were due to their reduced or decomposed products (S, Se, S2- and Se2-).

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1.46
Mn (no additive)
1.44 H2 (no additive)

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Mn (2 g/L (NH4)2SeO4)
1.42 H2 (2 g/L (NH4)2SeO4)
Potential vs. SHE / V

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1.40

1.38 MA
1.36

1.34
D

1.32
TE

-2.5 -2.0 -1.5 -1.0 -0.5 0.0

Log (current density / A cm -2)
P

Figure 6 Potential vs. log (current) for manganese deposition and hydrogen evolution in
CE

0.5 M MnCl2, 4 M NH4Cl and 2.5 M NH3 (Replotted from Gamali et al., 1975).

Dhananjayan (1970a, 1970b, 1970c) studied the effect of S, Se and Te on the

AC

structure of manganese deposits and found that -Mn was produced in pure MnSO4-
(NH4)2SO4 electrolyte while -Mn was produced with the addition of S, Se and Te
compounds. -Mn can be deposited on -Mn in the absence of S and Se compounds
while -Mn can be deposited on -Mn in the presence of S and Se compounds.

Agladze and his co-workers (Abuladze et al., 1975; Agladze et al., 1975; Agladze et
al., 1979; Agladze et al., 1986; Gofman and Sadunishvili, 1974; Gofman et al.,1975;
Kabzinadze et al., 1980) conducted a series of studies on the effect of sulfite and
selenium compounds on manganese electrodeposition. Pyridine was added to the
MnSO4-(NH4)2SO4 electrolyte and then reduced to piperidine at a fairly negative
potential. Piperidine inhibited the normal crystallization of manganese. The addition of

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0.1 g/L H2SeO3 eliminated the above inhibiting effect due to the displacement of the
organic surfactant by SeO32-, which was confirmed by differential capacitance
measurement at a mercury electrode (Agladze et al., 1975; Gofman and Sadunishvili,
1974).

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Abuladze et al. (1975) investigated the distribution of selenium in the electrolyte,

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manganese deposit and the colloidal red suspended material during manganese
electrowinning and reported that at 70-80 C, SeO42- introduced in the catholyte almost

SC
completely went into the anolyte. This indicates that SeO42- was practically not
discharged with manganese ions.

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In the presence of 0.1 g/L (NH4)2SeO4, the current efficiency of manganese
deposition decreased slightly with decreasing pH from 7 to 4 while it decreased from 85
MA
to 66% with increasing temperature from 20 to 80 C (Agladze et al., 1979; Gofman et
al., 1975). The optimized concentration of (NH4)2SeO4 depended on the temperature.
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The addition of organic substances containing azo or sulfamide groups decreased the
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Se content in the manganese deposit and increased the current efficiency of manganese
deposition. This favorable effect of organic additives was explained by their adsorption,
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their binding of low valency forms of Se and their blocking effect in the near-electrode
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layer (Agladze et al., 1979).

The reduction of SeO32- and SeO42- was studied using Mn, Zn and Ni amalgams
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(Kabzinadze et al., 1980). In the presence of SeO32-, the potential of Mn and Zn

amalgams shifted in a positive direction and the amalgam electrodes were covered with a
film of metal selenides while in the case of the Ni amalgam, no Se2- was formed since the
potential was not low enough to reduce SeO32- to Se2-. The polarization of Pt and Hg
electrodes in the solution containing 0.01-0.05 g/L SeO32- resulted in the reduction of
SeO32- to Se2- (or HSe-) via two steps. The polarization of amalgams in the solution
containing selenate gave metal selenides.

The effect of Se on the hydrogen content in the manganese deposit was investigated
at different pHs (Agladze et al., 1986). In the absence of SeO32-, the hydrogen content
increased rapidly with increasing pH. The addition of SeO32- decreased the hydrogen
content. The introduction of hydrogen resulted in an unstable tetragonal modification of

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Mn, the destruction of which was inhibited by OH-1. In the presence of SeO32-, the
development of the stable cubic modification of Mn was related to the displacement of
manganese hydroxide by the products of cathodic reduction of the anion (SeO32-) and
strong bond of Se-H, which prevent stabilization of the tetragonal Mn (-Mn).

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Shulgina and Polukarov (Polukarov, 1969; Sulgina and Polukarov, 1966a, 1966b)

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investigated the effect of H2SeO3 and H2TeO3 on manganese deposition from 108 g/L
MnSO4- 100 g/L (NH4)2SO4 electrolyte and found that the addition of 0.1 g/L HeSeO3

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increased the current efficiency of manganese deposition from 50 to 95-96% at 25 C and
pH 3.1-5.0 in the current density range from 2000 to 3000 A m-2. The addition of

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H2SeO3 also increased the brightness and hardness of manganese deposits. It was
proposed that colloidal selenium was formed on the cathode surface and acted as nuclei
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for manganese deposition in preference to hydrogen evolution.

Lewis et al. (1976) reported that the Se content in the manganese deposit increased
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with Se concentration in the catholyte (40 g/L Mn as MnCl2 and 120 g/L NH4Cl at pH 6
and 40 C) and it was lower with addition of Se(VI) (selenate) than Se(IV). The valence
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of the selenium added did not have a pronounced effect on current efficiency.
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Radhakrishnamurthy and Reddy (1977) reported that the addition of selenious acid
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into 0.2 M MnSO4 and 1 M (NH4)2SO4 solution increased hydrogen overpotential. The
effect of selenious acid on the manganese deposition is indirect and similar to that of SO2.
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Oniciu and his co-workers (Ilea et al., 1997a, 1999; Oniciu et al., 1992, 1995)
concluded that the increase in the manganese current efficiency is due to the increase in
hydrogen overpotential. Selenite and Mn2+ have a synergetic effect on hydrogen
evolution.

Gonsalves and Fletcher (1990) investigated the manganese deposition from MnCl2–
NH4Cl solution and found that the selenite adsorbed in the potential range of the
manganese deposition/dissolution has several effects. It certainly inhibits hydrogen
evolution and probably retards the Mn(II)/Mn couple. The net effect is to increase the
manganese current efficiency. Since the selenite has a strong inhibiting effect on the
hydrogen evolution on manganese, the corrosion of manganese is significantly decreased.

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Agladze et al. (2000) found that at a constant cathode potential, the rate of manganese
deposition from an ammonium sulfate electrolyte prepared using unpurified chemicals
(reagent grade) was about one tenth of that from the electrolyte prepared using chemicals
purified by double crystallization in the low potential region. The electrolyte probably

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contained inorganic and organic impurities retarding manganese electrodeposition. The
addition of selenate increased the rate of manganese deposition from unpurified

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electrolyte by about one decade since it eliminated the harmful effect of impurities and

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suppressed the hydrogen evolution. It was explained that the presence of selenium salt
stabilizes the active form of manganese deposits and reduces the chemical dissolution of

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manganese. The addition of selenate increased the overpotential of manganese deposition
in the low polarization region and decreased the overpotential of manganese in the high
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polarization region. This effect of selenate on the polarization behavior of manganese
deposition in ammonium sulfate solution was similar to that in ammonium chloride
solution (Gamali et al., 1975).
D

From the above discussion, the addition of selenite (or selenate) and sulfite has the
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following effects on the manganese electrodeposition process: (1) increases the

overpotential of hydrogen evolution, (2) facilitates the crystallization of stable -
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manganese, (3) improves the leveling effects of the electrolyte, and (4) increases the
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manganese current efficiency. The above effects result from their reduction products.
The leveling effect can improve the local current distribution uniformity and suppress the
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formation of galvanic micro-cells, preventing the re-dissolution of manganese and then

increasing the manganese current efficiency. The formation of stable -manganese
suppresses the dissolution of manganese and increases the manganese current efficiency.
The increase in the overpotential of hydrogen evolution on both manganese and
impurities retards the discharge of hydrogen donors and suppresses the dissolution of
manganese. The formation of insoluble selenides and sulfides with impurities contributes
to the increase in the current efficiency of manganese deposition since the formation of
the galvanic micro-cells was eliminated or impeded.

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5.2. Use of Alternative Additives

Although selenium compounds can effectively improve manganese electrodeposition,

electrolytic manganese is contaminated with selenium. Selenium compounds in the
electrolyte decompose to form colloid and precipitates, resulting in a high consumption

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of selenium and plugging of the diaphragm. Besides selenium and sulfur compounds,

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many other additives especially organic compounds, such as carboxylic acids, water-
soluble polyacrylamide, guar gum and thiourea, have been tested to improve manganese

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electrodeposition (Coleman and Griffin, 1984; Goddard and Habsen, 1979; Griffith,
1950; Hammerquist, 1951; Jacobs, 1962; Wei et al., 2010). Some organic additives were

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used in combination with sulfite and selenite. Polyacrylamide polymer has commercially
been used in manganese production to improve manganese deposit quality. However
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there is little information about its performance in manganese electrowinning.

6. Conclusions
D
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The hydrogen evolution on manganese in Mn-free electrolyte is limited by the

discharge of hydrogen donors (H3O+, H2O and NH4+) and it is very slow compared to
P

manganese electrodeposition while the hydrogen evolution from Mn-containing

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electrolyte exhibits similar electrochemical behavior to that of manganese deposition

since hydrogen evolution is catalyzed by manganese deposition.
AC

The manganese electrodeposition is very sensitive to the composition and purity of

the electrolyte. In the initial polarization region, the manganese deposition obeys a linear
Tafel relationship with a slope of 0.03 V per decade and the deposition of -Mn is
dominant. In the high polarization region, it deviates from the initial linear Tafel
relationship and the slope of the plot of the overpotential against logarithm of current
increases because the discharged manganese species probably changes and the
manganese deposit structure shifts from -phase to -phase, resulting in the change in the
deposit surface condition.

Heavy metal impurities such as Cu, Ni and Co are co-deposited with manganese, and
catalyze the dissolution of manganese and then hydrogen evolution mainly through the
formation of galvanic micro-cells. A rough and non-compact deposit promotes the

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formation of galvanic micro-cells and enhances hydrogen evolution. A smooth, compact

deposit can significantly reduce the harmful effect of impurities. Therefore additives are
used to counteract the harmful effects of impurities and improve the deposit quality.
Selenite, selenate and sulfite are very effective additives. NH3 plays an important role to

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increase the manganese current efficiency with addition of selenite (or selenate) and
sulfite.

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The addition of selenite or selenate inhibits hydrogen evolution, increases the

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overpotential of manganese deposition in the low polarization region and decreases the
overpotential of manganese deposition in the high polarization region, facilitates the

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crystallization of -manganese, improves the leveling effect of electrolyte, and finally
improves the manganese current efficiency. The above effects result from the adsorption
MA
of their reduction products such as Se, Se2- and SeH-. The increase in the overpotential of
hydrogen evolution on both manganese and impurities retards the discharge of hydrogen
donors and then suppresses the dissolution of manganese, resulting in a higher
D

manganese current efficiency.

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In the low polarization region, the addition of selenite or selenate inhibits the
deposition of γ-Mn and facilitated the formation of -Mn. The overall effect of selenite
P
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or selenate is the inhibition of manganese deposition as the overpotential of manganese

deposition was higher than that without the addition of selenite or selenate. Since only -
AC

Mn was deposited in the presence of selenite or selenate, the surface condition did not
change with increasing cathodic polarization as significantly as that without addition of
selenite or selenate. Therefore in the high polarization region, the overpotential for
manganese deposition decreases with the addition of selenite or selenate as the
manganese crystallization is not hindered like that without addition of selenite or selenate

The leveling effect of selenite or selenate contributes to increasing manganese

efficiency through suppression of the formation of galvanic micro-cells and improving
the current distribution uniformity. On a rougher surface, more galvanic micro-cell are
formed, and the local real current density deviates more from the current density
corresponding to the highest manganese current efficiency, resulting in a lower
manganese current efficiency. The formation of insoluble selenides with impurities also

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contributes to the increase in the current efficiency of manganese deposition. The

optimized concentration of selenite or selenate is a function of temperature, the
composition of electrolyte and the concentration of impurities. Sulfite has similar effects,
but to lesser degree.

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Alternative additives should inhibit hydrogen evolution significantly and manganese
deposition to an appropriate degree, promote the formation of α-Mn, function as a

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leveling agent, have a minimum contamination of manganese deposit and reducing

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capacity to stabilize the electrolyte. They may be used with other additives such as
sulfite to maximize the performance. While many of the studies have included

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investigations of the manganese electrocrystallization process, further work should be
done on how chemical factors affect deposit morphology, grain structure and other
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mechanical structural parameters of the manganese electrodeposit.
D

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Highlights
► Mn electrodeposition, H2 evolution and the effects of impurities have been reviewed.
► Successful Mn EW relies on optimum operation conditions and on the use of

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appropriate additives.
►The effects of the additives (e.g. sulfite and selenite) have been extensively discussed.

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► A better additive has always been desirable for a cost effective Mn EW process.
► The guidelines for the selection of new additives are proposed.

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