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Journal of Magnesium and Alloys 9 (2021) 1644–1655

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Development of a novel electrolytic process for producing high-purity
magnesium metal from magnesium oxide using a liquid tin cathode
Tae-Hyuk Lee a, Toru H. Okabe b, Jin-Young Lee a,c, Young Min Kim c,d, Jungshin Kang a,c,∗
a Korea Institute of Geoscience and Mineral Resources, 124 Gwahak-ro Yuseong-gu, Daejeon 34132, Republic of Korea
b Instituteof Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505, Japan
c University of Science and Technology, 217 Gajeong-ro Yuseong-gu, Daejeon 34113, Republic of Korea
d Korea Institute of Materials Science, 797 Changwondae-ro, Seongsan-gu, Changwon, Gyeongnam, 51508, Republic of Korea

Received 1 September 2020; received in revised form 23 November 2020; accepted 3 January 2021
Available online 20 February 2021

Abstract
The current electrolytic processes for magnesium (Mg) metal have several disadvantages, such as anhydrous magnesium chloride (MgCl2 )
preparation and generation of harmful chlorine (Cl2 ) gas. To overcome these drawbacks, a novel Mg production process to produce high-purity
Mg metal directly from magnesium oxide (MgO) was investigated in this study. The electrolysis of MgO was conducted using a liquid tin
(Sn) cathode and a carbon (C) anode in the eutectic composition of a magnesium fluoride (MgF2 ) – lithium fluoride (LiF) molten salt under
an applied voltage of 2.5 V at 1053 – 1113 K. Under certain conditions, the Mg – Sn alloys with Mg2 Sn and Mg (Sn) phases were obtained
with a current efficiency of 86.6 % at 1053 K. To produce high-purity Mg metal from the Mg – Sn alloy, vacuum distillation was conducted
at 1200 – 1300 K for a duration of 5 – 10 h. Following the vacuum distillation, the concentration of Mg in the Mg – Sn alloy feed decreased
from 34.1 to 0.17 mass%, and Mg metal with a purity of 99.999 % was obtained at 1200 K. Therefore, the electrolytic process developed
here is feasible for the production of high-purity Mg metal from MgO using an efficient method.
© 2021 Chongqing University. Publishing services provided by Elsevier B.V. on behalf of KeAi Communications Co. Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)
Peer review under responsibility of Chongqing University

Keywords: Magnesium; Magnesium oxide; Electrolytic process; Liquid tin cathode; Vacuum distillation.

1. Introduction shown in Fig. 1, Mg is produced commercially either through

Magnesium (Mg) is well known for its superior physical
properties, such as its lightweight, high specific strength, high
stiffness, and good damping capacity. These attractive prop-
erties make it very useful in diverse fields such as transporta-
tion, electronics, and other industrial fields [1,2]. In particular,
the demand for Mg will increase in the automobile industry
to improve fuel efficiency and reduce carbon dioxide (CO2 )
gas emissions [3].
Fig. 1 shows an outline of the materials flow for the com-
mercial processes to produce primary Mg metal [4-6]. As
∗ Corresponding author at: Korea Institute of Geoscience and Mineral Re-
sources, 124 Gwahak-ro Yuseong-gu, Daejeon 34132, South Korea.
E-mail addresses: t.lee@kigam.re.kr (T.-H. Lee), okabe@iis.u-tokyo.ac.jp
(T.H. Okabe), jinlee@kigam.re.kr (J.-Y. Lee), ymkim@kims.re.kr (Y.M.
Kim), jskang@kigam.re.kr, jskang@ust.ac.kr (J. Kang).
the thermal reduction or electrolytic method. Approximately
81 % of global primary Mg metal is produced by smelters in
China using the thermal reduction process, known as the Pid-
geon process. The Pidgeon process is based on the thermal
reduction of calcined dolomite (MgO·CaO) at 1373 – 1473 K
under vacuum, with ferrosilicon (Fe·Si) as a reducing agent.
The reduced Mg vapor is collected as a Mg crown (metal
deposit) in a condenser [6-8]. However, the Fe·Si is produced
through the carbothermic reaction at 1823 K [8], which is an
energy-intensive process. In addition, the use of coal as a
heat source generates a large amount of sulfur oxide (SOx )
gas. Furthermore, there are disadvantages such as high labor
requirements and lower productivity [6,9,10].
The electrolytic process is based on the molten salt elec-
trolysis of anhydrous magnesium chloride (MgCl2 ) or car-
nallite (MgCl2 ·KCl) at 928 – 993 K, derived from brines, as

https://doi.org/10.1016/j.jma.2021.01.004
2213-9567/© 2021 Chongqing University. Publishing services provided by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/) Peer review under responsibility of Chongqing University
 T.-H. Lee, T.H. Okabe, J.-Y. Lee et al. / Journal of Magnesium and Alloys 9 (2021) 1644–1655
Electrolytic process
(a) (b)
Brine (Mg2+) Brine (Mg2+)
Concentration Concentration
MgCl2·KCl·6 H2O MgCl2·6 H2O
Condensation & Condensation &
Dehydration Dehydration
MgCl2·KCl MgCl2
DSM / VAMI Magcorp
Mg (33 kt) Mg (58 kt)
World primary magnesium production in 2015 : 898.3 kt (Roskill, 2016)
Fig. 1. Flowchart of the commercial processes for the production of primary Mg metal: (a) DSM / VAMI, (b) Magcorp, (c) Pidgeon, and (d) Bolzano processes.
shown in Fig. 1 [6]. As a result, liquid Mg metal and chlorine
(Cl2 ) gas are produced at the cathode and anode, respectively.
The Magcorp [11], DSM [12], and VAMI processes [13] are
the commercial Mg production processes. However, the elec-
trolytic process also has several disadvantages such as the
high capital cost, generation of Cl2 gas, and high energy-
intensity for the preparation of MgCl2 [4,6]. Thus, thermal
reduction and electrolytic processes used to commercially pro-
duce Mg metal are energy-intensive and cause several envi-
ronmental risks such as SOx and Cl2 gas generation.
Several studies have been conducted to resolve the draw-
backs of the commercial Mg production processes. Most of
them focused on the aspects of an eco-friendly and efficient
Mg production. Wada et al. [14] investigated the Pidgeon pro-
cess using a microwave instead of coal. In addition, Aviezer
et al. [15] suggested a silicothermic reduction of magnesium
oxide (MgO) obtained from seawater using the ion-exchange
method. However, these processes still used Fe·Si as a reduc-
ing agent. Several researchers have suggested the use of solar
thermal energy to reduce energy consumption. However, Mg
metal production using solar thermal energy does not make
economic effects [16,17].
Among the several processes, the solid oxide membrane
(SOM) process is promising owing to its environmental-
friendly Mg production. The SOM process was developed
to produce Mg metal from MgO using a yttria-stabilized zir-
conia (YSZ) membrane. In the SOM process, MgO dissoci-
ates into Mg metal and oxygen (O2 ) gas during the elec-
trolysis. Oxygen anions migrated through the YSZ mem-
brane and are oxidized at the silver (Ag) anode. There-
fore, the preparation of MgCl2 is not necessary, and O2 gas
evolves at the anode. However, the current efficiency de-
creased from 90 to 40 – 50 % when the electrolysis contin-
1645
Thermal reduction process
(c) (d)
Dolomite Dolomite
(MgCO3·CaCO3) (MgCO3·CaCO3)
Calcination Calcination
MgO·CaO MgO·CaO
Pidgeon Bolzano
Mg (712 kt) Mg (16 kt)
ues without argon (Ar) gas bubbling. In addition, the degra-
dation of the YSZ membrane occurs during the electrolysis
without the decrease of the partial pressure of Mg in flux
[18–20].
Proof-of-concept of the molten salt electrolysis of MgO
using liquid metal cathode was investigated by the authors
[21]. In this study, for the production of high-purity Mg metal
directly from MgO feed without the use of MgCl2 feed, the
efficient molten salt electrolysis of MgO using a liquid tin
(Sn) cathode in a simple electrolytic cell and the vacuum
distillation of Mg alloys were investigated. Fig. 2 shows the
flowchart and schematic diagram of the novel Mg production
process investigated in this study. Because MgO is used as a
feedstock, the production of anhydrous MgCl2 via an energy-
intensive method is not necessary, and the generation of Cl2
gas during electrolysis can be prevented. The use of liquid
Sn cathode can hinder the reaction between Mg metal and
generated gas such as O2 at the anode because Mg – Sn alloy
with high-density is produced on the bottom of the electrolytic
cell. Owing to the use of the liquid Sn cathode, a simple
electrolytic cell, similar in structure to that used in the Hall-
Heroult process, was employed in this study. Finally, high-
purity Mg metal containing a low concentration of iron (Fe)
can be obtained owing to the vacuum distillation.
2. Experimental
2.1. Cyclic voltammetry
The materials used in this study are listed in Table 1, and a
schematic diagram and photographs of the experimental ap-
paratus used for cyclic voltammetry (CV) measurements is
shown in Fig. 3. The eutectic composition of magnesium flu-
1646 T.-H. Lee, T.H. Okabe, J.-Y. Lee et al. / Journal of Magnesium and Alloys 9 (2021) 1644–1655

Table 1
Materials used in this study.

Materials Form Purity (%) Supplier Note

MgF2 Powder 99.9 up Kojundo Chemicals Inc Anhydrous
LiF Powder 99.9 up Kojundo Chemicals Inc Anhydrous
MgO Powder 99.99 up Kojundo Chemicals Inc
Sn Shot 99.9 R&D Korea 1 – 3 mm
Mo Wire 99.95 up Alfa Aesar Chemical Co. Ltd. φ 0.5 mm
Pt Wire 99.95 up Alfa Aesar Chemical Co. Ltd. φ 0.5 mm
C Rod 99.9 SGL carbon Group Graphite, φ 3 mm
C Rod 99.9 SGL carbon Group Graphite, φ 8 mm
Ni Wire 99.5 up Alfa Aesar Chemical Co. Ltd. φ 1 mm
Ag Shot 99.99 Sungeel Himetal φ 1 – 3 mm
Al2 O3 -based Paste – Toagosei Co., Ltd. Aron Ceramic D
Al2 O3 Tube 99.8 up Samhwa Ceramic Co. φ = 6 mm, t = 1 mm

(a) MgO (s) Sn (l) air oven. To prepare the experiment, the mixture of MgF2 –
LiF or MgF2 – LiF – MgO was placed in a carbon (C) cru-
cible. In addition, 50 g of Ag shot was placed at the bottom
Electrolysis of the crucible to absorb the metals generated during the pre-
electrolysis. The crucible was placed inside a stainless-steel
reactor, and the electrodes that were assembled with the top
Mg-Sn (l) COx (g) flange were set up with the reactor, as shown in Fig. 3(b) and
(c). Then, the reactor was installed in the electric furnace. A
molybdenum (Mo) wire and C rod were used as the working
Vacuum distillation and counter electrodes, respectively during a cathodic sweep.
Meanwhile, C rod and Mo wire were used as the working
and counter electrodes, respectively during an anodic sweep
Mg (g) Sn (l) [22]. A platinum (Pt) wire was used as the quasi-reference
electrode.
After the assembly was finished, the reactor was evacuated
for 10 min, and the reactor was filled with Ar gas (purity:
(b) 99.9999 %) until the internal pressure reached 1 atm. After
COx (g) the final filling with Ar gas, Ar gas flowed at a controlled
Carbon
rate using a mass flow controller (MFC) while the internal
pressure of the reactor was maintained at 1 atm. Then, the
temperature was increased and kept at 773 K for 24 h to re-
move all residual moisture in the mixture of MgF2 – LiF or
Mg (g) MgF2 – LiF – MgO. Subsequently, the temperature was in-
creased and kept at 1083 K, and the CV measurements were
performed using the potentiostat (Model no.: VMP3, booster:
MgO in MgF2–LiF VMP3B, 2 A – 20 V, Biologic Science Instruments).
molten salt

Mg - Sn (l) Mg - Sn (l)
2.2. Electrolysis of MgO using liquid tin cathode

Refractory After the decomposition voltage of MgO was measured

Drain
Fig. 2. A novel Mg metal production process investigated: (a) flowchart and
(b) schematic diagram.
oride (MgF2 ) and lithium fluoride (LiF) was used as the elec-
trolyte and MgO was added as the Mg feedstock. Prior to
their use, MgF2 and LiF were dried for more than 72 h at
453 K in a vacuum oven (Model no.: VOS-601SD, EYELA)
and MgO was dried for more than 72 h at 343 K using an
using CV measurements, the electrolysis of MgO was carried
out. The MgO was weighed and added in the MgF2 – LiF
mixture, equivalent to 5 mass% of the electrolyte. Prior to
all electrolysis experiments, pre-electrolysis was conducted to
eliminate residual impurities in the molten salt at 1083 K. A
constant current of 0.5 A was applied for 4 h between the
C anode and nickel (Ni) cathode using the potentiostat. After
the pre-electrolysis was finished, the electrodes were removed
from the molten salt and the reactor was allowed to cool to
room temperature.
 T.-H. Lee, T.H. Okabe, J.-Y. Lee et al. / Journal of Magnesium and Alloys 9 (2021) 1644–1655 1647

Fig. 3. Experimental apparatus for cyclic voltammetry: (a) schematic diagram, (b) photographs of electrodes assembled with the top flange, and (c) stainless-
steel reactor.

Table 2 cible, which was assembled with a C rod shielded by Al2 O3

Experimental conditions for electrolysis of MgO using a liquid Sn cathode tube. The gap between the C rod and the Al2 O3 tube was
in a MgF2 – LiF molten salt.
filled using an Al2 O3 -based paste. Afterward, the Al2 O3 cru-
Exp. noa Temp., T / K Cathode weight, wc / g Time, t’ / ks cible was placed at the bottom of the C crucible, as shown
200420 1053 6.174 8.8 in Fig. 4(a) and (c). For the electrolysis of MgO at 1053 –
190930 1053 6.117 14.2 1113 K, 2.5 V was applied for 7.7 – 28.2 ks using the potentio-
190731 1053 6.022 28.2 stat. After the electrolysis, the reactor was gradually cooled
200403 1083 6.088 8.7 down to room temperature in the electric furnace, and the
191010 1083 6.052 10.4
Mg – Sn alloys produced were separated from the Al2 O3
190728 1083 6.099 21.7
crucible. The salt on the surface of the Mg – Sn alloys was
200401 1113 6.173 7.7
200330 1113 6.157 12.7
completely removed using abrasive paper.
200409 1113 6.187 18.1
a
2.3. Vacuum distillation
: Experimental conditions.
1) Weight of MgF2 = 270.0 g, weight of LiF = 230.0 g, weight of
MgO = 25.0 g. In order to demonstrate the separation of Mg metal from
2) Applied cell voltage = 2.5 V. the Mg – Sn alloy obtained through the electrolysis of MgO,
3) Carbon crucible was used for the electrolysis. vacuum distillation of the Mg – Sn alloy prepared from the
4) Al2 O3 crucible (φ 18 mm (O.D), 25 mm (h), 1.5 mm (t)) was used for melting of Mg and Sn was conducted. To prepare the Mg –
containing Sn metal.
5) Carbon rod (φ 8 mm × 50 mm (h)) was used for anode.
Sn alloy, a mixture of 34 mass% of Mg and 66 mass% of Sn
was charged in a C crucible, and it was melted under vacuum
at 1013 K for 15 h, using an electric furnace. The melting was
After pre-electrolysis, the electrolysis of MgO was con- conducted to use the sufficient amount of Mg – Sn alloy feed
ducted at 1053 – 1113 K using the liquid Sn cathode and C for the vacuum distillation.
anode. Fig. 4 shows the schematic of the experimental appa- Fig. 5 shows the schematic and photographs of the vertical
ratus used for the electrolysis of MgO, and the experimental type of vacuum distillation reactor used. The Mg – Sn alloy
conditions are listed in Table 2. The liquid Sn cathode was was placed at the bottom of the reactor and the open end of
prepared by holding Sn metal in an alumina (Al2 O3 ) cru- the reactor was plugged using a silicone stopper and evacu-
1648 T.-H. Lee, T.H. Okabe, J.-Y. Lee et al. / Journal of Magnesium and Alloys 9 (2021) 1644–1655

Fig. 4. (a) Schematic of the experimental apparatus for electrolysis of MgO, (b) appearance of the Sn metal used for cathode, and (c) Sn metal cathode.

ated during the experiments using a rotary pump (Model no.: sion electron microscopy (TEM: Talos F200X, FEI) with EDS
GLD-201B, ULVAC KIKO, Inc.). The steel reactor was posi- (Super-X EDS, Bruker).
tioned in the electric furnace preheated to 1200 – 1300 K for
a duration of 5 – 10 h. After the completion of the distillation, 3. Results and discussion
the reactor was immediately removed from the furnace and
allowed to cool down to room temperature. The reactor was 3.1. Cyclic voltammetry
cut, and the samples were collected.
Fig. 6 shows the result of the CV measurement of the
MgF2 – LiF molten salt before pre-electrolysis and MgF2
– LiF molten salt after pre-electrolysis, and the addition of
2.4. Characterization
MgO in MgF2 – LiF molten salt at 1083 K. The potential in
the results of the CV measurement was not corrected for the
The microstructure and elements distribution of the Mg –
ohmic drop. Before pre-electrolysis, a large cathodic current
Sn alloys were characterized using a field emission scanning
was observed at – 1.68 V (vs Pt quasi-reference electrode),
electron microscope (FE-SEM: JSM-7000F, JEOL) coupled
which corresponds to the reduction of Mg2+ to Mg in the
with an energy dispersive X-ray analyzer (EDS: INCA, Ox-
molten salt in Eq. (1). In addition, the large anodic current
ford Instruments) after the samples were mechanically pol-
was observed at 3.0 V (vs Pt quasi-reference electrode), which
ished. The crystalline phases of the Mg – Sn alloys were
corresponds to the generation of fluorine (F2 ) gas from the
analyzed using X-ray diffraction (XRD: SmartLab, Rigaku,
oxidation of F− , in Eq. (2). Then, small cathodic and anodic
Cu-Kα radiation). Additionally, the concentration of elements
currents were observed at – 1.08 V and 0.21 V (vs Pt quasi-
in the samples was determined using an inductively cou-
reference electrode), respectively. These results indicated that
pled plasma optical emission spectroscopy (ICP-OES: Optima
cations and anions of the impurities contained in the MgF2 –
5300DV, Perkin Elmer) or glow discharge mass spectroscopy
LiF molten salt were reduced and oxidized, respectively.
(GD-MS: GD90RF, MSI). The crystal orientation and struc-
ture of the produced Mg obtained after vacuum distilla- Mg2+ (in molten salt ) + 2 e− = Mg (l ) (1)
tion process were distinguished by using electron backscat-
ter diffraction (EBSD: OIM analysis, EDAX) and transmis- F− (in molten salt )= 1/2 F2 (g) + e− (2)
 T.-H. Lee, T.H. Okabe, J.-Y. Lee et al. / Journal of Magnesium and Alloys 9 (2021) 1644–1655 1649

(a) Vacuum (b)

Cooling
water

Z1

Z2

Z3

Z4

Z5

Z6

Z7
Mg-Sn
alloy 50 mm

Fig. 5. Experimental apparatus for vacuum distillation; (a) schematic diagram

and (b) photograph of reactor.

Fig. 6(b) shows the result of the CV measurement of the

MgF2 – LiF molten salt after pre-electrolysis. There is no Fig. 6. The results of CV measurement of the (a) MgF2 – LiF molten salt be-
additional current except the reduction of Mg2+ to Mg at – fore the pre-electrolysis, (b) MgF2 – LiF molten salt after the pre-electrolysis,
1.67 V (vs. Pt quasi-reference electrode) and oxidation of F− and (c) the addition of MgO in MgF2 – LiF molten salt at 1083 K.
to F2 gas at 3.04 V (vs. Pt quasi-reference electrode). These
results indicated that the estimated decomposition voltage of Table 3
MgF2 is 4.71 V at 1083 K. Theoretical decomposition voltages of several fluorides and MgO at 1083 K
After the addition of MgO, the large cathodic current at [23].
– 1.67 V (vs. Pt quasi-reference electrode) was observed and Reaction Decomposition
two anodic currents were observed at 0.12 V and 2.99 V (vs. voltage, E° / V
Pt quasi-reference electrode), as shown in Fig. 6(c). The large LiF (s,l) = Li (l) +1/2 F2 (g) 5.31
anodic current corresponds to the oxidation of F− to F2 gas at MgF2 (s) = Mg (l, g) + F2 (g) 4.85
2.99 V (vs. Pt quasi-reference electrode). In addition, a small MgO (s) = Mg (l, g) + 1/2 O2 (g) 2.51
anodic current was observed at 0.12 V (vs. Pt quasi-reference MgO (s) + C (s) = Mg (l, g) + CO (g) 1.43
MgO (s) + 1/2 C (s) = Mg (l, g) + 1/2 CO2 (g) 1.48
electrode), which corresponds to the generation of CO2 gas
through the reaction of O2 gas from the oxidation of O2−
with the C electrode, in Eq. (3). Therefore, the estimated de-
composition voltages of MgO under C and MgF2 were 1.79 V tion of O2− which was caused by the low solubility of MgO
and 4.66 V, respectively, at 1083 K. However, the decomposi- in the MgF2 – LiF molten salt at 1083 K [24,25].
tion voltage of MgO under C was larger than its theoretical
decomposition voltage of approximately 0.3 V, as shown in −
Table 3 [23]. It is expected that a large overvoltage for the C (s) + x O2 (in molten salt ) = COx (g) + 2x e− (x = 1, 2 )
decomposition of MgO existed owing to the low concentra- (3)
1650 T.-H. Lee, T.H. Okabe, J.-Y. Lee et al. / Journal of Magnesium and Alloys 9 (2021) 1644–1655

Table 4
The results of electrolysis of MgO and analytical results of the Mg – Sn alloys obtained after electrolysis.

Exp. no. Average current, I / mA Current density, J / mA·cm−2 Current efficiency, ƞ (%)b Concentration of element i, Ci (mass%)a

Mg Al Fe Ni Sn
200420 592.8 399.4 86.6 9.0 0.51 N.D 0.09 Bal.
190930 [21] 625.1 421.2 82.1 12.7 0.12 N.D N.D Bal.
190731 464.7 313.1 85.7 18.1 0.34 N.D N.D Bal.
200403 583.7 393.3 81.6 8.3 0.09 N.D N.D Bal.
191010 [21] 821.9 553.8 84.8 12.6 0.21 N.D N.D Bal.
190728 559.1 376.6 74.7 15.8 0.51 N.D N.D Bal.
200401 721.1 485.9 81.9 8.5 0.11 N.D N.D Bal.
200330 692.3 466.5 82.9 13.0 0.19 N.D N.D Bal.
200409 776.8 523.4 71.3 15.2 0.28 N.D N.D Bal.
a : Determined by inductively coupled plasma optical emission spectrometry (ICP-OES) analysis, N.D: Not Detected (< 0.005 mass%).
b : Current efficiency (%) = (actual weight of Mg obtained × 100) / theoretical weight of Mg obtained.

Fig. 7. Binary phase diagram of Mg – Sn system and isobaric vapor pressure of Mg as a function of temperature and concentration of Mg.

3.2. Electrolysis of MgO using liquid tin cathode
Table 4 shows the results of the electrolysis of MgO using
a liquid Sn cathode and the analytical results of Mg – Sn al-
loys obtained. When the electrolysis of MgO was conducted
at 1053 K, the current efficiency was maintained at 82.1 –
86.6 % while the Mg concentration in the Mg – Sn alloy in-
creased to 18.1 mass%. Meanwhile, although the electrolysis
temperature increased to 1083 and 1113 K, the current effi-
ciency remained 82.9 – 84.8 % until the concentration of Mg
in the Mg – Sn alloy reached 12.6 and 13.0 mass%. However,
when the Mg concentration in the Mg – Sn alloy reached 15.8
and 15.2 mass%, the current efficiency decreased to 74.7 and
71.3 %, respectively, as shown in Table 4.
These results could be explained by the vapor pressure of
Mg (pMg ) in the Mg – Sn alloy. Fig. 7 shows the binary phase
diagram of the Mg – Sn system, with the isobaric line of the
pMg as a function of the temperature and the concentration
of Mg [26]. As shown in Fig. 7, the pMg increased with in-
creasing temperature or concentration of Mg in the Mg – Sn
alloy. Generally, it is known that when the pMg is larger than
0.01 atm, the Mg metal will evaporate during the electrolysis
[23,27]. As a result, when the pMg is considered, the maxi-
mum concentrations of Mg in the Mg – Sn alloy are 29.8,
26.7, and 22.6 mass% of the Mg – Sn alloy at 1053, 1083, and
1113 K, respectively. Therefore, when the concentration of Mg
in the Mg – Sn alloy reached 15.2 – 15.8 mass% at 1083 –
1113 K, Mg in the Mg – Sn alloy is expected to have evapo-
rated while the evaporation of Mg at 1053 K is limited until
the concentration of Mg in Mg – Sn alloy is 18.1 mass%. For
this reason, when the electrolysis was conducted at 1053 K,
current efficiency was maintained until 18.1 mass% Mg – Sn
alloy was produced while the current efficiency was decreased
71.3 – 74.7 % when 15.2 – 15.8 mass% Mg – Sn alloys were
produced at 1083 – 1113 K. Consequently, when the results
of the electrolysis of MgO and pMg were taken into consid-
eration, the electrolysis temperature of 1053 K is preferred.
As shown in Table 4, when the electrolysis of MgO was
conducted in MgF2 – LiF molten salt at 1053 – 1113 K, the
current efficiency was 71.3 – 86.6 % and was not close to
100 %. The evaporation of Mg from the Mg – Sn alloy
even though the experiments were conducted at 1053 K, the
 T.-H. Lee, T.H. Okabe, J.-Y. Lee et al. / Journal of Magnesium and Alloys 9 (2021) 1644–1655 1651

electrode position of the impurities during the electrolysis of

MgO, and reaction between the Mg – Sn alloy and Al2 O3
crucible could be the reasons.
Table 4 also shows the concentration of impurities in the
Mg – Sn alloys obtained after electrolysis. Aluminum (Al)
is the main impurity for Mg – Sn alloys. It is expected that
the Al originated from the Al2 O3 crucible used for holding
the liquid Sn cathode due to the reaction of the Mg in the
Mg – Sn alloy with the Al2 O3 crucible. However, it should be
noted that the concentration of Al in the Mg – Sn alloy is less
than 0.51 mass%, as shown in Table 4. These results indicate
that the effect of Mg in the Mg alloys on the reduction of
Al2 O3 crucible was not large owing to the low activity of Mg.
In addition, it was expected that the reduction of Al2 O3 was
suppressed by the Mgx AlOy layer formed from the reaction
of Al2 O3 and Mg at the surface of the Al2 O3 crucible.
Fig. 8 shows the results of the XRD analysis of the Mg
– Sn alloys obtained after electrolysis of MgO using a liquid
Sn cathode and C anode at 1053 – 1113 K for 7.7 – 28.2
ks. The XRD patterns of all of the Mg – Sn alloys obtained
reveal the presence of two sets of patterns. The major diffrac-
tion patterns can be well indexed to Mg2 Sn, and the other set
of patterns with lower intensities results from Sn (Mg), as
expected from the Mg – Sn phase diagram when the concen-
tration of Mg is 8.3 – 18.1 mass%, as shown in Fig. 7 [26].
Fig. 9(a), (d), and (g) show the appearance of the Mg – Sn
alloys obtained after electrolysis of MgO at 1053, 1083, and
1113 K using a Sn cathode, respectively. A lump of the Mg –
Sn alloys was obtained after electrolysis of MgO. Fig. 9(b),
(e), and (h) show the microstructure of the cross-section of the
Mg - Sn alloys obtained after electrolysis. The microstructure
of the Mg – Sn alloy is a mixture of Sn-rich and Mg-rich
phases, as shown in Fig. Fig. 9(c), (f), (i), and (j). The con-
centrations of Mg in the Sn-rich phases are 0.8, 1.6, and 2.1
mass% and the concentrations of Mg in the Mg-rich phases
are 27.2, 25.9, and 28.4 mass% at 1053, 1083, and 1113 K,
respectively. This segregation is probably due to the slow
cooling of the Mg – Sn alloy in the electric furnace to form Fig. 8. The result of XRD analysis of the Mg – Sn alloys obtained after
Mg2 Sn phases and the low concentration of Mg in Sn phases, electrolysis at (a) 1053 K for 8.8 ks; (b) 1053 K for 28.2 ks; (c) 1083 K for
8.7 ks; (d) 1083 K for 21.7 ks; (e) 1113 K for 7.7 ks; (f) 1113 K for 18.1 ks,
as shown in Fig. 7. respectively.

3.3. Vacuum distillation

In order to demonstrate the feasibility of the production
of high-purity Mg metal from the Mg – Sn alloys, vacuum
distillation of the Mg – Sn alloys was conducted.
Table 5 shows the experimental conditions and analyti-
cal results of Mg metal obtained at the low-temperature part
and the residues obtained at the bottom of the reactor after
vacuum distillation.
Vacuum distillation of the Mg – Sn alloy was conducted
at 1200 – 1300 K for 5 – 10 h. Fig. 10 shows the temperature
gradient of the reactor at 1200 K and photographs of the Mg
metal and residues obtained after vacuum distillation. The Mg
metal obtained consists of a single crystal having some twin
boundaries generated during the mechanical polishing due to
the low stacking fault energy of pure Mg metal [28], as shown
in Fig. 11(a). In addition, the lattice parameter and the result
of EDS analysis of the produced Mg metal obtained indicated
that the Mg metal obtained is pure Mg metal, as shown in
Fig. 11(b), (c), and (d). As shown in Fig. 11 and Table 5, Mg
metal obtained at the low-temperature part of the reactor had a
single crystal structure with a purity of 99.998 – 99.999%. In
addition, the concentration of Mg in the Mg – Sn alloy feed
decreased from 34.1 to 0.17 mass%. As mentioned, when
the pMg is larger than 0.01 atm, the Mg metal produced will
evaporate. However, when the pressure of the system is lower
than 1 atm, the metal begins to evaporate at vapor pressures
lower than 0.01 atm [23,27]. Therefore, as shown in Fig. 7,
1652 T.-H. Lee, T.H. Okabe, J.-Y. Lee et al. / Journal of Magnesium and Alloys 9 (2021) 1644–1655

Fig. 9. The photograph and results of SEM and EDS analysis of the Mg – Sn alloys obtained after electrolysis at different temperatures (a,b,c) 1053 K for
28.2 ks, (d,e,f) 1083 K for 21.7 ks, (g,h,i) 1113 K for 18.1 ks, and (j) results of EDS analysis of points 1 – 6.

Table 5
Experimental conditions and analytical results of Mg metal obtained at the low-temperature part and the residues obtained at the bottom of the reactor after
vacuum distillation.

Exp.noa Temp., T / K Time, t / h Concentration of element i, Ci (mass%)

Mg metal obtained at low-temperature partb Residue at bottom of reactord

Mgc Sn Fe Ni Mg Sn
Feed alloy 34.1 65.3
181217 1200 5 99.998 N.D. N.D. N.D. 1.40 98.3
181211 1200 10 99.999 N.D. N.D. N.D. 1.57 95.5
181213 1300 5 99.999 N.D. N.D. N.D. 0.17 97.1
a : Weight of feed alloy = 150 g.
b : Determined by glow discharge mass spectrometry (GD-MS) analysis; N.D: Not Detected. Below the detection limit of the GD-MS (<0.001 ppm). All
other elements were not detected by analysis.
c : The purity of magnesium was calculated by subtracting the sum of all impurities except chlorine.
d : Determined by inductively coupled plasma optical emission spectrometry (ICP-OES) analysis.
 T.-H. Lee, T.H. Okabe, J.-Y. Lee et al. / Journal of Magnesium and Alloys 9 (2021) 1644–1655 1653

Fig. 10. The temperature gradient of the reactor and photographs of Mg metals and the residues obtained after the vacuum distillation of Mg – Sn alloys at
1200 K for 10 h.

although the pMg is in the range of 0.001 – 0.0001 atm at
1200 – 1300 K, almost all Mg in the Mg – Sn alloy evap-
orated during the vacuum distillation at 1200 – 1300 K, as
shown in Table 5. As a result, when the purity of Mg metal,
energy-efficiency, and the concentration of Mg in residues ob-
tained after the vacuum distillation were taken into consider-
ation, the vacuum distillation conditions of 1200 K for 10 h is
preferred.
4. Conclusions
To develop an efficient and scalable Mg production process
for producing high-purity Mg metal from MgO feedstock, a
novel electrolytic method using a liquid Sn cathode and 5
mass% MgO in MgF2 – LiF molten salt was investigated.
The estimated decomposition voltage of MgO under C anode
was 1.79 V at 1083 K by the results of CV measurements. The
electrolysis of MgO was conducted using a Sn cathode and
C anode by applying 2.5 V at 1053 – 1113 K. The electrol-
ysis results showed that the current efficiencies were 82.1 –
86.6 % at 1053 K and 81.6 – 84.8 % at 1083 – 1113 K until
the production of 9.0 – 18.1 mass% Mg – Sn and 8.3 – 13.0
mass% Mg – Sn alloys, respectively. However, the current ef-
ficiency decreased to 71.3 – 74.7 % at 1083 – 1113 K when
the concentration of Mg increased to 15.2 – 15.8 mass% ow-
ing to the evaporation of Mg by the increase of pMg . After
electrolysis at 1053 – 1113 K, Mg – Sn alloys with Mg2 Sn
and Sn (Mg) phases were obtained. In addition, after vacuum
distillation of the Mg – Sn alloy feed prepared in advance at
1200 K for 10 h, the concentration of Mg decreased from 34.1
to 1.57 mass% and Mg metal with a purity of 99.999 % was
obtained.
1654 T.-H. Lee, T.H. Okabe, J.-Y. Lee et al. / Journal of Magnesium and Alloys 9 (2021) 1644–1655

Fig. 11. (a) EBSD inverse pole figure map, (b) bright-field TEM image, (c) SAED patterns, and (d) results of EDS analysis of the produced Mg obtained
after vacuum distillation.

Acknowledgments (NST) grant by the Korea government (MSIT) (No. CRC-15-

The authors are grateful to Dr. DongEung Kim in Korea
Institute of Industrial Technology for the discussions through-
out this study. In addition, the authors thank Ms. Gyeonghye
Moon, Dr. Jae-Yeol Yang, and Dr. Jae-Sik Yoon for their
technical support. Furthermore, the authors are grateful to
all the members of the Geoanalysis Department of KIGAM
for their technical assistance. This research was supported by
the National Research Council of Science and Technology
06-KIGAM).
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