Electrochimica Acta 261 (2018) 289e295

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Electrochemical deposition of neodymium in LiF-CaF2 from Nd2O3

assisted by AlF3
Zi Chen, Changfeng She, Haiyang Zheng, Wei Huang, Tiejian Zhu, Feng Jiang, Yu Gong**,
Qingnuan Li*
Department of Radiochemistry, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China

a r t i c l e i n f o a b s t r a c t

Article history: This paper investigated the co-reduction process of Al-Nd alloys and the electrochemical extraction of
Received 30 October 2017 neodymium from neodymium oxide in LiF-CaF2 melt. Nd(III) at a tungsten electrode was reduced to
Received in revised form Nd(0) through a one-step process involving the exchange of three electrons: Nd(III) þ 3e ¼ Nd(0). The
22 December 2017
fluorination of Nd2O3 by AlF3 produced Nd(III) ions in the LiF-CaF2 molten salts. The co-reduction
Accepted 22 December 2017
Available online 28 December 2017
behavior of Nd(III) and Al(III) ions was studied on a W electrode in the LiF-CaF2-AlF3-Nd2O3 system.
Four types of intermetallic Al-Nd compound were detected through cyclic voltammetry and open circuit
chronopotentiometry. The Nd3Al and NdAl phases were identified through X-ray diffraction, and the
Keywords:
LiF-CaF2
NdAl3 and Nd3Al11 phases were characterized by a scanning electron microscope equipped with an
Nd2O3 energy dispersive spectrometer.
AlF3 © 2017 Elsevier Ltd. All rights reserved.
Al-Nd alloys
Electrochemical deposition

1. Introduction As a typical lanthanide, neodymium has been extensively

Sustainable solutions for the disposal of spent nuclear fuel (SNF)
have become increasingly crucial for worldwide. Strategies on the
separation of actinides (An) and fission products (FPs) have been
developed to improve utilization of spent fuel and reduce the
amount of radiotoxic nuclear waste [1e3].
Pyrochemical processing has been considered to have potential
applications in the separation of An and FPs in molten salt media,
which is particularly suitable for the treatment of SNF with high
radioactivity and poor aqueous solubility [4e6]. In addition to the
separation of An such as uranium, it is also necessary to remove FPs
from the molten salt medium to ensure the salt can be reused and
minimum of waste [7,8]. The electro-deposition for extracting
lanthanides exhibits the following advantages over other strate-
gies: i) lanthanide metals can be produced through electrolysis of
the raw material in many salts, such as fluoride, chloride or oxide
compounds; ii) molten salt electrolysis can be operated continu-
ously and is therefore more suitable for efficient lanthanide
extraction [7,9e13].
* Corresponding author.
** Corresponding author.
E-mail addresses: gongyu@sinap.ac.cn (Y. Gong), liqingnuan@sinap.ac.cn (Q. Li).
studied in molten salt electrochemistry. The reduction of Nd(III) to
neodymium metal occurs even if the cathode potential is more
positive than the Nd(III)/Nd potential in the situation of using
aluminum as cathode or co-reduction with aluminum ions. Yan
et al. proposed the extraction of neodymium through co-reduction
with aluminum ions in LiCl-KCl melts, and the extraction efficiency
of this process reached 99.2% [14].
Although most previous studies focused on molten chlorides, it
is also possible to separate actinide and lanthanide by electro-
chemical method in molten fluorides which are more resistant to
radiolytic degradation and better for dissolving fuel [15]. In molten
fluorides such as LiF-CaF2, Nd(III) is reduced to Nd(0) through a
single step with three exchanged electrons. Gibilaro et al. reported
the electrochemical deposition of Nd(III) through co-reduction
with aluminum in molten fluorides [16].
In this study, we investigated the co-reduction of Nd(III) with
Al(III) on an inert W electrode in LiF-CaF2 using Nd2O3 as precursor.
Electrochemical analysis technologies were performed in LiF-CaF2-
NdF3 and LiF-CaF2-Nd2O3-AlF3 melts to investigate the difference
between the two fluoride systems; Electrolysis was performed with
various conditions to reduce Nd2O3 into Al-Nd alloys with Al(III)
ions, and these alloys were characterized by X-ray diffraction (XRD)
and a scanning electron microscope (SEM) equipped with an en-
ergy dispersive spectrometer (EDS). Our results might provide

https://doi.org/10.1016/j.electacta.2017.12.147
0013-4686/© 2017 Elsevier Ltd. All rights reserved.
290 Z. Chen et al. / Electrochimica Acta 261 (2018) 289e295
useful information for the direct extraction and separation of
neodymium from oxides in molten fluoride media.
2. Experimental
2.1. Preparation and purification of the melts
The chemical reagents, LiF (99.99%), CaF2 (99.95%), AlF3
(99.99%), NdF3 (99.99%) and Nd2O3 (99.99%) were all provided by
Alfa Aesar Co. Ltd. An anhydrous mixture of LiF-CaF2 eutectic, at a
molar ratio of 79:21 was placed in a graphite crucible as the sup-
porting electrolyte. Before the experiments, the fluorides were
dehydrated by heating at 250  C for 24 h, and then heating up to
850  C for 48 h. AlF3 was used as the fluorinating solvent. Neo-
dymium ions were introduced into the electrolytic bath in the form
of NdF3 and Nd2O3, respectively.
2.2. Electrochemical experiments
Tungsten wire (99.99%) with a 1 mm diameter was used as the
working electrodes and purchased from Alfa Aesar Co. Ltd. Plat-
inum wire (99.95%) with a 1-mm diameter was purchased from
Sinopharm Chemical Reagent and was immersed in the molten
electrolyte as a Pt/PtOx/O2 quasi-reference electrode. Graphite
crucibles and graphite rods were used as the auxiliary electrode
and manufactured from high purity grade (EllorR DS-4) graphite by
Mersen Company.
All electrochemical studies and electrolysis were performed in a
glove box under an argon atmosphere. The cyclic voltammetry (CV),
open circuit chronopotentionmetry, and square wave voltammetry
(SWV) were employed to study the electrochemical behavior of
neodymium. All electrochemical experiments in this study were
performed with an Autolab PGSTAT302N potentiostat/galvanostat
controlled by Nova 2.1.
2.3. Analytical techniques
The elemental analysis of samples was measured through
inductively coupled plasma atomic emission spectroscopy (ICP-
AES). The structure and composition of the reduction products on
the cathode were characterized through XRD and an SEM equipped
with an EDS probe.
3. Results and discussion
3.1. Electrochemical behavior of Nd(III) and Al(III) in LiF-CaF2 melt
The CV curves of the LiF-CaF2 melt with and without NdF3 were
performed at a potential scan rate of 100 mV s1 on a W electrode at
850  C, as shown in Fig. 1. For the blank LiF-CaF2 melt, no reduction
or oxidation peaks were observed within the potential range
of 2.30 to 0.50 V (vs. Pt), except the cathodic limit of the elec-
trochemical window corresponding to the reduction of Li(I). The CV
curve of LiF-CaF2-NdF3 exhibited a cathodic peak (labeled A) at
approximately 2.10 V (vs. Pt), which was assigned to the reduction
of Nd3þ. In the reverse scan, an anodic peak (labeled B) was
observed at 1.95 V (vs. Pt), corresponding to the oxidation of the
deposited Nd. The SWV method was applied to determine the
exchanged electrons of this newly observed reaction. For a
reversible system, through the SWV curve illustrated in the inset of
Fig. 1, the number of exchanged electrons was calculated according
to Eq. (1) [17].
RT
W1=2 ¼ 3:52 (1)
nF
where W1/2 (V) is the peak width at half height, R (J mol1 K1) is
the ideal gas constant, T (K) is the absolute temperature, n is the
number of exchanged electrons, and F (C mol1) is the Faraday
constant. The W1/2 was obtained by Gaussian fitting for SWV curve.
The W1/2 was 0.117 V, and the number of exchanged electrons was
determined to be 2.9. As a result, it can be concluded that the
electro-reduction of Nd(III) is a single-step process with three ex-
change electrons (Eq. (2)).
NdðIIIÞ þ 3e /Nd (2)
Fig. 2 shows the CV curve of LiF-CaF2-AlF3 at 850  C
on a W
electrode at 100 mV s1. According to a previous study, the reduc-
tion of Al(III) to Al(0) occurs through the single exchange of three
electrons [18]. Only one cathodic signal (labeled A) was observed at
approximately 1.65 V (vs. Pt), assigned to the reduction process of
Al(III)/Al(0); the corresponding anodic signal (labeled B) was
associated with the oxidation of aluminum.
AlðIIIÞ þ 3e /Al (3)
3.2. Effect of AlF3 on the dissolution of Nd2O3 in LiF-CaF2 melt
The solubility of Nd2O3 in molten fluoride is quite low, and the
addition of oxides might be lead to the formation of neodymium
oxyfluorides and the precipitation of oxides in the bottom of melt
[19]. In our work, Nd2O3 (2 wt.%) was added to the LiF-CaF2 melt
and was kept at 850  C for at least 24 h. A layer of blue precipitate
was observed at the bottom of the crucible and was confirmed to be
the insoluble Nd2O3 by XRD analysis (Fig. 3(a)). The CV curve of the
LiF-CaF2-Nd2O3 system was recorded (inset of Fig. 3(a)), but no
obvious reduction peak corresponding to the reduction process of
Nd(III) to Nd(0) was detected near the reduction of Liþ. In fact, it
was similar to the voltammograms obtained from the LiF-CaF2
system (Fig. 1). It indicates that the Nd2O3 powder did not dissolve
in LiF-CaF2 melt at all and was precipitated. When AlF3 (2 wt.%) was
added to LiF-CaF2-Nd2O3 system, Nd2O3 was expected to be con-
verted to NdF3. The reaction could be expressed as follows:
Nd2 O3 ðsÞ þ 2AlF3 ðgÞ ¼ Al2 O3 ðsÞ þ 2NdF3 ðlÞ (4)
The Gibbs energy of this reaction was calculated to
be 364.823 kJ mol1 at 850  C [20], which means the reaction (4)
is energetically favorable. After the addition of AlF3, a thin layer of
white precipitate appeared at bottom of the cell, which was then
investigated through XRD (Fig. 3(b)). The result indicated that Al2O3
was formed in this process. Meanwhile, the CV curve of LiF-CaF2-
Nd2O3-AlF3 (inset of Fig. 3(b)) showed a series of reduction peaks
between the reduction of Al3þ and Liþ. Those peaks could be
associated with the formation of Nd-Al intermetallic compounds.
As a result, it suggest that the Nd2O3 powder has been fluoridized
by AlF3 and Nd3þ ions have been released into the LiF-CaF2 melt.
3.3. Electrochemical behavior of the LiF-CaF2-AlF3-NdF3 system
Fig. 4 shows the typical CV curves of LiF-CaF2-NdF3
(2.08  104 mol cm3) melt with different AlF3 concentration.
When AlF3 (4.99  104 mol cm3) was added into LiF-CaF2-NdF3
melt (as shown in Fig. 4(a)), the cathode peak A at 1.67 V (vs. Pt)
corresponding to the reduction of Al(III) to Al and the anodic peak
A0 caused by the oxidation of Al to Al(III) appeared. The signal B at
 Z. Chen et al. / Electrochimica Acta 261 (2018) 289e295 291

Fig. 1. Cyclic voltammogram of LiF-CaF2 and LiF-CaF2-NdF3 (2.08  104 mol cm3) at 100 mV s1 and 850  C. The inset shows square wave voltammogram of LiF-CaF2-NdF3 at 25 Hz
(measured curve: open circles, fitted curve: solid lines and decomposed curve: dash lines). Working electrode (WE): W (0.47 cm2); counter electrode (CE): graphite rod; quasi-
reference electrode: Pt.

3.4. Electrochemical behavior of the LiF-CaF2-AlF3-Nd2O3 system

The CV method was performed on the W electrode in the LiF-

CaF2-AlF3 (5.42  104 mol cm3)-Nd2O3 (1.39  104 mol cm3) and
LiF-CaF2-AlF3 (2.64  104 mol cm3)-NdF3 (2.78  104 mol cm3)
melts at 850  C, respectively. As shown in Fig. 5, four pairs of
cathodic/anodic signals were observed in both systems, and the lo-
cations and shapes of the characteristic peaks for the Al-Nd inter-
metallic compound were quite similar.
Gibilaro et al. investigated the co-reduction of Ln ions with
aluminium ions and found Al-Ln alloy on the inert cathodic ma-
terial [7]. Liu et al. also studied the formation of GdxAly by co-
reduction [21]. Similarly, the co-reduction process of Nd(III) and
Al(III) could be expressed as follows:

xNd3þ þ 3xe /xNd (5)

Fig. 2. Cyclic voltammogram of LiF-CaF2-AlF3 (2.64  104 mol cm3) at 100 mV s1 yAl3þ þ 3ye /yAl (6)
and 850  C. WE: W (0.32 cm2); CE: graphite rod; quasi-reference electrode: Pt.

xNd þ yAl/Ndx Aly (7)

about 1.87 V (vs. Pt) should be due to the formation of Al-Nd alloy The overall process is given as follows:
while the corresponding anodic signal B0 was not observed. The
absence of the signal related to Nd/Nd(III) in Fig. 4(a) might be
xNd3þ þ yAl3þ þ 3ðx þ yÞe /Ndx Aly (8)
due to the significant current background arising from Al oxidation
which might covered the Nd/Nd(III) peak. However, the electro- The equilibrium potential of Nd(III)/NdxAly from this system can
chemical behavior of LiF-CaF2-NdF3 containing AlF3 be described as follows:
(2.64  104 mol cm3) (Fig. 4(b)) was quite different. As shown in
Fig. 4(b), four pairs of peaks appeared in the curve, which were RT 

labeled I/I0 , II/II', III/III' and IV/IV', respectively. The redox couples ENd3þ =Nd ¼ E0 3þ  ln aNd inNdx Aly (9)
x Aly Nd =Nd 3F
labeled I/I0 and IV/IV' can be attributed to the deposition and
dissolution of metallic Nd and Al. The additional reduction peaks where E0 3þ is the equilibrium potential of the pure Nd element,
Nd =Nd
(II/II' and III/III') should arise from the formation of Nd-Al inter-
aNd ðinNdx Aly Þ is the activity of Nd in the NdxAly alloys, and R, T, F are
metallic compounds, which are located between the reduction
the same as defined in Eq. (1). Because aNd ðinNdx Aly Þ was less than
peaks of Nd(III)/Nd and Al(III)/Al.
1, it could be deduced that ENd3þ =Nd > E0 3þ . Therefore, the co-
x Aly Nd =Nd
292 Z. Chen et al. / Electrochimica Acta 261 (2018) 289e295
Fig. 3. XRD pattern of the bottom sample for LiF-CaF2-Nd2O3 system (a) before and (b) after the addition of AlF3. The inset of (a): Cyclic voltammogram of the LiF-CaF2- Nd2O3 melt
at 100 mV s1 and 850  C. The inset of (b): Cyclic voltammogram of the LiF-CaF2- Nd2O3-AlF3 melt at 100 mV s1 and 850  C. WE: W (0.32 cm2); CE: graphite rod; quasi-reference
electrode: Pt.
deposition potential of Nd with Al shifted toward more positive.
NdxAly intermetallic compounds were formed at a more positive
potential than those molten salts without Al(III), as was called the
“depolarization effect” [22,23]. Obviously, the presence of signals II/
II' and III/III' are corresponding to formation/dissolution of Al-Nd
alloy which are more positive than the neodymium reduction.
Open circuit chronopotentionmetry was also employed to
investigate the formation and dissolution mechanisms of alloys and
to determine the kinds of formed alloys. Fig. 6 shows the open
circuit potential transient curve after potentiostatic electrolysis
at 2.30 V (vs. Pt) for 20 s. The presence of several plateaus in-
dicates the formation of electrolytic products, which could be the
Nd-Al compounds. In Fig. 6, plateau 1 at about 2.02 V (vs. Pt) is
related to the reduction of Nd(III) on a W electrode. Plateau 6 with a
long step time at about 0.76 V (vs. Pt) is attributed to Al(III)/Al
redox couple. Plateaus 2, 3, 4 and 5 at about 1.50, 1.40, 1.34
and 1.09 V (vs. Pt) are associated with Nd-Al intermetallic
compounds.
3.5. The AleNd alloys
Potentiostatic electrolysis on the W electrodes was conducted
sequentially at 2.30, 1.85 and 1.70 V (vs. Pt) for 3600 s in LiF-
CaF2-AlF3 (5.42  104 mol cm3)-Nd2O3 (1.39  104 mol cm3).
The sample deposited at 2.30 V (vs. Pt) was analyzed by XRD
(Fig. 7), which was more negative than the deposition potential of
metallic Nd (2.10 V (vs. Pt)). Except for the prominent peaks cor-
responding to LiF-CaF2 eutectic, the XRD pattern indicated the
presence of Nd3Al and NdAl, which was also confirmed in the Al-Nd
phase diagram together with another three intermetallic com-
pounds Nd2Al, NdAl3, and Nd3Al11 [24,25]. The XRD analysis indi-
cated that Nd-rich phases instead of Nd metal were formed on the
surface of the electrode during potentiostatic electrolysis
at 2.30 V (vs. Pt), which might due to the rapid diffusion of Nd(III)
ions into the intermetallic compound. Compared to Fig. 1, the
higher reduction peak intensity of Nd(III) to Nd in Fig. 5 could be
attributed to the formation of Al-Nd phases. Similar phenomena
were observed by Massot et al. [16]. On the basis of these results,
the peaks labeled I and II should be assigned to Nd3Al and NdAl,
respectively.
The morphology and elemental composition of the cross section
of the W electrode were characterized through SEM-EDS analysis
after electrolysis at 1.70 V (vs. Pt) for 3600 s, as shown in Fig. 8.
Fig. 8(a) shows cross-section image of the interface between the
tungsten wire and the intermetallic compound. The concentrations
of W, Nd, and Al in different section were observed in Fig. 8(d)e(f).
The dark-field image in Fig. 8(a) contains both bright and gray re-
gions. The bright region was attributed to tungsten, whereas the
gray region was supposed to be Nd-Al alloys. Nd-Al phases were
coated as a film on the surface of the W electrodes. Elemental
analysis from the EDS experiments indicated the Nd-Al ratio of
1:0.27 corresponding to Nd3Al11. On the other hand, the reduction
peak of pure aluminum in Fig. 5 was enhanced when the Nd3þ and
Al3þ ions were simultaneously present. Pure Al metal was easily
deposited at 1.7 V and rapidly diffused to form Al-rich phases.
According to these results, the peak labeled IV in Fig. 5 should be
related to the formation of Nd3Al11. Another potentiostatic elec-
trolysis was performed at 1.85 V (vs. Pt), and the micrograph of
the cross section is presented in Fig. 9. The EDS analysis indicated
that the product was NdAl3. The intermetallic compound corre-
sponding to the peak labeled III (Fig. 5) might be NdAl3.
From the above results, it can be concluded that the composition
of AleNd alloys depends on the deposition potential of electrolysis
process, and the four plateaus revealed in open circuit potential
 Z. Chen et al. / Electrochimica Acta 261 (2018) 289e295 293

Fig. 6. Open circuit potential transient curve after polarization for 20 s at 2.30 V (vs.
Pt) in LiF-CaF2-AlF3 (5.42  104 mol cm3)-Nd2O3 (1.39  104 mol cm3) system at
850  C. WE: W; CE: graphite rod; quasi-reference electrode: Pt.

Fig. 4. Cyclic voltammograms in (a) LiF-CaF2-AlF3 (4.99  104 mol cm3)-NdF3

(2.08  104 mol cm3) melt and (b) LiF-CaF2-AlF3 (2.64  104 mol cm3)-NdF3
(2.08  104 mol cm3) melt at 100 mV s1 and 850  C. WE: W (0.32 cm2); CE: graphite
rod; quasi-reference electrode: Pt.

Fig. 7. XRD pattern for the deposits obtained after the electrolysis of the LiF-CaF2-AlF3
(5.42  104 mol cm3)-Nd2O3 (1.39  104 mol cm3) system at 2.30 V (vs. Pt) for
3600 s.

transient curve in Fig. 6 at 1.50, 1.40, 1.09, and 0.76 V (vs. Pt)
could correspond to the oxidation of Nd3Al, NdAl, NdAl3, and
Nd3Al11, respectively. The presence of these compounds was in
agreement with the results of XRD and SEM-EDS analysis.

4. Conclusions

The electrochemical behaviors of Nd(III) and Al(III) were

investigated in LiF-CaF2 melts at 850  C, and the reduction poten-
Fig. 5. Typical cyclic voltammograms in LiF-CaF2-AlF3 (5.42  104 mol cm3)-Nd2O3
tials of the three-electron transfer process were determined to
(1.39  104 mol cm3) and LiF-CaF2-AlF3 (2.64  104 mol cm3)-NdF3 be 2.10 and 1.65 V (vs. Pt), respectively. Nd2O3 could be fluori-
(2.78  104 mol cm3) at 100 mV s1 and 850  C. WE: W (S ¼ 0.32 cm2); CE: graphite dized by AlF3 in LiF-CaF2 melt, and the electrochemical deposition
rod; quasi-reference electrode: Pt. of neodymium was further studied in LiF-CaF2-AlF3-Nd2O3 system.
294 Z. Chen et al. / Electrochimica Acta 261 (2018) 289e295

Fig. 8. (a) Micrograph of the cross section of a tungsten wire after the electrolysis of LiF-CaF2-AlF3 (5.42  104 mol cm3)-Nd2O3 (1.39  104 mol cm3) at 1.70 V (vs. Pt) for
3600 s; (b) energy dispersive spectra of red square field image of the cross section; and mappings of (d) W, (e) Nd, and (f) Al in scanning area. (For interpretation of the references to
colour in this figure legend, the reader is referred to the Web version of this article.)

Fig. 9. (a) Micrograph of the cross section of a tungsten wire after the electrolysis of LiF-CaF2-AlF3 (5.42  104 mol cm3)-Nd2O3 (1.39  104 mol cm3) at 1.85 V (vs. Pt) for
3600 s and (b) energy dispersive spectra of the cross section.
 Z. Chen et al. / Electrochimica Acta 261 (2018) 289e295
Four typical types of Al-Nd alloys (Nd3Al, NdAl, Nd3Al11 and NdAl3)
were confirmed at different electrolysis potential through CV and
open circuit chronopotentionmetry, which were also demonstrated
by XRD and SEM-EDS analysis. In the electrolysis at relative positive
potential, Al-riched alloys were produced at the tungsten cathode.
To the contrary, Nd-riched alloys were achieved in the negative
potential conditions.
Acknowledgments
This work was supported by the ‘‘Strategic Priority Research
Program’’ and “Frontier Science Key Program” of the Chinese
Academy of Sciences (Grant No. XDA02030000 and QYZDYSSW-
JSC016), China Postdoctoral Science Foundation (Grant No.
2015LH0034, 2016M591731), National Natural Science Foundation
of China (21601200) and Youth innovation Promotion Association
of CAS (2017307).
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