CJCHE-01254; No of Pages 9

Chinese Journal of Chemical Engineering xxx (xxxx) xxx–xxx

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Chinese Journal of Chemical Engineering

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

Article

An energy saving and fluorine-free electrorefining process for ultrahigh

purity lead refining☆
Xuan Zhang, Junqing Pan ⁎, Yanzhi Sun, Yongjun Feng, Huixia Niu
State Key Laboratory of Chemical Resource Engineering, Beijing Engineering Center for Hierarchical Catalysts, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing
University of Chemical Technology, Beijing 100029, China

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

Article history: The present paper reports a new fluoride-free and energy-saving lead electrolytic refining process in order to
Received 27 June 2018 solve the serious problems of the existing Betts lead electrorefining process, such as low production efficiency,
Received in revised form 28 August 2018 high energy consumption and fluorine pollution. In the process, a mixed solution of perchloric acid and lead per-
Accepted 3 September 2018
chlorate (HClO4-Pb(ClO4)2) with the additives of gelatin and sodium lignin sulfonate is employed as the new
Available online xxxx
electrolyte. The cathodic polarization curves show that HClO4 is very stable, and there is no any reduction reac-
Keywords:
tion of HClO4 during the electrolytic process. The redox reactions of lead ions in HClO4 solution are very reversible
Lead refining with an ultrahigh capacity efficiency, so the HClO4 acts as a stable support electrolyte with higher ionic conduc-
Perchloric acid tivity than the traditional H2SiF6 electrolyte. The results of the scale-up experiments show that under the optimal
Fluoride-free conditions of 2.8 mol·L−1 HClO4, 0.4 mol·L−1 Pb(ClO4)2 and electrolysis temperature of 45 °C, the energy con-
Electrorefining process sumption is as low as 24.5 kW·h·(t Pb)−1, only about 20% of that by Betts method at the same current density
of 20 mA·cm−2, and the purity of the refined lead is up to 99.9992%, much higher than that specified by Chinese
national standard (99.994%, GB/T 469-2013) and European standard (99.99%, EN 12659–1999).
The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.

1. Introduction
As one of the non-ferrous metals with the largest output and highest
consumption, lead is the main raw material of lead acid batteries [1,2].
In 2015, about 82.9% global production of refined lead was consumed
to produce lead acid batteries [3]. Because of the rapid development of
automobile industry, the production of lead acid batteries increases
sharply. Until now, lead acid batteries have become the consumable sec-
ondary batteries of maximum quantity, leading to the rapid develop-
ment of refined lead production [4,5].
Refined lead is usually obtained by electrolytic refining and pyro-
metallurgical refining of crude lead (95wt%–99 wt%). The latter refers
to the production by pyrometallurgical smelting of lead paste and lead
ore (e.g., galena) [6–9]. The purity of the refined lead produced by elec-
trolytic refining method is much higher than that by pyrometallurgical
refining method [10]. Because of the poor solubility of lead in sulfuric
acid and hydrochloric acid as well as other strong acids, the option of
electrolyte is greatly limited for lead refining process. In 1901, Betts pro-
posed the fluosilicic acid and lead fluosilicate (H2SiF6-PbSiF6) solution
as the suitable electrolyte for lead refining method. In 1902–1903, this
process was successfully applied in industrial production at Trail Lead
☆ Supported by the National Natural Science Foundation of China (21676022) and the
Fundamental Research Funds for the Central Universities (BHYC170A & JD701).
⁎ Corresponding author.
E-mail address: jqpan@mail.buct.edu.cn (J. Pan).
Factory, Canada. Since then, Betts method [11,12] has become a classical
electro-refining technology of crude lead in the past 110 years. There-
fore, Betts method plays a prominent role in the existing refining tech-
niques in Japan, Canada and China.
In recent years, lots of serious problems have been exposed in the
traditional Betts electrorefining process, involving high energy con-
sumption (N120 kW·h·(t Pb)−1), low current density (20 mA·cm−2)
[13], low space–time yield efficiency, severe volatilization of fluoride
(HF and SiF4) [14,15] and emission of fluorine during the electrolytic
process at high operating temperature of 50 °C. The pollution is partic-
ularly severe in summer. To solve these problems, many researchers
have carried out numerous studies on developing new electrorefining
processes, including the electrorefining in chloride system [16,17], alka-
line xylitol system [18], NaOH-PbO system [19–22], tartaric acid system
[23] and citric acid system [24]. Unfortunately, some of the reported
electrolytes are hard to reuse and recycle, some are easy to carbonate
when exposed in the air, leading to high over-potential and low electro-
lytic efficiency [25]. So it is quite urgent and important to develop a new
green acidic and fluorine-free lead electrorefining method.
Perchloric acid (HClO4) is a kind of super strong acid. According to
the standard electrode potential in acidic solution, the reduction reac-
tion of HClO4 can be expressed as follows [26]:
 
− −
ClO4 þ 7e þ 8Hþ →Cl þ 4H2 O E0 ¼ 1:5537 V

https://doi.org/10.1016/j.cjche.2018.09.005
1004-9541/The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.

Please cite this article as: X. Zhang, et al., An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining, Chin. J. Chem.
Eng. (2018), https://doi.org/10.1016/j.cjche.2018.09.005
2 X. Zhang et al. / Chinese Journal of Chemical Engineering xxx (xxxx) xxx–xxx

Based on the traditional viewpoint, HClO4 is usually defined as a kind

of strong acid with strong oxidizability for its high standard potential
and the application of HClO4 solution as electrolyte was rarely reported
in the past. HClO4 and related chemicals are considered as a kind of dan-
gerous and explosive chemical reagents by traditional view. In fact, a
large number of studies have shown that HClO4 solution, even concen-
trated HClO4 solution is stable within a certain temperature range. Re-
cently, it has been found that the strong oxidizability of ClO4− is
proved to be very weak for its stable tetrahedron structure of Cl_O
bonds under the condition of high concentration and high temperature
(80 °C) [27]. It is also found that HClO4 solution is stable and safe at a
high concentration of 12.4 mol−1 at 70 °C [28].
Therefore, we propose a new lead electrorefining process, in which
HClO4-Pb(ClO4)2 with some electroplating additives are employed as
the electrolyte, designated as “perchloric acid system”. The experimen-
tal results show that more than 63% electric energy has been saved in
the new process. The current density of the new method can reach up
to 50 mA·cm−2, which can greatly increase the space–time yield of Pb
and shorten the production period. The refined lead with a purity of
99.9992% is obtained through high electrochemical reversibility and se-
lectivity of HClO4. So it will be an excellent raw material of high-
performance lead acid batteries [29,30]. This process is also very useful
for the enrichment and recycle of valuable metals from crude lead, such
as copper, silver, tin and antimony.
The schematic diagrams of the lead electrolytic refining process are
shown in Fig. 1. As can be seen in Fig. 1, during the electrolytic process,
the lead atoms on the anodic surface lose electrons, becoming lead (II)
ions and dissolving in the electrolyte. The metals with more positive
electrode potential like arsenic and antimony remain in the anode to
form the slime mud. The lead (II) ions close to cathodic surface obtain
electrons, becoming metallic lead. The metals with more negative elec-
trode potential remain in the electrolyte, thus high purity lead is ob-
tained on the cathode. In order to obtain a smooth and dense
electrodeposited lead layer, the electrolyte is continually circulated
throughout the whole process to minimize concentration polarization.

2. Experimental

2.1. Preparation of electrolyte

4.51 g PbO (AR, 99%, Beijing Huaye Chemicals) was dissolved in

50 ml 3.6 mol·L−1 HClO4 (71 wt%, Tianjin Eastern Chemicals) to form
the electrolyte containing HClO4 (2.8 mol·L−1) and Pb(ClO4)2 lead Impurity
(0.4 mol·L−1). Electrolytes with different concentrations of HClO4 and
Pb(ClO4)2 were also prepared in the same way. The dissolving reaction Fig. 1. Schematic diagrams of the lead electrolytic refining process.
takes place in accordance with the following equation:

PbO þ 2HClO4 →PbðClO4 Þ2 þ H2 O

2.3. The electrochemical tests

The traditional electrolyte of Betts method consisting of H2SiF6
(1.3 mol·L−1) and PbSiF6 (0.5 mol·L−1) was provided by Henan
Haoda Lead Electrolyte Group.
2.2. Preparation of electrodes
The refined lead samples (Minshan Non-Ferrous Industry Group)
with areas of 2 × 2 cm2 and 4 × 5 cm2 were washed by 10 ml 10 vol%
HCl, and dried in a vacuum oven at 60 °C to be used as the cathode.
The crude lead plates (Minshan Non-Ferrous Industry Group) with di-
mensions of 2 × 2 × 0.6 cm3 and 18 × 26 × 1.6 cm3 were polished
with abrasive papers of 48 （grain size） followed by 13 （grain size),
washed with 10 ml 10 wt% NaOH, and rinsed by deionized water until
the rinsing water became neutral. Finally, the lead plates were dried in
a vacuum oven at 60 °C for 1 h to be used as anode.
The potentiodynamic scanning tests were carried out by using a
CS300 electrochemistry workstation (Wuhan Corrtest Instrument) in
1 mol·L−1 HClO4, 1 mol·L−1 HNO3 and 0.5 mol·L−1 H2SiF6 respectively
at a scan rate of 1 mV·s−1. The temperature was changed from 30 to
70 °C. A refined lead plate with an area of 1 × 1 cm2 was used as
working electrode, a platinum plate with an area of 1 × 1 cm2 as
counter electrode and a Hg/Hg2Cl2 electrode as reference electrode.
The CV tests, Tafel tests and AC Impedance tests were carried out
with a CHI760D electrochemistry workstation (Shanghai CH instru-
ment) in HClO4 solution. In these experiments, two refined lead
plates with an area of 1 × 1 cm2 were used as working electrode
and counter electrode, respectively. The reference electrode was a
Hg/Hg2Cl2 electrode. The constant current charging test was carried
out with a LAND CT2001A cell test instrument (Wuhan Land
instrument).

Please cite this article as: X. Zhang, et al., An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining, Chin. J. Chem.
Eng. (2018), https://doi.org/10.1016/j.cjche.2018.09.005
 X. Zhang et al. / Chinese Journal of Chemical Engineering xxx (xxxx) xxx–xxx 3

2.4. Morphological and structural characterization
The X-ray powder diffraction (XRD) patterns of crude lead and re-
fined lead were collected by means of a Rigaku D/max 2500VB2+/PCX
diffractometer with a Cu anticathode (40 kV, 200 mA) at a scan rate of
10(°)·min−1 in a scan range (2θ) from 10° to 90°. The morphologies
and structures were examined by a field emission scanning electron mi-
croscopy (FSEM, Hitachi S-4700). The energy-dispersive X-ray micro-
analysis (EDX, Oxford EDS Inca Energy Counter 300, operated at 10 kV)
was conducted to analyze the element compositions of crude lead, re-
fined lead and lead anode slime. The contents of Pb and other elements
in the samples of crude lead, refined lead, lead anode slime and electro-
lyte were measured with an Inductively Coupled Plasma (ICP) analyzer
(Agilent7700).
3. Results and Discussion
The cathodic polarization curves of Pt electrode in nitric acid (HNO3),
H2SiF6 and HClO4 with 1 mol·L−1 H+ at 30 °C are shown in Fig. 2(a). It can
be seen that no reduction peak appears for H2SiF6 and HClO4 in the scan
range from −0.3 to 0.7 V. There is only one reduction peak at 0.1 V for
HNO3, representing the reduction of NO3−. The cathodic polarization
curves indicate that diluted HClO4, similar to diluted H2SiF6, only shows
the oxidizability of H+ at room temperature. Fig. 2(b) shows the cathodic
polarization curves for HClO4 (1 mol·L−1) at different temperatures. As
can be seen from Fig. 2b, there is no reduction peak of ClO4− appearing be-
tween −0.3 and 0.7 V in the range from 25 to 65 °C, and only a series of
peaks exist at −0.73 V, indicating that ClO4− is stable except that the ca-
thodic current of hydrogen evolution rises with increasing temperature.
Fig. 2 (c) shows the cathodic polarization curves of the electrode in the
HClO4 of different concentrations at 55 °C. The results show that the
curves keep flat and no characteristic reduction peak is observed in the
scan range from − 0.35 to 0.70 V when the concentration of HClO4
changes from 1 to 5 mol·L−1. Fig. 2 (d) shows the cathodic polarization
curves of the electrode in HClO4 with lead (II) ion of different
concentrations. Results indicate that there is no reduction peak appearing
between −0.3 and 0.7 V for pure HClO4 solution, only a reduction peak
obviously appears at −0.76 V, which is attributed to the reduction reac-
tion of Pb2+. It is also observed that the reduction current increases
with increasing the concentration of lead ions. Due to the high
overpotential of hydrogen evolution on metallic lead surface, the self-
discharge of lead (II) in HClO4 solution hardly occurs. Therefore, HClO4 so-
lution is suggested here as the appropriate electrolyte for the new lead
electrorefining process owing to its stable chemical properties and
ultra-strong ion conductive ability that can reduce the polarization and in-
crease electrochemical reaction rate, thus saving electric energy.
Panel labels (a) and (b) in Fig. 3 respectively show the electrochem-
ical impedance spectra and Tafel curves of lead in H2SiF6 and HClO4 so-
lutions with the same H+ concentration of 1 mol·L−1 and the same lead
(II) ion concentration of 0.3 mol·L−1 at 30 °C. According to the Lange's
Handbook of Chemistry, HClO4, as a typical super strong acid, has stron-
ger acidity and higher ion conductivity than H2SiF6 and other acids,
which is beneficial to reducing polarization and solution resistance,
thus decreasing cell voltage of electrolytic process.
As is seen in Fig. 3(a), the solution resistance of the HClO4 solution
is 0.67 Ω while that of the H2SiF6 solution is 1.24 Ω, indicating that
the ionic conductivity of HClO4 solution is much higher than that of
H2SiF6 solution at the same concentration of H+. The EIS show regu-
lar semi-circles in low frequency domain, and the radius of the semi-
circle in H2SiF6 solution is almost two times of that in HClO4 solution,
indicating that the reaction process in the HClO4 solution is faster
than that in the H2SiF6 solution. In order to better explain the effects
of different acids on the electrodeposition process of lead, the Tafel
experiments of Pb electrode in different acids of the same concentra-
tion were carried out. The exchange current densities extracted from
the Tafel curves in Fig. 3(b) are 0.0592 A·cm−2 and 0.0384 A·cm−2
in HClO4 solution and H2SiF6 solution, respectively. It is meant that
the HClO4 solution is beneficial to the increase in exchange current
and reaction rate of lead electrorefining process and decrease in
polarization.

20 20
(a) (b)
Current density/mA·cm-2
Current density/mA·cm-2

0 0

-20
-20 o
-40 25 C
o
35 C
-40 H2SiF6 -60 o
45 C
HNO3 -80
o
55 C
-60 o
HClO4 65 C
-100
-0.6 -0.3 0.0 0.3 0.6 0.9 1.2 -0.6 -0.3 0.0 0.3 0.6 0.9 1.2
Potential (vs. Hg/HG2Cl2)/V Potential (vs. Hg/Hg2Cl2)/V

100
20 (c) (d)
Current density/mA·cm-2
Current density/mA·cm-2

0 0

-20
-100
-40
0.5 mol·L-1 HClO4
-60 -200
1.0 mol·L-1 HClO4
2+
-80 0.00 mol·L-1 Pb
3.0 mol·L-1 HClO4 -300 2+
-100 0.05 mol·L-1 Pb
5.0 mol·L-1 HClO4 -1
0.10 mol·L Pb
2+
-120 -400
-0.6 -0.3 0.0 0.3 0.6 0.9 1.2 -1.0 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4
Potential (vs. Hg/Hg2Cl2)/V Potential (vs. Hg/Hg2Cl2)/V

Fig. 2. Cathodic polarization curves of Pt electrode in (a) nitric acid, fluosilicic acid and perchloric acid, (b) perchloric acid containing 1 mol·L−1 hydrogen ion at different temperatures,
(c) perchloric acids of different concentrations at 55 °C and (d) perchloric acids with different lead (II) ion contents.

Please cite this article as: X. Zhang, et al., An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining, Chin. J. Chem.
Eng. (2018), https://doi.org/10.1016/j.cjche.2018.09.005
4 X. Zhang et al. / Chinese Journal of Chemical Engineering xxx (xxxx) xxx–xxx

0.30
H2SiF6
(a) 0 (b) H2SiF6
0.25 HClO4 HClO4

0.20 -1

lg current
Z″/Ω
0.15
-2
0.10
-3
0.05

0.00 -4
0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 -1.00 -0.95 -0.90 -0.85 -0.80 -0.75 -0.70
Z′/Ω Potential/V

0.12 2.5

The concentration of H /mol·L-1

(c) H2SiF6
(d) HClO4
0.10 HClO4 H2SiF6
2.0

+
0.08
Potential/V

1.5
0.06

1.0
0.04

0.02 0.5

0.00 0.0
0 1 2 3 4 5 6 7 8 10 20 30 40 50 60 70 80
Time/h Temperature/°C

Fig. 3. (a) Electrochemical impedance spectra (EIS) and (b) Tafel curves of the lead sample in fluosilicic acid and perchoric acid with same H+ concentration of 1 mol·L−1 and same lead (II)
ion concentration of 0.3 mol·L−1 at 30 °C; (c) constant current electrolysis curves of crude lead in 1.3 mol·L−1 fluosilicic acid plus 0.4 mol·L−1 lead (II) ion at 35 °C and in
2.4 mol·L−1perchloric acid plus 0.4 mol·L−1 lead (II) ion at 45 °C for the electrode distances of 20 mm; (d) concentrations changes of fluosilicic acid solution and perchloric acid
solution with the same initial H+ concentration of 2 mol·L−1 at different temperatures for 3-day-electrolysis.

The constant current electrolysis curves of crude lead in H2SiF6 and
HClO4 solutions are presented in Fig. 3(c). The cell voltage of electrolytic
process in HClO4 solution keeps 32 mV at 20 mA·cm−2 while that in
H2SiF6 solution is as high as 88 mV. It is calculated that the current effi-
ciencies in the H2SiF6 solution and in the HClO4 solution are 97.8% and
99.5%, respectively. As a result, the energy consumption in H2SiF6 solu-
tion is 23.81 kWh per tonne Pb while that in HClO4 solution is only
7.80 kW·h per tonne Pb. It is obvious that the energy consumption in
HClO4 solution is much lower than that in H2SiF6 solution. That is also
consistent with the results from EIS and Tafel tests. In order to reveal
the volatilization characteristic of H2SiF6 and HClO4 solutions of the
same concentration under different temperatures, titration tests were
performed. It is observed that the evaporation speed of H2SiF6 obviously
increases with increasing temperature (Fig. 3(d)), meanwhile the con-
centration decreases gradually when the electrolyte is above 30 °C,
and almost 1/4 of H2SiF6 losses when temperature increases to 60 °C.
Besides, it is known that H2SiF6 easily decomposes at high temperature
above 60 °C in accordance with the following equation:
H2 SiF6 →2HF þ SiF4
However, Titration results reveal that the concentration of HClO4 is
very stable and keeps between 1.95 and 1.98 mol·L−1, indicating that
HClO4 is hardly decomposed and volatilized in the temperature range
from 30 to 70 °C. It can be concluded that the HClO4 is more suitable
as the non-fluoride electrolyte for lead electrorefining process than
the traditional H2SiF6 when the electrolyte temperature is above 30 °C.
Fig. 4 presents the influences of the concentration of (a) HClO4 and
(b) lead (II) ion and (c) temperature on Tafel tests. The corresponding
exchange current are calculated and presented in Fig. 4(d). In the aspect
of H+ influence, the exchange current increases from 0.064 to 0.082 A as
the concentration of H+ increases from 1.2 to 2.8 mol·L−1, showing that
the reversibility of electrode process is improved by increasing the con-
centration of HClO4. However, when the concentration of HClO4 is over
2.8 mol·L−1, the exchange current of the lead electrode decreases
slightly, indicating that exorbitant concentration of HClO4 inhibits the
electrodeposition of lead. Therefore, the optimal concentration of
HClO4 solutions will be 2.8 mol·L−1. It is also observed that the increase
in Pb2+ concentration in the range of 0.1–0.4 mol·L−1 can improve ex-
change current. If the Pb2+ concentration is above 0.4 mol·L−1, the in-
crease in exchange current becomes much slower as the concentration
increases. Considering the solubility of Pb2+ in HClO4 solution,
0.4 mol·L−1 of Pb2+ should be the optimal concentration of the electro-
lyte for lead electrorefining. Fig. 4(c) shows the influence of temperature
on exchange current. The results indicate that the increase in tempera-
ture can promote ionic diffusion and exchange current, beneficial to
the decrease in polarization and the electricity consumption. However,
too high temperature causes extra high heating load. So, considering
total energy consumption of heat and electricity, 45–50 °C will be chosen
as the optical operation temperature range for lead electrorefining.
Panel labels (a) and (b) in Fig. 5 are the galvanostatic electrolysis
curves of anodic stripping and cathodic depositing of the Pb electrode
at different current densities, respectively. As is seen from Fig. 5(a),
the anodic potential increases with increasing anodic current density.
When the current density is 10 mA·cm−2, the potential is 6.1 mV. How-
ever, when the current density reaches 50 mA·cm−2, the potential is
only 20.3 mV. However, there appears a big jump of potential when
the current density further increases from 50 to 60 mA·cm−2. The rea-
son might be that too high current density limits the lead (II) ion diffu-
sion from the surface of the anode to the electrolyte in the anodic
process. The optimal anodic current density thus should be controlled
between 10 to 50 mA·cm−2. A similar phenomenon of the cathodic

Please cite this article as: X. Zhang, et al., An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining, Chin. J. Chem.
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 X. Zhang et al. / Chinese Journal of Chemical Engineering xxx (xxxx) xxx–xxx 5

0 (a) 0 (b)

-1 -1
lg current

lg current
1.2 mol·L-1 0.1 mol·L-1
-2 -2
1.6 mol·L-1 0.2 mol·L-1
2.0 mol·L-1 0.3 mol·L-1
2.4 mol·L-1 -3 0.4 mol·L-1
-3 0.5 mol·L-1
2.8 mol·L-1
3.2 mol·L-1 0.6 mol·L-1
-4
-0.16 -0.08 0.00 0.08 0.16 -0.16 -0.08 0.00 0.08 0.16
Potential/V Potential/V

9.5
0 (c) 9.0 (d)

Exchange current×102/A
8.5
8.0 Temperature
-1 10
lg current

35 40 45 50 55 60
8
6
35 C
-2 4 Pb
2+
40 C
45 C 9
2
0.1 0.2 0.3 0.4 0.5 0.6
50 C 8
-3 55 C
7 +
60 C H
6
-0.16 -0.08 0.00 0.08 0.16 1.2 1.6 2 2.4 2.8 3.2
Potential/V The factors

Fig. 4. Tafel curves of electro-refining lead in perchloric acid: (a) of different perchloric acid concentrations, (b) with different lead (II) ion concentrations, (c) at different temperatures;
(d) the curves of exchange current corresponding to the above conditions.

10 mA·cm-2 20 mA·cm-2
0.06 (a) 10 mA·cm-2
30 mA·cm-2
20 mA·cm-2
40 mA·cm-2
0.06 (b) 30 mA·cm-2 40 mA·cm-2
50 mA·cm-2 60 mA·cm-2 50 mA·cm-2 60 mA·cm-2
Cathodic potential/V

0.05 0.05
Anodic potential/V

0.04 0.04

0.03 0.03

0.02 0.02

0.01 0.01

0 1 2 3 4 5 6 0 1 2 3 4 5 6
Time/h Time/h

0.12 0.08
(c) 10 mA·cm-2 20 mA·cm-2
(d)
Potential or cell voltage/V

30 mA·cm-2 40 mA·cm-2
0.10 50 mA·cm-2 60 mA·cm-2
0.06
Potential/V

0.08
0.04
0.06

0.02
0.04 anode
cathode
cell voltage
0.02 0.00
0 1 2 3 4 5 6 10 20 30 40 50 60
Time/h Current density/mA·cm-2

Fig. 5. (a) Anodic potential vs. time curves, (b) cathodic potential vs. time curves, (c) electrolytic cell voltage vs. time curves, and (d) potential of the anode and cathode and cell voltage vs.
current density curves. The electrolyte was perchloric acid - lead perchlorate solution.

Please cite this article as: X. Zhang, et al., An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining, Chin. J. Chem.
Eng. (2018), https://doi.org/10.1016/j.cjche.2018.09.005
6 X. Zhang et al. / Chinese Journal of Chemical Engineering xxx (xxxx) xxx–xxx

process is also found in Fig. 5(b). Compared with the data of the anodic
process, the cathodic process shows much higher polarization. The lead
cathode gives a potential of 38.5 mV, which is 17.2 mV higher than that
of the anode at the same current density of 50 mA·cm−2.
Panel labels (c) and (d) in Fig. 5 display the cell voltages in the whole
electrolysis course at different current densities. The increase in cell
voltage is approximately directly proportional to the increase in current
density when the current density is in the range of 10–50 mA·cm−2. A
big jump of cell voltage is also observed in Fig. 5(c) when the current
0.12
(a)
0.10
density increases from 50 to 60 mA·cm−2. Considering the energy con-
sumption and space time yield, the optimal current density may be con-
trolled lower than 50 mA·cm−2.
In order to evaluate the quality of deposited lead, the photographs
and SEM images of the above cathodic electrodeposited lead at different
current densities are presented in Figs. S1 and S2 (Supporting Informa-
tion), respectively. As is seen in Fig. S1, the samples formed in the
range from 10 to 50 mA·cm−2 show smooth and flat morphology.
When the current density is over 50 mA·cm−2, the lead dendrites and

0.08
Potential/V

st
1
nd
0.06 2
rd
3
th
0.04 4
th
5
th
6
0.02
0 10 20 30 40 50 60
Time/h

Fig. 6. (a) Constant current electrolysis curves, (b) photographs and (c) SEM images of the electrodeposited lead obtained in the electrolyte of 2.8 mol·L−1perchoric acid plus 0.4 mol·L−1
lead (II) ion at 50 mA·cm−2 and 45 °C after 60 h electrolysis per cycle in the first 6 cycles.

Please cite this article as: X. Zhang, et al., An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining, Chin. J. Chem.
Eng. (2018), https://doi.org/10.1016/j.cjche.2018.09.005
 X. Zhang et al. / Chinese Journal of Chemical Engineering xxx (xxxx) xxx–xxx 7

Table 1
ICP analysis results of refined lead after first 6 cycles of the scaled up test

Cycle number Concentration/wt%

Sn Sb Bi Cu As Ag Zn Cd Ni Fe total

1st 0.0001 0.0001 0.00026 0.0005 0.00013 0.00006 0.00012 0.000001 0.000001 0.000001 0.001273
2nd 0.00006 0.0001 0.00014 0.00033 0.00008 0.00031 0.00009 0.000001 0.000001 0.000001 0.001113
3rd 0.00005 0.0001 0.00012 0.00032 0.000001 0.00026 0.00006 0.000001 0.000001 0.000001 0.000914
4th 0.00004 0.0001 0.00042 0.00023 0.0003 0.00007 0.00008 0.000001 0.000001 0.000001 0.001243
5th 0.00005 0.00008 0.00053 0.00021 0.00005 0.000011 0.00006 0.000001 0.000001 0.000001 0.000994
6th 0.00004 0.00002 0.00061 0.00029 0.00015 0.00009 0.00005 0.000001 0.000001 0.000005 0.001257

non-uniform particles appear on the surface of the cathode plate. The
photographs well conform to the SEM images shown in Fig. S2. Ex-
tremely high current density causes too fast electrodeposition process
of lead particles on the cathodic surface, leading to the instantaneous
impoverishment of lead (II) ion and formation of heterogeneous crys-
tals. On the other hand, extremely high current density at high potential
leads to the dissolution of impurities from the anode plate, leading to
poorer quality of cathodically electrodeposited lead. In order to obtain
the electrodeposited lead product with good morphology and quality,
the current density should not be higher than 50 mA·cm−2 during the
electrolytic process.
0.12
(a)
0.11
Cell voltage/V
It is observed that the additives such as bone glue and sodium lignin
sulfonate are gradually adsorbed along with the lead deposition pro-
ceeding [23]. So the additive supplement is needed during the cycling
of electrolyte. The effects of cyclic process on the cell voltage and the
morphology of the electrodeposited lead were studied. Fig. 6(a) pre-
sents the cell voltage of the electrolytic process versus cycling number
of electrolysis, and panel labels (b) and (c) in Fig. 6 show the photo-
graphs and SEM images of the electrodeposited lead in the first
6 cycles, respectively. The results indicate that the cell voltages of the
first 6 cycles all maintain around 80 mV, meaning that the cell voltages
keep steady for the first 6 cycles. From Fig. 6(b) and (c), we can also see
(b)

0.10

0.09

0.08

0.07

0.06
0 10 20 30 40 50
Time/h

Fig. 7. (a) Cell voltage of the electrolytic process vs. time, (b) photographs of the cell and (c) photographs of the original crude lead anode (185 × 260 × 15.8 mm3) and cathode
(185 × 260 × 1 mm3, 1390 g), residual lead anode and cathodic electrodeposited lead in 2.8 mol·L−1perchloric acid plus 0.4 mol·L−1 lead (II) ion at 20 mA·cm−2 and 45 °C after
60 h electrolysis. (d) Comparison of the novel electrolytic process with Betts process: (d1) energy consumption, (d2) lead purity, (d3) F emission and (d4) current density.

Please cite this article as: X. Zhang, et al., An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining, Chin. J. Chem.
Eng. (2018), https://doi.org/10.1016/j.cjche.2018.09.005
8 X. Zhang et al. / Chinese Journal of Chemical Engineering xxx (xxxx) xxx–xxx

that both the surface and the micro morphologies are almost consis-
tently smooth and dense, showing the electrolysis process is very stable.
In addition, if there are a few metallic impurities of the electrolyte
slowly accumulated after the electrorefining processes, sodium lignin
sulfonate was regularly added into the electrolyte to adsorb the impuri-
ties to form the flocculate of impurities, which can be removed by filtra-
tion process. As seen from Table 1, the purities of the refined lead
obtained in the first 6cycles are all higher than 99.997%.
The scale-up experiments of the electrolytic process were carried
out in the laboratory. Panel labels (a) and (b) in Fig. 7 show the cell volt-
age curves and the photographs of the installation, respectively. The
photographs of the original anode crude lead (c1), residual anode
(c2), cathode lead (c3) and cathodically electrodeposited lead (c4) are
shown in Fig. 7(c). As is seen in Fig. 7(a), the cell voltage in the whole
electrolytic process is very stable and keeps 94–95 mV, which benefits
from the favorable conductivity of HClO4. Finally, the obtained
net weight of the refined lead is 5570 g. According to Faraday law,
the current efficiency is 99.7% and the consumed electrical energy
is 24.5 kWh·tPb−1. Fig. 7(d) shows the comparison between the
properties of the traditional Betts electrorefining process and our new
electrorefining process ((d1) energy consumption, (d2) lead purity,
(d3) Fluorine emission and (d4) current density). In Fig. 7(d1), it is
clearly seen that the energy consumption in perchloric acid system
only accounts for about 20% in Betts system at the same current density.
Furthermore, the purity of the refined lead obtained by our method
reaches up to 99.9992%, much higher than that by Betts method
(99.994%), as seen in Fig. 7(d2). It is obvious that there is no fluorine
emission in our process while that in Betts electrorefining process
reaches up to 4.2 kg·(t Pb)−1 in Fig. 7(d3). In Fig. 7(d4), the current den-
sity of our method reaches up to 50 mA·cm−2 while that of Betts
method is only 20 mA·cm−2, indicating that the production efficiency
by our new process is 2.5 times of that by Betts electrorefining process.

(a1)

Pb
Count

Cd
Sb As Cd Pb
Cu Cd Sb Cu Cu Pb

0 2 4 6 8 10 12 14
Energy/keV

(b1)

Pb
Count

Pb
Pb

0 2 4 6 8 10 12 14
Energy/keV

(c1)

Sb
Pb
Count

As
Sb
Sb Cd
Cu Cd Cu As
Cd Cu As Pb

0 2 4 6 8 10 12 14
Energy/keV

Fig. 8. EDX spectra of (a1) crude lead, (b1) refined lead, (c1) anode slime; SEM images of (a2) crude lead, (b2) refined lead, (c2) anode slime for the electrolytic process in 2.8 mol·L−1
perchloric acid solution plus 0.4 mol·L−1 lead (II)ion at 50 mA·cm−2 and 45 °C.

Please cite this article as: X. Zhang, et al., An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining, Chin. J. Chem.
Eng. (2018), https://doi.org/10.1016/j.cjche.2018.09.005
 X. Zhang et al. / Chinese Journal of Chemical Engineering xxx (xxxx) xxx–xxx
Table 2
Pb mass balance before and after electrolytic process in certain 3 batches
Batches Anode/g
1 Before electrolysis 9.4080
After electrolysis 3.2203
2 Before electrolysis 9.6815
After electrolysis 3.4957
3 Before electrolysis 9.9573
After electrolysis 3.7702
Fig. 8 presents the EDX spectra of crude lead (a1), refined lead (b1)
and anode slime (c1), and SEM images of crude lead (a2), refined lead
(b2) and anode slime (c2). From Fig. 8(a1) and (a2), we can see the
anode crude lead with a rough and rugged surface contains 98 wt.%
lead and other impurities, such as cadmium, copper, arsenic and anti-
mony. Panel labels (b1) and (b2) in Fig. 8 show that cathodically elec-
trodeposited sample only contains metallic lead, presenting a smooth,
dense and bright surface without irregular corners. Panel labels (c1)
and (c2) in Fig. 8 indicate that the main impurities in the anode slime
are cadmium, copper, arsenic and antimony and the sample shows a se-
ries of spherical particle structure. During the electrolytic process, the
impurities are removed from crude lead and into anode slime. Finally,
not only the refined lead with good morphology and quality but also
the anode slime containing noble metals can be obtained.
The ICP analysis results of the impurities of the original crude lead
(a), the refined lead (b), the anodic slime (c) and the electrolyte
(d) are shown in Table S1. It can be seen that the purity of the refined
lead exceeds 99.9992%, which is higher than that specified by 1# stan-
dard metallic lead (GB/T 468-2005, Chinese national standard,
99.994%) and PB990R grade Pb (EN 12659-1999, European standard,
99.99%). The refined lead will be excellent raw materials for the manu-
facture of advanced lead-acid batteries and special lead alloys.
The recovery efficiency of Pb = the gain mass of cathode / (The loss
mass of anode − the mass of anodic slime in electrolyte) × 100%.
The concentration of Pb2+ was titrated by EDTA method. Table 2
shows the Pb mass balance before and after electrolytic process in cer-
tain 3 batches. The volume of the solution is 100 ml. Calculated from
Table 2, the recovery efficiencies of Pb of the above 3 batches are
99.57%, 99.65%, 99.53%, respectively.
4. Conclusions
A lead electrorefining process with a new fluoride-free electrolyte
system, perchloric acid system, has been proposed in the present
paper. It is proved that the HClO4 solution is stable without the reduc-
tion reactions of the ClO4− ions in 1–5 mol·L−1 HClO4 below 65 °C, so
there is no any fluorine and other toxic gas emission during the
electrorefining process. The energy consumption per tonne of lead in
perchloric acid system is 24.5 kW·h·(t Pb)−1, which accounts for only
about 20% in Betts system at the same current density of
20 mA·cm−2. Moreover, the current density is able to increase to
50 mA·cm−2, meaning the production efficiency can be 2.5 times as
compared with the limitation of 20 mA·cm−2 in Betts Process. That
benefits from superior conductivity and dissolution ability of HClO4.
The purity of the refined lead obtained by perchloric acid system can
reaches up to 99.9992%, much higher than that specified by the
Chinese national standard (99.994%, GB/T 469–2013) and European
standard (99.99%, EN 12659–1999), and the recovery efficiencies of Pb
reach up to 99.5%.
Supplementary Material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cjche.2018.09.005.
Please cite this article as: X. Zhang, et al., An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining, Chin. J. Chem.
Eng. (2018), https://doi.org/10.1016/j.cjche.2018.09.005
9
Cathode/g Pb in electrolyte/g Anodic slime/g
2.6532 8.5346 0
8.7829 8.5532 0.032
2.5702 8.3380 0
8.6998 8.3587 0.035
2.5266 8.4622 0
8.6910 8.4850 0.029
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