batteries

Article
Recovery of Cobalt from Spent Lithium-Ion Mobile
Phone Batteries Using Liquid–Liquid Extraction
Daniel Quintero-Almanza 1 , Zeferino Gamiño-Arroyo 1, *, Lorena Eugenia Sánchez-Cadena 2 ,
Fernando Israel Gómez-Castro 1 , Agustín Ramón Uribe-Ramírez 1 ,
Alberto Florentino Aguilera-Alvarado 1 and Luz Marina Ocampo Carmona 3
1 Departamento de Ingeniería Química, Universidad de Guanajuato, Campus Guanajuato, Noria Alta s/n,
Col. Noria Alta, Guanajuato 36050, Mexico; danielquintero92@live.com.mx (D.Q.-A.);
fgomez@ugto.mx (F.I.G.-C.); agustin@ugto.mx (A.R.U.-R.); alaguile@ugto.mx (A.F.A.-A.)
2 Departamento de Ingeniería Civil, Universidad de Guanajuato, Campus Guanajuato, Avenida Juárez No. 77,
Col. Centro, Guanajuato 36050, Mexico; hau10@hotmail.com
3 Departamento de Materiales y Minerales, Universidad Nacional de Colombia, Sede Medellín,
Calle 75 N. 79 A 51 Bloque M17 of 407-05, Medellín 050034, Colombia; lmocampo@unal.edu.co
* Correspondence: gaminoz@ugto.mx; Tel.: +52-473-7320006 (ext. 8140)




Received: 25 March 2019; Accepted: 18 April 2019; Published: 6 May 2019


Abstract: The aim of this paper was to propose and test a continuous cobalt recovery process from
waste mobile phone batteries. The procedure started with dismantling, crushing, and classifying
the materials. A study on leaching with sulfuric acid and hydrogen peroxide was carried out with
subsequent selective separation of cobalt by means of liquid–liquid extraction. The best extraction
conditions were determined based on a sequence of experiments that consisted of selecting the best
extractant for cobalt, then assessing the impact of extractant concentration, pH, and contact time on
the extraction yield. With these conditions, an extraction isotherm was obtained and correlated with
a mathematical model to define the number of extraction stages for a countercurrent process using
the McCabe–Thiele method. Then, a similar study was done for stripping conditions and, as a last
step, cobalt electroplating was performed. The proposed process offers a solution for the treatment of
these batteries, avoiding potential problems of contamination and risk for living beings, as well as
offering an opportunity to recover valuable metal.

Keywords: cobalt; spent lithium batteries; recovery

1. Introduction
In recent decades, the use of lithium-ion batteries (LiBs) in a large number of portable devices, such
as mobile phones, laptops, tablets, toys, medical equipment, and tools, has increased. This consumption
has generated a large number of spent batteries. The Global E-waste Monitor [1] classifies this e-waste
within the category “small IT and telecommunication equipment”, with an estimated generation of
3.9 million metric tons in 2016 [1]. In a mobile phone, the battery represents 21.12% of the total weight,
together with other materials such as plastics (25.75 wt%), printed circuit boards (PCBs) (17.67 wt%),
metals (17.30 wt%), and displays (8.37 wt%) [2]. Worldwide, there are around 780,000 metric tons of
spent LiBs, and for China alone, there is an estimated increase to 500,000 metric tons for 2020 [3].
There are two main reasons to recycle batteries: to recover valuable materials, especially if their
supply is limited, and to comply with any government regulations on the disposal of this type of spent
battery [4]. LiBs are composed of an anode, a cathode, a separator, and an electrolyte. The average
composition of the materials in LiBs is presented in Table 1 [5].

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Table 1. Material percentage %(w/w) in lithium-ion batteries (LiBs) [5].

Anode Cathode Plastic Electrolyte Case Loss

18 35 6 11 26 4

In more than half of these batteries, the cathode contains any of the following compounds: LiCoO2
and LiNi0.33 Co0.33 Mn0.33 O2 [6]. As previously mentioned, cobalt accounts for around 20 wt% of
spent LiBs. These residues also contain lithium, nickel, copper, and aluminum; however, there is
a higher composition of cobalt than the other metals, which is why it is important to recover [5,7].
Due to the complicated assembly of the batteries and the composition of the electrodes, recycling
LiBs requires physical and chemical processes. Physical processes include pretreatments, such as
dismantling, crushing, screening, magnetic separation, washing, and thermal pretreatment. Chemical
processes include acid leaching, bioleaching, ultrasonic-assisted separation, solvent extraction, chemical
precipitation, and electrochemical processes [6,8,9].
Many articles have focused on the stage of leaching with minerals acid [4,7,10,11], bioleaching [5],
and organics acids [12–15]. Other proposed processes include precipitation [16,17], thermal treatment [18],
reduction roasting [19], and mechanical separation [20].
While solvent extraction has industrial applications in the recovery and purification of metals
from lixiviation liquors and residues of materials [21], few works have proposed solvent extraction
to recover cobalt [22,23], copper [24], and other metals of spent batteries [25]. This work focused
on the recovery of cobalt by solvent extraction, measuring the effect of parameters such as time,
pH, and concentration of the extractant. Liquid–liquid extraction was used because of its flexibility,
high selectivity, and lower energy requirements in comparison with pyrometallurgic methods [26].
The number of extraction and stripping stages required to perform the separation in a continuous
scheme was estimated using the McCabe–Thiele method. After stripping, it was possible to achieve
the electrodeposition of cobalt in sulfate medium [27], and it may be possible even with the presence of
organic impurities [28]. With this last stage, the process of cobalt recovery was complete and could be
used at the industrial level. The electrodeposition of cobalt was also studied in this work.

2. Materials and Methods

2.1. Materials
The first step of this research was to gather mobile phone batteries from collection centers, mobile
phone repair shops, and friends and relatives. To dissolve the spent battery material, sulfuric acid
(Karal) and hydrogen peroxide (Karal) were used. For the recovery of cobalt, the selected extractant
was Cyanex 272 (bis-(2,4,4-tri-methyl-pentyl) phosphinic acid), which was supplied by Cytec Solvay
and used without further purification. The organic phase was prepared by diluting the extractant in
kerosene (Reasol, technical grade). All other chemical products were of analytical reagent grade.

2.2. Experimental Procedure

The experimental procedure is illustrated in Figure 1, and it indicates the components that were
removed at each stage.
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Al, Cu, Fe,

Spent Libs Discharge Dismantling Crushin Sieving
plastics
g

Co Electrodeposition Stripping Liquid–liquid extraction Acid leaching

Li

Figure1.1.Experimental
Figure Experimentalprocedure
procedure for
for recovery
recovery of
ofcobalt.
cobalt.

Each
Each stepstep is described
is described below.
below.
Collection.
Collection. Aftercollecting
After collectingabout
about40 40 batteries
batteries ofof different
different brands,
brands,they
theywere
wereclassified
classifiedinto two
into two
groups by weight: batteries of 20–30 g and those
groups by weight: batteries of 20–30 g and those of 30–40 g. of 30–40 g.
Discharge.
Discharge. ToTo discharge
discharge theresidual
the residualenergy,
energy,each
eachbattery
battery was was connected
connectedto toaalamp
lampuntil
untilitsits
energy
energy
was minimal. This was measured with a multimeter
was minimal. This was measured with a multimeter model MP9600-MITZU. model MP9600-MITZU.
Dismantling and crushing. Each battery was cut into three or four parts with the help of metal-
Dismantling and crushing. Each battery was cut into three or four parts with the help of metal-cutting
cutting scissors, which were then crushed with a 500-W blender.
scissors, which were then crushed with a 500-W blender.
Sieving and classification. After crushing, a sieve was applied for 1 min, which consisted of four
Sieving and classification. After crushing, a sieve was applied for 1 min, which consisted of four
meshes corresponding to mesh 18, 35, 60, and 140 with openings of 1 mm, 0.50 mm, 0.25 mm, and
meshes corresponding to mesh 18, 35, 60, and 140 with openings of 1 mm, 0.50 mm, 0.25 mm, and
0.105 mm, respectively. Then, each mesh was taken apart to weigh its contents.
0.105 mm, respectively. Then, each mesh was taken apart to weigh its contents.
Leaching. The leaching process was carried out using a sulfuric acid and hydrogen peroxide
Leaching.
solution The leaching
to dissolve process was
the components of thecarried outcontaining
batteries using a sulfuric acidlithium,
cobalt and and hydrogen peroxide
using a solid-to-
solution to dissolve the components of the batteries containing cobalt and lithium,
liquid ratio of 1:10, with controlled temperature and time. Cobalt concentration in solution was using a solid-to-liquid
ratio of 1:10,bywith
detected controlled temperature
stoichiometry. Corresponding and time. Cobalt
dilutions concentration
were prepared in solution
and defined by AASwasusing
detected
a
by Perkin
stoichiometry. Corresponding
Elmer AAnalyst 200. dilutions were prepared and defined by AAS using a Perkin Elmer
AAnalyst 200.
Liquid–liquid extraction. In order to define the extraction operation conditions, batch
Liquid–liquid extraction.
experimentation In orderintoa define
was performed 30-mLthe extraction
beaker using an operation conditions, batch experimentation
aqueous-to-organic-phase ratio of 10:10
wasmL.
performed
The phases in a were
30-mLinbeaker
contactusing
withan aqueous-to-organic-phase
constant stirring at 700 rpm ratio for 30ofmin,
10:10which
mL. Thewasphases were
sufficient
time to with
in contact reachconstant
equilibrium. Once
stirring the rpm
at 700 extraction
for 30 time
min, waswhich over,
wasthe phases time
sufficient were to separated and the
reach equilibrium.
concentration
Once the extraction of metal in the
time was aqueous
over, phase were
the phases ([Co]aqseparated
) was determined by AAS, and inofthe
and the concentration metalorganic
in the
phase,phase
aqueous ([Co]org([Co]
) wasaqdetermined by mass
) was determined bybalance.
AAS, and Every point
in the of the phase,
organic pH range between
([Co] org ) was2 and 7 was
determined
by evaluated
mass balance.with unitary steps, of
Every point adjusting
the pH the rangepHbetween
by using 2concentrated alkaline orwith
and 7 was evaluated acid solutions. A
unitary steps,
Hanna Digital pH meter model HI2209 with a combined glass electrode
adjusting the pH by using concentrated alkaline or acid solutions. A Hanna Digital pH meter modelwas used to measure the pH
of thewith
HI2209 aqueous solutions.
a combined Every
glass point ofwas
electrode theused
proposed extractant
to measure the concentration
pH of the aqueousrange solutions.
was evaluated Every
between 0.1 mol/L and 0.5 mol/L, with steps of 0.1 mol/L. A contact
point of the proposed extractant concentration range was evaluated between 0.1 mol/L and 0.5 mol/L, time test was performed,
monitoring the extraction yield for each time interval. All of these experiments were performed at 22
with steps of 0.1 mol/L. A contact time test was performed, monitoring the extraction yield for each
± 1 °C. The cobalt extraction rate was:
time interval. All of these experiments were performed at 22 ± 1 ◦ C. The cobalt extraction rate was:
Cobalt Extraction % = 100 [Co]org/([Co]org + [Co]aq) (1)
Cobalt Extraction % = 100 [Co]org /([Co]org + [Co]aq ) (1)
Isotherms of extraction and continuous process. To obtain the isotherms, the parameters found by
the experimental procedures were used at different rates of the aqueous phase in relation to the
Isotherms of extraction and continuous process. To obtain the isotherms, the parameters found by the
organic phase (A/O). The concentration of cobalt in the organic phase was calculated as follows:
experimental procedures were used at different rates of the aqueous phase in relation to the organic
phase (A/O). The concentration of cobalt [Co]orgin= the
A/Oorganic
([Co]aq initial
phase − [Co]
wasaq)calculated as follows: (2)
where [Co]aq initial is the initial cobalt concentration before extraction, [Co]aq is the final silver
[Co]org = A/O ([Co]aq initial − [Co]aq ) (2)
concentration after extraction, while A and O are the volumes of aqueous and organic phases,
respectively. Aiming for industrial application, the number of stages required for a continuous
where [Co]aq initial is the initial cobalt concentration before extraction, [Co]aq is the final silver
process was computed by using the McCabe–Thiele method [21]. Figure 2 shows the experimental
concentration after extraction, while A and O are the volumes of aqueous and organic phases,
mixer-settler with a size of 3.8 × 23.3 × 6.5 cm and a stirring section of 3.8 × 3.8 × 6.5 cm. Stirring was
respectively. Aiming for industrial application, the number of stages required for a continuous process
performed with a magnetic stirrer, and to control flows, pumps and valves were used.
was computed by using the McCabe–Thiele method [21]. Figure 2 shows the experimental mixer-settler
with a size of 3.8 × 23.3 × 6.5 cm and a stirring section of 3.8 × 3.8 × 6.5 cm. Stirring was performed
with a magnetic stirrer, and to control flows, pumps and valves were used.
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Figure
Figure 2.
2. Mixer-settler
Mixer-settler for
for continuous
continuous process.
process.

Electrodeposition.
Electrodeposition. The
Electrodeposition. stripping
The stripping solution
strippingsolution
solutionof of cobalt
ofcobalt was
cobaltwas treated
treatedinin
wastreated inaaasystem
system
systemwithwith
witha aalead
lead anode
leadanode
anode and
and
and a
astainless-steel
stainless-steel cathode,
cathode, both
both with
with an
an area
area of
of 0.00499
0.00499 mm2 2
. . The
The electrodes
electrodes were
were cleaned
cleaned and polished
a stainless-steel cathode, both with an area of 0.00499 m . The electrodes were cleaned and polished
2

and
and the temperature
the temperature
temperature waswas controlled.
wascontrolled.
controlled.TheThe system
Thesystem
systemfor for electrodeposition
electrodepositionisis
forelectrodeposition shown
showninin
isshown the
inthe Figure
Figure3 3with
theFigure 3 with
witha
aregulated
a regulated
regulatedDCDC
DC power
power
power supply.
supply. TheThe
supply. effect
effect
The of
of the
effect the
the current
ofcurrent over the
current over the
the cobalt
overcobalt deposition
deposition
cobalt was
was studied
was studied
deposition by
by testing
studied by
testing
five five
values values
for for
current current
(0.25 A, (0.25
0.5 A, A,
0.750.5
A, A,
1 0.75
A, and A,1.51 A,
A). and
The 1.5 A).
current The current
efficiency
testing five values for current (0.25 A, 0.5 A, 0.75 A, 1 A, and 1.5 A). The current efficiency was was efficiency
computed was
as:
computed
computed as: as:
Current efficiency = (deposited mass/theoretical deposition mass) ∗ 100 (3)
Current
Current efficiency
efficiency == (deposited
(deposited mass/theoretical
mass/theoretical deposition
deposition mass)*100
mass)*100 (3)
(3)

Figure 3.
3. System
Figure 3. System for electrodeposition
electrodeposition of
of cobalt.
Figure System for
for electrodeposition of cobalt.
cobalt.

3.
3. Results
Results

3.1. Collection, Discharge,

3.1. Collection,
Collection, Discharge, Dismantling,
Dismantling, Drushing,
Drushing, and
and Sieving
Sieving
Commercial
Commercial LiBs LiBsof
LiBs ofdifferent
of differentbrands
different brandswere
brands were
were collected
collected
collected fromfrom
from numerous
numerous
numerous sources
sources
sources suchsuch
such as as markets
as markets
markets and
and
and stores.
stores. For For
safe safe handling,
handling, they they
were were discharged,
discharged, and and
the the remaining
remaining voltage voltage
was
stores. For safe handling, they were discharged, and the remaining voltage was less than 0.2 V. The was
less less
than than
0.2 V.0.2 V.
The
The batteries
batteries
batteries were were discharged
were discharged
discharged at at a controlled
at aa controlled
controlled rate rate
rate to to avoid
to avoid overdischarge-related
avoid overdischarge-related phenomena,
overdischarge-related phenomena,
phenomena, such such
such asas
those reported by Ouyang et al. [29]. In the
the first
first step
step of
of dismantling,
those reported by Ouyang et al. [29]. In the first step of dismantling, the plastic or metallic cases were
dismantling, the plastic or metallic cases were
removed,
removed, and the batteries
and the were crushed
batteries were with aa blender
crushed with blender at at 500
500 W W for
for 555 min.
min. The
min. The batteries
batteries collected
collected
were
were classified
classified into
into two
two groups: batteries between
groups: batteries
batteries between 15
between 15 ggg and
15 and 30
and 30 g,
30 g, and
g, and those
and those between
those between 30
between 30 ggg and
30 and 40
and 40 g.
40 g.
g.
Table
Table 22 presents
presents the
the fractions
fractions obtained
obtained from
from the
the batteries
batteries after
afterthe
the
Table 2 presents the fractions obtained from the batteries after the classification.classification.
classification.

Table 2.
Table 2. Material
Material percentage
percentage % (w/w) present
% (w/w) present in
in LiBs.
LiBs.
Cover
Cover
Cover Plastic,
Plastic, Paper
Paper Cu
Cu Al
Cu Al
Al Co
CoLi
Co LiLiPowder
Powder
Powder
Battery
Battery Group
Group
Battery (g)(g)
Group Average
(g) Average Weight
AverageWeight
Weight (g)
(g)
(g)
(%w/w)
(%
(% w/w)
w/w) (% w/w)
(% w/w) (% w/w)
(% w/w) (%(% w/w)
w/w)
(% w/w)
15–30
15–30
15–30 21.20
21.20
21.20 24.52
24.52
24.52 24.16
24.16 8.84
8.84 41.90
41.90
41.90
30–40
30–40
30–40 34.23
34.23
34.23 21.73
21.73
21.73 4.83
4.83 15.97
15.97 57.40
57.40
57.40
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Figure
Figure 44 shows
shows the
the fractions
fractions obtained
obtained inin this
this study.
study. Figure
study. Figure 4c
4c shows
shows the
the copper
copper and
and aluminum
aluminum
fractions
fractions with
fractions with a particle
with aa particlesize
particle sizegreater than
size greater 0.25
greater than mm,
than 0.25 while
0.25 mm, Figure
mm, while 4d presents
while Figure
Figure 4d the cobalt–lithium
4d presents
presents the powder
the cobalt–lithium
cobalt–lithium
with
powder
powdera particle
with aasize
with smaller
particle
particle sizethan
size 0.105
smaller
smaller mm.
than
than 0.105
0.105 mm.
mm.

(a)
(a) Cover
Cover material
material (b)
(b) Plastic
Plastic and
and paper
paper (c)
(c) Cu–Al
Cu–Al (d)
(d) Co–Li
Co–Li powder
powder
Figure 4.
4. Fractions
Figure 4. Fractions obtained
obtained from
from the
the crushing
crushing and sieving
and sieving of
sieving of batteries.
of batteries.
batteries.
Figure Fractions obtained from the crushing and

3.2. Leaching
3.2. Leaching
Leaching
Leaching was performedininsulfuric
sulfuric acid (2 mol/L) and hydrogen peroxide (6 vol%) at a
Leaching was
was performed
performed in sulfuric acid
acid (2
(2 mol/L)
mol/L) and
and hydrogen
◦ C for hydrogen peroxide
peroxide (6 (6 vol%)
vol%) at
at aa solid-
solid-
solid-to-liquid
to-liquid ratio of 1/10 and a temperature of 75 90 min; the system is shown in Figure 5.
to-liquid ratio
ratio of
of 1/10
1/10 and
and aa temperature
temperature of of 75
75 °C°C for
for 90
90 min;
min; the
the system
system isis shown
shown inin Figure
Figure 5. 5.
Operating
Operating conditions were taken fromfrom
a preliminary work, which reportedreported
that such leaching conditions
Operating conditions
conditions were
were taken
taken from aa preliminary
preliminary work,work, which
which reported that that such
such leaching
leaching
allow for
conditions obtaining the highest efficiency [30].
conditions allow
allow for
for obtaining
obtaining the
the highest
highest efficiency
efficiency [30].
[30].

Figure
Figure 5.
5. Experimental
Figure 5. Experimental setup
setup for
setup for acid
for acid leaching.
acid leaching.
leaching.

It
It has been reported
has been reported that the addition
that the addition ofof hydrogen
hydrogen peroxide
peroxide helps
helps to
to dissolve
dissolve cobalt
cobalt and
and lithium
lithium
oxides [10].
[10]. After
After the
the leaching
leaching step,
step, the
the product
product solution
solution waswas filtered,
filtered, and and
the the cobalt
cobalt
oxides [10]. After the leaching step, the product solution was filtered, and the cobalt concentration concentration
concentration was
was
was analyzed
analyzed
analyzed by
by atomic
by atomic atomic absorption
absorption spectrometry
spectrometry
absorption (AAS)
spectrometry (AAS)
usingusing
(AAS) aa Perkin
a Perkin
using Elmer
Perkin Elmer AAnalyst
AAnalyst
Elmer 200. 200.
AAnalyst WithWith
200. this
With
this process,
process, an an average
average concentration
concentration of of 10–12
10–12 g/Lg/L
forfor cobalt
cobalt was
was obtained.
obtained. The
The Co–Li
Co–Li
this process, an average concentration of 10–12 g/L for cobalt was obtained. The Co–Li powder before powder
powder before
leaching
leaching
leachingand and residue
andresidue after
residueafter leaching
afterleaching were
leachingwere characterized
werecharacterized
characterized using
using aa D8
a D8
using D8 Bruker
Bruker
Bruker X-ray
X-ray diffractometer,
diffractometer,
X-ray andand
diffractometer, the
and
the results are shown in Figure 6. Figure 6a shows the presence of different cobalt–lithium
the results are shown in Figure 6. Figure 6a shows the presence of different cobalt–lithium oxides and oxides and
aluminum,
aluminum, copper,
copper, and
and graphite.
graphite. Figure
Figure 6b
6b confirms
confirms that
that the
the decrease
decrease of of these
these metal
metal oxide
oxide peaks
peaks was
was
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results are
Batteries shown
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REVIEW and
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aluminum, copper, and graphite. Figure 6b confirms that the decrease of these metal oxide peaks was
observed
observed only
onlyin in
thethe
presence
presence of of
carbon
carbon peaks
peaksininthe
theresidue.
residue.The
Thegraphite
graphitepeaks
peaksreported
reported to
to appear
appear in
thein2θthe 2θ range
range werewere ◦ , 43–46
at 25–28°,
at 25–28 ◦ , andand
43–46°, ◦ [7,10].
54–56°
54–56 [7,10].

Figure 6. Spectra of X-ray diffraction analysis before (a) and after (b) leaching. Al2O3 PDF Card #00-
Figure 6. Spectra of X-ray diffraction analysis before (a) and after (b) leaching. Al2 O3 PDF Card
010-0173, Cu PDF Card #00-004-0836, C (graphite) PDF Card #00-026-1079, Li0.9Ni0.5Co0.5O2−x PDF Card
#00-010-0173, Cu PDF Card #00-004-0836, C (graphite) PDF Card #00-026-1079, Li0.9 Ni0.5 Co0.5 O2−x
#00-050-0509, LiAlO2 PDF Card #00-044-0224, and LiCoO2 PDF Card #00-050-0653. PDF = Powder
PDF Card #00-050-0509, LiAlO2 PDF Card #00-044-0224, and LiCoO2 PDF Card #00-050-0653. PDF =
Diffraction File.
Powder Diffraction File.

3.3.3.3. Effect
Effect of of
pHpHonon Extraction
Extraction
Based on preliminary tests, an evaluation pH range between 2 and 7 was used, with steps of 1
Based on preliminary tests, an evaluation pH range between 2 and 7 was used, with steps of 1 unit.
unit. After sulfur acid leaching, the aqueous phase obtained a pH near 0. Then, in order to control
After sulfur acid leaching, the aqueous phase obtained a pH near 0. Then, in order to control pH,
pH, a sodium hydroxide concentrated solution was added. Figure 7 shows that the extraction
a sodium hydroxide concentrated solution was added. Figure 7 shows that the extraction percentage
percentage increased as pH increased. For cobalt extraction, pH was a key factor. Within the
increased as pH increased. For cobalt extraction, pH was a key factor. Within the evaluation range for
evaluation range for pH values, there were low extraction percentages, starting from 7% to 12% for a
pHpH values, there were low extraction percentages, starting from 7% to 12% for a pH range from 2 to 3,
range from 2 to 3, up to yield values as high as 92% or 93% with pH values of 6 and 7.
up to yield
The values
effect ofaspH
high
onas 92% or 93%
extraction can with pH values
be explained in of 6 and
terms of 7.
the extraction mechanism, which
The effect of pH on extraction
occurs by ionic exchange, as follows [31]:can be explained in terms of the extraction mechanism, which
occurs by ionic exchange, as follows [31]:
Co2+aq + 2(RH)2 org ↔ Co(R2H)2 org + 2H+aq (4)
2+ +
Co aq
where RH is the acid extractant + 2(RH)
Cyanex 272 ↔ Co(Rand
molecule,
2 org 2 org +2 2H
2 H)2(RH) the organic complex formed(4)
org is aq

in the organic phase.

where RH is the acid extractant Cyanex 272 molecule, and 2(RH)2 org is the organic complex formed in
the organic phase.
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Figure 7. Effect of pH on extraction: aqueous-to-organic-phase ratio (A/O) = 1, initial concentration of

Figure 7.7.Effect
Effectof(Xi)
ofpH
pH ononextraction:
extraction:aqueous-to-organic-phase ratio (A/O) ==1,1,initial
initialconcentration of
Figure
aqueous phase = 12 g/L, [Cyanexaqueous-to-organic-phase
272] = 0.4 mol/L, time = 12ratio
min,(A/O)
and temperature concentration
= 22 ± 1 °C. of
aqueous phase (Xi) = 12 g/L, [Cyanex 272] = 0.4 mol/L, time = 12 min, and temperature
aqueous phase (Xi) = 12 g/L, [Cyanex 272] = 0.4 mol/L, time = 12 min, and temperature = 22 ± 1 C. = 22 ± 1 °C.◦

3.4. Effect
3.4. of Extractant
Effectofof Extractant Concentration
Concentration
3.4. Effect Extractant Concentration
Cobalt was
Cobalt was extracted
extracted using
using the
the extractant
extractant Cyanex
Cyanex 272272 diluted
diluted inin kerosene.
kerosene. The
The extractant
extractant
Cobalt was extracted using the extractant Cyanex 272 diluted in kerosene. The extractant
concentration
concentrationwas was evaluated
wasevaluated in the
evaluatedininthe range
therange between
rangebetween
between0.10.1 mol/L
0.1mol/L and
mol/Land 0.5
and0.5 mol/L,
0.5mol/L, with
mol/L,with 0.1-mol/L
with0.1-mol/L steps.
0.1-mol/Lsteps.
steps.
concentration
Figure 88 shows
Figure shows that
that the
the extraction
extraction yield
yield increased
increased asas the
the extractant
extractant concentration
concentration increased.
increased. Within
Within
Figure 8 shows that the extraction yield increased as the extractant concentration increased. Within
the evaluation
the evaluation range
range for
for concentration
concentration values, slightly
values,slightly
slightlylowlow values
lowvalues around
valuesaround
around27% 27% were observed
27%were
were observed for
for aa
the evaluation range for concentration values, observed for a
0.1-mol/L extractant
0.1-mol/L extractantconcentration;
concentration; onthe theother
other hand, values as high as 97% or 99% were obtained
0.1-mol/L extractant concentration; on other hand,
hand, values
valuesasashigh
highasas97%
97%oror99%
99% were obtained
were obtainedfor
for concentration
concentration values
values between
between 0.4 mol/L
0.40.4
mol/L and and 0.5 mol/L.
0.50.5
mol/L.
for concentration values between mol/L and mol/L.

100
100
Cobalt extraction %

80
Cobalt extraction %

80

60
60

40
40

20
20

0
0
0 0.1 0.2 0.3 0.4 0.5 0.6
0 0.1 0.2 0.3 0.4 0.5 0.6
Extractant (mol/L)
Extractant (mol/L)
8. Effect of
Figure 8. of extractant
extractant concentration:
concentration: extraction at A/O == 1, Xi
at A/O Xi =
= 11 g/L, pH =
= 6, time =
= 12
12 min,
Figure 8. Effect of extractant concentration: extraction at A/O = 1, Xi = 11 g/L, pH = 6, time = 12 min,
and temperature = ◦ C.
= 22 ±±11 °C.
and temperature = 22 ± 1 °C.
 Batteries2019,
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FOR PEER REVIEW 8 8ofof1313

3.5. Extraction Kinetics

3.5. Extraction Kinetics
Contact time is a key parameter for defining an extraction process. Based on preliminary tests,
Contact time is a key parameter for defining an extraction process. Based on preliminary tests,
an evaluation range for contact time between 2 min and 30 min was used. Figure 9 shows that
an evaluation range for contact time between 2 min and 30 min was used. Figure 9 shows that
extraction percentage increased as the contact time increased. Within the evaluation range, there were
extraction percentage increased as the contact time increased. Within the evaluation range, there were
relatively high values in the extraction percentage that varied from 57% for a contact time of 2 min,
relatively high values in the extraction percentage that varied from 57% for a contact time of 2 min,
up to recovery values as high as 98% from 10 min of operation.
up to recovery values as high as 98% from 10 min of operation.

Figure9.9.Extraction
Figure A/O== 1,1,Xi
Extraction at A/O Xi==10.2
10.2g/L,
g/L,[Cyanex 272]
[Cyanex = 0.4
272] mol/L,
= 0.4 pH =pH
mol/L, 6, and
= 6, temperature = 22 ±=1 22
and temperature ◦ C.

± 1 °C.
3.6. Extraction Isotherm and Stages
3.6. Extraction Isotherm and
The concentration Stages
experimental data was obtained for each phase and is represented in graphical
form,Thewith the aqueousexperimental
concentration phase in thedata
horizontal axis andfor
was obtained theeach
organic
phasephase
and in
is the vertical axis.
represented in
graphical form, with the aqueous phase in the horizontal axis and the organic phase in the
The correlation between the concentration of cobalt in the organic phase ([Co]org ) and the aqueous
vertical
phaseThe
axis. ([Co] aq ) was defined
correlation by Equation
between (4), with: aof= cobalt
the concentration 0.005634419
in theand b = 10198.184.
organic Figure
phase ([Co] 10 shows
org) and the
the isotherm
aqueous phasefrom experimental
([Co] data for cobalt extraction.
aq) was defined by Equation (4), with: a = 0.005634419 and b = 10198.184. Figure

10 shows the isotherm from experimental data for cobalt extraction.

[Co]org = b (1 − e−a[Co]aq ). (5)
[Co]org = b (1 − e−a[Co]aq). (5)
Calculation of Theoretical Stages
3.6.1. Calculation
Based on of theTheoretical
proposed Stages
isotherm model and the McCabe–Thiele method using iterative
software, the extraction steps were calculated by performing parameter variations, such as the
Based on the proposed isotherm model and the McCabe–Thiele method using iterative software,
aqueous-to-organic-phase ratio (A/O) and the initial concentration of aqueous phase (Xi). This method
the extraction steps were calculated by performing parameter variations, such as the aqueous-to-
allowed for obtaining the concentration profiles through steps and a proper extraction process. For an
organic-phase ratio (A/O) and the initial concentration of aqueous phase (Xi). This method allowed
initial concentration of 10 g/L of cobalt in sulfate medium in the aqueous phase, two theoretical
for obtaining the concentration profiles through steps and a proper extraction process. For an initial
extraction stages were obtained. With a rate of A/O = 1.0 and a final concentration of cobalt (Xf) of
concentration of 10 g/L of cobalt in sulfate medium in the aqueous phase, two theoretical extraction
12.18 mg/L, the calculation of these steps is shown in Figure 10.
stages were obtained. With a rate of A/O = 1.0 and a final concentration of cobalt (Xf) of 12.18 mg/L,
the calculation of these steps is shown in Figure 10.
Batteries 2019,
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2019, 5, x FOR PEER REVIEW 9 of 13 13
9 of
Batteries 2019, 5, x FOR PEER REVIEW 9 of 13

Figure
Figure
Figure 10.10.
10. Extraction
Extraction
Extraction stages
stages
stages at at
at A/O
A/OA/O= = 1,
1,
= 1, XiXi
Xi = = 10
10
= 10 g/L,
g/L,
g/L, Xf == 12.18
XfXf =12.18
12.18 mg/L,
mg/L,
mg/L, [Cyanex
[Cyanex
[Cyanex 272]
272] =
272] = 0.4
0.4
= 0.4 mol/L,
mol/L,
mol/L, pH =
pHpH = 6,
6,
= 6,
time
time =
time = 10
10
= 10 min,
min,
min, and
and
and temperature
temperature
temperature ==22
=2222 ◦
±±1±1°C.
1 C.
°C.

InIn
In the
the extraction
the extraction
extraction study
study
study inin
in the
the continuous
the continuous
continuous mixer-settler,
mixer-settler,
mixer-settler, aa flow
aflow ofof
flow
of 5.55.5
5.5 mL/min
mL/min
mL/min was
was used
was used
used for the
forfor the
the
organic phase and a flow of 5.5 mL/min was used for the aqueous phase (A/O = 1), obtaining
organic phase and a flow of 5.5 mL/min was used for the aqueous phase (A/O = 1), obtaining yield ofof
organic phase and a flow of 5.5 mL/min was used for the aqueous phase (A/O = 1), yield
obtaining yieldof
global
global extraction
global
extraction ofof
extraction
of 99%,
99%,
99%, which
which
which allowed
allowed
allowed forfor
for validation
validation
validation ofof
of the
the
the results obtained
results
results obtained
obtained by
bybythe
the
the McCabe–Thiele
McCabe–Thiele
McCabe–Thiele
method.
method. The equipment
The equipment is shown
is shown in the
in
method. The equipment is shown in the Figure 11. Figure
the Figure 11.
11.

Figure 11.
Figure Extraction of cobalt in the continuous mixer-settler.
Figure 11.
11. Extraction
Extraction of
of cobalt
cobalt in
in the
the continuous
continuous mixer-settler.
mixer-settler.

InInorder
order to regenerate the extractant and obtain a cobalt electrolyte solution for subsequent
to regenerate the extractant and obtain a cobalt electrolyte solution for subsequent
electrodeposition,
electrodeposition, the the correlation
correlation between
between the
the concentration
concentration ofof cobalt
cobalt inin
thethe aqueous
aqueous phase
phase ([Co]
([Co] aq)
aq)
aqueous phase ([Co] aq
and the organic phase ([Co]
and org) was defined by Equation (6):
org)) was
the organic phase ([Co]org was defined
defined byby Equation
Equation (6):
(6):
[Co] aq = 23.1338 [Co]org.
[Co]aq = 23.1338 [Co]org. (6)(6)
[Co]aq = 23.1338 [Co]org . (6)
For
For anan initial
initial concentration
concentration ofof 9.630
9.630 g/L
g/L ofof cobalt
cobalt inin the
the organic
organic phase,
phase, two
two theoretical
theoretical extraction
extraction
stages
stagesFor were
were obtained,
an initial
obtained, with
concentration
with a rate
a rate of
ofof9.630
O/AO/A
g/L= of
1.5
= 1.5 and
cobalt
and ainfinal
a finalthe concentration
organic phase,
concentration ofof
twocobalt
ofof 37.87
theoretical
cobalt 37.87 mg/L. The
extraction
mg/L. The
calculation of these
stages wereofobtained,
calculation steps
these stepswithis shown
a rate in
is shown in Figure
O/A =12.
ofFigure 12.
1.5 and a final concentration of cobalt of 37.87 mg/L.
The calculation of these steps is shown in Figure 12.
Batteries 2019, 5, x FOR PEER REVIEW 10 of 13
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13

28
28
Isotherm
24
Isotherm
Experimental
24
Experimental
20
20 stage 1
stage 1
(g/L) 16
16
(g/L)
aq aq

12
[Co]

12
[Co]

8
8

4
4 stage 2
0 stage 2
0 0 4 8 12 16
0 4 8 [Co] org (g/L) 16
12
[Co] org (g/L)
Figure 12. Stripping stages at O/A = 1.5, Xi = 9630 mg/L, Xf = 37.87 mg/L, [H2SO4] = 1 mol/L, time = 4
Figure
min, and
Figure 12. Stripping
Stripping stages
temperature
12. = 22 ±at
stages O/A= =
O/A
1at°C. 1.5,1.5,
Xi Xi = 9630
= 9630 mg/L, Xf = Xf
mg/L, = 37.87
37.87 mg/L,mg/L,
[H2SO[H
4] = SO
4 ] = 1 time
2 1 mol/L, =4
mol/L,
time = 4 min, and temperature = 22 ± 1 C.
min, and temperature = 22 ± 1 °C. ◦

In the stripping operation in the continuous mixer-settler, a flow of 11.0 mL/min was used for
In
Inthe
thestripping
the aqueous stripping
phase andoperation
that ofin16.5
operation the
in continuous
the for mixer-settler,
continuous
mL/min the a flow
mixer-settler,
organic phase of 11.0
a flow
(O/A mL/min
of=11.0 was was
1.5),mL/min
obtainingused for the
used
a yield for
of
aqueous
global phasephase
the aqueous
extractionand
of that
andof
97% 16.5ofamL/min
that
using 16.5 for thefor
mL/min
single organic
extraction phase
the organic
stage after 40 min=of
(O/A
phase 1.5),
(O/A obtaining a yield in
= 1.5), obtaining
operation, as shown aofyield
globalof
Figure
extraction of 97% using
2.global extraction of 97%a using
single aextraction stage after
single extraction 40 after
stage min of40operation, as shown
min of operation, asin Figurein2.Figure
shown
2. Figure
Figure 13
13 shows
shows the
the UV–VIS
UV–VIS spectra
spectra obtained
obtained inin the
the organic
organic phase,
phase, which
which shows
shows that
that the organic
organic
solution
solution could
Figure 13be
could regenerated.
shows
be the UV–VIS spectra obtained in the organic phase, which shows that the organic
regenerated.
solution could be regenerated.

Figure 13.
Figure 13.UV-VIS
UV-VISspectra:
spectra:(a)(a) Cyanex
Cyanex 272272 in kerosene,
in kerosene, (b) organic
(b) organic phasephase after stripping,
after stripping, and (c)
and (c) organic
Figure
organic 13.
phaseUV-VIS
complexspectra: (a) Cyanex
cobalt–Cyanex 272272 in
after
phase complex cobalt–Cyanex 272 after extraction. kerosene,
extraction. (b) organic phase after stripping, and (c)
organic phase complex cobalt–Cyanex 272 after extraction.
Batteries 2019, 5, 44 11 of 13

Batteries 2019, 5, x FOR PEER REVIEW 11 of 13

3.7. Electroplating
2.7. Electroplating
Cobalt was recovered from a cobalt solution with a concentration of 9 g/L using a lead anode and
Cobalt was cathode.
a stainless-steel recoveredInfrom
Tablea cobalt solution
3, the results ofwith a concentration
the current efficiencyofare
9 g/L usingAs
shown. a lead anode
the current
and
was aincreased,
stainless-steel cathode.
the current In Table was
efficiency 3, thehigher.
results This
of theimplies
currentthat
efficiency are shown.
high values As the
of current current
allow for
was increased, the current efficiency was higher. This implies
obtaining cobalt deposition closer to the theoretical deposition mass. that high values of current allow for
obtaining cobalt deposition closer to the theoretical deposition mass.
Table 3. Results of the electrodeposition of cobalt.
Table 3. Results of the electrodeposition of cobalt.
Current (A) Potential (V) Current Density (A/m2 ) Mass (g) Current Efficiency (%)
Current (A) Potential (V) Current Density (A/m2) Mass (g) Current Efficiency (%)
0.25 2.71 50.1 1.1947 66.37
0.25
0.50 2.71
3.07 50.1
100.2 1.1947
1.5484 66.37
68.82
0.50
0.75 3.07
4.02 100.2
150.3 1.5484
1.3698 68.82
76.10
1.00
0.75 4.19
4.02 200.4
150.3 1.3194
1.3698 73.30
76.10
1.50
1.00 5.51
4.19 300.6
200.4 1.4410
1.3194 80.06
73.30
1.50 5.51 300.6 1.4410 80.06
The Figure 14 shows the cobalt layer deposited on the stainless-steel cathode after removing it
fromThe Figure 14 shows
the electrolytic cell. the cobalt layer deposited on the stainless-steel cathode after removing it
from the electrolytic cell.

Figure 14.
Figure Cobalt deposited
14. Cobalt deposited in
in the
the cathode.
cathode.

4. Conclusions
4. Conclusions
A process for the recovery of cobalt from spent lithium-ion mobile phone batteries has been
A process for the recovery of cobalt from spent lithium-ion mobile phone batteries has been
proposed and analyzed. The process involved mechanical conditioning of the batteries, leaching,
proposed and analyzed. The process involved mechanical conditioning of the batteries, leaching,
liquid–liquid extraction, and electrodeposition. The best conditions for the selective separation of
liquid–liquid extraction, and electrodeposition. The best conditions for the selective separation of
cobalt from the leaching-based treatment step, using the commercial extractant Cyanex 272 dissolved
cobalt from the leaching-based treatment step, using the commercial extractant Cyanex 272 dissolved
in kerosene, were defined. It has been determined that the extraction yields were higher, in the range
in kerosene, were defined. It has been determined that the extraction yields were higher, in the range
97–99%, for pH between 6 and 7 and concentration of extractant between 0.4 mol/L and 0.5 mol/L. It is
97–99%, for pH between 6 and 7 and concentration of extractant between 0.4 mol/L and 0.5 mol/L. It
important to mention that the temperature was ambient; thus, no external energy input was required
is important to mention that the temperature was ambient; thus, no external energy input was
in this stage.
required in this stage.
A mathematical model to define the number of extraction and stripping steps for cobalt recovery
A mathematical model to define the number of extraction and stripping steps for cobalt recovery
was established, and its reliability was tested in a continuous process in an experimental mixer-settler
was established, and its reliability was tested in a continuous process in an experimental mixer-settler
system. The best conditions were established for the electrodeposition of cobalt. It has been determined
system. The best conditions were established for the electrodeposition of cobalt. It has been
that increasing the current also increases the current efficiency.
determined that increasing the current also increases the current efficiency.
The proposed process has proved to be efficient for the recovery of cobalt from spent lithium-ion
The proposed process has proved to be efficient for the recovery of cobalt from spent lithium-
mobile phone batteries and has the potential to be scaled to an industrial level, allowing the second
ion mobile phone batteries and has the potential to be scaled to an industrial level, allowing the
use of waste materials and the recovery of high-value metal.
second use of waste materials and the recovery of high-value metal.
Batteries 2019, 5, 44 12 of 13

Author Contributions: All the authors made significant contributions to the development of the experimental
tests, the analysis of results, and the writing of this manuscript.
Funding: The authors wish to thank to Direccción de Apoyo a la Investigación y Posgrado of Universidad de
Guanajuato for the financial support given to this project, 1078/2016.
Acknowledgments: To Enrique Villegas of Cytec Solvay for supplying the extractants. We thank Dra Marina Vega
of the Institute of Geology of the UNAM and M.I.Q. Paloma Eloisa Ramírez of the Universidad de Guanajuato for
their assistance in DRX analysis. Daniel Quintero Almanza thanks the National Council of Science and Technology
(CONACYT, Mexico) for the scholarship granted for his Master degree studies.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design of the
study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; nor in the decision to
publish the results.

References
1. Baldé, C.P.; Forti, V.; Gray, V.; Kuehr, R.; Stegmann, P. The Global E-Waste Monitor 2017; United Nations
University (UNU), International Telecommunication Union (ITU) & International Solid Waste Association
(ISWA): Bonn, Germany; Geneva, Switzerland; Viena, Austria, 2017.
2. Song, Q.; Liang, Y.; Li, J.; Liu, L.; Tan, Q.; Dong, Q. Potential recycling availability and capacity assessment on
typical metals in waste mobile phones: A current research study in China. J. Clean. Prod. 2017, 148, 509–517.
[CrossRef]
3. Zeng, X.; Li, J.; Ren, Y. Prediction of various discarded lithium batteries in China. IEEE Int. Symp. Sustain.
Syst. Technol. 2012, 1–4. [CrossRef]
4. Chagnes, A.; Pospiech, B. A brief review on hydrometallurgical technologies for recycling spent lithium-ion
batteries. J. Chem. Technol. Biotechnol. 2013, 88, 1191–1199. [CrossRef]
5. Horeh, N.B.; Mousavi, S.M.; Shojaosadati, S.A. Bioleaching of valuable metals from spent lithium-ion mobile
phone batteries using Aspergillus Niger. J. Power Sources 2016, 320, 257–266. [CrossRef]
6. Huang, B.; Pan, Z.; Su, X.; An, L. Recycling of lithium-ion batteries: Recent advances and perspectives.
J. Power Sources 2018, 399, 274–286. [CrossRef]
7. Aaltonen, M.; Peng, C.; Wilson, B.; Lundström, M. Leaching of Metals from Spent Lithium-Ion Batteries.
Recycling 2017, 2, 20. [CrossRef]
8. Ordoñez, J.; Gago, E.J.; Girard, A. Processes and technologies for the recycling and recovery of spent
lithium-ion batteries. Renew. Sustain. Energy Rev. 2016, 60, 195–205. [CrossRef]
9. Zheng, X.; Zhu, Z.; Lin, X.; Zhang, Y.; He, Y.; Cao, H.; Sun, Z. A Mini-Review on Metal Recycling from Spent
Lithium Ion Batteries. Engineering 2018, 4, 361–370. [CrossRef]
10. Shin, S.M.; Kim, N.H.; Sohn, J.S.; Yang, D.H.; Kim, Y.H. Development of a metal recovery process from Li-ion
battery wastes. Hydrometallurgy 2005, 79, 172–181. [CrossRef]
11. Meshram, P.; Pandey, B.D.; Mankhand, T.R. Hydrometallurgical processing of spent lithium ion batteries
(LIBs) in the presence of a reducing agent with emphasis on kinetics of leaching. Chem. Eng. J. 2015, 281,
418–427. [CrossRef]
12. Nayaka, G.P.; Manjanna, J.; Pai, K.V.; Vadavi, R.; Keny, S.J.; Tripathi, V.S. Recovery of valuable metal ions
from the spent lithium-ion battery using aqueous mixture of mild organic acids as alternative to mineral
acids. Hydrometallurgy 2015, 151, 73–77. [CrossRef]
13. Nayaka, G.P.; Pai, K.V.; Santhosh, G.; Manjanna, J. Dissolution of cathode active material of spent Li-ion
batteries using tartaric acid and ascorbic acid mixture to recover Co. Hydrometallurgy 2016, 161, 54–57.
[CrossRef]
14. Nayaka, G.P.; Pai, K.V.; Manjanna, J.; Keny, S.J. Use of mild organic acid reagents to recover the Co and Li
from spent Li-ion batteries. Waste Manag. 2016, 51, 234–238. [CrossRef]
15. Li, L.; Dunn, J.B.; Zhang, X.X.; Gaines, L.; Chen, R.J.; Wu, F.; Amine, K. Recovery of metals from spent
lithium-ion batteries with organic acids as leaching reagents and environmental assessment. J. Power Sources
2013, 233, 180–189. [CrossRef]
16. Jian, G.; Guo, J.; Wang, X.; Sun, C.; Zhou, Z.; Yu, L.; Kong, F.; Qiu, J. Study on Separation of Cobalt and
Lithium Salts from Waste Mobile-phone Batteries. Procedia Environ. Sci. 2012, 16, 495–499. [CrossRef]
Batteries 2019, 5, 44 13 of 13

17. Yang, Y.; Xu, S.; He, Y. Lithium recycling and cathode material regeneration from acid leach liquor of spent
lithium-ion battery via facile co-extraction and co-precipitation processes. Waste Manag. 2017, 64, 219–227.
[CrossRef] [PubMed]
18. Yang, Y.; Huang, G.; Xu, S.; He, Y.; Liu, X. Thermal treatment process for the recovery of valuable metals
from spent lithium-ion batteries. Hydrometallurgy 2016, 165, 390–396. [CrossRef]
19. Zhang, J.; Hu, J.; Zhang, W.; Chen, Y.; Wang, C. Efficient and economical recovery of lithium, cobalt, nickel,
manganese from cathode scrap of spent lithium-ion batteries. J. Clean. Prod. 2018, 204, 437–446. [CrossRef]
20. Xiao, J.; Li, J.; Xu, Z. Recycling metals from lithium ion battery by mechanical separation and vacuum
metallurgy. J. Hazard. Mater. 2017, 338, 124–131. [CrossRef] [PubMed]
21. El-Nadi, Y.A. Solvent Extraction and Its Applications on Ore Processing and Recovery of Metals: Classical
Approach. Sep. Purif. Rev. 2017, 46, 195–215. [CrossRef]
22. Kang, J.; Senanayake, G.; Sohn, J.; Shin, S.M. Recovery of cobalt sulfate from spent lithium ion batteries by
reductive leaching and solvent extraction with Cyanex 272. Hydrometallurgy 2010, 100, 168–171. [CrossRef]
23. Wang, F.; He, F.; Zhao, J.; Sui, N.; Xu, L.; Liu, H. Extraction and separation of cobalt(II), copper(II) and
manganese(II) by Cyanex272, PC-88A and their mixtures. Sep. Purif. Technol. 2012, 93, 8–14. [CrossRef]
24. Nan, J.; Han, D.; Zuo, X. Recovery of metal values from spent lithium-ion batteries with chemical deposition
and solvent extraction. J. Power Sources 2005, 152, 278–284. [CrossRef]
25. Nan, J.; Han, D.; Yang, M.; Cui, M.; Hou, X. Recovery of metal values from a mixture of spent lithium-ion
batteries and nickel-metal hydride batteries. Hydrometallurgy 2006, 84, 75–80. [CrossRef]
26. Tanong, K.; Tran, L.-H.; Mercier, G.; Blais, J.-F. Recovery of Zn (II), Mn (II), Cd (II) and Ni (II) from the
unsorted spent batteries using solvent extraction, electrodeposition and precipitation methods. J. Clean. Prod.
2017, 148, 233–244. [CrossRef]
27. Sharma, I.G.; Alex, P.; Bidaye, A.C.; Suri, A.K. Electrowinning of cobalt from sulphate solutions.
Hydrometallurgy 2005, 80, 132–138. [CrossRef]
28. Mishra, K.G.; Singh, P.; Muir, D.M. Electrowinning of cobalt from sulphate solutions contaminated with
organic impurities. Hydrometallurgy 2002, 65, 97–102. [CrossRef]
29. Ouyang, D.; Chen, M.; Liu, J.; Wei, R.; Weng, J.; Wang, J. Investigation of a commercial lithium-ion battery
under overcharge/over-discharge failure conditions. RSC Adv. 2018, 58, 33414–33424. [CrossRef]
30. Rodriguez Godinez, M.A. Estudio de lixiviación para la recuperación de cobalto, litio, cobre, aluminio
y niquel de las baterias de teléfonos móviles (Spanish). Bachelor’s Thesis, Universidad de Guanajuato,
Guanajuato, Mexico, 2017.
31. Evans, H.A.; Bahri, P.A.; Rumball, J.A.; Barnard, K.R. Modelling cobalt extraction with Cyanex 272.
In Proceedings of the International Solvent Extraction Conference 2008—Volume I, Tucson, AZ, USA, 15–19
September 2008; pp. 459–465.

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