Beruflich Dokumente
Kultur Dokumente
Department of Environmental Science and Engineering, Graduate School of Science and Engineering, Yamaguchi University, 2-16-1 Tokiwadai, Ube, Yamaguchi 755-8611, Japan
Department of Chemical, Energy and Environmental Engineering, Kansai University, 3-3-5 Yamate, Suita, Osaka 564-8680, Japan
a r t i c l e
i n f o
Article history:
Received 23 March 2012
Received in revised form 24 June 2012
Accepted 26 June 2012
Available online 6 July 2012
Keywords:
Spent lithium-ion secondary batteries
Solvent extraction
Lithium
Cobalt
a b s t r a c t
Acid leach liquors from spent lithium-ion batteries that use lithium cobalt dioxide (LiCoO2) as a cathode
active material contain valuable metals such as cobalt and lithium, as well as common metals such as
aluminum and copper. The objective of this study was to develop a hydrometallurgical process that provides a degree of high selectivity between aluminum, cobalt, copper, and lithium from acidic sulfate
media.
The results from batch experiments showed that a selective hydroxide precipitation approach was not
suitable because a signicant amount of cobalt was coprecipitated with aluminum and/or copper hydroxides. In contrast, batch experiments and the subsequent data analysis indicated that the sequence of solvent extraction circuits using PC-88A, Acorga M5640, and tri-n-octylamine (TOA) extractants effectively
separates four metals of interest. In the rst circuit of the proposed process, copper was selectively
extracted by Acorga M5640 at pH 1.52.0. Aluminum, cobalt, and lithium remained in the aqueous phase.
In the second circuit, aluminum was selectively extracted by PC-88A at pH 2.53.0. For separation of the
remaining cobalt and lithium, Acorga M5640 provided higher cobalt selectivity (separation factor could
not be accurately obtained due to negligible lithium extraction) compared to PC-88A (bCo, 90%/Li = 350 at
pH 4.5) and PC-88A/TOA (bCo, 90%/Li = 1,170 at pH 5.4). However, the stripping efciency of cobalt from the
Acorga M5640 organic phase was found to be low (less than 10%). Therefore, the PC-88A/TOA mixed
extractant rather than Acorga M5640 is a suitable choice for the separation of cobalt and lithium.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Lithium-ion secondary batteries (LIBs) offer several advantages
over other secondary batteries (e.g., nickel metal-hydride batteries) including higher energy density and slower charge loss when
not in use. Because of these favorable characteristics, LIBs are currently widely used for portable electronic apparatuses, and keeps
substituting for other secondary batteries. In Japan, for instance,
according to the machinery statistics released by the Japanese Ministry of Economy, Trade and Industry (METI), LIBs share went from
28% in 2001 to 67% in 2010 market share of secondary batteries [1].
In addition, it is anticipated that their use for automotive and
renewable energy storage applications will further expands their
consumption in the near future. Hence, it is highly desirable to develop a recycling process capable of properly treating spent LIBs for
environmental protection and recovering valuable metals from
them for resource conservation.
At present, lithium cobalt dioxide (LiCoO2) is one of the most
widely adopted cathode active material, although other active
Corresponding author.
E-mail address: tsuzuki@yamaguchi-u.ac.jp (T. Suzuki).
1383-5866/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.seppur.2012.06.034
397
performance of the processes based on these two separation technologies was evaluated in terms of metal recovery and metal selectivity. The proposed process in this study was then compared with
other processes from the literature to determine the advantages of
the proposed process.
It is important to clearly state the reason behind our choice of
H2SO4 to prepare articial acid leach liquors because the counter
anion of metals inuences the metal recovery and separation efciencies in selective precipitation and solvent extraction processes.
The acid leaching of LiCoO2 is usually performed with either H2SO4
[612,15,17,19,23,24], HCl [2,3,8,14] or HNO3 [4,5,8,20,25], often
combined with reducing agents such as H2SO3, NH2OH, and
H2O2. Among these inorganic acids, we assumed H2SO4 is used
for acid leaching based on the following reasons, and the articial
acid leach liquors were prepared using metal sulfate and H2SO4.
First, HCl is highly corrosive and attacks metal materials that are
commonly used in acid leaching facilities. Therefore, to avoid
devoting considerable attention to materials selection, HCl was excluded for the choice of acids. Second, although HNO3 is less corrosive compared to HCl due to its ability to form passive layers, it has
been reported that oxime-type extractants become degraded under prolonged contact time with HNO3 solutions [22]. For these
reasons, in our opinion, H2SO4 is the most appropriate inorganic
acid for acid leaching.
2. Experimental methods
2.1. Materials
All solutions were prepared with distilled deionized (DDI) water
with a resistivity greater than 18 MX cm1 (WA200, Yamato Scientic Co. Ltd., Japan). All chemical reagents (guaranteed reagent
grade) were purchased from Nacalai Tesque, Inc. (Kyoto, Japan)
or Wako Pure Chemical Industries, Ltd. (Osaka, Japan) and used
without further purication. Tri-n-octylamine (TOA, guaranteed
reagent grade) was purchased from Nacalai Tesque, Inc. PC-88A
(2-ethylhexyl 2-ethylhexylphosphonic acid, minimum purity is
95 wt.%) and Acorga M5640 (5-nonyl-2-hydroxy-benzaldoxime,
purity is 3060 wt.%) were kindly donated by Daihachi Chemical
Industry Co. Ltd. (Osaka, Japan) and Cytec Industries Inc. (Woodland Park, NJ, USA), respectively. Kerosene, used as a diluent for organic phases in solvent extraction experiments, was purchased
from Nacalai Tesque, Inc., and its main component was saturated
aliphatic hydrocarbons.
Al: MINEQL+
Cu: MINEQL+
Co, Li: MINEQL+
Al: Experiment
Cu: Experiment
Co: Experiment
Li: Experiment
80
Precipitation (%)
An aqueous solution containing 2.0 103 mol/L of target metal(s) and 0.2 mol/L of Na2SO4 as a back electrolyte was prepared
by dissolving Al2(SO4)31418H2O, CuSO45H2O, CoSO47H2O,
Li2SO4H2O, and Na2SO4 in DDI water. 15 ml of the aqueous
solution was transferred into a 50 ml glass conical ask, and the
pH of the solution was adjusted to the predetermined pH by
slowly adding concentrated H2SO4 or NaOH solutions as required.
The change in volume during pH adjustment was negligible.
Immediately after the pH adjustment, the ask was tightly sealed
with a glass cap and shaken at 160 rpm using a horizontal shaker
(NTS-4000, Tokyo Rikakikai Co. Ltd., Japan) for 2 h at 25 C.
After 2 h of reaction time, the suspension was ltered through a
0.2-lm mixed cellulose ester type membrane lter, and the nal
pH was measured. The ltrate was immediately acidied by
HNO3 to avoid additional metal precipitation and analyzed for
aqueous metal concentrations.
100
60
40
20
0
0
3
4
5
Equilibrium pH
398
100
100
Al: MINEQL+
Cu: MINEQL+
Co, Li: MINEQL+
Al: Experiment
Cu: Experiment
Co: Experiment
Li: Experiment
60
Al
Cu
80
Co
Extraction (%)
Precipitation (%)
80
40
20
Li
60
40
20
0
1
3
4
5
Equilibrium pH
3
4
5
Equilibrium pH
100
Al
Cu
80
Co
Extraction (%)
Li
60
40
20
0
0
3
4
5
Equilibrium pH
Fig. 5. Metal pH isotherms with 10 vol.% PC-88A and 5 vol.% TOA in a kerosene
diluent. Experiments were performed using a single-metal system. Experimental
conditions: Metal concentrations = 2.0 103 mol/L, A/O ratio = 1.0, 25 C.
100
Al
80
Extraction (%)
Cu
Co
60
Li
40
20
0
0
3
4
5
Equilibrium pH
399
Mm
aq nHR2org MRm 2n mHR org mHaq
where (HR)2 represents PC-88A molecules in dimeric form, n represents the number of the dimeric PC-88A molecules involved in the
extraction, and the subscripts aq and org represent the aqueous
and organic phases, respectively. Eq. (1) can be rearranged into Eq.
(3) by combining with the denition of the distribution coefcient D
(Eq. (2))
Al (PC-88A)
Table 1
Separation factor between the metals at the pH 90% of Me1 was extracted.
Me1/Me2
Extractant
Extraction pH
Al/Co
10 vol.% PC-88A
10 vol.% PC-88A
+ 5 vol.% TOA
10 vol.% PC-88A
10 vol.% PC-88A
+ 5 vol.% TOA
10 vol.% PC-88A
10 vol.% PC-88A
+ 5 vol.% TOA
2.8
3.8
2480
1550
2.8
3.8
17,400
51,300
4.5
5.4
350
1170
Al/Li
Co/Lia
Table 2
Effect of H2SO4 concentration on metal stripping efciencies from loaded organic
phases.
Element
Extractant
Aqueous
equilibrium
pH for
loaded
extractants
preparationa
Stripping
H2SO4 conc.
(mol/L)
Stripping
efciency
(%)
Cu
10 vol.%
Acorga M5640
1.9
Al
10 vol.%
PC-88A
2.3
Co
10 vol.%
Acorga M5640
5.7
Co
10 vol.%
PC-88A + 5 vol.% TOA
5.7
1.0
2.0
3.0
1.0
2.0
3.0
1.0
2.0
3.0
1.0
2.0
3.0
80.1
94.6
98.7
92.7
100
100
4.5
3.9
8.8
91.9
98.8
98.9
a
The metal extraction efciencies at these pH values were nearly 100% as shown
in Figs. 35.
Co (PC-88A)
Li (PC-88A)
Al (PC-88A/TOA)
Co (PC-88A/TOA)
Li (PC-88A/TOA)
2
2
3
log D
1
1
1
-1
1
1
-2
0
3
4
5
Equilibrium pH
Fig. 6. Relationship between the metal distribution coefcient (log D) and the
aqueous equilibrium pH for 10 vol.% PC-88A (solid) and 10 vol.% PC-88A/5 vol.%
TOA (open). Experimental conditions: Metal concentrations = 2.0 103 mol/L, A/O
ratio = 1.0, 25 C.
Additional batch experiments were performed to obtain information on the metal stripping efciency, which is also an essential
aspect to be considered in developing the solvent extraction process. For these experiments, organic phases containing extracted
metals were rst prepared by repeating the experiments represented by Figs. 35. The initial aqueous pH was adjusted so that
nearly 100% of the metals were extracted into the organic phases.
Then, 15 ml of the loaded organic phase were shaken for 2 h with
15 ml of H2SO4 solutions of various concentrations, and the metal
stripping efciency was obtained. The experimental results are
shown in Table 2. While more than 95% of metal stripping efciency was obtained in most cases, cobalt extracted with Acorga
M5640 was not easily stripped, even with the 3.0 mol/L H2SO4
solution. Unfortunately, it was beyond the scope of this study to
investigate the chemical reactions between extracted cobalt and
Acorga M5640 in kerosene, which is why the low cobalt stripping
efciency from Acorga M5640 organic phases was not fully elucidated. However, it has been well documented in the literature that
cobalt(II) is oxidized to cobalt(III) by hydroxyoxime-type extractants and stabilized in the organic phase. As a result, the recovery
of cobalt(II) by stripping is difcult [2931]. Therefore, although
400
Acorga M5640 provided higher cobalt selectivity over lithium compared to PC-88A/TOA, PC-88A/TOA mixed extractant rather than
Acorga M5640 is an advisable choice for the separation of cobalt
and lithium.
3.5. A proposed hydrometallurgical process for separating Al, Co, Cu,
and Li
In the literature, chemical precipitation methods are often applied for valuable metal separation from acid leach liquors of spent
secondary batteries [3,5,11,13,15,17,18,32,33]. For instance, Dorella and Mansur [11] performed selective precipitation and solvent
extraction experiments aiming to develop a hydrometallurgical
process for the recovery of cobalt from spent LIBs. It is important
to note that they manually separated the anode and cathode before
the acid leaching step. Therefore, the metal components included
in the acid leach liquors were aluminum, cobalt, and lithium (copper used for the anode substrate was not included). According to
the separation process they proposed, aluminum was rst removed
by hydroxide precipitation, followed by solvent extraction with
Cyanex 272 to extract cobalt. However, a signicant amount (more
than 50%) of cobalt was coprecipitated with aluminum hydroxide
when the pH increased to 7.0 to precipitate nearly 100% of the aluminum. As a result, a high recovery of cobalt with high purity was
not feasible with this process. These ndings are qualitatively consistent with our results (Fig. 2). More recently, Provazi et al. [18]
comprehensively compared selective precipitation and solvent
extraction processes for the selective separation of metals contained in the main types of spent secondary batteries. Based on
their experimental results, they concluded that selective precipita-
Table 3
Comparison of cobalt/lithium separation factors between the processes used in this study and those in the literature. All studies were performed at ambient temperature, O/A
ratio = 1.0, using kerosene as a diluent and sulfate media.
References
This studya
This studya
Swain et al. [8]
Swain et al. [10]
Chen et al. [19]
a
Lithium
0.118
0.118
0.59
6.52
20
0.013
0.013
0.138
4.49
2.5
Extractant
10 vol.% PC-88A
10 vol.% PC-88A + 5 vol.% TOA
0.03 M Na-Cyanex 272 + 5 vol.% TBPc
0.75 M Cyanex 272 + 5 vol.% TBPc
25 wt.% PC-88A (known as P507 in China)
Separation factor
90
90
85
100
80
350
1,170
60
380
55
Quoted from Table 1; 2.0 103 mol/L corresponds to 0.118 g/L and 0.014 g/L for cobalt and lithium, respectively.
Separation factors for our previous study were calculated using slope analysis. Conversely, separation factors reported in the literature were calculated directly from
experimental results.
c
TBP (tributyl phosphate) was added as a phase modier.
b
[10]
[11]
[12]
[15]
[13]
[14]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
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