Waste Management 30 (2010) 2615–2621

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Waste Management
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Environmental friendly leaching reagent for cobalt and lithium recovery

from spent lithium-ion batteries
Li Li a,b, Jing Ge a, Renjie Chen a,b,⇑, Feng Wu a,b,⇑⇑, Shi Chen a, Xiaoxiao Zhang a
a
School of Chemical Engineering and the Environment, Beijing Key Laboratory of Environmental Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
b
National Development Center for High Technology Green Materials, Beijing 100081, China

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

Article history: We investigated an environmentally friendly leaching process for the recovery of cobalt and lithium from
Received 16 March 2010 the cathode active materials of spent lithium-ion batteries. The easily degradable organic acid DL-malic
Accepted 6 August 2010 acid (C4H5O6) was used as a leaching reagent. The structural, morphology of the cathode materials before
Available online 3 September 2010
and after leaching were characterized by X-ray diffraction (XRD) and scanning electronic microscopy
(SEM). The amount of Co and Li present in the leachate was determined by atomic absorption spectropho-
tometry (AAS). Conditions for achieving a recovery of more than 90 wt.% Co and nearly 100 wt.% Li were
determined experimentally by varying the concentrations of leachant, time and temperature of the reac-
tion as well as the initial solid-to-liquid ratio. We found that hydrogen peroxide in a DL-malic acid solu-
tion is an effective reducing agent because it enhances the leaching efficiency. Leaching with 1.5 M
DL-malic acid, 2.0 vol.% hydrogen peroxide and a S:L of 20 g L1 in a batch extractor results in a highly
efficient recovery of the metals within 40 min at 90 °C.
Crown Copyright Ó 2010 Published by Elsevier Ltd. All rights reserved.

1. Introduction
Secondary or rechargeable lithium-ion batteries (LIBs) are the
batteries of choice in the consumer electronics market (Lupi
et al., 2005; Swain et al., 2007) and are used to manufacture
popular portable electronic devices such as cellular phones, laptop
computers and camcorders because of their favorable characteris-
tics including, high energy density, long life cycles, low self-
discharge and safe handling. With the development of these
products, the number of the secondary batteries has increased tre-
mendously. The higher number of LIBs in use worldwide means
that a higher number of spent batteries will need to be recycled
(Dorella and Mansur, 2007).
A lithium-ion secondary battery consists of a cathode, an anode,
organic electrolyte and a separator. LiCoO2, LiMn2O4, LiNiO2 or re-
lated oxides are used as cathode materials for almost all commer-
cial lithium-ion secondary batteries (Wang et al., 2009). Layered
LiCoO2 is the most widely used cathode material in commercial
LIBs because of its high energy density, high operating voltage
and good electrochemical performance. This material also has sev-
eral disadvantages such as high cost, limited cobalt resources and
⇑ Corresponding author at: School of Chemical Engineering and the Environment,
Beijing Key Laboratory of Environmental Science and Engineering, Beijing Institute
of Technology, Beijing 100081, China. Tel.: +86 10 68912508; fax: +86 10 68451429.
⇑⇑ Corresponding author at: School of Chemical Engineering and the Environment,
Beijing Key Laboratory of Environmental Science and Engineering, Beijing Institute
of Technology, Beijing 100081, China.
E-mail addresses: chenrj@bit.edu.cn (R. Chen), wufeng863@vip.sina.com (F. Wu).
toxicity (Hayashi et al., 2009; Rabah et al., 2008). LIBs contain hea-
vy metals, organic chemicals and plastics including 5–20 wt.% co-
balt, which is a very significant strategic resource, 5–7 wt.%
lithium, 15 wt.% organic chemicals and 7 wt.% plastics (Fouad
et al., 2007; Shin et al., 2005). The metal residues are normally
present at very high concentration levels, sometimes even higher
than those found in natural ores. Metals are among the most com-
monly encountered and difficult to treat environmental pollutants.
Currently, the main options for the treatment of spent LIBs are
reuse, remanufacturing, recycling, incineration and landfilling. In
general, spent LIBs are discarded as domestic waste, which is envi-
ronmentally unacceptable. According to the directives published in
many countries, adequate disposal of spent batteries may involve
landfilling, stabilization, incineration or recycling. In landfills, hea-
vy metals have the potential to leach slowly into soil, groundwater
or surface water (Karnchanawong and Limpiteeprakan, 2009). The
heavy metals contained in spent LIBs such as Co, Li, Fe and Cu may
accumulate in the environment and metal oxides will be converted
into their metallic forms during the incineration of garbage and
may thus result in water pollution (Grimes et al., 2000). Addition-
ally, safe disposal in landfills or the stabilization of battery residues
becomes more and more expensive because of the larger amount of
waste produced and because of the limited storage capacity of san-
itary landfills and/or special waste dumpsites. The environmental
advantage of recovering spent LIBs is not only limited to the reuse
of metals such as Co, Li, Cu, Al and Fe but the use of a toxic and
flammable non-aqueous solvent is not required. The recovery of
major spent cell components is, therefore, beneficial in terms of

0956-053X/$ - see front matter Crown Copyright Ó 2010 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.wasman.2010.08.008
2616 L. Li et al. / Waste Management 30 (2010) 2615–2621
Table 1
Summary of operational conditions for metal recovery from spent Li-ion batteries.
References Process Reagents
Dorella and Hydrometallurgical Acid leaching tests with
Mansur (2007) H2SO4
Mantuano et al. Hydrometallurgical Acid leaching with H2SO4
(2006) and H2O2
Paulino et al. Pyrometallurgical Fusion with KHSO4
(2008)
Zhang et al. (1998) Hydrometallurgical Leaching with H2SO3/
NH2OHHCI/HCI
Lee and Rhee Hydrometallurgical Acid leaching with HNO3
(2003) and H2O2
Contestabile et al. Hydrometallurgical Leaching with 4 M HCl
(2001)
Xin et al. (2009) Bioleaching Sulfur-oxidizing iron-
oxidizing bacteria
Shin et al. (2005) Hydrometallurgical Acid leaching with HCl
environmental protection and also for the provision of raw materi-
als (Pietrelli et al., 2005; Briffaerts et al., 2009).
Considering the undesirable properties of LiCoO2, the develop-
ment of recycling technology for spent LIBs has many advantages
such as being an alternative cobalt resource and mitigation of envi-
ronmental pollution, among others. Several methods have been pro-
posed to treat spent LIBs to recover their valuable metals and these
are shown in Table 1. The existing processes for recycling spent LIBs
are pyrometallurgy (Paulino et al., 2008), hydrometallurgy (Dorella
and Mansur, 2007) and biometallurgy (Mishra et al., 2008). Pyro-
metallurgical processes are often associated with high air emissions
and they require stringent air filtration standards. Economic recy-
cling plants depend on the quality of the recovered products and
on the flexibility of the implemented processes. The bio-hydromet-
allurgical processes have been gradually replacing the hydrometal-
lurgical one due to their higher efficiency, lower costs and few
industrial requirements (Mishra et al., 2008), but the treatment per-
iod is long and the bacteria required are difficult to incubate.
Hydrometallurgy is a well-established process for the separa-
tion and recovery of metal ions, with such benefits as the complete
recovery of metals with high purity, low energy requirements
(Huang et al., 2009), the minimization of wastewater and no air
emissions (Pietrelli et al., 2005). The leaching of LIBs has been
investigated using H2SO4 (Pietrelli et al., 2005; Swain et al.,
2007), HCl (Zhang et al., 1998) and HNO3 (Lee and Rhee, 2003) as
leaching agents followed by treatment of the acid leachate and
management of the final waste (Paulino et al., 2008). When a
strongly acidic solution is used as a leachant more than 99 wt.%
lithium and cobalt can be recovered. However, Cl2, SO3 and NOx
are released during the leach and the acid obtained after leaching
is a threat to the environment.
For the sustainable management of natural resources and to re-
duce environmental pollution, it is important to develop a simple
and environmentally acceptable recycling process to recover as
much of the valuable metals as possible. In this paper, a natural or-
ganic acid was introduced as an environmentally friendly leaching
reagent. DL-malic acid is a member of the C4-dicarboxylic acid
family (Moon et al., 2008), and it dissolves in water easily. The ion-
ization constants K1 and K2 of DL-malic acid are 4.0  104 and
9  106 (Donald and Gellan, 1993). It has been extensively used
in the food industry, the medical field and the manufacturing
industry, among others. Wang used malic acid to dissolve the kao-
linite in soil (Wang et al., 2005). DL-malic acid degrades easily un-
Reaction step Results
1
H2SO4 6% (v/v), S/L ratio 1/30 g L , 55 wt.% of Al, 80 wt.% of Co and 95 wt.% of Li were
1h leached, Li and Al was removed from the solution to
make pure Co2+, and 85 wt.% Co was separated
S:L ratio is 1/50 g ml1, 80 °C, 8 vol.% 37 wt.% Co, 1 wt.% Cu, 85 wt.% Al, and 55 wt.% Li was
leached
1:8–9 sample/flux mass ratio, at Co(OH)2,MnO2, LiF, CaF2, K2SO4, Na2SO4, CaSO4
500 °C for 5 h
T = 60 °C, t = 30 min, S:L = 1:100 About 92wt.% of cobalt and lithium can be leached
within 30 min, NH2OH.HC1 and HCl can leach
cobalt and lithium more effectively than H2SO3
1 M HNO3 20 g L1, 75 °C, 1.7 vol.%, 95 wt.% Co and 95 wt.% Li were leached with
1h 1.7vol.%
80 °C, 1 h Co was leached and NaOH was added to form cobalt
hydroxide in order to synthesize LiCoO2
Energy materials (5%, v/v) 30 °C, at More than 90 wt.% Co 80 wt.% Li were attained
120 rpm, 10–12 d
4 M HCl, 80 °C, 1 h, S/L = 0.02 g ml1 99.5 wt.% Co, 99.9 wt.% Li, 99.8 wt.% Ni and 99.8
wt.% Mn was leached out, NaOH C4H8N2O2, Na2CO3
was added to separate Mn, Ni, Co, Li
der aerobic and anaerobic conditions by comparison to HCl, HNO3
and H2SO4, so these waste solutions can be treated easily. The
remaining DL-malic acid can also be recycled and reused for subse-
quent leaching.
This work focused on finding an environmentally friendly recy-
cling process to recover valuable metals such as cobalt, lithium,
copper and aluminum while avoiding negative impacts on the
environment and human health resulting from spent LIBs.
2. Materials and methods
2.1. Materials and reagents
The spent LIBs used in our study were kindly donated to us by the
students of the Beijing Institute of Technology. N-Methyl-2-pyrroli-
done (NMP) was used to separate the cathode materials from alumi-
num foil. The leaching reagents used in this work consisted of HCl for
characterization at specific concentrations, DL-malic acid (C4H6O5)
and hydrogen peroxide (H2O2) for battery leaching studies.
2.2. Dismantling and characterization of the cathode materials
The material was produced by crushing, sieving, magnetic sepa-
ration and fine crushing. The flow sheet of this process is shown in
Fig. 1. A thermal pretreatment was necessary to eliminate acetylene
black and polyvinylidene fluoride (PVDF) in the cathodic active
materials. The cathode materials from the spent batteries were then
calcined at 700 °C for 5 h in a muffle and then cooled to room tem-
perature. The off gases were purified in a system that consisted of a
cooler, a condensation chamber, filters with activated carbon for
heavy metals removal and bag filters. After roasting and cooling,
the cathodic active materials and dried samples of the powdered
materials were ground with a planetary ball mill for 2 h to enable
easy leaching. Smaller particle sizes lead to better dissolution and
increased leaching efficiency (Shin et al., 2005), and the particle size
of spent LiCoO2 powders after ball milling are <106 lm.
2.3. Metal leaching
All leaching experiments were carried out in a 100 mL three-
necked and round-bottomed thermostatic Pyrex reactor with a
temperature control facility (Lupi et al., 2005). The reactor was fit-
 L. Li et al. / Waste Management 30 (2010) 2615–2621 2617

Fig. 1. Flow sheet for the recovery of Co and Li from spent Li-ion batteries using DL-malic acid as a leachant.

ted with an impeller, a vapor condenser to reduce the loss of water
by evaporation and a thermometer (Swain et al., 2007). A mea-
sured amount of waste LiCoO2 powder was added to the reactor
with agitation provided by the impeller. A known strength and
amount of DL-malic acid and hydrogen peroxide (H2O2) solution
were added into the reactor by a pipettor, and allowed to reach
thermal equilibrium. H2O2 was added to convert cobalt and man-
ganese to their +2 state for subsequent recovery using electro-
chemical, precipitation or solvent extraction techniques (Lupi
et al., 2005). During the leaching experiment, samples were taken
at scheduled intervals. After filtration and washing with water for
three times and then a black residue and a pink solution were ob-
tained. Upon cathode leaching, the following operational variables
were take into account to determine the optimum conditions: con-
centration of DL-malic acid (0.5–3.0 M), the amount of H2O2 (0–2.5
vol.%), solid/liquid ratio (33–17 g L1), temperature (20 –100 °C)
and reaction time (10–50 min).
2.4. Analytical methods
The performance of DL-malic acid was evaluated using an elec-
trochemical workstation (Chi660a). To determine the total
amounts of cobalt and lithium, a sample of cathodic active material
was dissolved completely in concentrated HNO3/HCl (ratio 1/3)
and analyzed using an atomic absorption spectrophotometry
(AAS, huayang-AA-7000) (Vassura et al., 2009; Nan et al., 2005),
and the result was showed in Table 2. The cathode materials were
well as the cathodic active materials that were directly dismantled
from spent LIBs, treated with NMP and calcined at 700 °C for 5 h.
From X-ray diffraction, the cathode composition of the spent LIBs
was found to be LiCoO2, Co3O4 and C, for their peaks could be found
in Fig. 2(a), and the crystalline LiCoO2 phase was clearly identified in
the XRD. The carbon peak difference between the spectra in Fig. 2(b)
and (c) indicates that the carbon powder burnt out during the calci-
nation. However, Co3O4 was present in the calcined dust. XRD data
indicated that the cathodic material contained LiCoO2 and Co3O4
as the carbon and binder burnt off during the calcination at 700 °C.
Fig. 3 shows scanning electron micrographs (SEM) of the leach
residues as well as the LiCoO2 powders that were dismantled from
the cathode of the spent LIBs after treatment with NMP and calci-
nation in a muffle. In Fig. 3(a), the size of LiCoO2 particle is about
1–2 lm, floccules which is PVDF adhere to the LiCoO2 particle sur-
faces. The difference between Fig. 3(a) and (b) is the presence of
these floccules, which means that most of the PVDF dissolved in
NMP and the LiCoO2 particles separated. However, acetylene black
was still present in the cathode materials and Fig. 3(c) shows that
most of the acetylene black burned up. The residue micrographs in
Fig. 3(d) shows irregular morphology compared to Fig. 3(c) (Mukai
et al., 2009). The residues were remaining PVDF from the previous
treatment and unleached Co3O4 because Co3O4 does not dissolve
completely in DL-malic acid.
(003)

characterized using X-ray diffraction (XRD Rigaku, Cu-Ka) and −−LiCoO2

scanning electron microscopy (SEM, Hitachi, S-570), respectively. −−Co3O4
For XRD, the samples were powdered using a tungsten carbide im- −− C
pact mill. The samples were then scanned from 10° to 100° over 2 h
Intencity / a.u.

using 0.5° steps and a count time of 1 s. (104)

(101) (107) (110)

3. Results and discussion (006) (015) (018) (113)

a
3.1. Dismantling and characterization of lithium cobalt oxide in spent
LIBs b

c
The spent LIBs were dismantled and calcined by the route de-
scribed above. Fig. 2 shows XRD patterns of the leach residues as d

Table 2 0 10 20 30 40 50 60 70 80 90 100 110

Li and Co content in cathodic active material of the spent
LIBs. 2 θ / degree
Element Content (w/w) Fig. 2. XRD patterns of the samples: (a) the dismantled cathodic material from a
Li 4.40% spent LIB, (b) the cathodic material after treatment with NMP, (c) the cathodic
Co 53.8% material after dismantling and calcination at 700 °C for 5 h and (d) the leach
residues.
2618 L. Li et al. / Waste Management 30 (2010) 2615–2621

Fig. 3. SEM images of different cathode materials: (a) the dismantled cathodic material from a spent LIB, (b) the cathodic material after treatment with NMP, (c) the cathodic
material after dismantling and calcination at 700 °C for 5 h and (d) the leach residues.

3.2. Performance of the DL-malic acid solution 3.3. Leaching of waste LiCoO2

The amount of released H+ in a solution is determined by the pH
of that solution and the dissociation reaction of DL-malic acid can
be expressed as follows:
COOHCHOHCH2 COOH ! COOHCHOHCH2 COO þ Hþ
COOHCHOHCH2 COO ! COO CHOHCH2 COO þ Hþ
The conductivity of the DL-malic acid solution was measured
and the results are shown in Fig. 4. With an increase in tempera-
ture, the conductivity of the malic acid solution also increases.
When the concentration of malic acid increases from 0.5 to
2.0 M, the conductivity increases significantly. However, when
the concentration of the DL-malic acid was increased from 2.0 to
The leaching reaction between LiCoO2 and DL-malic acid is a
multiphase reaction (Tkáčová et al., 1993) and the reaction
mechanism is shown in Fig. 5. This mechanism takes place at the
surface of the liquid and solid, and the reaction rate is affected
ð1Þ by the concentration of the DL-malic acid and other properties of
ð2Þ the DL-malic acid solution and the LiCoO2 particles. The mecha-
nism of multiphase reactions is generally determined by the chem-
ical reaction and by ion transfer in the solution, while the leaching
reaction is generally governed by whichever of the ion transfer rate
or the chemical reaction rate is the slowest.
Theoretically, the leaching reaction of waste LiCoO2 with a
malic acid solution can be represented as follows:

4LiCoO2 ðsÞ þ 12C4 H6 O5 ðAq:Þ ! 4LiC4 H5 O5 ðAq:Þ þ 4CoðC4 H5 O5 Þ2 ðAq:Þ þ 6H2 OðlÞ þ O2 ðgÞ ð3Þ
þ
4LiCoO2 ðsÞ þ 12C4 H5 O5 ðAq:Þ þ 4Li ðAq:Þ þ 4Co2þ ðAq:Þ ! 4Li2 C4 H4 O5 ðAq:Þ þ 8CoC4 H4 O5ðAq:Þ þ 6H2 OðlÞ þ O2 ð4Þ

3.0 M, the conductivity decreased. At 100 °C, the conductivity of From equations (3) and (4), we can predict that the addition of a
the 2.0 M DL-malic acid solution was highest and the ion transfer reductant will facilitate the forward reaction since the Co(III) in the
rate was also highest. reactant is reduced to Co(II). The chemical reaction in the presence
of a solution containing H2O2 can be represented as:

2LiCoO2 ðsÞ þ 6C4 H6 O5 ðAq:Þ þ H2 O2 ! 4LiC4 H5 O5 ðAq:Þ þ 2CoðC4 H5 O5 Þ2 ðAq:Þ þ 4H2 OðlÞ þ O2 ðgÞ ð5Þ
þ
2LiCoO2 ðsÞ þ 6C4 H5 O5 ðAq:Þ þ 2Li ðAq:Þ þ 2Co2þ ðAq:Þ þ H2 O2 ! 2Li2 C4 H4 O5 ðAq:Þ þ 4CoC4 H4 O5 ðAq:Þ þ 4H2 OðlÞ þ O2 ðgÞ ð6Þ
 L. Li et al. / Waste Management 30 (2010) 2615–2621 2619

90ºC,2.0M 100

90
0.012

Leaching efficency (%)

80

70
.cm-2)

0.010 60

50
Conductivity/ (S

40
0.008
30 Co
20 Li
0.006

ture/( ºC)
100 10
80
0
0.004 60
0.5 1.0 1.5 2.0 2.5 3.0

Tempera
40
Concentration (M)
0.5 1.0 1.5 20
2.0 2.5 3.0 Fig. 6. Effect of DL-malic acid concentration on the leaching of waste LiCoO2 at
Concentr
ation/(M 90 °C for 40 min. (H2O2 = 2.0 vol.%., S:L = 20 g L1 and agitation speed = 300 rpm).
)

Fig. 4. The conductivity of DL-malic acid at different concentrations and

temperatures. Therefore, further studies for waste leaching were carried out using
1.5 M DL-malic acid.

3.3.1. Effect of DL-malic acid concentration on leaching
We also studied the effect of DL-malic acid concentration on the
leaching efficiency of waste LiCoO2. The concentration of DL-malic
acid was varied from 0.5 to 3 M at a S:L of 20 g L1, temperature of
90 °C, reductant concentration of 2.0 vol.% H2O2 and a leaching
time of 40 min. Fig. 6 shows that the leaching efficiency increases
from 26 to 93 wt.% for cobalt and 42 to 99 wt.% for lithium as the
DL-malic acid concentration increases from 0.5 to 1.5 M. The leach-
ing efficiency decreases from 93 to 57 wt.% for cobalt and 99 to 68
wt.% for lithium as the DL-malic acid concentration increases from
1.5 to 3 M. The leaching efficiency trend is the same as that of con-
ductivity for the DL-malic acid at different concentrations. With an
increase in the concentration, the rate of chemical reaction is accel-
erated initially and the transfer rate of ions in the solution begins
to decrease when the concentration of the malic acid increases.
The governing factor for the leaching reaction begins to change
from the chemical reaction rate to the progress of ion transfer.
3.3.2. Effect of H2O2 on leaching
The effect of H2O2 concentration on the leaching efficiency of
the waste cathode active materials was investigated. The waste Li-
CoO2 material was leached with 1.5 M DL-malic acid solution at a
S:L of 20 g L1. During leaching, the temperature was maintained
at 90 °C and the leaching time was 40 min. The results are pre-
sented in Fig. 7 and this figure shows that only 37 wt.% of the co-
balt and 54 wt.% of the lithium were leached in the absence of
H2O2. We also observed that the leaching efficiency of cobalt in-
creased significantly with an increase in the concentration of the
reductant by comparison to the leaching efficiency in the absence
of reductant. From the data presented in Fig. 7, more than 93 wt.%
Co and 99 wt.% Li were leached when the amount of H2O2 exceeded
2.0 vol.%. When the addition of H2O2 was increased from 2.0 to 2.5
vol.%, the increase in leaching efficiency of cobalt and lithium was
insignificant. The solubilization of LiCoO2 involves the reduction
of Co3+ in the solid to Co2+ in the aqueous phase. Eqs. (5) and (6)

Fig. 5. Possible multiphase reaction of the DL-malic acid solution and LiCoO2 particles.
2620 L. Li et al. / Waste Management 30 (2010) 2615–2621

Considering the lower chemical consumption and a relatively bet-

100
ter leaching efficiency, the best conditions for the leaching of co-
balt and lithium from waste LiCoO2 was therefore determined to
be 20 g L1.
Leaching efficency (%)

80

3.3.4. Effect of temperature and time on leaching

60
The effect of temperature and reaction time on the leaching effi-
ciency were studied using 1.5 M malic acid at a S:L ratio of 20 g L1
40 Co and at a reductant concentration of 2.0 vol.%. The leaching results
Li for cobalt and lithium are shown in Fig. 9(a) and (b), respectively.
This figure illustrates that the metal leaching is significantly af-
20 fected by temperature and reaction time. An increase in tempera-
ture and time significantly enhances the leaching efficiency of Co
and Li. The results indicate that only 8 wt.% of the cobalt and 17
0 wt.% of the lithium can be leached at 20 °C and within 10 min.
0.0 0.5 1.0 1.5 2.0 2.5 The leaching efficiency of the metals increased with an increase
Amount of H2O2 (vol. %) in the leaching temperature and the reaction time. At 90 °C and
40 min, 93 wt.% of the cobalt and 99 wt.% of the lithium were lea-
Fig. 7. Effect of H2O2 quantity on the leaching of waste LiCoO2 with 1.5 M DL-malic ched. When the temperature was increased to 75 °C, the recovery
acid at 90 °C for 40 min. (S:L = 20 g L1 and agitation speed = 300 rpm). of cobalt and lithium was found to be 93 and 94 wt.%, respectively.

suggest that the leaching efficiency of lithium and cobalt depends

on the H2O2 concentration. The chemical bond between cobalt and
(a) o
Tm=90 C, time=40min

oxygen is extremely strong and, therefore, the acidic leaching of

100
lithium cobalt oxide is difficult. When hydrogen peroxide is added,
the evolved oxygen from the decomposition of hydrogen peroxide

iency (%)
converts Co(III) to Co(II) and this helps the dissolution (Saeki et al., 80
2004). While hydrogen peroxide helps the dissolution of cobalt, the
dissolution of lithium is also promoted because the two metals are
contained in the same oxide compound. 60

leaching effic
3.3.3. Effect of the solid-to-liquid ratio on leaching 40
Fig. 8 shows the S:L dependency of the leaching of cobalt and
lithium at 90 °C, 1.5 M DL-malic acid, 2.0 vol.% H2O2 and a leaching
20
time of 40 min. The results indicate that the leaching efficiency of 50
cobalt and lithium decreased as the S:L was increased. This figure lea 40 100
ch 80
also shows that 46 wt.% of the cobalt and 63 wt.% of the lithium 30
60
in o )
was leached at a S:L of 33 g L1. When the S:L ratio was decreased g 20 40 (C
tim
to 25 g L1, 78 wt.% of the cobalt and 88 wt.% of the lithium was e( 10 20 at ure
m per
leached. At a S:L ratio of 20 g L1, 93 wt.% of the cobalt and 94 in
) tem
wt.% of the lithium was leached. Total recovery of cobalt and lith-
ium was possible at 17 g L1 but a filtration problem was evident.
(b) o
Tm=90 C, time=40min
100
100
leaching efficiency (%)

80
80
leaching efficency (%)

60

60
40

40 20
Co
Li 100
20 50 80
40
lea 60 o C)
ch
ing
30 40 r e(
tim
20
20 ratu
0 e( 10 pe
15 20 25 30 35 mi
n) tem
Solid/Liquid (g.L-1)
Fig. 9. Effect of leaching temperature and leaching time on the leaching of waste
Fig. 8. Effect of the solid/liquid ratio on the leaching of waste LiCoO2 with 1.5 M DL- LiCoO2 with 1.5 M malic acid (H2O2 = 2.0 vol.%., S:L = 20 g L1 and agitation
malic acid at 90 °C for 40 min. (H2O2 = 2.0 vol.% and agitation speed = 300 rpm). speed = 300 rpm) (a) leaching efficiency of Li and (b) leaching efficiency of Co.
 L. Li et al. / Waste Management 30 (2010) 2615–2621
A further increase in the temperature and reaction time did not
show any significant increase in the recovery of cobalt and lithium.
The apparent activation energy of Co and Li was calculated from
an Arrhenius plot and found to be 12.5 and 11.4 kcal/mol (Lee and
Rhee, 2003), respectively. Both the chemical reaction rate and the
ion transfer rate are significantly affected by the temperature. At
lower temperatures, the leaching reaction is governed by the
chemical reaction and as the temperature increases, the rate of
the chemical reaction increases too, and so the leaching progress
is determined by ion transfer.
From the above-studied parameters and considering the lowest
energy consumption, lowest chemical consumption and improved
leaching efficiency, the best conditions for the leaching of cobalt
and lithium from waste LiCoO2 was determined. Our results
showed that 93 wt.% of the cobalt and 94 wt.% of the lithium can
be leached using a 1.5 M DL-malic acid solution with 2.0 vol.%
H2O2, a 20 g L1, S:L ratio, a 40 min leaching time and a tempera-
ture of 90 °C.
4. Conclusions
Spent LIBs are important raw materials for metals such as lith-
ium, cobalt, aluminum and copper and by recycling the environ-
mental benefits are obvious. In this paper, a hydrometallurgical
route for the recovery of cobalt from spent LIBs was investigated.
Based on our findings, the concentration of DL-malic acid greatly
affects the leaching efficiency of both Co and Li. An increase in tem-
perature and reaction time also increases the leaching efficiency of
Co and Li. The use of a reducing reagent such as H2O2 was found to
be essential in accelerating the dissolution.
We determined the best conditions for cobalt and lithium
leaching from waste LiCoO2 by considering chemical consumption
and leaching efficiency. Using 1.5 M DL-malic acid, 2.0 vol.% hydro-
gen peroxide, a leaching temperature of 90 °C, a S:L ratio of 20 gL1
and a time interval of 40 min nearly 100 wt.% Li and more than 90
wt.% Co were extracted from the spent LIBs.
Acknowledgments
This work was financially supported by the National 973 Pro-
gram (2009CB220106), National High-tech 863 key program
(2007AA03Z226), the National Natural Science Foundation of
China (20803003) and New Century Educational Talents Plan of
Chinese Education Ministry (NCET-10-0038).
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