Hydrometallurgy 151 (2015) 73–77

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Recovery of valuable metal ions from the spent lithium-ion battery using
aqueous mixture of mild organic acids as alternative to mineral acids
G.P. Nayaka a, J. Manjanna b,⁎, K.V. Pai a, R. Vadavi c, S.J. Keny d, V.S. Tripathi d
a
Dept. of Industrial Chemistry, Kuvempu University, Shankaraghatta 577 451, India
b
Dept. of Chemistry, Rani Channamma University, Belagavi 591 156, India
c
PG Dept. of Chemistry, B.K. College, Club Road, Belagavi 590 001, India
d
Chemistry Group, Bhabha Atomic Research Centre, Mumbai 400 085, India

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

Article history: A well characterized cathode material (LiCoO2) recovered from spent lithium-ion battery is dissolved in aqueous
Received 14 May 2014 mixture of citric acid (chelating agent) and ascorbic acid (reductant) at 80 °C. The dissolution proceeds with a
Received in revised form 7 November 2014 reductive-complexing mechanism, and complete dissolution occurs in about 6 h when stoichiometric amount
Accepted 13 November 2014
of C/A is used. The dissolution rate constants (k) are 3.1 × 10−3 min−1 for Li and 0.8 × 10−3 min−1 for Co ions
Available online 18 November 2014
as determined by ‘cubic rate law’ plots. The formation of Co(III)– to Co(II)–citrate during the dissolution is con-
Keywords:
firmed from the UV–Vis spectra. The dissolved solution was subjected for selective precipitation of cobalt as Co-
Lithium-ion battery oxalate and lithium as LiF using oxalic acid and NH4F, respectively. The present study has a merit when compared
Recovery of cobalt and lithium to literature reports as we make use of mild organic acids as alternatives to mineral acids.
Chemical extraction © 2014 Elsevier B.V. All rights reserved.
Citric acid
Oxalic acid
Ammonium fluoride

1. Introduction electrolytes stable at high potential with greater ionic conductivity

Recovery of commercially important metal ions like Co and Li from
spent Li-ion batteries is advantageous considering the limited availabil-
ity of these metal ions and environmental regulations. LiCoO2 as cath-
ode materials was discovered by the research group of Goodenough in
1980 at Oxford University, which established a rechargeable cell within
the 4 V range using LiCoO2 as cathode and lithium metal as anode ma-
terial (Mizushima et al., 1980). LIBs have been introduced to the market
by Sony Corp. in 1991 (Zou et al., 2013; Georgi-Maschler et al., 2012;
Nishi, 2001). These batteries have substituted Ni–Cd and Ni–MH batte-
ries in many applications due to their high energy density, low auto-
discharge rate, and excellent cycle life. Presently, lithium-intercalating
material, typically graphitic carbon is used as anode (negative elec-
trode) and LiCoO2 is the most used cathode (positive electrode) materi-
al in LIB due to their good performance (Armstrong and Bruce, 1996;
Freitas and Garcia, 2007; Xin et al., 2009; Nan et al., 2005), although sev-
eral other oxides such as Ni, Mn-doped LiCoO2, LiMn2O4 and LiFePO4
have been investigated (Castillo et al., 2002). Also, significant improve-
ments in electrolyte (liquid and polymer) system are also underway.
For instance, Nanini-Maury et al. (2014) have reported new liquid
⁎ Corresponding author.
E-mail address: jmanjanna@rediffmail.com (J. Manjanna).
than polymer electrolytes.
LIBs are put to use in all personal computers, cellular phones, cam-
eras and many other modern-life appliances (Ra and Han, 2006; Nan
et al., 2005; Lizuka et al., 2013; Wee, 2007; Swain et al., 2007) and re-
cently in electric vehicles. Thus, LIB consumption is considerably high
around the world. For instance, the household battery industry in the
USA is estimated to be a US $ 2.5 billion industry with annual sales of
nearly 3 billion batteries. These batteries, also known as dry cells, are
used in over 900 million battery-operated devices. In Europe, 5 billion
units of batteries were produced in year 2000 (Bernardes et al., 2004).
In the USA and Europe, the consumption of batteries is estimated to
be 8 billion units per year. In Japan, around 6 billion batteries were pro-
duced in 2004, while almost 1 billion units are consumed every year in
Brazil (Georgi-Maschler et al., 2012; Xu et al., 2008; Salgado et al., 2003;
Gupta and Manthiram, 1996). World LIB production reached 500 mil-
lion units in 2000 and almost 4.6 billion in 2010. Therefore, equally
large amounts of spent LIBs have to be handled after their lifetime.
The increasing public concern on environmental sustainability in
the last decade has resulted in stricter regulations worldwide, for the
adequate destination of hazardous residues from electronic wastage,
including LIBs. These regulations have impelled the society to look for
technical solutions such as e-waste management and resource recycling
techniques. Consequently, the spent LIB material has become an

http://dx.doi.org/10.1016/j.hydromet.2014.11.006
0304-386X/© 2014 Elsevier B.V. All rights reserved.
74 G.P. Nayaka et al. / Hydrometallurgy 151 (2015) 73–77

environmental burden. In China, consumer battery waste amounted from a typical spent LIB and the selective precipitation of constituent
to 200–500 t/year from 2002 to 2006 with significant amounts of metals are reported here. To the best of our knowledge, the present
metals, organic chemicals and plastics in the following proportions: study is the first report for the dissolution of LiCoO2 using ascorbic acid
5–20% Co, 5–10% Ni, 5–7% Li, ~ 15% organic chemicals and ~ 7% plas- as reductant.
tics. This composition varies slightly with different manufacturers
(Li et al., 2010a, 2010b, 2013; A.K. Jha et al., 2013; Sun and Qiu,
2. Experimental
2011). The use of cobalt in LIBs has grown from 700 to 1200 tpa
during the year 1995–2005, which is ~ 25% of cobalt demand global-
Several spent Li-ion batteries of BL-5CA (Nokia) series available in
ly. The other important metal, lithium, has a current demand of
the local market were collected. For safe handling, they were discharged
110,000 tpa and is expected to rise three fold within ten years
completely and then dismantled to separate the cathode and anode ma-
(M.K. Jha et al., 2013; Al-Thyabat et al., 2013; Dewulf et al., 2010;
terials coated on Al- and Cu-foil, respectively. The cathode material was
Georgi-Maschler et al., 2012). A typical LIB contains about 27.5%
scrubbed carefully and heated at 700 °C for 2 h to burn off the organics
LiCoO 2 , 24.5% steel/Ni, 14.5% Cu/Al, 16% carbon, 3.5% electrolyte
such as polyvinylidene fluoride (Li et al., 2010b). More than 90% of the
and 14% polymer (Li et al., 2013). Thus, toxic but commercially im-
this cathode material was found to be LiCoO2 based on X-ray diffraction,
portant metals and flammable compounds (LiBF4 and LiPF6 dissolved
scanning electron microscopy (SEM) and energy dispersive X-ray (EDX)
in organic solvent) present in these spent LIBs must be treated for re-
analysis. The remaining 5–10% is expected to be carbon residue formed
source recycling due to limited availability of these natural resources
due to organic burn off.
and also to meet the environmental regulations. It is impervious to
The above cathode material was subjected for chemical dissolution
note that there is hardly any natural resource of lithium in India.
using mild chemical formulation, an aqueous mixture of citric acid and
The existing methods for recycling spent LIBs are mainly pyro-
ascorbic acid (C–A). In a typical stoichiometric case, 20 mM metal ion
metallurgical and hydrometallurgical processes (Xu et al., 2008;
worth of LiCoO2 sample (0.2 g) was added to 100 ml water containing
Georgi-Maschler et al., 2012). In the pyrometallurgical processes, or-
100 mM of citric acid and 20 mM ascorbic acid (C–A) at 80 °C. The mix-
ganic electrolytes and binder are burnt off and make leaching of
ture was kept stirred for about 6 h. The pH of the formulation before and
valuable metals more easy (Li et al., 2010a; Freitas et al., 2010;
after dissolution was 2.05 and 2.66, respectively. The periodically col-
Wang et al., 2009; Chen et al., 2011). In the hydrometallurgical pro-
lected samples were syringe filtered (0.2 μm) and estimated for Co
cesses, the dismantled electrodes are first dissolved in concentrated
and Li ions using atomic absorption spectrometer (AAS). Also, the UV–
acids followed by recovery of metal ions by precipitation (Castillo et al.,
Vis absorption spectra of the formulation during dissolution (as it
2002; Shin et al., 2005; Ferreira et al., 2009; Li et al., 2010b; Espinosa
turned pink color) were recorded to known the complexation behavior
et al., 2004; Contestabile et al., 1999; Chagnes and Pospiech, 2013).
of Co ions. At the end of dissolution, the undissolved black carbon resi-
Therefore, recycling of constituent metal ions in LIBs has become inev-
due was separated by filtration.
itable towards the development of green technologies and to achieve
On adding stoichiometric amount of oxalic acid to the above dis-
some economical benefits.
solved solution, selective precipitation of Co as Co-oxalate occurred. It
There are many studies on the dissolution of active cathode materials
was separated by filtration, and NH4F (100 mM) was added to the fil-
from spent LIBs using strong acids viz., 2 M H2SO4 (A.K. Jha et al., 2013;
trate to precipitate Li as LiF. The recovery of Co and Li from the dissolved
Chen et al., 2011; Contestabile et al., 2001), 4 M HCl (Contestabile et al.,
solution was estimated by analyzing the filtrate solution for Co and Li by
2001) and 1 M HNO3 (Lee and Rhee, 2002) as leaching agents. The
AAS.
leaching efficiency of Co is highest in HCl when compared to H2SO4
and HNO3 at 80 °C. However, on adding H2O2 (5–20 vol.%) to H2SO4
and HNO3, the leaching efficiency was increased (Chen et al., 2011; 3. Results and discussion
Mantuano et al., 2006; Lee and Rhee, 2003) because H2O2 acts as a
reducing agent in acidic medium. Recently, a novel method to recycle Fig. 1 shows the XRD pattern of the cathodic active material obtained
mixed cathode materials for LIBs has been reported by Zou et al. from the spent LIBs. All the peaks could be indexed to rock-salt struc-
(2013). The authors have dissolved mixtures of LiCoO2, LiMn2O4, tured LiCoO2 (JCPDS 44-0145). The SEM/EDX analysis (not shown
Li(Ni0.33Mn0.33Co0.33)O2 and LiFePO4 in 4 M H2SO4 + 30 wt.% H2O2 at here) confirmed the residual carbon, 5–10 wt.%, present along with
70–80 °C for 2–3 h. The dissolved ions were precipitated as metal this cathode material due to organic burn off. The origin for such carbon
hydroxides at different pH and the Li as Li 2 CO 3 at 40 °C. Finally, might be from the acetylene black (used to ensure the electronic con-
they have succeeded in preparing the same active cathode material, ductivity in the cathodes) and polyvinylidene fluoride (used as a binder
Li(Ni0.33Mn0.33Co0.33)O2, by decomposing these metal hydroxides. to ensure the electrode cohesion).
There are few studies on the use of mild organic acids viz., 1.25 M citric
acid (Li et al., 2010b), 1.0 M oxalic acid (Sun and Qiu, 2012), 1.5 M
aspartic acid (Li et al., 2013) and 1.5 M malic acid (Li et al., 2010a) to
leach metal ions from spent LIBs. All of these reagents have not shown
complete dissolution of Co and Li ions, however, the dissolution was en-
hanced by adding 1–6 vol.% of H2O2 (reducing agent).
To develop environmentally benign process i.e. to avoid using the
mineral acids, we have formulated an aqueous mixture of mild organic
acids containing reductant (ascorbic acid) and chelating cum buffering
agent (citric acid). We believe such a mild formulation should be of
great help in the recovery of metal ions from spent LIBs and/or electron-
ic gadgets, especially during large scale treatment. In fact, it is shown
here that the leaching or chemical extraction efficiency is not compro-
mised with this mild formulation. This is because of the availability of
stoichiometric amounts of H+ ions from these reagents during dissolu-
tion. In the next step, we have succeeded in selective precipitation of co-
balt as Co-oxalate and lithium as LiF towards the recycling of active Fig. 1. Powder XRD patterns of the cathodic material (calcinated at 700 0C for 2 h) from a
cathode material. The details on dissolution behavior of cathode material spent LIB.
 G.P. Nayaka et al. / Hydrometallurgy 151 (2015) 73–77
Fig. 2 shows the % Li and Co ions released from LiCoO 2 in C–A
(100 mM–20 mM) mixture at 80 °C over a period of 6 h. We see about
80% leaching of Co ions whereas almost complete leaching of Li ions.
Such a discrepancy could be ascribed to the nature of spent cathode ma-
terial used here. It is well known that a fraction of Li ions are irreversibly
interacted with the anode (graphite) material during the life-time
charging/discharging process of LIB (Besenhard, 1999). Thus, it is plau-
sible that the oxide sample used here is Li-depleted to about 20%. In our
calculation, we have assumed nominal composition of LiCoO2 instead of
Li1 − xCoO2 and hence we have obtained 100% of Li and about 80% of Co.
However, the presence of 5–10 wt.% carbon residue along with the sam-
ple must be taken into account for knowing the actual amount of metal
ions released here. A small fraction (b5 wt.%) of undissolved black res-
idue was not found to contain any Co or Li ions. Based on these consid-
erations, it is clear that the mild organic acid mixture of CA used here is
able to dissolve the cathode material almost completely. Thus, it is pos-
sible to overcome from the use of mineral acids (M.K. Jha et al., 2013;
Chen et al., 2011; Contestabile et al., 2001; Lee and Rhee, 2002, 2003)
for recovery of valuable metal ions from spent LIB.
We have determined the dissolution rate constant (k) by using a
cubic rate law (Segal and Sellers, 1982), k t = (1 − f)1/3 where f — is
the fraction dissolved at different intervals of time, t. The inset of
Fig. 2 shows the kinetic plots and the corresponding rate constants.
For slow second-stage dissolution, k = 3.1 × 10− 3 min− 1 for Li and
k = 0.8 × 10−3 min−1 for Co. Although the cubic rate law has been de-
rived for spherical particles, it is well demonstrated to be applicable
even for polydispersed particles (Manjanna and Venkateswaran,
2002). We have reported the dissolution behavior only for stoichiomet-
ric (optimum) C/A ratio with respect to the cathode material used here
(LiCoO2). However, it was observed that rate of dissolution increases
with increase in C/A ratio and decreases with decrease in C/A ratio.
We have not paid much attention on these kinetic aspects as the main
focus of this study is to recover the Co and Li though selective precipita-
tion. In the real system application, it is essential to maintain the opti-
mum C/A ratio considering the post processing modalities in this
valuable metal ion recovery.
On adding H2O2 to citric acid, the leaching efficiency of Co and Li in-
creased from 25% to 91% and 54% to 99%, respectively (Li et al., 2010b).
In similar studies, on adding H2O2 in malic acid (Li et al., 2010a) the
leaching of Co increased from 37% to 93% and Li from 54% to 99%;
H2O2 in aspartic acid (Li et al., 2013) increased the leaching of Co and
Li from only 1% to 60%. In all these studies, 1–6 vol.% of H2O2 is used.
Thus, it is beneficial to have a reducing agent along with organic acids.
The reason for enhanced dissolution in all these cases is presumed to
100
80
Dissolution, %
1.0
60
5.2 x 10-3/ min
0.8
0.83 x 10-3/ min
40
(1-f)1/3
0.6
3.1 x 10-3/ min
20
0.4
0.2
0 50 100 150 200 250 300
Dissolution time, min
0 350
0 50 100 150 200 250 300 350
Time, min
Fig. 2. Dissolution profiles of Co and Li. Inset shows cubic rate-law, (1 − f)1/3 vs. time, plots.
75
be due to reductive-complexing mechanism. The Co3+ (d6; r = 0.63 Ǻ)
in the oxide lattice can be easily ejected by reduction to Co2 + (d7;
r = 0.74 Ǻ), which is stabilized by complexation with chelating
agent. In our study, we used ascorbic acid as reducing agent
along with complexing/buffering agent, citric acid. Ascorbic acid
(H2A → 2H+ + 2e + A) is an environmentally benign weak reducing
agent (E = 0.2 V vs. SHE), however, kinetically it has been proven to
be a strong reductant in the metal oxide dissolution studies (Manjanna
et al., 2001). It gives two electrons to form a neutral dehydroascorbic
acid (A). Thus the dissolution follows a reductive-complexing mecha-
nism: Co3+}oxide + e (H2A) → Co2+}oxide → Co2+}(aq.) → Co(II)–citrate.
Such a heterogeneous reaction is expected to occur at the interface of
solid (oxide lattice) and liquid. Once the lattice is disturbed, the sur-
rounding Co3+ as well as Li+ ions will also be leached to solution
through complexation. Both Li and Co ions are expected as citrate com-
plexes because citrate is a strong complexing agent and available in
stoichiometric amount (assuming 1:2 metal-to-ligand ratio), unlike
ascorbate. As the dissolution proceeds, the initially colorless solution
turned pink color and the intensity increased with dissolution time.
This is an indication of Co ion (3d metal) complexation preferably with
citrate ligand. To our knowledge, there are no reports available on the
spectral features of Co(III)– and Co(II)–citrate complexes. Thus, we
have recorded the UV–Vis spectra of the dissolution mixture.
As shown in Fig. 3, it is clear that the absorbance of the solution in-
creased with dissolution time. The maximum absorption (λmax) around
350 nm and 512 nm observed here is attributed to the Co(II)–citrate and
Co(III)–citrate, respectively. Initially, the absorption peak for Co(III)–
citrate alone is seen showing that Co(III) is dominant in the spent
cathode material (LiCoO2). After about an hour, the concentration
of Co(II)–citrate starts building-up due to the reduction of Co(III)–
to Co(II)–citrate by ascorbic acid. Thus, the intensity of Co(II)–citrate
increases rapidly when compared to Co(III)–citrate over the period
of dissolution. Nevertheless, the hump at 512 nm did not disappear
because there was an increase in the entire UV–Vis region, due to
the formation of Co(II)–citrate. In other words, the pull exerted by
the increased absorbance at 350 nm undermines the decrease in ab-
sorbance at 512 nm. A similar behavior is seen during the oxidation
of V(II) to V(III)–formate/NTA (Tripathi et al., 2004). Furthermore,
one cannot rule out the fraction of Co(III)–citrate remaining because
some amount of ascorbic acid is also utilized for deoxygenation of
water in the dissolving medium.
The main reason for choosing the citric acid as complexing agent
here is due to its weak stability constant with metal ions, unlike strong
metal complexes such as Co(III)–EDTA and (log K = 41.4) and Fe(III)–
EDTA (log K = 25.1) (Martell and Smith, 1989). For instance, the log K
of Co(II)–citrate is reported to be 6.187 (Armstrong and Bruce, 1996;
Lee and Reeder, 2006). Such a weak complexation is advantageous
here for the subsequent precipitate of Co(II) ions either as hydroxide
Li 350 nm
a (5 min), b (10 min), c (20 min),
0.4 j d (30 min), e (60 min) f (90 min),
Co g (120 min), h (180 min) i (240 min)
i and j (280 min)
0.3
Absorbance
h
0.2
Co(II)-citrate Co(III)-citrate
g
512 nm
0.1
f
e
350 400
0.0
400 450 500 550 600
400 Wavelength (nm)
Fig. 3. UV–Visible spectra of the dissolved solution at different intervals of time showing
the Co(II)–citrate complex.
76 G.P. Nayaka et al. / Hydrometallurgy 151 (2015) 73–77
Fig. 4. Powder X-ray diffraction pattern of CoC2O4 2H2O precipitate. Inset is the FTIR spec-
tra and photo of cobalt oxalate powder.
or oxalate. And also can be passed through cation-exchange resin to pick
metal ions through dissociation (Ananthan et al., 2003).
At the end of dissolution, on adding oxalic acid (0.63 g which is
worth of 100 mM) to the dissolved solution, the Co(II)–citrate ions
were precipitated as Co(II)–oxalate immediately at room temperature.
Such a solid product could be easily separated by filtration. It was
washed with excess water and dried in oven at ~90 °C for 24 h. Fig. 4
shows the XRD pattern and FTIR spectra (given as inset) of this solid
powder sample. The photo of this sample is also given in the inset of
Fig. 4. The XRD pattern is in good agreement with the reported pattern
for the orthorhombic β-phase of pure crystalline CoC2O4 2H2O with
space group of Cccm (JCPDS file: 25-0250) (Chen et al., 2011). The
FTIR band ~3373 cm−1 has been assigned to O–H stretching vibration
and the band ~ 1623 cm−1 has been assigned to CO stretching. The
two peaks around 1359 cm−1 and 1316 cm−1 are due to the presence
of carbonyl group. These values are similar to the report by Sun and
Qiu (2012). The TG/DTA of this product (not shown here) further con-
firmed the high purity of Co-oxalate with a nominal composition of
CoC2O4 2H2O. This can be readily used as a Co precursor for preparing
the parent cathode material.
After separating the Co-oxalate by centrifugation and membrane fil-
tration (0.2 μm) unit, there was no measurable Co present in the filtrate.
Thus, a complete removal of Co is achieved here. In order to precipitate
the Li-ions, about 100 mM worth of NH4F was added to the above fil-
trate, which led to complete precipitation of LiF as confirmed from the
flame photometry. Although, Co-oxalate and LiF could be used as pre-
cursors to synthesize LiCoO2 for reuse in LIB, we are not in favor of
using LiF for the well-known reason of fluoride contamination. In fact,
we tried to precipitate Li as Li2CO3, however, there was no precipitation
when dry ice (CO2) or Na2CO3 was added to the dissolved solution ei-
ther before or after Co removal. Contestabile et al. (1999), Nan et al.
(2005) and Freitas and Garcia (2007) have reported the precipitation
of Li as Li2CO3 by passing CO2 gas or Na2CO3 in the dissolved medium
wherein only mineral acids (HCl, HNO3 or H2SO4) are used and not
the chelating agents. Thus, it is essential that free Li ions are available
for precipitation. However, in our study, such free Li ions are not avail-
able as we have used complexing agent (citric acid) in the dissolution
formulation. Therefore our efforts are on to oxidize/decompose the cit-
rate ions and then use dry ice to form Li2CO3.
4. Conclusions
Aqueous mixtures of mild organic acids are used here as an alterna-
tive to mineral acids for the recovery of valuable metal ions from spent
Li-ion batteries. As a typical case, the cathode material, LiCoO2, collected
from the spent Li-ion battery (BL-5CA Nokia series) was subjected for
dissolution in a mixture of citric acid (chelating agent) and ascorbic
acid (reductant) at 80 °C. Almost complete dissolution was achieved
via a reductive-complexation mechanism. Based on the cubic rate law,
the dissolution rate constants for the slow second stage were found to
be 3.1 × 10−3 min−1 for Li and 0.8 × 10−3 min−1 for Co ions. UV–Vis
spectra of pink colored dissolved solution confirm the build-up of
Co(II)–citrate (λmax ≈ 350 nm) through the reduction of Co(III)–citrate
(λmax ≈ 512 nm). The dissolved solution was subjected for selective
precipitation of cobalt as Co-oxalate and Li as LiF. There was a complete
removal of both Co and Li from the dissolved solution. Nevertheless, our
attempts are on to recover Li as Li2CO3 which is a suitable precursor for
obtaining the starting material.
Acknowledgment
One of the authors (G.P. Nayaka) gratefully acknowledges Kuvempu
University for financial support (Grant No.: 52/914).
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.hydromet.2014.11.006.
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