research-article2014

Original Article

Waste Management & Research

Hydrometallurgical process for the

2014, Vol. 32(11) 1083­–1093
© The Author(s) 2014
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DOI: 10.1177/0734242X14557380

lithium-ion batteries in citric acid media wmr.sagepub.com

Xiangping Chen and Tao Zhou

Abstract
In this paper, a hydrometallurgical process has been proposed to recover valuable metals from spent lithium-ion batteries in citric
acid media. Leaching efficiencies as high as 97%, 95%, 94%, and 99% of Ni, Co, Mn, and Li were achieved under the optimal
leaching experimental conditions of citric acid concentration of 2 mol L−1, leaching temperature of 80 °C, leaching time of 90 min,
liquid–solid ratio of 30 ml g−1, and 2 vol. % H2O2. For the metals recovery process, nickel and cobalt were selectively precipitated by
dimethylglyoxime reagent and ammonium oxalate sequentially. Then manganese was extracted by Na-D2EHPA and the manganese-
loaded D2EHPA was stripped with sulfuric acid. The manganese was recovered as MnSO4 in aqueous phase and D2EHPA could be
reused after saponification. Finally, lithium was precipitated by 0.5 mol L−1 sodium phosphate. Under their optimal conditions, the
recovery percentages of Ni, Co, Mn, and Li can reach 98%, 97%, 98%, and 89%, respectively. This is a relatively simple route in
which all metal values could be effectively leached and recovered in citric acid media.

Keywords
Leaching, recovery, spent lithium-ion batteries, selective precipitation, solvent extraction, citric acid media

Introduction
Since lithium-ion batteries (LIBs) were first made available on
the market by Sony Corp. in the early 1990s (Castillo et al., 2002;
Contestabile et al., 1999), LIBs have been widely used in mobile
devices (e.g. iPad, iPhone, etc.), personal computers, video cam-
eras, and other modern-life appliances. Their desirable character-
istics, such as modest size and weight, high cell voltage, low
self-discharge rates, and higher energy density, may enable LIBs
to gradually replace nickel–cadmium, nickel–metal hydride, and
other batteries (Castillo et al., 2002; Contestabile et al., 1999;
Zhang et al., 1998). The world’s LIB consumption reached 4.6
billion units in 2010 (500 million in 2000 (Lee and Rhee, 2003)
and 250 million in 1998 (Lee and Rhee, 2002)). The consequence
of the expansion of LIB usage will be an increased demand for
the disposal of spent LIBs in forthcoming years (Contestabile
et al., 1999; Lain, 2001; Lupi and Pasquali, 2003; Zhang et al.,
1998). They usually consist of valuable metals, organic chemi-
cals, and plastics in proportions of 5–20% cobalt, 5–10% nickel,
5–15% manganese, 5–7% lithium, 15% organic chemicals, and
7% plastics, varying with different manufacturers and different
types of batteries (Shin et al., 2005). Since spent LIBs contain a
certain amount of valuable materials, recycling of spent batteries
may result in economic benefits.
Recently, research activities have usually focused on the recov-
ery of cobalt and lithium from spent LIBs by pyro-, hydro-, and bio-
hydrometallurgy processes. Pyro-metallurgical processes may be
not preferable because of intensive energy consumption, hazardous
gases release (such as sulfur dioxide and carbon dioxide), etc. (Li
et al., 2010a; Mishra et al., 2008; Paulino et al., 2008). Bio-
hydrometallurgy processes using Cu2+ as catalyst were studied by
Zeng et al. (2012). The hydrometallurgy processes often consist of
an acid leaching step and a separation or recovery step. Usually, the
acid leaching step is performed using H2SO4 (Chen et al., 2011;
Dorella and Mansur, 2007; Ferreira et al., 2009; Kang et al., 2010;
Mantuano et al., 2006; Nan et al., 2005; Swain et al., 2006, 2007) or
HNO3 (Castillo et al., 2002; Lee and Rhee, 2002, 2003; Li et al.,
2011) and reductants such as H2SO3, NH2OH, and H2O2. For the
recovery of valuable metals from spent LIBs, numerous studies have
reported the solvent extraction method using di-(2-ethylhexyl)phos-
phoric acid (D2EHPA), bis-(2,4,4-tri-methyl-pentyl)phosphinic acid
(Cyanex 272), trioctylamine (TOA), diethylhexylphosphoric acid
(DEHPA), and 2-ethylhexylphosphonic acid mono-2-ethylhexyl
ester (PC-88A) (Dorella and Mansur, 2007; Nan et al., 2005; Zhang
et al., 1998) and the chemical precipitation method using NaOH,
Key Laboratory of Resources Chemistry of Nonferrous Metals,
College of Chemistry and Chemical Engineering, Central South
University, Changsha, China
Corresponding author:
Tao Zhou, Key Laboratory of Resources Chemistry of Nonferrous
Metals, College of Chemistry and Chemical Engineering, Central
South University, Changsha 410083, China.
Email: zhoutao@csu.edu.cn

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1084 Waste Management & Research 32(11)

NH4OH, citric acid, and ammonium oxalate as precipitant

(Contestabile et al., 1999; Lee and Rhee, 2002; Li et al., 2010a,
2010b; Mishra et al., 2008).
As an environment-friendly organic acid, citric acid’s superior
leaching performance, such as high leaching efficiency, absence
of toxic gases during leaching, easy natural degradation, rela-
tively low price, etc., may make it a preferable candidate for the
leaching process. Moreover, several relevant studies have
reported this method for the recovery of Co and Li from LiCoO2
(Li et al., 2010a, 2010b, 2013, 2014). Besides, Hu et al. (2013)
have recently reported the preparation of nano-Co3O4 as anode
materials from spent Li-ion batteries (LiCoO2) and good results
were obtained after the electrochemical performance test.
However, the recovery of valuable metals from spent lithium
nickel cobalt manganese oxide (Li[NixCo1-2xMnx]O2)-based lith-
ium-ion batteries has rarely been reported. Li[NixCo1-2xMnx]O2,
especially LiNi1/3Co1/3Mn1/3O2, provides better performance,
such as higher reversible capacity, improved thermal stability,
lower toxicity, lower cost, etc., over Li–M (M = Ni, Co, Mn)
oxides (Fouad et al., 2007). Therefore, this study was focused on
the recovery of valuable metals from the waste cathode material
LiNi1/3Co1/3Mn1/3O2.
In this study, citric acid and H2O2 were employed as the leach-
ing reagents. For the recovery process, a combined method of
selective precipitation and solvent extraction was performed to
separate and recover each metal from the leach solution. Firstly,
cobalt and nickel were selectively precipitated by ammonium
oxalate ((NH4)2C2O4) and dimethylglyoxime (C4H8N2O2) Figure 1.  Process for the pretreatment of spent LIBs.
sequentially. Manganese was then separated by liquid–liquid
extraction using D2EHPA. Finally, lithium was precipitated ground into powders of cathode active materials. The main steps
using sodium phosphate solution. This hydrometallurgical pro- are listed as follows:
cess is a relatively simple and environment-friendly route and all
valuable metals could be recycled effectively. (1) Dismantling and physical separation: the spent LIBs were
manually dismantled and the plastic and steel cases were
Experimental details removed and recycled. Then the anodes and cathodes were
separated and the cathodes foils were cut into small pieces.
Materials and reagents (2) Ultrasonic-assisted NMP immersion and thermal treatment:
All chemical reagents employed during the experiments were of after dismantling and physical separation, the cathodes foils
analytical grade and all the solutions at specified concentrations were immersed in NMP in an ultrasonic washing container for
were prepared or diluted with deionized water. The extraction 30 min at 80 °C (ultrasonic frequency of 40 Hz at 100 W). The
reagent (D2EHPA) was received from Luoyang Aoda Chemical cathode active materials were effectively peeled off from the
Co., Ltd. with 70%−75% saponification. Tributyl phosphate aluminum foils. NMP could be recycled and reused after filtra-
(TBP) and sulfonated kerosene were also received from Luoyang tion. The aluminum foil was recovered in its metallic form and
Aoda Chemical Co., Ltd. without further treatment. the cathode active materials were calcined in a muffle oven at
800 °C for 2 h to remove carbon and PVDF. Then the powders
were ground in a planetary ball mill for 30 min to reduce parti-
Pretreatment of spent LIBs
cle size and increase surface area of cathodic active materials
The spent LIBs used were collected from different manufacturers which could promote the leaching efficiency.
and with different sizes. The spent LIBs were first discharged and (3) Drying, calcination, and grinding: cathode active materials
dismantled and the cathodes were cut into small pieces. Then were then dried, calcined, and ground subsequently into
N-methyl-2-pyrrolidone (NMP) was employed to separate cath- powders of cathode active materials.
ode active materials from the aluminum foil in an ultrasonic
oscillator. The cathode active materials were then calcined at The pretreatment process for spent LIBs is presented in
800 °C for 2 h to remove carbon, binder, and other impurities and Figure 1. It can be observed that plastics, metallic shells, anodes

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Chen and Zhou 1085
(copper foils), and separator can be directly recycled after dis-
mantling and separation operation. The aluminum foil can be
also recycled in its metallic form after ultrasonic-assisted NMP
immersion operation. The powders of cathodic active materials
with little impurities can be obtained after drying, calcination,
and grinding operations.
Leaching process
Citric acid and H2O2 were used as leaching reagents to leach metals
from spent cathode active materials. As a common organic acid,
citric acid (H3Cit) can be ionized to H+, H2Cit−, HCit2−, and Cit3− in
distilled water. The ionization process can be expressed as follows:
H3Cit → H + + H 2Cit − (1)
H 2Cit − → H + + HCit 2− (2)
HCit 2− → H + + Cit 3− (3)
As a reductant, H2O2 can be oxidized and decomposed to H2O
and O2, which can promote the forward leaching reaction (Kang
et al., 2010; Li et al., 2011). Therefore, this study was focused on
the leaching of waste cathode active materials by H3Cit and H2O2
solution. The leaching reaction can be represented as
2Li [ Ni1/ 3Co1/ 3Mn1/ 3 ] O 2 +
2H3Cit + H 2O 2 = 2Li + +
(4)
2 / 3Ni 2+ + 2 / 3Co 2+ + 2 / 3Mn 2+ +
4Cit 3− + 4H 2O + O 2
The leaching experiments were carried out in a 250-mL three-
necked and round-bottomed thermostatic reactor, which was
placed in a water bath to control the reaction temperature. An
impeller stirrer and a vapor condenser were installed in the reac-
tor to control the stirring rate and water evaporation, respectively.
A fixed amount of waste cathode active material (about 5 g) was
precisely measured and a known quantity of citric acid and H2O2
solution were prepared. They were added to the reactor simulta-
neously. Leaching conditions of citric acid concentration, H2O2
content, liquid–solid ratio (L/S), reaction temperature, and reac-
tion time were manipulated individually to obtain the appropriate
reaction conditions. After leaching, the slurry was filtered and the
residue was washed with distilled water. Then, volume of the fil-
trate was accurately measured and a small amount of it (2 mL)
was used for analysis. The leaching efficiency can be calculated
according to:
M × C0 × V0
L= ×100% (5)
m × w%
where L is the metal leaching efficiency; M and C0 are the molec-
ular mass and concentration of metal ions in the leach liquor,
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respectively; V0 is the volume of the leach liquor; m is the mass
of the waste cathode active materials; and w% is the mass frac-
tion of different metals.
The initial pH of the leach liquor is 2.31 after the filtration of
the leaching residue in this experiment. Figure 2 shows scanning
electron microscopy (SEM) images of waste cathode active
materials after pretreatment and the residues after leaching.
According to the SEM images, it is clear that most of the waste
cathode active materials were dissolved during the leaching reac-
tion. In order to obtain the optimum leaching conditions, leach-
ing experiments under different conditions were investigated,
such as leaching temperature, reaction time, concentration of cit-
ric acid, the liquid–solid ratio, etc. A factor was changed while
other factors were fixed in order to obtain the suitable condition
of each single factor.
Table 1 shows the contents of different metals in cathodic
active materials (w/w) and leach liquor (mg/L). As revealed in
Table 1, the mass contents of nickel, cobalt, and manganese are
equal to each other and lithium holds a less content. After the
pretreatment operation, almost no other impurities ions were
detected, which will greatly facilitate the following metals recov-
ery procedure.
Metals recovery procedure
Nickel and cobalt were selectively precipitated by adding dimethyl-
glyoxime reagent (C4H8N2O2) and ammonium oxalate ((NH4)2C2O4)
to the leach solution, respectively. The leach liquor was treated with
0.05 mol L−1 C4H8N2O2 reagent to recover nickel. The red precipi-
tate of nickel C4H8N2O2 chelate was then dissolved in 4 mol L−1
hydrochloric acid to separate nickel and C4H8N2O2 from each other.
Nickel and C4H8N2O2 were recovered as NiCl2 in aqueous phase
and white powder of C4H8N2O2 after filtering. The reaction of
nickel with C4H8N2O2 can be expressed as follows:
The recycled C4H8N2O2 could be reused as precipitant of
nickel. However, it is impossible to recover nickel only by an
electrolysis method from such a strong acid. Nickel ions in aque-
ous phase can only be precipitated using ammonium hydroxide
(2 mol L−1) in the pH range 4–5 after removal of most of the
hydrochloric acid. Furthermore, Li et al. (2012) reported the sep-
aration and recovery of hydrochloric acid using DF-120 anion
exchange membrane and good results were obtained. Thus,
hydrochloric acid was recovered by membrane separation and
nickel was then selectively precipitated using ammonium
hydroxide (2 mol L−1) under a pH of about 3.5.
Cobalt was subsequently precipitated by ammonium oxalate
and recovered as cobalt oxalate hydrate (CoC2O4·2H2O) after
1086 Waste Management & Research 32(11)

Figure 2.  SEM images of different cathode active materials: (a1, a2) waste cathode active materials after dismantling,
calcination, and grinding; (b1, b2) residues after citric acid leaching.

Table 1.  Contents of different metals in cathodic active impeller stirrer and a vapor condenser were installed in the
materials (w/w) and leach liquor (mg/L). reactor to control the stirring rate and water evaporation,
respectively. A pH meter (PHS-3D, 2000) was applied for pH
Elements Cathodic active Leach liquor
materials (w/w) (mg/L) monitoring and regulating of the leach liquor during the pre-
cipitating of cobalt and nickel.
Ni 17.38 5861
After the recovery of nickel and cobalt, the separation of man-
Co 18.23 6319
Mn 16.77 4097
ganese from the leach solution was conducted by solvent extrac-
Li 6.77 2930 tion in a 125-mL separation funnel. Saponified D2EHPA (70−75%
Others — — saponification rate) was employed as extraction reagent to sepa-
rate Mn2+ from Li+. TBP and sulfonated kerosene were used as
phase modifier and diluent, respectively. Then the Mn-loaded
precipitating and drying operations. Dilute oxalic acid was organic phase was stripped with sulfuric acid solution. Mn2+ was
employed as washing solution to scrub Mn2+ and Li+ from the recovered as MnSO4 in the aqueous phase while D2EHPA in the
precipitate. The precipitation efficiency of each metal can be organic phase was regenerated and reused as the extraction agent
determined as: after being saponified. When the D2EHPA is simplified to ‘HA’,
C0V0 − C1V1 the saponification reaction can be expressed as:
P= ×100% (6)
C0V0
NaOH +1/ 2(HA) 2(org) → NaA (org) + H 2O (7)
where P is the precipitation efficiency of the metal, C0 and C1 are
the concentrations of metal ions in the solution before and after
The mechanism (Chang et al., 2008), in which a metal ion (Men+)
precipitating, and V0 and V1 are volumes of the solution before
is extracted from the aqueous phase using the partially saponified
and after precipitating.
extractant, conforms to the reaction given by:
All the precipitating reactions (including the following pre-
cipitating of lithium) were carried out in a 250-mL three- −
Men + + xA (org) + y / 2(HA) 2(org) →
necked and round-bottomed thermostatic reactor, which was (8)
placed in a water bath to control the reaction temperature. An Me(A) n • ( x + y − n)(HA)(org) + ( n − x)H +

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Chen and Zhou 1087

The extraction efficiency of different metals can be calculated 100

from differences of the concentrations of metals in aqueous phase

before and after extraction, as expressed by:

Leaching efficiency /%
80

C1V1 − C2V2
E= ×100% (9)
C1V1 60

Ni
where E is the metal extraction efficiency, C1 and C2 are the metal Co
concentrations in the aqueous phase before and after extraction, 40 Mn
Li
and V1 and V2 are the aqueous phase volumes before and after
extraction.
20
The recovery of lithium was carried out after the separation of
nickel, manganese, and cobalt. The leach liquor was treated with 20 40 60 80 100

0.5 mol L−1 sodium phosphate to precipitate lithium as lithium Temperature / C o

phosphate (Li3PO4). The solubilities for Li3PO4 and Li2CO3 are

0.039 and 1.33 g/100 mL at 20 °C, indicating the feasibility of Figure 3.  Effect of reaction temperature on leaching
efficiency.
precipitating lithium using sodium phosphate solution (Borgstedt
and Guminski, 2001).
100

Analytical methods Leaching efficiency / %

Cathodic active materials (about 2 g) used were first dissolved in
concentrated hydrochloric acid solution (10 mol L−1) completely 80

and atomic absorption spectrometry (AAS Model 3000, Varian)

was employed to determine the mass percentage of cobalt, nickel,
manganese, and lithium in waste cathode materials. Contents of
nickel, manganese, cobalt, and lithium in the leachate were meas-
ured by inductively coupled plasma/optical emission spectrome-
try (ICP-OES, Optima 2100 DV, Perkin Elmer Instruments,
USA) during the leaching and metals recovery processes. The
precipitate of CoC2O4·2H2O and spent cathode active materials
after pretreatment and leaching were characterized by X-ray dif-
fraction (XRD, Rigaku, Cu-Kα) and SEM (Hitachi, S-570),
respectively. A pH meter (PHS-3D, 2000) was used for the pH
monitoring and regulating.
To avoid random errors, three parallel experiments were per-
formed during the whole leaching and metals recovery processes
and the mean values of leaching and metals recovery efficiency
would be treated as the final experimental results.
Results and discussion
Leaching
Effect of temperature.  As an important reaction condition, the
effect of temperature on leaching efficiency was investigated.
The temperature varied from 20 °C to 90 °C while other condi-
tions were fixed (liquid/solid ratio of 20 mL g−1, 1 vol.% H2O2,
citric acid concentration of 1 mol L−1, and reaction time of 60
min). As can be seen from Figure 3, only about 20% of Ni, Co,
Mn and 35% Li were leached under a low temperature of 20 °C.
Then the leaching efficiencies of Ni, Co, Mn, and Li experienced
a steady increase from 20 °C to 80 °C and attained 92%, 90%,
87%, and 92% for Ni, Co, Mn, and Li at 80 °C, respectively.
Further increase of leaching temperature could not improve the
leaching efficiencies of different metals effectively, which may
Ni
Co
60 Mn
Li
40
40 60 80 100 120 140
Reaction time / min
Figure 4.  Effect of reaction time on the leaching efficiency.
be ascribed to the instability of H2O2 and the decomposition of
H2O2 to H2O and O2.
Effect of reaction time.  The effect of the reaction time on the
leaching efficiency was investigated from 30 min to 150 min
with an interval of 30 min at 80 °C. It is clear that prolonging the
leaching time can effectively promote the leaching efficiencies of
different metals (Figure 4). About 58%, 55%, 51%, and 67% of
Ni, Co, Mn, and Li can be leached within 30 min. Then the leach-
ing efficiency of Ni, Co, Mn, and Li increase rapidly to 93%,
97%, 93%, and 98% under a reaction time of 90 min. Afterwards,
the leaching efficiencies of different metals witness no obvious
change from 90 min to 150 min, indicating that the leaching reac-
tion achieves its reaction equilibrium within 90 min.
Effect of citric acid concentration.  The effect of the citric acid
concentration was investigated at a range of 0.25 mol L−1 to
3.0 mol L−1, under conditions of 80 °C, a liquid–solid ratio of 20
mL g−1, 1 vol.% H2O2, and a reaction time of 60 min. According
to Figure 5, only about 19%, 16%, 14%, and 26% of Ni, Co, Mn,
and Li were leached at a low citric acid concentration of
0.25 mol L−1. Then there is a sharp increase of leaching efficiency

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1088 Waste Management & Research 32(11)

100
100
Leaching efficiency / %

80

Leaching efficiency / %
80

60
Ni Ni
Co 60 Co
Mn Mn
40 Li Li

20 40

0.0 0.5 1.0 1.5 2.0 2.5 3.0

0 2 4 6

Concentration of citric acid / molL-1 Content of H2O2 / vol.%

Figure 5.  Effect of citric acid concentration on leaching Figure 7.  Effect of content of H2O2 on leaching efficiency.
efficiency.

Figure 7 illustrates the effect of the volume concentration of

100 H2O2 (vol.%) on leaching efficiencies of Ni, Co, Mn, and Li for a
controlled leaching time of 60 min at 80 °C. Without the addition
of H2O2, only relatively low leaching efficiencies (51%, 48%,
43%, and 59% for Ni, Co, Mn, and Li, respectively) can be
Leaching efficiency/%

80
60
40
0 10 20 30
L/S (ml•g ) -1
Figure 6.  Effect of the liquid–solid ratio (L/S) on leaching
efficiency.
for each metal from 0.25 mol L−1 to 1.0 mol L−1 and 89%, 86%,
86%, and 80% of Ni, Co, Mn, and Li were leached at a citric acid
concentration of 1.0 mol L−1. From 1.0 mol L−1 to 3.0 mol L−1,
there is a moderate increase for different metals. Therefore, a cit-
ric acid concentration of 2.0 mol L−1 would be a suitable concen-
tration for the effective leaching of Ni, Co, Mn, and Li.
Effect of the liquid–solid ratio and the concentration of
H2O2.  Figure 6 shows the effect of liquid–solid ratio (L/S) on
leaching under a leaching time of 60 min at 80 °C. Only about
44%, 43%, 40%, and 51% of Ni, Co, Mn, and Li were leached at
a low L/S of 5. For L/S values from 5 to 20, there was a drastic
increase in the leaching efficiencies for Ni, Co, Mn, and Li. When
the L/S reaches 30, about 89%, 85%, 83%, and 92% of Ni, Co,
Mn, and Li were leached. Afterwards, the leaching efficiencies of
Ni, Co, Mn, and Li remain stable. Therefore, an increase of L/S
would greatly improve the leaching efficiencies of different met-
als if the L/S is below 30 and an L/S of 30 would be enough to
meet the leaching requirements.
obtained. With the increase of H2O2 concentration from 0 to 2
vol.%, the leaching efficiencies experience a drastic increase to
Ni 85%, 85%, 80%, and 89% for Ni, Co, Mn, and Li, respectively.
Co
Mn Subsequently, the leaching efficiencies increase slowly with the
Li
increase of H2O2 concentration from 2 vol.% to 6 vol.%, arriving
at 93%, 85%, 84%, and 81% of Ni, Co, Mn, and Li, respectively.
This confirmed that the addition of H2O2 can promote the reac-
tion towards the positive direction and effectively improve the
40 50 leaching efficiencies of different metals and excessive H2O2
(over 2 vol.%) cannot further increase the leaching efficiency
effectively. A concentration of 2 vol.% of H2O2 is suitable for the
leaching efficiency.
Metals recovery process
Recovery of nickel.  For the recovery of nickel, 0.05 mol L−1
dimethylglyoxime reagent (C4H8N2O2) was added to the leach
solution while controlling the reaction temperature at 25 °C
and agitation speed of 300 r/min. As a typical analytical chem-
istry reagent, C4H8N2O2 can react with Ni2+ and form nickel
C4H8N2O2 chelate compound (red precipitate) while other
metal ions cannot, which can selectively separate Ni2+ from
other metal ions in citric acid media. Equilibrium pH and the
molar ratio of Ni2+ to C4H8N2O2 (MRNC) were investigated
under conditions of reaction time of 30 min, room temperature,
and stirring rate of 300 r/min.
Equilibrium pH has a significant effect on the precipitation
percentages of different metals (Figure 8). As the equilibrium pH
increases from 2 to 8, the recovery percentage of nickel experi-
enced a continuous increase and reached a maximum of 98% at a
pH of 8. Further increase of pH will lead to adverse results which
may be attributed to unfavorable chelating reactions of nickel and
C4H8N2O2. Co, Mn, and Li cannot be precipitated by C4H8N2O2,

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Chen and Zhou 1089

100 Table 2.  Comparison of precipitation performance between

fresh C4H8N2O2 and recycled C4H8N2O2.
80 Precipitation efficiency (%)a

Elements Fresh C4H8N2O2 Recycled C4H8N2O2

%Recovery

60
Ni Ni 97.98 97.23
Co Co 0.31 0.25
40
Mn Mn 0.06 0.09
Li Li <0.01 <0.01
20
aExperimental conditions: equilibrium pH = 8, MRNC = 0.5, 10 min, 25

°C, and 300 r/min.

0

2 4 6 8 10 12
100
Equilibrium pH

Figure 8.  Effect of equilibrium pH on the recovery of nickel, 80

cobalt, manganese, and lithium (MRNC = 0.5, 25 °C, 10 min,
300 r/min).
60

% Recovery
Co
100
40
Mn
Li
80
20
Ni
Co
%Recovery

60 Mn 0
Li
4 5 6 7 8 9 10
40
Equilibrium pH

20 Figure 10.  Effect of equilibrium pH on the recovery of

0
0.0 0.5 1.0 1.5
MRNC
Figure 9.  Effect of MRNC on the recovery of nickel, cobalt,
manganese, and lithium (equilibrium pH = 8, 25 °C, 10 min,
300 r/min).
which may be attributed to the complicated complexation of cit-
ric acid with these metals. Figure 9 shows the effect of MRNC on
the precipitation efficiency of different metals. For MRNC val-
ues from 0.1 to 0.5, the recovery percentage of nickel remains
stable and a further increase of MRNC from 0.5 to 2.0 will result
in a rapid decline of recovery percentage of nickel from 98% to
18%. Therefore, an equilibrium pH of 8 and MRNC of 0.5 would
be the suitable precipitating conditions under which 98% of
nickel can be precipitated while little other metals are precipi-
tated (less than 1%).
The red precipitate was then dissolved with 4 mol L−1 hydro-
chloric acid and dissociated into NiCl2 in aqueous phase and
white powder of C4H8N2O2. Table 2 lists a comparison of pre-
cipitation performance between fresh C4H8N2O2 and recycled
C4H8N2O2. It can be concluded that fresh C4H8N2O2 and recy-
cled C4H8N2O2 provide similar precipitation performance, which
further confirms that the C4H8N2O2 regenerated can be reused as
precipitant.
different metals (25 °C, MRCC = 1.0, 30 min, and 300 r/min).
2.0 Recovery of cobalt. After the recovery of nickel, ammonium
oxalate (0.5 mol L−1 (NH4)2C2O4) was then added to the leach
solution and cobalt was selectively precipitated as CoC2O4·2H2O
after filtration and drying. The co-precipitation MnC2O4 can be
stripped with dilute oxalic acid (0.01 mol L1 H2C2O4) solution
while CoC2O4 cannot. Therefore, dilute oxalic acid solution (0.01
mol L−1) was used as washing solution to scrub Mn2+ from the
precipitate. To obtain the maximum recovery percentage of cobalt,
effects of equilibrium pH and molar ratio of C2O42− to Co2+
(MRCC) were investigated under conditions of reaction time of
30 min and agitation speed of 300 r/min at room temperature.
Figure 10 shows the effect of equilibrium pH on the recovery
percentages of different metals. For pH values from 2 to 6, the
recovery percentage of cobalt witnesses a sharp increase from
40% to 95%. Then the recovery percentage of cobalt declines
slightly while the recovery percentage of manganese increase
from 1.4% to 8%, which indicate that manganese will be co-pre-
cipitated with Co. The increase of MRCC can promote the recov-
ery percentage of cobalt and manganese from 0.25 to 1.2 (Figure
11), while there is a gradual decline for recovery percentage of
cobalt from MRCC of 1.2 to 2.0. The reason for this phenomenon
may be attributed to the complexation of Co2+ and C2O42−.
Therefore, equilibrium pH of 6 and MRCC of 1.2 are the opti-
mum experimental conditions for the separation and precipitation
of cobalt from the leach solution.

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1090 Waste Management & Research 32(11)

100 sodium hydroxide (10 mol L−1 NaOH) and a small amount of
TBP (5 vol.%) were used as saponifying reagent and phase modi-
fier, respectively. A variety of experimental conditions, such as
80
extraction time, volume content of D2EHPA, equilibrium pH,
etc., were considered to determine the maximum extraction per-
% Recovery

60 Co centage of Mn2+ from the leach solution. After extraction, the

Mn loaded organic phase was washed with dilute sodium carbonate
Li (5 w/v% Na2CO3) to scrub entrained Li+ from the organic phase.
40
Then sulfuric acid with different concentration (0–0.2 mol L−1
H2SO4) was employed to strip Mn2+ from the organic phase.
20 Figure 13 shows the effects of extraction time (t), pH value,
volume ratio of aqueous phase and organic phase (A/O), and vol-
0 ume content of D2EHPA on the extraction of Mn2+ and Li+,
0.5 1.0 1.5 2.0
respectively. From Figure 13(a) it can be concluded that the
MRCC
extraction of Mn2+ and Li+ is a relatively fast chemical reaction
Figure 11.  Effect of MRCC on the recovery of different metals which can reach extraction equilibrium within about 150 s under
(25 °C, equilibrium pH = 6, 20 min, and 300 r/min). conditions of pH = 4, A/O = 1, and 20 vol.% D2EHPA.
Equilibrium pH plays an important role during the extraction
operation (Figure 13(b)) under conditions of reaction time of 300
2000
s, A/O = 1, and 20 vol.% D2EHPA. Only about 66% and 0.2% of
Mn2+ and Li+ were extracted from the leach solution under a low
1600
pH of 1. The extraction percentage of Mn2+ experienced a grad-
CoC2O4•2H2O ual increase and reached 92% for pH values from 1 to 4.
1200 Afterwards, a higher pH will lead to the co-extraction of Li+ with
Intensity

Mn2+, which would not be beneficial to the separation of Mn2+

800
400
0 age of Mn2+ and Li+. About 94% of the Mn2+ was extracted under
0 10 20 30 40 50
2θ ( )
o of 4. Therefore, A/O = 0.5 would be the suitable volume ratio of
Figure 12.  XRD pattern of the precipitate after treating with
(NH4)2C2O4 solution.
Figure 12 shows the XRD pattern of the precipitate after treat-
ment with (NH4)2C2O4 solution, filtering, and drying. From
Figure 12, it can be deduced that the precipitate is mainly consti-
tuted of cobalt oxalate hydrate (CoC2O4·2H2O) while little other
precipitate was detected.
Recovery of manganese. After the separation of nickel and
cobalt, there are mainly manganese and lithium ions left in the
leach solution. D2EHPA and sulfonated kerosene were used as
extractant and diluent to separate and extract Mn2+ from the leach
solution. D2EHPA is a phosphoric acid extraction reagent that
has wide application in the extraction of rare earth metals and
non-ferrous metals. For example, a battery recycling plant in
Spain for spent dry zinc/MnO2 batteries uses D2EHPA to extract
zinc and separate it from manganese (Martin et al., 1999). Usu-
ally, acidic organic extractants should be saponified by alkalis
such as sodium hydroxide (NaOH), ammonium hydroxide
(NH3·H2O), etc. Therefore, D2EHPA was 70−75% saponified by
concentrated sodium hydroxide (10 mol L−1 NaOH) before the
extraction operation. To prevent emulsification, concentrated
and Li+. So the suitable pH would be 4. Figure 13(c) indicates the
effect of A/O on the extraction of Mn2+ and Li+ under conditions
of reaction time of 300 s, pH = 4, and 20 vol.% D2EHPA. The
increase of the A/O ratio would decrease the extraction percent-
60 70 80 A/O values of 0.25 and 0.5 while it declined to 28% under an A/O
aqueous phase and organic phase. Figure 13(d) represents the
volume content of D2EHPA on extraction of Mn2+ and Li+ under
conditions of reaction time of 300 s, pH = 4, and A/O = 1. Under
lower volume percentages of D2EHPA, such as 5 vol.%, 10
vol.%, and 15 vol.%, Mn2+ could not be sufficiently extracted
from the leach solution. The maximum extraction percentage of
Mn2+ (95%) was achieved under 20 vol.% D2EHPA. Further
increase of volume percentage of D2EHPA cannot increase the
extraction percentage of Mn2+ effectively while the extraction
percentage of Li+ experienced a slight increase to about 2%; 20
vol.% of D2EHPA, therefore, would be enough for the recovery
and separation of Mn2+.
After extraction, Mn-loaded D2EHPA was stripped with
H2SO4 solution under different concentrations and different vol-
ume ratios of A/O at room temperature and a stripping time of
300 s. According to Figure 14, a higher volume ratio of A/O and
concentration of H2SO4 solution would be beneficial for the strip-
ping of Mn from the organic phase. About 99% of Mn could be
stripped by a single stripping step on conditions of A/O of 1 and
H2SO4 concentration of 0.2 mol L−1.
Recovery of lithium.  After the recovery of Co, Ni, and Mn, the
leach solution was treated with sodium phosphate (0.5 mol L−1

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Chen and Zhou 1091

100
(a) (b)
80
80

60
%Extraction

%Extraction
60

40
40
Mn Mn
Li
20
Li
20

0 0
0 100 200 300 400 500 600 1 2 3 4 5 6

100
t/s 100
pH
(d)
(c)
80 80
Mn
Li

%Extraction
%Extraction

60 60
Mn
Li
40 40

20 20

0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 5 10 15 20 25 30
A/O Volume content of D2EHPA / vol.%

Figure 13.  Effects of (a) extraction time, (b) pH value, (c) volume ratio of aqueous phase and organic phase (A/O), and (d)
volume content of D2EHPA on the extraction of Mn2+ and Li+ under room temperature and 70−75% saponification of D2EHPA.

100 Table 3.  Ionization equilibrium constants of citric acid,

phosphoric acid, and carbonic acid (25 °C).

80 Items Citric acid Phosphoric acid Carbonic acid

Mn stripping (%)

K1 7.4 × 10−4 7.52 × 10−3 4.2 × 10−7

60
40
20
0 Therefore, Na3PO4 was employed to precipitate Li+ from the
0.00 0.05
Concentration of sulfuric acid / M
Figure 14.  Effects of sulfuric acid concentration and A/O ratio
on the stripping of Mn2+ on conditions of room temperature
and stripping time of 300 s.
Na3PO4) to precipitate Li+ as lithium phosphate (Li3PO4) after
filtrating and drying. Previously, several studies (Ferreira et al.,
2009; Paulino et al., 2008 etc.) had reported the precipitation of
Li+ by saturated sodium carbonate. However, only relatively low
precipitation percentage (around 70–80%) can be achieved by
precipitating Li with Na2CO3. Besides, as revealed in Table 3, the
ionization equilibrium constants (K1, determining the acidity) of
K2 1.7 × 10−5 6.3 × 10−8 5.6 × 10−11
K3 4.0 × 10−7 4.4 × 10−13 —
A/O=0.5
A/O=0.2
A/O=0.1 citric acid is higher than that of carbonic acid while lower than
that of phosphoric acid. So it is impossible to effectively precipi-
tate Li+ by carbonate (Na2CO3 for example) in citric acid media.
0.10 0.15 0.20
leach liquor and about 89% of Li could be recovered.
Purity analysis and recovery route. A purity analysis of the
recovered metals was conducted by using ICP-OES after dissolv-
ing weighted powders (about 0.5 g) of Ni-C4H8N2O2 chelate pre-
cipitate, Co2C2O4·H2O, and Li3PO4 in a concentrated hydrochloric
acid (10 mol L−1) at 80 °C for 30 min. The aqueous phase vol-
umes of the above solutions were precisely measured, and a small
amount (2 mL) of these solutions was drawn out and diluted to an
appropriate concentration for analysis. Manganese in the strip-
ping liquor was directly drawn out (2 mL) and diluted to an
appropriate concentration for analysis. Table 4 shows the results
of the purity analysis. It can be concluded that the purities of Ni,
Co, and Li are 98.46%, 98.47%, and 99.07%, respectively, and

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1092 Waste Management & Research 32(11)

Table 4.  Purity analysis for the recovered metal values: nickel, cobalt, manganese, and lithium.

Elements powder Ni powder (wt %) Co (wt %) Mn solution (mg/L) Li powder (wt %)

Li <0.01 <0.01 15.8 99.07
Ni 98.46 — — —
Co 0.37 96.47 — —
Mn 0.21 1.07 4895.6 —
Others 0.96 2.46 — 0.93

Spent LIBs leaching temperature of 80 °C, leaching time of 90 min, a

liquid–solid ratio of 30 mL g−1, and 2 vol.% H2O2. About
Pretreatment 97%, 95%, 94%, and 99% of Ni, Co, Mn, and Li could be
leached under the above conditions.
2) For metals recovery process, it was possible to recover valu-
Cathode active materials able metals sequentially from the leach liquor as follows:

a. Nickel was selectively precipitated by C4H8N2O2 under

Reductive leaching
Leach solution (Ni2+,
Co2+, Mn2+and Li+)
Precipitating of Ni
Leach solution (Co 2+,
Mn2+and Li+)
Precipitating of Co
Leach solution(Mn 2+and Li+)
Extraction of Mn2+
Leach solution( Li+)
Precipitating of Li
Li3PO4
Figure 15.  Flowchart of the simplified hydrometallurgical
recovery process.
Residues
conditions of an equilibrium pH of 8 and MRNC of 0.5,
which provided a maximum recovery percentage of 95%,
and the recycled C4H8N2O2 could be reused as precipitant.
b. A maximum recovery percentage of 97% for cobalt
Ni-C4H8N2O2
could be achieved under optimum experimental condi-
tions of equilibrium pH of 6 and MRCC of 1.2. The
XRD pattern (Figure 12) shows that the precipitate is
CoC2O4·2H2O.
c. About 98% of Mn was extracted by Na-D2EHPA with
70−75% saponification rate under optimal extraction
CoC2O4·2H2O conditions of 20 vol.% Na-D2EHPA, an A/O of 2, an
equilibrium pH of 4, and extraction time of 300 s. Then
about 99% of Mn could be stripped by a single stripping
step on conditions of A/O of 1 and H2SO4 concentration
of 0.2 mol L−1.
d. Lithium was precipitated by 0.5 mol L−1 Na3PO4 and
Mn loaded D2EHPA
about 89% of the lithium was recovered as Li3PO4.
3) In the citric acid system, the properties of different metal
ions were changed by the complexation of citric acid. It is
difficult and impossible to separate Ni, Co, Mn, and Li from
each other by a single separation method, such as precipita-
tion or solvent extraction. Therefore, a combined method of
selective precipitation and solvent extraction could be a can-
didate to effectively recover and separate each metal from
the leach solution in citric acid media.

the content of Mn in the stripping liquor was much higher than
that of Li.
Figure 15 shows the simplified hydrometallurgical process for
the recovery of metal values from spent LIBs. From the flow-
chart, valuable metals (Ni, Co, Mn, and Li) in cathode active
materials can be recovered by a combined hydrometallurgical
method of selective precipitation and solvent extraction.
Declaration of conflicting interests
The authors declare that there is no conflict of interest.
Funding
This work was supported by the National Natural Science Foundation
of China (grant number 21176266) and the Fundamental Research
Funds for the Central Universities of Central South University (grant
number 72150050350).

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