Waste Management 93 (2019) 153–161

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Recycling valuable metals from spent lithium-ion batteries by

ammonium sulfite-reduction ammonia leaching
Caibin Wu a,⇑, Bensheng Li a,b, Chengfang Yuan a, Shuainan Ni a, Lifeng Li c
a
School of Resources and Environmental Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, China
b
Jiangxi Key Laboratory of Mining & Metallurgy Environmental Pollution Control, Ganzhou 341000, China
c
Jiangxi Mingxin Metallurgical Equipment Co., Ltd, Ganzhou 341000, China

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

Article history: The cathode powder is obtained by wet crushing and screening, and the leaching behavior of Li, Ni, Co, Cu,
Received 5 February 2019 and Al is then investigated using a ternary leaching system composed of ammonia, ammonium sulfite,
Revised 19 April 2019 and ammonium bicarbonate. Ammonium sulfite is necessary as a reductant to improve the Li, Ni, and
Accepted 19 April 2019
Co leaching efficiencies, and ammonium bicarbonate acts as a buffer in ammoniacal solutions. A detailed
Available online 25 May 2019
understanding of the selective leaching process is obtained by investigating the effects of parameters
such as the leaching reagent composition, leaching time (0–300 min), temperature (40–90 °C), solid-
Keywords:
to-liquid ratio (10–50 g/L), and agitation speed (300–700 rpm). It is found that Ni and Cu could be almost
Spent lithium-ion battery
Ammonia leaching
fully leached out, while Al is hardly leached and Li(60.53%) and Co(80.99%) exhibit a moderate leaching
Metals recycling efficiency. The results show that the optimum solid-liquid ratio of the leaching system is 20 g/L, and the
Kinetics increase of temperature and reaction time is beneficial to metal leaching. The leaching kinetics analysis
shows that the chemical reaction control explains the leaching behavior of Li, Ni, and Co well. Therefore,
this work may be beneficial for further recycling valuable metals from leaching solutions by introducing
an extraction agent.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction
Lithium-ion batteries (LIBs) are currently widely used for pro-
viding electrochemical power to mobile phones, laptops, new
energy vehicles, and other modern appliances as they have a high
energy density (Hou et al., 2018), long life cycles, low self-
discharge, and are safe to handle (Paulino et al., 2008; Li et al.,
2011). To achieve these properties, various multifunctional carbon
materials are used to prepare lithium ion battery electrodes. Such
as carbonized melamine foam (Qu et al., 2019), graphene
nanosheets (Kirubasankar et al., 2018), nitrogen-doped porous hol-
low carbon spheres (Zhao et al., 2019) and nitrogen sulfur dual
doped graphene sheets (Idrees et al., 2019). In 2016, the global
LIB market exceeded 90 GWh, a year-on-year increase of 18%,
and the industrial scale reached $37.8 billion, a year-on-year
increase of 16% (Cedi Think Tank Institute, 2017). China’s Ministry
of Industry and Information Technology stated that the output of
LIBs in China was 118 million natural in 2017. The recent develop-
ment of the electric vehicle industry has stimulated growth in the
use of LIBs. However, the battery performance is rarely specified
⇑ Corresponding author.
E-mail address: wushirle@sina.com (C. Wu).
for over 1000 cycles on average (Li et al., 2016), therefore, LIBs have
a short life of 3–5 years whether they are used or not
(Whittingham, 2004; Tarascon and Armand, 2001). This growing
consumption will generate significant amounts of spent LIBs. It is
estimated that the quantity and weight of discarded LIBs will
exceed 25 billion units and 500 thousand tons in 2020, respectively
(Zeng et al., 2014). Spent LIBs contains many toxic materials,
including heavy metals such as Cu, Co, and Ni, and organic chem-
icals such as electrolytes and separators (Choubey et al., 2017). The
disposal of spent LIBs into landfill may result in the seepage of
heavy metals into groundwater, causing significant damage to
organisms and the environment (Zhang et al., 2014). However,
the recovery of valuable metals from spent LIBs would be an
important secondary source of these metals, which is higher than
the metal grades in natural minerals and ores (Ilyas et al., 2017;
Nayl et al., 2014). Recovering valuable metals from spent LIB pow-
ders mainly involves pyrometallurgical or hydrometallurgical pro-
cesses or a combination of both (Chagnes and Pospiech, 2013; Chen
et al., 2015; Xiao et al., 2017). The typical pyrometallurgy process is
costly because it involves calcination and smelting at elevated
temperatures, as well as refining and separation of the metal after
leaching. Lithium is lost in slag and is difficult to recycle due to its
high reactivity. Hydrometallurgical processes are widely used to

https://doi.org/10.1016/j.wasman.2019.04.039
0956-053X/Ó 2019 Elsevier Ltd. All rights reserved.
154 C. Wu et al. / Waste Management 93 (2019) 153–161
separate and recycle metal ions in industry as they have high effi-
ciency and low emissions of toxic chemicals to the atmosphere
(Ordonez et al., 2016). The hydrometallurgical process includes
the discharging/dismantling of spent LIBs, the removal of alu-
minum by sodium hydroxide, leaching of cathode materials and
the recycling of metals from leachate by other chemical methods
(Zheng et al., 2016).
Leaching is an essential step for hydrometallurgy owing to its
low cost and simple operation (Li et al., 2015). Leaching agents,
such as HCl (Niinae et al., 2014), H2SO4 (Rabia et al., 2019;
Pagnanelli et al., 2017), H3PO4 (Chen et al., 2017; Zhuang et al.,
2019), CO2 (Bertuol et al, 2016), and various organic acids (Li et
mal., 2017; Nayaka et al., 2016; Chen and Zhou, 2014), in the pres-
ence of a reductant, such as H2O2 (Sun et al., 2017), NaHSO3 or
organic reductants (Chen et al., 2018), are used for leaching Li,
Ni, Co, Al, Cu, and Mn from spent LIBs powders. However, the
use of strong inorganic acids results in the release of Cl2, SO3,
and NOx during leaching, which pose a threat to the environment
and human health. The organic acids used for LIB leaching are
easily recycled in the same process. However, the spent LIB leach-
ing solution often contains target metals (Co, Ni and Li) (Rabia
et al., 2019), as well as common metals (Al, Fe, and Cu) (Gratz
et al., 2014). Complex purification processes for separating metals
from a solution are costly and the additional wastewater discharge
is of significant concern.
Recently, ammonia leaching has received great concern due to
its selective leaching characteristics between desired (Li, Ni, and
Co) and undesired metals (Al, Fe, and Mn) (Wang et al., 2017).
According to Eh-pH diagrams, the main principle of ammonia
leaching relies on its thermodynamic feasibility for transition met-
als such as Li, Ni, and Co, which have high complexation ability
with ammonia. Undesired metals, such as Mn, Al and Fe, do not
leach or leaching little due to their poor complexing ability with
ammonia. In addition, ammonia can be recycled when used as a
leaching agent (Meng and Han, 1996) and has the potential to form
stable metal-ammonia complexes at relatively low (or moderate)
temperatures (Mishra et al., 2011).
In this study, the cathode material is obtained through a wet
crushing-ball milling-sieving process, which prevents the loss of
lithium and the release of toxic and harmful gases while conven-
tional combustion treatment does not. Selective leaching of target
metals from spent LIBs cathode materials is then conducted using
an ammonia-ammonium bicarbonate system in the condition of
ammonium sulfite as a reductant. To provide the necessary basis
for the development of a closed-loop process for recycling spent
LIBs, this study is devoted to the determination of the apparent
leaching behaviors of Ni, Co, Li, Al, and Cu from cathode powders.
The factors studied during the leaching process include composi-
tion of the leaching reagent, pulp density, magnetic stirring speed,
temperature, and leaching time. The leaching kinetics of metals in
cathode materials provide the basis for understanding the impor-
tance of different factors, The steps and reaction mechanisms that
control metal extraction are critical to further process design.
2. Experimental
2.1. Materials and reagents
The spent 18,650 LIBs used in this study were provided by Hao
Peng Technology Co., Ltd (Ganzhou, China). The cathode material
Table 1
Composition of the mixed electrode powder.
Elements Li Ni
Content (wt. %) 3.60 11.86
was obtained by sieving the wet impact-crushed spent LIBs
through a 0.18 mm standard sieve, and the chemical composition
is shown in Table 1. The results show that major components of
the cathode powders were Co, Li, and Ni, while the trace elements
included Cu and Al. From the X-ray diffractometry patterns (Fig. 6),
we can find the phase of cathode powders were composed of LiNix-
CoyO2, LiNiO2, and graphite, which supports the analysis results of
Table 1. Large-particle copper and aluminum foil can be recovered
by shaking table sorting after removing a small amount of the
attached electrode materials by grinding using a ceramic ball as a
medium. All chemicals used in this work (ammonia, ammonium
sulfite and ammonium bicarbonate) were of analytical grade with-
out further purification, and all solutions were prepared using
ultrapure water.
2.2. Experimental procedures
Leaching experiments were conducted in a 250 mL conical flask
equipped with a thermostatic magnetic stirrer and perforated rub-
ber to prevent leachate loss due to evaporation. The leaching sys-
tem comprises a cathode powder of known mass and a leaching
agent consisting of ammonia, ammonium bicarbonate, ammonium
sulfite, and deionized water. The effect of leaching reagent compo-
sition, magnetic stirring speed (300–700 rpm), solid-to-liquid ratio
(10–50 g/L), reaction time (0–300 min), and leaching temperature
(40–90 °C) during leaching were investigated to determine the
optimum leaching conditions.
After leaching, the leachate was filtered and the residue was
washed several times and then dried at 120 °C for 12 h. The phase
and morphology of the residue was determined by X-ray diffrac-
tometry (XRD; Rigaku, Japan) and scanning electron microscopy
(SEM; MLA650F, FEI, America), respectively. The amounts of Li,
Ni, Co, Cu, and Al in the leachate were determined using induc-
tively coupled plasma-optical emission spectroscopy (ICP-OES;
IRIS Intrepid II, TEB, America). The leaching efficiency was defined
as the ratio of the amount of a component in the leachate to the
total amount of that species in the original cathode powder.
3. Results and discussion
3.1. Optimum leaching reagent composition
Fig. 1a presents the relationship between ammonia concentra-
tion and the leaching efficiency of Li, Co, Ni, Cu, and Al. Minimal
amounts of target metal (Li, Co, and Ni) in the cathode powder
were leached out in the ammonia single-component leaching
agent, even though the ammonia concentration reached 3 M. How-
ever, little of aluminum and all of the Cu leached out as the ammo-
nia concentration increased. This can be explained by the Cu
Pourbaix diagram in the presence of NH3 presented in a previous
study (Han et al., 1974). According to Han et al., the soluble stable
complex Cu(NH3)+2 is mainly present in the ammonia leaching sys-
tem with a pH range of 8–11 and an Eh value of 0–0.4. The pH and
Eh values of the present leaching system are within the above
range, so that copper can be efficiently leached. Therefore, the
addition of other reagents is necessary to increase the leaching effi-
ciency of valuable metals, such as Co and Ni. According to the
results in Fig. 1a, the ammonia concentration was constant at
1.5 M to further optimize the leaching agent composition.
Co Cu Al
5.63 1.57 0.55
 C. Wu et al. / Waste Management 93 (2019) 153–161
Fig. 1. Effect of (a) ammonia concentrations ranging from 0.5 to 3 M on the leaching efficiency of metals (20 g/L pulp density, 600 rpm, at 60 °C for 180 min), Effect of (b)
ammonium sulfite and (c) ammonium bicarbonate concentrations ranging from 0 to 2 or 3 M on the leaching efficiency of the metals (1.5-M NH3, 20 g/L pulp density,
600 rpm, 60 °C, and 180 min).
Ammonium bicarbonate or ammonium sulfite was introduced
into the single-component leaching agent ammonia to investigate
the leaching efficiency of valuable metals. Fig. 1b presents the
effect of different ammonium sulfite concentrations (0–2 M) in
the ammonia solution (1.5 M) on the leaching efficiencies of Ni,
Co, Li, Cu, and Al. The results of the effect of the presence and
absence of ammonium sulfite on the leaching efficiency of each
metal were compared. The leaching rates of Li, Ni, and Co were sig-
nificantly improved from 8.36%, 1.30%, and 1.88% to 76.93%,
77.30%, and 72.47%, respectively, when the ammonium sulfite con-
centration varied from 0 to 1 M in an ammonia solution. Mean-
while, the leaching rate of Cu was further increased from 78.88%
to 100%, and the Al leaching rate decreased slightly. Ammonium
sulfite was an indispensable component in the efficient leaching
of Co, Li and Ni. Due to the mixed state of the cathode powder,
Li, Co, and Ni exist in +1, +3, and +2 oxidation states (Cho et al.,
2005). Co3+ was reduced to Co2+ in the presence of sulfite-
containing reductants, which easily dissolves in solutions and
forms stable complexes with ammonia to increase the leaching
rate; Meanwhile, according to Fig. 3, leaching of Li can be simulta-
neously promoted due to its association with Ni of Li-Co-Ni-oxide
(LiNixCoyO2). Unfortunately, in the next experiment, the leaching
rate of Li was low (60.53%), although the high leaching rate of Ni
favored Li leaching, However, the complexing ability with ammo-
nia is Cu > Ni > Co > Li when the ammonia concentration is con-
stant, Cu, Ni and Co occupy a large number of ammonia binding
sites, so that the ammonia sites which can bind to Li are greatly
reduced, resulting in a lower leaching rate of Li.
155
Moreover, after the ammonia sulfite concentration exceeded
1 M, the leaching efficiency of Co, Li, and Ni hardly increased while
the extraction rate of undesired metal Al was only 5.96%. There-
fore, it is considered that 1-M ammonium sulfite concentration is
optimal for Co, Li and Ni leaching on the basis of 1.5 M ammonia.
The effect of different ammonium bicarbonate concentrations
(0–3 M) in 1.5-M ammonia on the leaching efficiency of the cath-
ode powder was investigated under the following conditions:
20 g/L pulp density, 600 rpm, and 60 °C for 180 min. As shown in
Fig. 1c, the leaching efficiencies of Li, Ni, and Co increased as the
ammonia bicarbonate concentration increased. However, there
were clear differences between these leaching efficiencies of Li,
Ni, and Co and those obtained when low-concentration ammonia
sulfite was used. For example, the leaching efficiencies of Li, Ni,
and Co were only 10.15%, 7.69%, and 17.90% with 1-M ammonia
bicarbonate, while they were 76.93%, 77.30%, and 72.47% with 1-
M ammonia sulfite, respectively. Therefore, the ammonia sulfite
in the ammonia solution can more effectively improve the leaching
rates of valuable metals from the cathode powder. Moreover, Al
and Cu exhibited similar leaching behavior, regardless of whether
ammonia bicarbonate or ammonia sulfite was present. These find-
ings confirmed that ammonium sulfite is a suitable reductant dur-
ing the leaching process.
To verify whether ammonium bicarbonate acts as a buffer solu-
tion in the leaching system, concentrations of ammonium sulfite or
ammonium bicarbonate ranging from 0 to 1.5 M were added to a
binary (1.5-M ammonia + ammonium sulfite) or ternary (1.5-M
ammonia + 1-M ammonium sulfite + ammonium bicarbonate) sys-
156 C. Wu et al. / Waste Management 93 (2019) 153–161

tem. As shown in Fig. 2a, the change in the pH value in the binary
system was more significant than that in the ternary system. For
example, the pH value in the binary system changed from 12.69
to 11.08 as the ammonium sulfite concentration increased from 0
to 0.2 M (25 °C). However, that of the ternary system changed from
10.82 to 10.61 when the ammonium bicarbonate concentration
increased from 0 to 0.2 M. The ternary system could be advanta-
geous as there was no significant pH change that could cause
adverse conditions for soluble complex ion formation (Ku et al.,
2016). Therefore, it is necessary to add ammonium bicarbonate
with a sufficient concentration to serve as a buffer solution in a
ternary leaching system and allow the maximum leaching effi-
ciency of each metal to be reached. The pH value in the leaching
system was determined by the base NH3 and its conjugate acid
NH+4 from a pH buffer, and the relationship can be described as fol-
lows (Das et al., 1986):
different concentrations (0.5–3 M) and explore the leaching effi-
ciency of each metal; the conditions were as follows: pulp density
of 20 g/L and stirring at 600 rpm, at 60 °C for 180 min. The data in
Fig. 2b shows that the leaching rates of Li, Ni, and Co were
improved when the ammonia concentration was low. The leaching
rates of Li, Ni and Co reached 60.53%, 96.32% and 80.99%, respec-
tively, at the ammonia concentration of 1.5 M. However, the leach-
ing efficiencies began to decrease when the ammonia
concentration exceeded 1.5 M. In contrast, the leaching behaviors
of Cu and Al were similar to the above experiment results and
exhibited almost no change.
The leaching behavior of Co, Li and Ni can be expressed as fol-
lows when the pH of the leaching system is within a suitable range
for the generation of Li, Ni and Co complex ions.
Liþ + nNH3 $ Li (NH3 )n 2þ ð2Þ

Co2þ + nNH3 $ Co (NH3 )n 2þ ð3Þ

pH = 9.26 + log ([NH3 ]/[NH4 þ ]) ð1Þ
Ni2þ + nNH3 $ Ni(NH3 )n 2þ ð4Þ
According to Eq. (1), as ammonium sulfite has two NH+4, the pH
of the binary (ammonia + ammonium sulfite) system was altered The higher value and oxidation-state metals could be reduced
substantially with the initial addition of ammonium sulfite. How- through ammonia leaching by ammonium sulfite. Subsequently,
ever, when there is ammonium bicarbonate in a ternary (ammo- Li, Ni and Co can leach out and remain in the ammonia leaching
nia + ammonium sulfite + ammonium bicarbonate) leaching solution as either metallic ions or amine complexes (Zheng et al.,
system, the pH does not change significantly as it is a weak acid 2016). Complex ions such as Co(NH3)2+ 2+
6 and Ni(NH3)6 would be
salt that can hydrolyze to ammonia. Namely, ammonium bicarbon- formed if excess ammonia was added to a leaching solution con-
ate can act as a pH buffer and maintain the pH of the system during taining Co2+ and Ni2+, as shown in following reactions (Han et al.,
leaching to allow the formation of stable ammonia complexes. 1974; Kumbasar and Kasap, 2009).
To determine optimum leaching agent composition, 1-M
ammonia bicarbonate and sulfite were to ammonia solutions with Co2þ + 6NH3 $ Co (NH3 )6 2þ ð5Þ

Fig. 2. (a) pH and Eh change of the binary (1.5 M ammonia + ammonium sulfite) or ternary (1.5 M ammonia + 1 M ammonium sulfite + ammonium bicarbonate) systems.(b)
Effect of the ammonia concentration of the ternary system on the leaching efficiency (20 g/L pulp density, 600 rpm, 60 °C, and 180 min), (c) Effect of the ammonium
bicarbonate concentration of the ternary system on the leaching efficiency (20 g/L pulp density, 600 rpm, 60 °C, and 180 min).
 C. Wu et al. / Waste Management 93 (2019) 153–161
Ni2þ + 6NH3 $ Ni (NH3 )6 2þ
Formation constants for the complexes of Ni(NH3)2+
6 ,
are given as 5.5  108 and 1.3  105 at 25 °C, respectively
(Kumbasar and Kasap, 2009). We supplemented the Eh value of
the leaching system in Fig. 2a. The pH and Eh values of the ternary
leaching system (1.5-M NH3 + 1-M NH4HCO3 + 1-M (NH4)2SO3) at
60 °C were 9.89, 0.041, respectively. According to Kim et al.
(2018) and Han et al. (1974), the main complexes of Ni, Co with
ammonia under this condition are soluble Ni(NH3)2+ 6 and Co
(NH3)2+
6 , respectively, so at the same time as Cu leaching, Ni and
Co can also be leached. Due to the excess of ammonia, the presence
of a constant concentration of ammonium sulfite in the leachate
does not reduce the high valence Ni and Co to a low valence,
thereby reducing the leaching efficiency.
Then, we tested the effect of the ammonia bicarbonate concen-
tration (0–2 M) on the leaching efficiencies of metals; the ammo-
nia and ammonia sulfite concentrations were fixed at 1.5 M and
1 M, respectively, and the other conditions were the same as those
listed above. The leaching efficiencies of Li, Ni, and Co slowly
increased as the ammonia bicarbonate concentration improved,
as shown in Fig. 2c. The leaching rate of each metal hardly changes
when the concentration of ammonium bicarbonate reaches 1 M.
This depends to a large extent on the pH of the leaching solution,
which remained almost unchanged as the ammonium bicarbonate
concentration further increased as it formed a buffer solution in
the ternary system (ammonia + ammonium sulfite + ammonium
bicarbonate). It provides conditions for the formation of soluble
ammonia complexes to ensure the leaching rates of Li, Ni and Co.
Fig. 3. Effect of different temperatures (a), pulp densities (b), leaching times (c) and agitation speed (d) on the leaching efficiency of each metal (1.5-M NH3, 1-M (NH4)2SO3, 1-
M NH4HCO3).
157
ð6Þ From comparing and analyzing the data from the above exper-
iments, it can be found that the ternary leaching system exhibited
Co(NH3)2+
6
better Li, Ni, and Co leaching efficiencies when the ratio of ammo-
nia, ammonium sulfite, and ammonium bicarbonate was constant
at 1.5:1:1. The leaching efficiency of low-reactivity Al was only
3.87%, while the highly reactive Cu leached out completely. The
leaching behavior of both metals changed very little, regardless
of the changes in the leaching conditions that enabled the more
economical recovery of Co (80.99%), Ni (96.32%), and Li(60.53%)
from spent LIB cathode materials.
3.2. Effect of leaching temperature
Temperature is typically an important factor that influences the
rate of chemical reactions by increasing the collision frequency
between the corresponding ions. Moreover, it can accelerate the
mass transfer and diffusion of ions in leaching systems, which
influences the leaching kinetics. The influence of different temper-
atures on the leaching efficiency of each metal was determined
under the following conditions: 1.5-M NH3, 1-M (NH4)2SO3, 1-M
NH4HCO3, 20 g/L pulp density, and stirring at 600 rpm for
180 min. As shown in Fig. 3a, the leaching efficiencies of Li, Ni,
and Co rapidly increased from 19.33%, 11.33%, and 10.23% to
60.53%, 96.32%, and 80.99%, respectively, when the temperature
increased from 40 to 60 °C. However, the leaching efficiencies of
Cu and Al did not greatly fluctuate. Despite the higher metal
leaching efficiencies that could be acquired by further increasing
the leaching temperature, it has been reported that Co-ammine
158 C. Wu et al. / Waste Management 93 (2019) 153–161
complexes become unstable and the leaching efficiency decreases
when the leaching temperature exceeds 90 °C. Therefore, accord-
ing to the data in Fig. 3a, the optimum leaching temperature was
60 °C.
3.3. Effect of the solid-to-liquid ratio
In this section, the pulp density is defined as the ratio of the
weight of the cathode powder to the volume of the leaching solu-
tion. To investigate the effect of pulp density on the leaching effi-
ciency of each metal, the experiments were conducted with the
following conditions: 1.5-M ammonia, 1-M ammonium sulfite, 1-
M ammonium bicarbonate, 60 °C, and stirring at 600 rpm for
180 min. As shown in Fig. 3b, the leaching efficiencies of Li, Ni,
and Co increased from 59.47%, 68.80%, and 63.09% to 60.53%,
96.32%, and 80.99%, respectively, as the pulp density increased
from 10 to 20 g/L. The leaching efficiencies then exhibited a
decreasing trend. However, the Cu and Al leaching efficiencies
exhibited almost no change. This is a remarkable result as an
excessively high pulp density was disadvantageous to the leaching
out of metals from the cathode powder. This may be because
higher pulp densities reduced the available solid (the cathode pow-
der) and liquid (ammoniacal solution) contact areas, decreasing
the occurrence of leaching reactions. In addition, it is difficult for
the formed ammines to diffuse from the solid–liquid reaction
interfaces to the bulk solution, which reduced the leaching of Li,
Ni, and Co from the cathode powder into the ammoniacal solution.
However, there was too little cathode powder to react with the
excess ammoniacal solutions when the pulp density was lower,
which results in excess ammonia binding sites and a lower metal
leaching rate. Therefore, the pulp density was set to 20 g/L for
the subsequent experiments.
3.4. Effect of leaching time
The effect of different leaching times on the leaching efficien-
cies of valuable metals from the cathode powder was examined
under the following conditions: 1.5-M NH3, 1-M (NH4)2SO3, 1-M
NH4HCO3, 20 g/L pulp density, and 60 °C for 180 min. Fig. 3c pro-
vides the time dependency of the leaching efficiencies of the met-
als. The leaching efficiencies of Li, Ni, and Co increased slowly
before 1 h, and were 21.33%, 26.31%, and 28.99%, respectively.
The leaching efficiencies then plateaued at 180 min. However,
the leaching kinetics of Cu was rapid and it has completely leached
out within 20 min of reacting with the ammoniacal solution. The
leaching rate of Al can be almost ignored from the beginning of
the experiment. Although the Li leaching efficiency slightly
improved over time, 3 h is sufficient for the leaching of valuable
metals from the cathode powder as the leaching efficiencies of
Cu, Ni, and Co stabilized within this period.
3.5. Effect of stirring speed
Increasing the agitation speed would improve the leaching
kinetics as it would improve the mixing of sample and accelerate
mass transfer (Sun et al., 2015). The experimental conditions were
set at 1.5-M NH3, 1-M (NH4)2SO3, 1-M NH4HCO3, 20 g/L pulp den-
sity, and 60 °C for 180 min to illustrate the effect of stirring speed
on the leaching efficiency of metals. Fig. 3d shows that the leaching
efficiencies of Li, Ni, and Co increased notably before the agitation
speed reached 600 rpm. Their leaching efficiencies then only
improved slightly when the agitation surpassed 700 rpm. Mean-
while, it is clear that the leaching efficiencies of Al and Cu were
unaffected by the agitation speed. To guarantee sufficient contact
between the ammoniacal solution and the cathode powder,
600 rpm was selected as the most suitable agitation speed.
3.6. Apparent kinetics of leaching
The dissolution kinetic behaviors of Li, Co, and Ni were explored
at different temperatures (50–80 °C) in the ternary (1.5-M ammo-
nia + 1-M ammonium sulfite + 1-M ammonium bicarbonate) sys-
tem with 20 g/L pulp density and stirring at 600 rpm. To confirm
the likely reaction mechanisms for the leaching of the cathode
powder, leaching data was fitted based on the diffusion (Eq. (7))
or chemical reaction control models (Eq. (8)). The two kinetic mod-
els are presented as (Levenspiel, 1999; Jha et al., 2013):
1  2=3x - ð1  xÞ2=3 ¼ k1 t ð7Þ
1  ð1  xÞ1=3 ¼ k2 t ð8Þ
where k1 and k2 are the apparent constants of different steps, t is the
time, and x is the fraction of metals leached.
To obtain the apparent activation energy of Co, Li and Ni, we use
the Arrhenius equation to explain the relationship between the
rate constant and temperature:
Ea
Lnk ¼ lnA  ð9Þ
RT
where A is the frequency factor, k is the reaction rate constant, Ea is
the apparent activation energy, and R is the gas constant (8.314 J/
K mol).
The fitting results show that the reaction-controlled shrinking
core model was more supportive than the ash diffusion-
controlled model. Fig. 4a–c and Table 2 show the 1  (1  x) 1/3
vs t plots of the chemical reaction control at different tempera-
tures. The leaching processes of Li, Ni, and Co were controlled by
the chemical reaction on the surface of the unreacted core. Plotting
ln k vs. 1000/T, as shown in Fig. 4d, indicates that the activation
energies of Li, Ni, and Co were 59.99, 53.53, and 49.94 kJ/mol,
respectively, which agreed well with the expected activation ener-
gies (>40 kJ/mol) that were reported previously (Habashi, 1969;
Bhuntumkomol et al., 1982).
To explore the change in the appearance of the cathode powder,
SEM images of residues obtained at different leaching times (leach-
ing conditions: 1.5-M NH3, 1-M (NH4)2SO3, 1-M NH4HCO3, 20 g/L
pulp density, 60 °C, and 600 rpm) were captured and are presented
in Fig. 5. It can be observed that some particles agglomerated,
although the shape was still relatively regular. The particle size
decreased over time. For example, the average particle size before
leaching was 29.09 mm (Fig. 5a), while it decreased to 12.14 mm
(Fig. 5d) after 300 min of leaching. This may be because the metals
leached out into the ammoniacal solution with a sufficient reaction
time, therefore, the particle size decreased.
The XRD analysis of the leached residue obtained under differ-
ent leaching times is shown in Fig. 6, and the leaching conditions
were as follows: 1.5-M NH3, 1-M (NH4)2SO3, 1-M NH4HCO3, 20 g/
L pulp density, 60 °C, and 600 rpm. The cathode powders were
composed of LiNixCoyO2, LiNiO2, and graphite, which were always
present in the residue. The Cu and Al may be introduced from the
copper and aluminum foils during the crushing process as simple
substances, therefore, they could not be found in the XRD patterns.
Moreover, the intensities of the LiNixCoyO2, and LiNiO2 phases
were significantly lower than those of the original powder after
leaching for 1, 3, and 5 h. This supports the characterization results
of SEM analysis presented in Fig. 5. It is worth mentioning that the
peaks of LiNixCoyO2 and LiNiO2 in Fig. 6 have the same decreasing
tendency with the increase of the leaching time, which means that
the metal ions in the two phases have the similar leaching behavior
in the conditions.
 C. Wu et al. / Waste Management 93 (2019) 153–161 159

Fig. 4. Chemical reaction control models for the kinetics of the leaching of (a) lithium, (b) cobalt, and (c) nickel at different temperatures, (d) Arrhenius plot for the leaching of
lithium, nickel, and cobalt in the temperature range of 50–80 °C (1.5-M ammonia + 1-M ammonium sulfite + 1-M ammonium bicarbonate, 20 g/L pulp density and stirring at
600 rpm).

Table 2
Leaching kinetic parameters of Li, Ni, and Co calculated by the chemical reaction model.

T (°C) Li Ni Co
1 1
k (min ) R 2
k (min ) R2
k (min1) R2
4 4
50 6.5773  10 0.9786 8.8851  10 0.9808 0.00103 0.9795
60 0.00121 0.9749 0.00153 0.9818 0.00179 0.9939
70 0.00238 0.9962 0.00281 0.9895 0.00312 0.9972
80 0.00380 0.9949 0.00475 0.9995 0.00495 0.9990

3.7. Spent battery management
In order to meet the various needs of people’s chemical power
supply, Today however a wide variety of lithium Compounds used
as cathode materials mostly commonly LiCoO2, LiNiO2, LiMn2O4,
LiNi0.33Mn0.33Co0.33O2, and LiFePO4. However, the most expensive
cathode material in the battery has attracted the attention of many
scholars due to its resource and pollution. Fig. S1 (Gratz et al.,
2014) shows the value of each component in a 1 ton lithium ion
battery. The amount of each battery material in a 1 ton battery
was calculated using wt% provided by Georgi-Maschler et al.
(2012). As can be clearly seen from the figure, the inherent mate-
rial value of a 1-ton lithium-ion battery is $7708.
Hydrometallurgical processes have been the main recycling
way for waste batteries, because of the high recovery rate of valu-
able metals (Li et al., 2016; Randhawa et al., 2016). However, acid
leaching faces a large number of acidic wastewater treatment
problems and the difficulty of separating metals in the leachate.
Selective leaching of the target metals Li, Ni and Co by ammonia
may be a promising alternative. With this consideration, we
recover valuable metals from the cathode material through a tern-
ary ammonia leaching system. The leaching rates of Li, Ni and Co
after leaching for 5 h were 72.67%, 99.16% and 86.96%, respectively.
However, the leaching rate of the non-target metal Al is only 3.99%,
which greatly simplifies the recovery step and avoids the genera-
tion of alkaline wastewater relative to Gratz et al. (2014) treatment
of the cathode material by sodium hydroxide. The experimental
results show that the leaching efficiency of Li is low, and in the
subsequent studies we will optimize the leaching conditions in
order to achieve high metal recovery.
160 C. Wu et al. / Waste Management 93 (2019) 153–161
Fig. 5. SEM images of the mixed electrode power (a), leaching residue after 60 min (b), leaching residue after 180 min (c), and leaching residue after 300 min (d).
Fig. 6. X-ray diffraction patterns of the (a) cathode power, (b) leaching residue after
60 min, (c) leaching residue after 180 min, and (d) leaching residue after 300 min
(1.5-M NH3, 1-M (NH4)2SO3, 1-M NH4HCO3, 20 g/L pulp density, 60 °C, and
600 rpm).
4. Conclusions
This work demonstrates a hydrometallurgical process that can
selectively leaching Co, Ni, and Li from the hybrid electrode pow-
der of a lithium-ion battery (18,650) using a ternary (ammonia,
ammonium sulfite, and ammonium bicarbonate) ammoniacal
solution. The leaching kinetics of valuable metals in the ammonia-
cal solution are dependent on ammonium sulfite, which is neces-
sary as a reductant. Ammonium bicarbonate can act as pH buffer
in ternary leaching systems, which minimizes variations in pH dur-
ing leaching. Using favorable conditions for soluble ammonia-
complex ion formation is advantageous for enhancing the leaching
efficiency of Li, Ni, and Co. Under optimum conditions with 1.5-M
ammonia, 1-M ammonium sulfite, and 1-M ammonium bicarbon-
ate at 60 °C, a pulp density of 20 g/L, and leaching time of 180 min,
Ni and Cu could be almost completely leached out, and the leach-
ing efficiencies of Li and Co were 60.53% and 80.99%, respectively.
However, very little Al leached out, regardless of changes in the
leaching conditions, and the leaching efficiency is negligible owing
to Al’s low content in the cathode powder. The concentrations of
ammonium sulfite and ammonium bicarbonate, time, and temper-
ature positively influenced the leaching efficiencies of Li, Ni, and
Co. However, the leaching behavior of Al was significantly different
to that of these metals. The leaching behaviors of Co, Ni, and Li
appeared to fit well to the reaction-controlled shrinking core
model, and their activation energies were 59.99, 53.53, and
49.94 kJ/mol, respectively. The XRD patterns confirmed that the
phases in the original cathode powder were LiNixCoyO2 and LiNiO2.
To further recycle Li, Ni, and Co in the next study, a further precip-
itation and synthesis process will be explored after removing the
copper by introducing an extracting agent.
Acknowledgement
This work is financially supported by the National Natural
Science Foundation of China (51764015) and the Ganzhou Science
and Technology Bureau. The authors acknowledge Hao Peng Tech-
nology Co., Ltd (Ganzhou, China) for their material support. This
research was also supported by the Jiangxi Key Laboratory of Min-
ing & Metallurgy Environmental Pollution Control.
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