Journal of Cleaner Production 251 (2020) 119665

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

A novel and efficient ammonia leaching method for recycling waste

lithium ion batteries
Yaping Qi a, Fansong Meng a, Xiaoxia Yi a, Jiancheng Shu a, Mengjun Chen a, *, Zhi Sun b,
Shuhui Sun c, Fu-Rong Xiu d
a
Key Laboratory of Solid Waste Treatment and Resource Recycle, Ministry of Education, Southwest University of Science and Technology, Mianyang, 621010,
PR China
b
Institute of Process Engineering, Chinese Academy of Sciences, Beijing, 100190, PR China
c

Institute National de la Recherche Scientifique-Energie, Mat

eriaux et T
el

ecommunications, Varennes, QC, J3X 1S2, Canada
d
College of Geology and Environment, Xi’an University of Science and Technology, Xi’an, 710054, PR China

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

Article history: Effective recycling waste lithium-ion batteries (LIBs) are of great economic and environmental benefits.
Received 25 May 2019 This study proposes a novel and efficient ammonia leaching method for recovering Co and Li from waste
Received in revised form LIBs. This method yields a Co and Li leaching rate of 91.16% and 97.57%, respectively, under the optimal
4 December 2019
conditions (NH3$H2O 120 g/L, NH4HCO3 75 g/L, n (Na2SO3): n (Co) ¼ 2:1, 353 K, 240 min). Leaching
Accepted 10 December 2019
kinetics also show that the speed-limiting step in this process is the interfacial chemical reaction, and the
Available online xxx
activation energy of Co and Li is 58.45 kJ mol1 and 50.05 kJ mol1, respectively. Moreover, scanning
Handling editor: Jin-Kuk Kim electron microscopy (SEM), energy dispersion spectrum (EDS), and x-ray diffraction (XRD) results
indicate that the morphology of waste LIB powder are irregular granular and lamellar. Under the optimal
Keywords: condition, however, the leaching residues are scattered particles at a smaller size and the as formed
Waste LIBs MnCO3 particles are smooth with a uniform cubic structure. Besides, MnCO3 and graphite in the leaching
Recovery residues can be separated and recovered. After that MnCO3 was further calcined to Mn3O4, a precursor
Leaching kinetics for the production of new LIBs. Hence, a new and effective way for spent LIBs circular recycling is put
Ammonia leaching
forward, providing another choice for spent LIBs recycling industry.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction
Lithium-ion batteries (LIBs) are involve in almost all facets of
human life because of their high-energy density and efficiency as
well as long cycle life and environmental friendliness (Tan et al.,
2019). As these batteries can be used in portable devices, laptops,
PCs, and cellphones and will likely comprise high-energy power
sources for electric vehicles. Their potential future applications are
significant (Huang et al., 2018). As energy storage technology and
higher requirements for battery performance across have been
advanced, developments in battery technology have also accelerated
(Dehghani-Sanij et al., 2019). As the service lives of LIBs are usually
two or three years, the amount of discarded LIBs is going to increase
dramatically (Wang et al., 2018). One previous study predicted that
the number of waste LIBs will reach 25 million by 2020, a weight of
* Corresponding author.
E-mail address: kyling@swust.edu.cn (M. Chen).
about 50 thousand tons (Li, 2014). The composition of discarded el-
ements include cathode components (e.g., LiCoO2), negative material
(graphite), and other components, such as lithium hexa-
fluorophosphate electrolytes (LiPF6), polyvinylidene fluoride (PVDF)
binders, current collectors (aluminum and copper foil) (Li et al.,
2018). The batteries also contain toxic metals such as cobalt (Co),
lithium (Li), nickel (Ni), copper (Cu), aluminum (Al), and manganese
(Mn). Some of these metals, such as Co and Li, are much valuable than
their counterparts (Fro€hlich et al., 2017). This means that if waste LIBs
can be effectively recycled, a greater economic benefit is foreseeable.
Waste LIBs would also threaten the ecosystem and human health if it
was treated improperly, such as the leaching of toxic metals and the
release of electrolytes (Cerdas et al., 2018). Thus, it is therefore
important to consider the recycling of waste LIBs with environmental
friendly approaches for the benefits of economy and the ecosystem.
Previous studies for waste LIBs recycling can be divided into
physical, biological, and chemical methods (Ordon ~ ez et al., 2016).
The first, physical methods, is usually combined with other tech-
nologies and mainly used as pretreatment with the aim to remove

https://doi.org/10.1016/j.jclepro.2019.119665
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
2 Y. Qi et al. / Journal of Cleaner Production 251 (2020) 119665

impurities such as shells, separators, and binders via mechanical electronic waste recycling enterprise in China. Once collected,
separation (Bertuol et al., 2015), thermal treatment (Song et al., waste LIBs were discharged in a 10 wt% NaCl solution for 240 min
2014), or dissolution (PVDF) (Zhang et al., 2017). These ap- (details are given in Fig. S1 in the supporting Information, SI). Then
proaches enable the further recovery of valuable components from it was crushed by a shear crusher (SM2000 smf/UpM, Retsch,
waste LIBs. Physical methods are also easy to operate when Germany) and screened via a series of sieves with holes set at
compared with other methods. At the same time, they are low in 2 mm, 0.83 mm, and 0.45 mm, the results of sample screening are
efficiency and sometimes highly polluting. For example, dioxins, shown in Fig. 1. From Fig. 1a, b and c, it could be found that the main
furans, and other polluting gases can be produced during thermal components were Cu foil, Al foil, metal shell and diaphragm ma-
treatment and these are all highly detrimental to the environment terial, a very small amount of adherent black powder. Fig. 1d, almost
(Chen et al., 2015). Biological methods remain in the laboratory all the samples are black powders and accompanied by a very small
stage though it is perspective for a lower investment, higher effi- amount of metal materials, such as Cu, Al, Ni and Fe, proving that
ciency, etc. (Biswal et al., 2018; Heydarian et al., 2018). Chemical most part of anode and cathode materials were concentrated in this
approaches include hydrometallurgy approaches such as acid part of particle size <0.45 mm. This was also confirmed in Wang
leaching (Porvali et al., 2019; Peng et al., 2019; Yao et al., 2018), et al. research (Wang et al., 2012). Thus, these powders were
solvent extraction (Sattar et al., 2019; Vasilyev et al., 2019; He et al., selected for further experiments after dried at 70  C for 24 h.
2018), chemical precipitation (Zhang et al., 2018; Rapulenyane These specimens were digested using a HNO3eH2O2eHF system
et al., 2018; Heo et al., 2018), and electrochemical treatments (Güngo €r and Elik, 2007) and their chemical composition was
(Sun et al., 2019; Song et al., 2019; Liu et al., 2018). Hydrometallurgy analyzed using an inductively coupled plasma optical emission
is an effective method for recycling waste LIBs because of its strong spectrometer (ICP-OES, PerkinElmer, Optima 8300, USA), as shown
adaptability to this complex system (Swain et al., 2007). In one in Table 1. These data show that Co is the main metal within this
previous study, Dutta et al., (2018) reported a typical hydrometal- waste materials, about 24.40 wt%. Meanwhile, a small amount of Li,
lurgy process in which waste LIBs were wet crushed and separated Mn, Ni, Al, Cu and Fe are also presented. This possibly indicates that
first with a physical method before being leached with H2SO4 and the waste LIBs collected contain a small amount of NieCoeMn
H2O2. The results revealed that the leaching rates of Co and Li were ternary cathode materials. Data also show that this specimen
97% and 99.9%, respectively. While common metal ions, such as Fe, contains some non-metallic components, graphite, which plays an
Mn, and Al, also existed in the leaching solution, disturbing the important role in conducting electricity. A small number of impu-
subsequent extraction of Co and Li. This approach requires pre- rities are also present, including diaphragm and plastic, introduced
cipitation and organic extractants to further separate and purify the by the mechanical crushing process.
leaching solution. Indeed, this complex purification process not
only increases reagent consumption cost but also adds to the
2.2. Leaching experiments
additional environmental problems caused by residual waste acid.
The development of a selective leaching method will therefore be
All the leaching experiments were carried out in a batch of
competitive for recycling valuable metal from waste LIBs.
250 ml conical bottles placed in a magnetic stirrer (DF-101S, Lichen
Ammonia is also regarded as a green leaching reagent because
Technology, Shanghai, China), shaking at 400 rpm. Details of this
of its low toxicity, low cost, and evaporative recyclability. This
experiment are summarized in Table 2. The chemical reagents used
molecule also has certain selectivity. One reason for this is that
were all analytical. Once preset reaction time was reached, the
numerous metals such as Co, Li, Ni and Cu are able to form stable
samples were immediately taken to analyze lixivium metal con-
soluble ammonia complexes in solution, while Fe, Al, and Mn
tent, which was first filtered using a vacuum suction device and
hardly form such complexes (Chen et al., 2018; Jana et al., 1999),
then analyzed by ICP-OES. The specimen and leaching residues
thereby improving both metal leaching and reducing further pu-
were then further analyzed using x-ray diffraction (XRD; D/
rification processes.
MAX2500; Rigaku, Almelo, Holland), Fourier transform infrared
A novel and efficient ammonia leaching method for recycling
spectroscopy (FT-IR; Frontier, Almelo, Holland), scanning electron
waste LIBs is proposed in this study. The leaching system selected in
microscopy (SEM, Karl Zeiss, EV081A, Heidenheim, Germany) with
this study is composed of NH3$H2OeNH4HCO3 and Na2SO3. This is
an energy dispersion spectrum (EDS, Karl Zeiss, EV081A, Hei-
because, on the one hand, NH4HCO3 forms a relatively stable buffer
denheim, Germany). Metal leaching rate was calculated as
system with NH3$H2O, providing a suitable condition for leaching. At
the same time, the ammonia-carbon system is superior to the com-
plex sulfur system because of wastewater recycling efficiency (Jiang-
Hua et al., 2015). As Na2SO3 is introduced into a strong reductant
system, it reduces the high valence state metal to a lower valence one
and therefore makes them easier to dissolve, strengthening metal
leaching. The effect of leaching conditions, the concentrations of
NH3$H2O and NH4HCO3 as well as Na2SO3 dosage, temperature, and
leaching time, on the recovery of Co and Li are also discussed here in
detail. The leaching kinetics of Co and Li in waste LIBs are studied and
the morphology and phase composition of the obtained products
before, and after, leaching are also analyzed. The leaching residue was
further separated and purified in order to create a theoretical foun-
dation for the application in waste LIB recycling.

2. Materials and methods

2.1. Sample preparation

Waste LIBs used in this study were provided by a certified Fig. 1. Waste LIBs separated by sieves.
 Y. Qi et al. / Journal of Cleaner Production 251 (2020) 119665 3

Table 1 NH3$H2O concentration therefore creates a stable pH value envi-

Chemical composition of specimen. ronment for the formation of metal-ammonia complexes and
Component Co Li Mn Ni Al Cu Fe promotes metal leaching. However, when excessive concentration
wt.% 24.40 4.18 6.76 2.40 1.83 1.79 0.08
of NH3$H2O is added, the solution pH value becomes unsuitable for
the stable existence of metal-ammonia complexes and therefore
reduces metal leaching rate. A number of definite ionization re-
Table 2
actions are also seen within the ammonia medium, as described in
Experimental arrangement. equation (2). The ionization equilibrium will move and increase the
number of hydroxyl groups when a high concentration of ammonia
Factors Level
is present in solution; this will be beneficial to the precipitation of
NH3$H2O concentration, g/L 80, 100, 120, 140, 160 hydroxides, including the formation of a complex co-precipitation
NH4HCO3 concentration, g/L 45, 60, 75, 90, 105
reaction between Ni and Co (Das et al., 1986). This reaction is also
Na2SO3 dosage n (Na2SO3): n (Co) ¼ 1:1, 1:1.5, 1:2, 1:2.5, 1:3
Temperature, K 313, 323, 333, 343, 353 unfavorable for the improvement of Co leaching rates; subsequent
Time, min 10, 30, 60, 90, 120, 150, 180, 210, 240, 300 experiments were therefore carried out under 120 g/L NH3$H2O
conditions in order to obtain a high Co leaching rate and reduce the
amount of NH3$H2O.
following:
NH3 þ H2 O4NH3 ,H2 O4NHþ
4 þ OH

(2)
m
Pi ¼ i  100% (1)
Mi
3.2. NH4HCO3 concentration
where Pi is the metal leaching rate, %, while mi denotes the metal
weight extracted into the lixivium, g, and Mi is the metal weight The data presented in Fig. 3 reveal the effect of NH4HCO3 con-
within the sample, g. centrations on Co and Li leaching rates. These rates increase as the
extension of reaction time different NH4HCO3 concentration and
3. Results and discussion the two values remained approximately unchanged after 240 min.
Indeed, when the initial concentration of NH4HCO3 in the leaching
3.1. NH3·H2O concentration solution is low, Co and Li rates are 70.57% and 78.41% at 45 g/L,
respectively. These values rapidly reach 91.16% and 97.57% at 75 g/L,
The data in Fig. 2 summarizes the effect of NH3$H2O concen- exhibiting a great promotion effect. Leaching rates of Co and Li
tration on Co and Li leaching rates. These results show that the decreases to 81.92% and 93.83%, respectively, when the initial
leaching rates of these two metals exhibit similar trends under concentration of NH4HCO3 further increases to 105 g/L. This implies
different NH3$H2O concentrations, increasing in tandem with re- that a higher initial concentration of NH4HCO3 shows a negative
action time within the range of 80e160 g/L. Rates for Co and Li effect on Co and Li leaching rates.
remain basically unchanged when the reaction time reaches These phenomena may be also related to the solution pH since
240 min. NH4HCO3 could adjusting pH value of the leaching solution. In
The leaching rates of Co and Li increase from 81.10% to 80.26%e other words, an appropriate leaching solution pH value is essential
91.16% and 97.57%, respectively, as NH3$H2O concentration for the formation of metal-ammonia complexes. In the buffer
increased from 80 g/L to 120 g/L. This indicates that a high con- leaching solution of NH3$H2OeNH4HCO3, the pH value of the sys-
centration of NH3$H2O is conducive to the leaching of these metals. tem solution is determined by NH3 and NHþ 4 (Ku et al., 2016), as
Indeed, in contrast, these leaching rates decrease to 88.78% and described in equation (3). Thus, with the exception of an optimum
91.64%, respectively, when the NH3$H2O concentration was concentration of NH4HCO3, 75 g/L, when the concentration of
increased from 120 g/L to 160 g/L; this indicates that an excessive NH4HCO3 is lower or higher, the pH value of the leaching solution
NH3$H2O concentration is not conducive to metal leaching. This is will either be much higher or lower, therefore unconducive for the
mainly related to the fact that the stability of metal-ammonia leaching of Co and Li. Excessive carbon concentration is also
complexes is influenced by numerous factors including, for conducive to precipitation of Co. An inclusion precipitated will also
example, solution pH value (Wang et al., 2017). An appropriate cause a slight loss of Li (Li-Wen et al., 2013). Hence, 75 g/L NH4HCO3

Fig. 2. Effect of NH3$H2O concentration on Co and Li leaching rate (NH4HCO3 75 g/L, Na2SO3 dosage n (Na2SO3): n (Co) ¼ 2:1, 353 K).
4 Y. Qi et al. / Journal of Cleaner Production 251 (2020) 119665

Fig. 3. Effect of NH4HCO3 concentration on Co and Li leaching rate (NH3$H2O 120 g/L, Na2SO3 dosage n (Na2SO3): n (Co) ¼ 2:1, 353 K).

!
was selected as the appropriate optimal for subsequent SO2
experiments. where fq 4
is a constant value, 0.936 V (CRC Handbook of
SO2
3

 
  Chemistry and Physics, 97th Edition); R denotes the gas constant

pH ¼ pKa þ log ½NH3  NH þ
4 z 9:26 þ log ½NH3  NH þ
4
(8.3144 J/(K$mol)); T is the thermodynamic temperature (K); n is
(3) the number of electrons transferred in the electrode reaction; and F
is Faraday constant (96,485.3 C/mol).
!
SO2
3.3. Na2SO3 dosage Based on equation (5), f 4
, the pH of the leaching solution
SO2
3

The molar ratio of Na2SO3 and Co is used to represent the dosage and the ratio of [SO2 2
4 ] and [SO3 ] can be determined. This means

of Na2SO3 and the effects of Na2SO3 dosage on Co and Li leaching that as the pH and temperature of the system remain unchanged,
!
rates is given in Fig. 4. The leaching rate of Co and Li significantly SO2
increasing the dosage of Na2SO3 could reduce the value of f 4
,
increases as the extension of reaction time under different Na2SO3 SO2
3

dosages and the two values remained approximately unchanged at improving the reduction capacity of sulfite. This also means that the
240 min. Leaching rates of Co and Li increases from 66.74% to reason for the increase of metal leaching is the increase of Na2SO3
80.49%e91.16% and 97.57%, respectively, when the Na2SO3 dosage dosage. However, if the Na2SO3 dosage is continually increased to
increases from 1:1 to 2:1, a sharp increasing. This could be attrib- 2.5:1, Co leaching rate increases to 95.21% while Li leaching rate
uted to the reduction of sulfite in alkaline solution, as shown in decreases to 91.8%. As the dosage of Na2SO3 is increased to 3:1, Co
equation (4): and Li leaching rates declines to 87.74% and 88.91%, respectively.
These results mean that excessive sulfite addition would case the
 
SO2 2
3 þ 2OH 4SO4 þ H2 O þ 2e (4) deposition of other metal ions such as Co2þ, Ni2þ, and Mn2þ. Liþ can
According to the Nernst equation: be included within the deposition process, resulting in additional
losses.
! ! h i
SO2 SO2 RT SO24
f 4
¼ fq 4
þ ln h i (5) 3.4. Temperature
SO2
3 SO2
3
nF
SO2 ½OH 
2
3
The data presented in Fig. 5 illustrate the effects of temperature
on the leaching rate of Co and Li. Leaching rates of Co and Li are

Fig. 4. Effect of Na2SO3 dosage on l Co and Li leaching rate (NH3$H2O 120 g/L, NH4HCO3 75 g/L, 353 K).
 Y. Qi et al. / Journal of Cleaner Production 251 (2020) 119665
enhanced with both reaction time and temperature. When reaction
time is prolonged to 240 min, the optimal leaching rate for Co and Li
is attained. At the same time, however, leaching rates of Co and Li
remain low, 13.49% and 25.33%, respectively, when the reaction
temperature is held at 313 K. If the reaction temperature is
continually improved to 343 K, then the leaching rate of Co and Li
also raises significantly to 73.80% and 76.87%, respectively. These
results indicate that leaching temperature plays an important role.
Indeed, if the reaction temperature is further increased to 353 K, Co
and Li leaching rate reaches 91.16% and 97.57%, respectively. This
might be explained by endothermic reactions of these elements in
the leaching process, as confirmed by previous studies (Yu et al.,
2019; Nayl et al., 2014). Increasing the reaction temperature can
enhance collision frequency, mass transfer, and diffusion rates be-
tween reactants and therefore improves metal leaching rates. It is
true that the leaching rate of Co and Li still has room to increase.
However, solvent swing within the leaching system will occur as
further increasing the reaction temperature. A temperature of
353 K was therefore selected for rest reactions in order to reduce
volatilization losses and ensure the metal leaching efficiency.
3.5. Co and Li leaching kinetics analysis
Leaching reactions usually comprise a complex multi-phase
process. Possible rate control steps involved in this process are
divided into external, interfacial chemical, and internal diffusion
controls, as well as mixed control on the basis of the nuclear
shrinkage model (Levenspiel, 1962). These relationships corre-
spond to equations (6)e(8).
X ¼ k1 t
1 (Fig. S3 and SI). Moreover, a series of repeated experiments were
1  ð1  XÞ3 ¼ k2 t
and
2 2
1  X  ð1  XÞ3 ¼ k3 t
3
where k1 (min1), k2 (min1), and k3 (min1) denote the apparent
rate constants of the steps above, while t is the leaching time (min),
and X is the leaching rate of metal elements.
The relationship between these possible rate control steps and
time were tested using the software package SPSS (IBM, SPSS Sta-
tistics 20.0). As it is clear that if a linear correlation between X and
leaching time (t) does not occur, we can infer that external diffusion
Fig. 5. Effect of temperature on Co and Li leaching rate (NH3$H2O 120 g/L, NH4HCO3 75 g/L, Na2SO3 dosage n (Na2SO3): n (Co) ¼ 2:1).
5
is not the control step. In addition, we find that the control of in-
ternal diffusion is also no suitable for this leaching reactions (Fig. S2
and Table S1 in SI). Hence, we consider the interface chemical re-
action control model to be more consistent with this process, as
shown in Fig. 6(a) and (b) and in Table 3. The results of this analysis
suggest that 1-(1-X)1/3 is linear with leaching time (t) between
313 K and 353 K, (R2 > 0.90, Sig. (two-tailed) < 0.01), proving the
presence of a significant linear correlation between the two vari-
ables. The Arrhenius equation, expressed in (9), also suggests a
relationship between chemical reaction rate and temperature, as
follows:
 
Ea
k ¼ Aexp  (9)
RT
The results presented in Fig. 6c and (d) show that the activation
energy of Co and Li in the NH3$H2OeNH4HCO3 leaching system is
58.45 kJ mol1 and 50.05 kJ mol1, respectively. These results are in
line with those reported previously (Das et al., 2008): the reaction
controlled by interfacial chemicals must be greater than
40 kJ mol1. It is therefore clear that when Co and Li are leached by
the NH3$H2OeNH4HCO3 system, the speed-limiting step is the
interfacial chemical reaction.
3.6. Repeated experiments and analysis
The experimental results presented here show that the optimal
leaching conditions for recovering waste LIBs are NH3$H2O of 120 g/
L, NH4HCO3 of 75 g/L, Na2SO3 dosage of n (Na2SO3): n (Co) ¼ 2:1,
353 K and 240 min. In the process of exploring the optimum con-
(6) ditions, in addition to the effects of leaching conditions on the
leaching of Co and Li, the effects on Ni and Cu were also studied
(7)
carried out under the optimal leaching conditions and chemical
composition results for both lixivium and leaching residue are
presented in Table 4. Results show that lixivium mainly contains Co
and Li as well as a small amount of Ni and Cu. The chemical
(8) properties of Co and Ni are similar, important for their separation
and recovery. At present, the separation methods of cobalt and
nickel in solution have also been studied by many researchers,
including chemical precipitation (Li et al., 2019), solvent extraction
(Janiszewska and Sanak-Rydlewska. 2019), ion exchange resin
(Bozecka et al., 2018) and electro-reverse extraction (Prabaharan
and Barik et al., 2016). Additionally, Fe, Mn and Al do not
combine with ammonia in significant volumes and most of them
enter leaching residue, accounting for 10.66 wt%, 2.73 wt%, and
6 Y. Qi et al. / Journal of Cleaner Production 251 (2020) 119665

Fig. 6. The relationship between 1-(1-X) 1/3 and time at different temperatures: (a) Co, (b) Li; Arrhenius plot of metal leaching reaction in the temperature range of 313 Ke353 K: (c)
Co, (d) Li.

Table 3
Leaching kinetic parameters of Co and Li at different temperatures.

T Co Li

k1(min1) R2 Sig. (2-tailed) k2(min1) R2 Sig. (2-tailed)

313 2  104 0.925 0.003 1  104 0.946 0.001

323 2  104 0.908 0.005 3  104 0.936 0.002
333 5  104 0.984 0.000 5  104 0.971 0.000
343 1.4  103 0.997 0.000 1.6  103 0.996 0.000
353 2.9  103 0.993 0.000 3.2  103 0.996 0.000

Table 4
The chemical composition of lixivium and leaching residue under comprehensive
conditions.

Component Co Li Mn Ni Al Cu Fe

Lixivium, g/L 6.67 1.22 0.05 0.62 Nda 0.53 Nda

Leaching residue, wt.% 2.53 0.51 10.66 0.01 2.73 0.05 0.85
a
Nd meant that this value is below the detection limit and undetected.

0.85 wt%, respectively.

The morphologies and phase compositions of waste LIBs before
and after leaching were also measured using XRD, FT-IR, SEM, and
EDS. The results are shown in Figs. 7e9.
The results in Fig. 7 show that the phase of waste LIBs mainly
comprises LiCoO2 as the cathode material and graphite as the anode
material. Compared with waste LIB powder, the main phase of the
leaching residue is graphite, alongside a new substance, MnCO3.
Peaks of LiCoO2 is extremely weak, confirming that the cathode
material was successfully leached out.
Fig. 8 presents the result of FT-IR spectra of waste LIBs and
leaching residue. In Fig. 8a and (b), a broad peak is observed at
3500 cm1 which could be attributed to the overlapping of various
eOH stretching vibrations. The CeOeH peak observed at
1600 cm1 is the characteristic band of graphite, indicating that the
structure of graphite has not changed much before and after
Fig. 7. XRD patterns of waste LIBs and leaching residue.
leaching. In addition, the symmetrical stretching vibrating HeNeH
bonds appear at 1400 cm1 after leaching, which is related to the
ammonia leaching system. In Fig. 8a, a peak is observed near
600 cm1, which could be attributed to CoeO stretching vibrations.
However, there is no such peaks in Fig. 8b, but a small peak of
MneO observed at 640 cm1, which further indicates that LiCoO2 in
waste LIBs powder is completely leached under the optimum
conditions, and manganese carbonate (MnCO3) is formed in the
leaching residue, which is consistent with the results of Fig. 7.
The data presented in Fig. 9A reveals that the morphology of
waste LIB powders at low and high magnifications. These results
suggest that waste LIB powders are irregular granular and lamellar
 Y. Qi et al. / Journal of Cleaner Production 251 (2020) 119665
Fig. 8. FT-IR spectra of waste LIBs powders and leaching residues under the optimum
conditions: (a) Leaching residue, (b) Waste LIBs powders.
Fig. 9. SEM and EDS results of waste LIBs before and after leaching.
7
at different sizes under low magnification. Three points were
therefore taken for further analysis under high magnification
(Fig. 9A1, A2, and A3), correspondingly with EDS-A1, A2, and A3 on
the right side of this figure, respectively. The data in Fig. 9A1 shows
that the morphology of particles at different sizes are densely
agglomerated. In tandem with corresponding EDS analysis, these
results show that this material is mainly LiCoO2. This might be
related to the repeated charge-discharge cycles of Li-ion batteries,
resulting in the destruction of the original large-grained single
crystal structure (Li, 2018). On the basis of the results in EDS-A2, it
is clear that the material with a clear lamellar structure in Fig. 9A2
is graphite, an electrode material. While Fig. 9A3 shows a spherical-
like structure containing particles with smaller sizes (less than
1 mm). The main elements within this composition as revealed by
EDS include Ni, Co, and Mn. This indicates that waste LIBs also
include ternary cathode materials, similar to the morphology of
NieCoeMn ternary materials synthesized previously by Liu et al.,
(2018).
The data presented in Fig. 9B illustrates the morphology of
leached residues at low and high magnifications. It is clear that the
8 Y. Qi et al. / Journal of Cleaner Production 251 (2020) 119665
Fig. 10. Flow chart for further separation and purification of the obtained leaching residues.
morphology changed a lot before and after leaching. Scattered
particles at smaller sizes are observed under low magnification and
seems to adhere to the surface of the leaching residues indicating
new reactions. We took three points for further analysis under high
magnification (Fig. 9B1, B2, and B3). Fig. 9B1, B2 and B3 show
similar morphologies including numerous smooth and uniform
cubic materials adhering to the surface of particles. Based on the
analysis outlined in Fig. 7, it is clear that this new substance is
MnCO3. One difference is that the quantity of adhering particles is
more in Fig. 9B1 and B2. Fig. 9C suggests that each manganese
carbonate crystal is about 200 nm in length. In order to further
explore the morphology of leaching residues, we conducted further
EDS analysis on two points in Fig. 9C. Each cube in this case is a
manganese carbonate crystal and adhered to graphite particles. In
an earlier work, Qu (2018) noted that both temperature and the
concentration of NH4HCO3 played important roles in the formation
of MnCO3 crystals, in connected with our conclusions.
3.7. Leaching residues separation and purification
Our analyses show that the leaching residues mainly contain
graphite and MnCO3. Therefore, we further separated the leaching
residues to recovery MnCO3 and graphite (Fig. 10). Data show that
both MnCO3 and graphite can be recovered successfully by simple
hydrometallurgical separation treatment. The specific processing
steps are as follows: firstly, leaching residue is dissolved with sul-
furic acid, and then graphite can be separated by filtration. Next, pH
of the filtrate is adjusted by NH3$H2O, so that iron ion and
aluminum ion can be completely precipitated. After that, we use
NH4HCO3 to neutralize the purified liquid and finally MnCO3 crystal
can be obtained by filtering, washing and drying. What’s more, XRD
patterns of graphite and MnCO3 obtained are shown in Figs. S4 and
SI. Fig. 10A and B shows the morphology of the obtained graphite
and MnCO3, in which graphite is obvious lamellar and MnCO3
spherical with a particle size of about 50 nm. This means that
MnCO3 can be used as raw materials for other industrial products,
such as telecommunications equipment soft magnets, manganese
dioxides and salts. And graphite can be used to produce high
temperature resistant materials, conductive materials, and carbon
materials. This graphite could also be subject to further treatment
to produce high-quality graphene sheets with fewer layers (Lin
et al., 2017). Besides, MnCO3 can be calcined to Mn3O4, XRD pat-
terns of the MnCO3 after calcining are shown in Fig. S5 and SI, an
aggregate formed by particles less than 1 mm, as shown in Fig. 10C.
These obtained Mn3O4 can be used as a precursor for the produc-
tion of new LIB cathode materials (Liu et al., 2018).
4. Conclusions
This research elucidates a new ammonia leaching method for
recovering waste LIBs with a high Co and Li removal rate. At the
optimum conditions (NH3$H2O 120 g/L, NH4HCO3 75 g/L, n
(Na2SO3): n (Co) ¼ 2:1, 353 K and 240 min), the leaching rates of Co
and Li are 91.16% and 97.57%, respectively. The leaching kinetics
results show that the speed-limiting step in this leaching process is
the interfacial chemical reaction. The activation energy of Co and Li
leaching revealed here is 58.45 kJ mol1 and 50.05 kJ mol1,
respectively. SEM, EDS and XRD results indicate that the
morphology of waste LIB powder is irregular and lamellar at
different sizes. Meanwhile, a new substance, MnCO3 can be found
on the surface of graphite. The surface of this new compound is
smooth and show a uniform cubic structure, with an edge length of
about 200 nm. Both manganese carbonate and graphite can be
recovered directly from the residue. Besides, MnCO3 obtained can
be calcined to Mn3O4, which can be used as a precursor for the
production of new LIBs cathode materials. The application of an
ammonia leaching method in the recycling process of waste LIBs
achieves a high leaching level of Co and Li as well as recovering
MnCO3, graphite and Mn3O4. This approach provides a new idea for
the effective recovery and resource utilization of waste LIBs.
Declaration of competing interest
We declare that we do not have any commercial or associative
interest that represents a conflict of interest in connection with the
work submitted.
Acknowledgements
The research is supported by the National Natural Science
Foundation of China (51974262) and Research Fund of Southwest
University of Science and Technology (14tdgk01, 17LZX422,
17LZXT05, 18LZX412).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jclepro.2019.119665.
 Y. Qi et al. / Journal of Cleaner Production 251 (2020) 119665
Author contributions
Yaping Qi: Conceptualization, Methodology, Software, Investi-
gation, Writing - Original Draft.
Fansong Meng: Validation, Formal analysis, Visualization,
Software.
Xiaoxia Yi: Validation, Formal analysis, Visualization.
Jiancheng Shu: Resources, Writing - Review & Editing, Super-
vision, Data Curation.
Mengjun Chen: Resources, Writing - Review & Editing, Super-
vision, Data Curation.
Zhi Sun: Writing: Review & Editing.
Shuhui Sun: Writing: Review & Editing.
Fu-Rong Xiu: Writing: Review & Editing.
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