Waste Management 79 (2018) 545–553

Contents lists available at ScienceDirect

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

A sustainable process for metal recycling from spent lithium-ion

batteries using ammonium chloride
Weiguang Lv a,b, Zhonghang Wang a, Hongbin Cao a, Xiaohong Zheng a, Wei Jin c, Yi Zhang a, Zhi Sun a,⇑
a
Beijing Engineering Research Center of Process Pollution Control, Division of Environment Technology and Engineering, Institute of Process Engineering, Chinese Academy of
Sciences, Beijing 100190, China
b
University of Chinese Academy of Sciences, Beijing 100190, China
c
School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China

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

Article history: In this paper, a sustainable process to recover valuable metals from spent lithium ion batteries (LIBs) in
Received 16 April 2018 sulfuric acid using ammonium chloride as reductant was proposed and studied. Being easily reused,
Revised 3 August 2018 ammonium chloride is found to be efficient and posing minor environmental impacts during the overall
Accepted 12 August 2018
process. By investigating the effects of a wide range of parameters, e.g., H2SO4 concentration, NH4Cl con-
Available online 24 August 2018
centration, temperature, leaching time, and solid-to-liquid mass ratio, the leaching behaviour of Li, Ni, Co,
and Mn was systematically investigated. And the leaching mechanism and kinetics were determined by
Keywords:
mineralogically characterization of residues at various reaction times and by fitting using different
Spent lithium ion batteries
Valuable metals
kinetic models. With this research, it is possible to provide a win-win solution to improve the recycling
Sulphuric acid effectiveness of spent LIBs by using waste salt that is easily reused as the reductant.
Ammonium chloride Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction Nowadays, spent LIBs are usually processed by using either

Rapid development of mobile phone, energy storage device and
electric vehicles, leads to an ever-increasing demand of recharge-
able lithium-ion batteries (Gao et al., 2017; Wu et al., 2018). Mean-
while, the amount of waste LIBs substantially climbed due to the
rapid increase in the consumption of LIBs (Lv et al., 2018). Richa
et al. has estimated that 0.33–4 million metric tons of LIBs are pro-
jected to enter the waste stream from electric vehicles between
2015 and 2040 (Winslow et al., 2018). The waste will lead to the
issues in supply chains, resource, and environment (Mishra and
Gostu, 2017). For example, some of waste LIBs are not completely
discharged, which may catch fire or explode under improperly
handle. Sol-vent electrolyte lithium hexafluorophosphate (LiPF6)
and some of the heavy metals contained within the batteries are
dangerous to leach into solution and soil (Natarajan et al., 2018;
Winslow et al., 2018). Besides, LIBs contains many valuable metals
such as cobalt and lithium. As a result, it is highly required to recy-
cle spent LIBs in an environmentally friendly and economic way
(Helbig et al., 2018; Lv et al., 2018; Sun et al., 2017).
⇑ Corresponding author at: Beijing Engineering Research Center of Process
Pollution Control, Division of Environment Technology and Engineering, Institute
of Process Engineering, Chinese Academy of Sciences, No. 1 Beierjie, Zhongguancun,
Beijing, China.
E-mail address: sunzhi@ipe.ac.cn (Z. Sun).
pyrometallurgical or hydrometallurgical methods, to recover valu-
able metals or other components. Pyrometallurgical methods usu-
ally carried out under harsh reaction conditions, during which
toxic gases would be released and some metals like Li and Al can
hardly be recovered (Li et al., 2017; Xiao et al., 2017; Zeng et al.,
2014). Thus, a growing number of studies have focused on the
hydrometallurgical processes, because of its high extraction effi-
ciencies of valuable metals, especially Li, controlled environmental
influence, and low energy consumption (Chagnes and Pospiech,
2013; Peng et al., 2018). A hydrometallurgical process mainly con-
sists of leaching, purification, and fabrication procedures. In the
leaching procedure, reductants are usually needed to be added into
the inorganic/organic acid (Joulié et al., 2017; Meshram et al.,
2015; Senćanski et al., 2017) or ammonia-based alkaline (Ku
et al., 2016; Wang et al., 2017a) leaching reagents to enhance the
leaching process. The most common reductant used in experi-
ments is H2O2, because of its lower redox potential and no intro-
duction of impurities. However, the instability of hydrogen
peroxide leads to some issues in leaching process, storage, and
transport (Meng et al., 2017). Recent studies have attempted to
investigate alternative reductants, like Na2S2O5 (Vieceli et al.,
2018), NaHSO3 (Meshram et al., 2015), glucose (Pant and Dolker,
2016), ascorbic acid (Nayaka et al., 2018), etc. These alternatives
are more stable than H2O2. However, all of these reductants
cannot be directly or simply regenerated and reused. Besides, the

https://doi.org/10.1016/j.wasman.2018.08.027
0956-053X/Ó 2018 Elsevier Ltd. All rights reserved.
546 W. Lv et al. / Waste Management 79 (2018) 545–553

productive processes of raw materials also need to be considered 35000

from the environmental and life cycle assessment perspective. Li(Ni0.5Co0.2Mn0.3)O2

(003)
For example, the commercial anthraquinone oxidation (AO) pro- 30000
cess for producing H2O2 generates substantial organic by-product
wastes, which are necessary to remove. The separation of product 25000

(104)
from these waste organics requires high investment in equipment

Intensity
and high temperature (Campos-Martin et al., 2006). 20000
Fortunately, no reductant is needed when leaching with HCl,
this is because that the NCM could be reduced by Cl
in this system 15000

(101)

(018) (110)
(006) (102)
(Takacova et al., 2016). Barik et al. (2016) used HCl as leaching
reagent to recover valuable metals from spent cathode, and over 10000

(107)
(105)

99% of Li, Co, and Mn in the cathode were extracted into the solu-
tion. Wang et al. used HCl as leaching reagent with 99% of Li, Ni, Co,
and Mn leached from the mixture contained spent LiCoO2, LiMn2-
O4, and NCM cathode materials (Wang et al., 2009). However,
when using HCl barely as the leaching reagent, the volatility and
corrosion of HCl with concentration of 2–4 M should not be
ignored.
Therefore, to achieve a similar reaction performance, chloride
components, like ammonium chloride, sodium chloride, could be
introduced into non-HCl acidic systems as a reductant, without
causing the above-mentioned volatility and corrosive problems.
Besides, it was reported that more than 2.4 million m3 waste water
containing ammonium chloride was discharged in China in 2013
(Li et al., 2016), and a lot of waste NH4Cl water produced in extract-
ing cobalt production need to be solved through concentration and
crystallization (Guideline on Available Technologies of Pollution
Prevention and Control for Cobalt Smelting Industry (on Trial),
2015, Ministry of Ecology and Environment of the People’s Repub-
lic of China). If the waste ammonium chloride can be reused in
industrial production, it will reduce environment pollution and
increase profit.
In this paper, ammonium chloride was adopted as a new reduc-
tant to achieve high leaching efficiencies of Ni, Co, Mn, and Li from
the spent cathode materials in the sulfuric acid. The effect of leach-
ing agent concentrations, reductant concentrations, solid-to-liquid
mass ratio (S/L mass ratio), temperature, and leaching time on the
leaching efficiencies of various valuable metals were systemati-
cally investigated. Then the leaching mechanism and kinetics were
determined by mineralogically characterization of residues at var-
ious reaction times and by fitting using the unreacted contraction
nuclear model. On one hand, the ammonium chloride is a stable
(easy to transport and store) and cheap reductant corresponding
to the H2O2. It can be obtained from factory waste, which has a
huge stock and is urgent to be disposed. Therefore, this is a win-
win solution. On the other hand, the recycling of chlorine during
the leaching procedure was also proposed. Although, there is still
a lot of work need to be done on this technology, it has great poten-
tial to be applied in the future.
2. Material and methods
2.1. Materials and reagents
(113)
5000
0
0 10 20 30 40 50 60 70 80 90
Fig. 1. XRD patterns of cathode materials.
grade from Alfa Aesar Chemical Co. Ltd and all solutions were pre-
pared with ultrapure water (Milli-pore Milli-Q).
2.2. Leaching of cathode scraps
The leaching experiments were carried out in a 250 mL round-
bottom flask, equipped with condensing unit to reduce the influ-
ence from evaporation, magnetic stirrer, and a sensor based tem-
perature controller (DF-101SZ, Gongyi, Yuhua Equipment Co.,
Ltd). A given mass of scraps was added to a 100 mL solution con-
taining sulphuric acid and the reductant. The residue was dried
at 80 °C in a drying cabinet (DHG-9070A, Shanghai Yiheng Equip-
ment Co., Ltd). To investigate the leaching kinetics, 0.5 mL of liquid
sample was taken out from the leachate at a certain reaction time,
to get the local leaching efficiency of each metal. The leaching effi-
ciencies of metals from the cathode scraps were determined as
follows:
x ¼ C M;t  V=mM  100% ð1Þ
where x (%) is the leaching efficiency of metal M (M = Co, Ni, Mn, Li),
CM,t (g/L) is the concentration of M ions in the leachate, mM is the
mass of M in the initial scraps, and V (L) is the volume of the
leachate.
2.3. Characterization
The cathode scrap was characterized by X-ray diffraction
(X’pert PRO, PANalytical) with Cu Ka radiation and the data was
collected from 5 to 90°. The concentrations of Li, Ni, Co, and Mn
ions in leachate were analysed by ICP-OES (iCAP 6300 Radial,
Thermo Scientific). The morphology and the surface composition
of scrap were characterized using a mineral liberation analyzer
(MLA 250, FEI) equipped with an energy dispersive spectrometer
(EDS, EDAX GenesisSiLi) and a scanning electron microscope
(SEM, Quanta 250).

The cathode scraps were supplied by a local spent LIBs recycling
company (Ganzhou highpower technology Co., Ltd) in China. A
complete dissolution of cathode scrap was carried out in aqua regia
to determine the chemical composition using ICP-OES (iCAP 6300
Radial, Thermo Scientific). The contents of Li, Co, Ni and Mn in
scrap were 6.15%, 10.70%, 26.08%, and 14.58%, respectively. The
XRD patterns of the cathode scrap shown that Li(Ni0.5Co0.2Mn0.3)
O2 is the major phase (Fig. 1). Sulfuric acid was used as the leaching
reagent with ammonium chloride used as the reductant. All chem-
ical reagents (H2SO4, HCl, HNO3, NH4Cl, NaOH) were of analytical
3. Results and discussion
3.1. Leaching metals from spent LIBs
The reaction between NCM cathode scraps and H2SO4 in the
absence of reductant like NH4Cl was described as Eq. (2). The cal-
culation demonstrates that the reaction is thermodynamically fea-
sible. For the absence of the Gibbs free energy of NCM, the data of
LiCoO2, LiNiO2 and LiMnO2 (Yokokawa et al., 1998) were used to
calculate a possible range of DGh298K (Eq. (2)). The Eqs. (3)–(6)
 W. Lv et al. / Waste Management 79 (2018) 545–553 547

describe the reaction between cathode scraps and acid with NH4Cl. 100
Though the calculated values of DGh298K are negative, the leaching
speed of different metals all have a low value, which can be attrib-
uted to the influence of kinetics, system complexity, side effect, etc. 80

Leaching efficiency (%)

(Pinna et al., 2017; Takacova et al., 2016).

2Li(Ni0:5 Co0:2 Mn0:3 )O2 +3H2 SO4 !Li2 SO4 +0.4CoSO4 +NiSO4 60
ð2Þ
+0.6MnSO4 +3H2 O+0.5O2 " DG298 K h =
424.001 KJ/mol

2LiCoO2 +4H2 SO4 +2NH4 Cl!2CoSO4 +Li2 SO4 +(NH4 )2 SO4 +Cl2 " 40
h
þ4H2 O DG298 K =
300.246 KJ/mol ð3Þ Li
Ni
20 Co
2LiMnO2 +4H2 SO4 +2NH4 Cl!Li2 SO4 +2MnSO4 +Cl2 " Mn
ð4Þ
+4H2 O+(NH4 )2 SO4 DG298 K h =
309.724 KJ/mol
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
2LiNiO2 +4H2 SO4 +2NH4 Cl!2NiSO4 +Li2 SO4
ð5Þ H2SO4 concentration (mol/L)
+(NH4 )2 SO4 +4H2 O+Cl2 " DG298 K h =
491.164 KJ/mol
Fig. 2. Effect of H2SO4 concentration on the leaching efficiencies of metals (NH4Cl
2Li(Ni0:5 Co0:2 Mn0:3 )O2 +4H2 SO4 +2NH4 Cl!Li2 SO4 +NiSO4 concentrarion: 0.8 mol/L, temperature: 353 K, agitation speed: 400 rpm, S/L mass
+0.4CoSO4 +0.6MnSO4 +4H2 O+(NH4 )2 SO4 +Cl" DG298 K h =
398.548 KJ/mol ration: 100 g/L and reaction time: 60 min).

ð6Þ

Besides, the Cl2 can be converted into Cl
in a mild atmosphere

through following reaction: 100

Cl2 +H2 O!HClO+HCl ð7Þ

80
Leaching efficiency (%)

The reaction of charge from ClO to Cl could also be achieved
(Belluati et al., 2007). Therefore, NH4Cl is chosen as an excellent
reductant in the following experiments to reduce the usage of
reductant and enhance the profile. Previous studies have found
that the concentration of H2SO4 and NH4Cl played the key role in
the leaching process corresponding to other conditions (Chen
et al., 2018; Yang et al., 2018). The agitation speed (400–800
rpm) showed no obvious effect on leaching efficiencies (He et al.,
2017). Meanwhile, a large solid-to-liquid like 100 g/L is considered
to obtain a high throughput. Therefore, the order of conditions to
be researched is the sulfuric acid concentration, the ammonium
chloride concentration, the temperature, the leaching time and
the solid-to-liquid.
3.1.1. Effect of acid concentration
The effect of sulphuric acid concentration on the leaching effi-
ciencies of Ni, Co, Mn and Li was studied in the concentration range
of 0–3 mol/L, with the results presented in Fig. 2. The experiments
were carried out with S/L mass ratio of 100 g/L, reaction tempera-
ture of 353 K, reaction time of 60 min, agitation speed of 400 rpm,
and NH4Cl concentration of 0.8 mol/L. The result in Fig. 2 show that
the leaching efficiencies of Co, Ni, Mn and Li increase sharply with
increasing sulphuric acid concentration from 0 to 2.5 mol/L and
then a platform appears when the sulphuric acid concentration
increase further from 2.5 to 3.0 mol/L. In the correspondence of
kinetics law, an increase in the H2SO4 concentration enhances
the leaching rate. In consideration of the cost and efficiency, all fur-
ther experiments were carried out using 2.5 mol/L sulphuric acid.
3.1.2. Effect of reductant amount
With the addition of ammonia chloride, the leaching reaction of
cathode scrap with sulphuric acid is described in Eq. (6). To inves-
tigate the effect of NH4Cl concentration on the leaching of different
valuable metals from cathode scraps, the experiments were carried
out under the conditions as follows: NH4Cl concentrations ranging
from 0 to 1.2 mol/L, H2SO4 concentration of 2.5 mol/L, S/L mass
ratio of 100 g/L, leaching temperature of 353 K, agitation speed of
400 rpm and reaction time of 60 min. Results presented in Fig. 3
clearly indicate that the leaching efficiencies of valuable metals
60
40
Li
Ni
20 Co
Mn
0
0.0 0.2 0.4 0.6 0.8 1.0
NH4Cl concentration (mol/L)
Fig. 3. Effect of NH4Cl concentration on the leaching efficiencies of metals (H2SO4
concentrarion: 2.5 mol/L, temperature: 353 K, agitation speed: 400 rpm, S/L mass
ration: 100 g/L and reaction time: 60 min).
increase with the addition of NH4Cl. This increase tendency should
be ascribable to the reducibility of Cl
in this system. As NH4Cl as a
reductant helps to dissolve cobalt and nickel in LiNi0.5Co0.2Mn0.3O2,
the dissolution of manganese is at the same time promoted, for the
whole crystal structure is destroyed with breaking down chemical
bonds between metal atoms and oxygen atom. Hence, in consider-
ation of the cost and efficiency, 0.8 mol/L NH4Cl can be taken as the
optimum value for the further experiments.
3.1.3. Effect of reaction temperature
Temperature is usually a main factor that would influence the
chemical reactions on both thermodynamic and kinetic aspects.
The effect of temperature was investigated in the range of 293–
353 K with all other conditions maintained unchanged (reaction
time 60 min, H2SO4 concentration 2.5 mol/L, NH4Cl concentration
0.8 mol/L, agitation speed 400 rpm and S/L mass ration 100 g/L).
Fig. 4 shows that the leaching efficiencies of valuable metals over
leaching temperatures. It can be observed that the leaching effi-
ciencies of valuable metals are all significantly enhanced with
increasing temperature from 293 to 353 K. Because, there is a
548 W. Lv et al. / Waste Management 79 (2018) 545–553

100 leaching process. It can also be observed that almost all metals
are removed from scrap to leachate, after leaching for 60 min. This
90 might could because of the fact that the amounts of H+ and Cl
in
the solution are sufficient in the initial stage of the leaching pro-
Leaching effciency (%)

80 cess. Then they are gradually consumed as the reaction proceeded,

70
60
50
40
30
290 300 310 320 330
Temperature (K)
Fig. 4. Effect of temperature on the leaching efficiencies of metals (H2SO4
concentration: 2.5 mol/L, NH4Cl concentration: 0.8 mol/L, agitation speed: 400
rpm, S/L mass ration: 100 g/L and reaction time: 60 min).
significant enhancement in kinetics rate to remarkably promote
the leaching of valuable metals with increasing temperature.
Meanwhile, the above variation could also be explained by using
the E-pH diagram, as shown in Fig. S1. With the increase in
temperature, the redox potential of Cl2/Cl
will decrease, and the
overlap of Cl2/Cl
, MnO2/Mn2+ and Co(OH)3/Co2+ is enlarged to
enhance the reduction of Co3+ and Mn4+. In consideration of the
energy consumption, the temperature was set to be 353 K in the
subsequent research.
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.wasman.2018.08.
027.
3.1.4. Effect of leaching time
The effect of reaction time (0–120 min) on the leaching efficien-
cies of metals was examined under the conditions as follows:
NH4Cl concentrations 0.8 mol/L, H2SO4 concentration of 2.5 mol/L,
S/L mass ratio of 100 g/L, leaching temperature of 353 K, and agita-
tion speed of 400 rpm. The result presented in Fig. 5 shows that the
leaching efficiencies of Ni, Co, Mn and Li rapidly increase in the
initial ten minutes and then slowly increase in the subsequent
100
80
Leaching efficiency (%)
resulting in the decrease in reaction kinetic in the latter stages.
Fig. 6 shows SEM images of residues over different leaching time
in 2.5 mol/L H2SO4-0.8 mol/L NH4Cl solution at 353 K. It can be
seen from Fig. 6 that along with leaching time, particle size of
Li spherical-like crystal decreases from nearly 10 to less than 2 lm,
Ni and finally the spherical-like crystal is replaced by amorphous
Co morphology mainly consisting of organic binder. The organic bin-
Mn der involved in cathode scrap has agglomerated along leaching
time. Besides, the result of liner scanning is shown in Fig. S2, which
gives the distribution of metal elements, indicates the decrease of
340 350 Ni, Co, and Mn and increase of C in particles.
3.1.5. Effect of solid-to-liquid mass ratio
Effect of pulp density on the leaching efficiencies of metals was
examined under the conditions as follows: H2SO4 concentration of
2.5 mol/L, NH4Cl concentrations 0.8 mol/L, reaction temperature of
353 K, and agitation speed of 400 rpm, with results shown in Fig. 7.
It is obvious that S/L mass ration has a negative effect on the leach-
ing process when it is more than 100 g/L. When it is less than
100 g/L, nearly all of Ni, Co, Mn, and Li can be leached out, whereas
the leaching efficiencies drops to 75.5% for Li, 68.5% for Ni, 67.6%
for Co, and 69.9% for Mn, respectively when the pulp density
increase to 150 g/L. To hold a high production capacity and obtain
a high economic efficiency, a 100 g/L of solid-to-liquid ratio is
considered to be the optimal condition.
3.2. Leaching mechanism determination
3.2.1. The analysis of structure of leaching residues
The leaching residues obtained from different leaching time
under the optimal conditions were analyzed through XRD, with
results summarized in Fig. 9(a). It can be seen that the intensity
of characteristic peaks of NCM weaken gradually as leaching pro-
ceeds from 0 to 120 min. However, the special peaks are still found
in the XRD pattern even after reacting for 120 min. And this is cor-
responding to the ICP result of leachate, which indicates that
nearly 3–4% of Ni, Co, and Mn are still not leached. It is illustrated
that the peak position of (0 0 3) has evident shift from high angle to
low angle, which means the increase of c lattice parameter and the
decrease of a lattice parameter. The shift supports the conclusion
that the leaching of Li is quicker than other metals. The change
of (0 1 8) and (1 1 0) also prove this conclusion.
The analysis of leaching mechanism is shown in Fig. 8(b).
Firstly, the leaching of metals from cathode scrap would destroy
the crystal structure with no new phase formed, resulting in no

obvious change occurred in XRD patterns of leaching residues. Sec-

ondly, with rapid extraction of lithium from crystal structure, the
60
layer of O2
—Li+—O2
loses the lithium ions with the repulsive
force of O2
—O2
increasing, leading to the increase in c lattice
40 parameter and the decrease in a lattice parameter (Takahashi
Li et al., 2007). Meanwhile, the remaining crystal will be easy to react
Ni with H+ and Cl
without Li+. The changes of a and c lattice param-
20 Co eter lead to the shift of peak position. With the dissolution of other
Mn metals, the crystal structure of NCM will be destroyed with no
intermediate products. Therefore, there is no obvious shift of every
0 peak position of NCM in the later leaching process.
0 2 4 20 40 60 80 100 120
Time (min) 3.2.2. Apparent kinetics of leaching
Fig. 5. Effect of leaching time on the leaching efficiencies of metals (H2SO4
The dissolution kinetics behaviour of Co, Ni, Mn and Li were
concentration: 2.5 mol/L, NH4Cl concentration: 0.8 mol/L, temperature: 353 K, studied at various temperatures. As shown in Fig. 5, the leaching
agitation speed: 400 rpm, and S/L mass ration: 100 g/L). speed is so rapid that the fast-rising period can finish in the initial
 W. Lv et al. / Waste Management 79 (2018) 545–553 549

(a) (b)

(c) (d)

Fig. 6. SEM images residues after leaching for (a) 0 min; (b) 10 min; (c) 60 min; (d) 120 min.

100
1
ð1
xÞ2=3 ¼ k2 t ð9Þ

1
2=3x
ð1
xÞ2=3 ¼ k3 t ð10Þ

80
Leaching efficiency (%)

where x is the leaching efficiency, k1, k2 and k3 (min
1) are the reac-
tion rate constants and t (min) is reaction time. Table 1 summarized
60 the fitting results by using the above three equations. It was found
that the chemical reaction control model exhibits the best fitting in
comparison with the other models.
40
The apparent activation energy is calculated through the empir-
Li
ical Arrhenius law (Eq. (11)) and the data of the reaction rate con-
Ni
20 Co stant and temperature obtained from Eq. (8).
Mn
k ¼ Aexpð
Ea =RT Þ ð11Þ
0 In Eq. (11), k is the apparent constant of different model, A is the
70 80 90 100 110 120 130 140 150 160
frequency factors, T is the temperature, R is the gas constant
S/L mass ratio (g/L)
(8.314 J K
1 mol
1) and Ea is the apparent activation energy. For
Fig. 7. Effect of S/L mass ratio on leaching of metal from NCM (523) scraps (H2SO4 the easiness of calculation, the Eq. (10) is further converted into
concentration: 2.5 mol/L, NH4Cl concentration: 0.8 mol/L, temperature: 353 K, Eq. (12).
agitation speed: 400 rpm, and reaction time: 60 min).
ln k ¼ ln A
Ea =RT ð12Þ
1/3
The relevant data about the plots of 1
(1
x) = kt at different
three to five minutes. The kinetic models including chemical reac- temperature were calculated using Eqs. (8) and (12). The plots of
tion control (Eq. (8)), internal diffusion control model (Eq. (9)) and lnk vs 1/T of Li, Ni, Co and Mn (Fig. 9) illustrate that the
external diffusion model (Eq. (10)) are presented as: apparent activation energies for Li, Ni, Co and Mn are 27.50 kJ/mol,
23.52 kJ/mol, 22.91 kJ/mol, and 24.12 kJ/mol, respectively. Further-
1
ð1
xÞ1=3 ¼ k1 t ð8Þ more, the chemical reaction control also illustrates the effect of
550 W. Lv et al. / Waste Management 79 (2018) 545–553

(a) Li(Ni0.5Co0.2Mn0.3)O2

(003)

(104)
(101)
120min

60min
Intensity

(105)

(107)
30min

10min

(113)
3min
(006)
(102)

(018)
(110)
0min

0 20 40 60 80 16 18 20 22 34 36 38 40 42 44 46 48 5055
5 60 6
65 70 75
2 CuK (Deg.) CuK (Deg.) CuK (Deg.)

(b)

Cl-
H+
O2-
Li+
NiCoMn

Fig. 8. (a) The X-ray powder diffraction patterns of leaching residue and (b) the mechanism of H2SO4 leaching process with NH4Cl.

-1.0
waste source management are often needed to be researched as
Li
Ni well. Certainly, the topic of how hazards can be treated from waste
Co LIBs have arose attentions from governmental agencies and organi-
-1.5 RLi2=0.997
Mn zations. Many efforts have been made to manage spent LIBs in
parts of the world such as the European Union (EU), the United
states, Japan, China, etc. However, under the current condition,
-2.0 RNi2=0.996
the composition of waste LIBs is still complex increasing the diffi-
RCo2=0.993
lnk

culty for recycling methods (Ojanen et al., 2018; Wang et al.,

R2Mn=0.997
-2.5
-3.0
0.0028 0.0030
1/T (K-1)
Fig. 9. Arrhenius plots for leaching of Mn, Ni, Co, and Li from the cathode scrap
under the surface chemical control model.
pulp density on the leaching process. Because it is a chemical con-
trol reaction, the effect of diffusion can be ignored in the initial
reaction time, when the leaching reagent is abundant. However,
H+ and Cl
are not abundant in the subsequent leaching process,
in which the mechanism of leaching will be controlled by internal
diffusion (Takacova et al., 2016).
3.3. Spent battery management
The composition of waste waiting for recycling impacts our
judgement in the selection of appropriate recycling methods. In
order to ameliorate the pollution problem, the pretreatment meth-
ods and extraction methods are needed to be polished, in addition,
2017b).
The first region that pays attention to manage waste LIBs was
EU. According to the Directive from EU, the obligation to manage
waste LIBs belongs to manufacturers and dealers, for which all
waste LIBs are needed to be recycled and classified (Zhang et al.,
2018). Though the US has no federal law established to bolster
0.0032 0.0034 waste electrical and electronic equipment recycling, yet there are
some relevant bills already passed in some states in the US. In Aus-
tralia, waste LIBs are not regarded as hazardous materials (Boxall
et al., 2018). As for China, many active measures have been taken
to treat waste LIBs, considering the fact that the production stream
rapidly increased in recent years (Gu et al., 2017). It is also fortu-
nate to see that the recycling method of waste LIBs has been mod-
ified at least. For example, the recovery rate of waste batteries has
reached 95% in Sweden and 75% in Denmark (Zhang et al., 2018).
However, with the development of LIBs, waste structures are grow-
ing in complexity. This raised the question of whether government
should keep enforce strict laws to direct and to assist R&Ds.
Besides, the public awareness of environmental protection,
especially the classification of waste, is also important for the recy-
cling of waste LIBs. As we all know, the simpler the component of
waste is, the simpler the treatment technology is. The difficulty of
the laboratory technology applying to the factory is usually from
the complex composition. In this situation, many purification pro-
cesses, which will increase the consumption of energy and the loss
of valuable metals, need to be designed to remove the impurity and
 W. Lv et al. / Waste Management 79 (2018) 545–553 551

Table 1
The data of kinetic parameters during the leaching process with NH4Cl calculated using three models (Chemical control model, external diffusion model and internal diffusion
model).

T (k) Li Co Ni Mn
k (min
1) R2 k (min
1) R2 k (min
1) R2 k (min
1) R2
Chemical reaction control
303 0.062 0.983 0.050 0.978 0.051 0.978 0.050 0.979
313 0.088 0.998 0.062 0.995 0.064 0.996 0.065 0.997
323 0.175 0.973 0.108 0.960 0.118 0.973 0.120 0.977
353 0.285 0.980 0.179 0.985 0.186 0.982 0.190 0.988
Internal diffusion control
303 0.010 0.850 0.007 0.749 0.006 0.852 0.007 0.850
313 0.019 0.921 0.011 0.923 0.010 0.932 0.011 0.919
323 0.048 0.985 0.024 0.982 0.021 0.989 0.025 0.980
353 0.084 0.981 0.040 0.963 0.038 0.968 0.042 0.959
External reaction control
303 0.113 0.987 0.095 0.981 0.094 0.9801 0.093 0.982
313 0.152 0.993 0.116 0.993 0.112 0.9891 0.117 0.994
323 0.288 0.949 0.208 0.958 0.192 0.945 0.211 0.962
353 0.456 0.950 0.323 0.971 0.313 0.967 0.330 0.975

extract pure products (Yang et al., 2017). Therefore, as the source
of waste LIBs, the public has to duty to sort the waste at first before
transporting out from their neighbourhood, this tends to help firms
to better classify them before feeding wastes into next stage. This
can be very essential to help bring up the extraction efficiency of
valuable metals and to reduce the complexity of technology.
3.4. A preliminary discussion for reusing of reductant NH4Cl
A flowchart of the whole technology was given in Fig. 10(a). In
this technology, the waste solution will contain high concentration
of Cl
, which can be reused as leaching reagent with addition of
certain amount of H2SO4. Firstly, the valuable metals are leached
out from cathode scrap. After that, the raffinate containing Cl
is
obtained from solvent extraction. In the end, the solution from sol-
vent extraction will be purified and regenerated by using Ca(OH)2
to remove the redundant sulphate. Meanwhile, the common
extractants to separate Co and Ni are usually used in a chloride sys-
tem, like the leachate from HCl leaching and the exist of Cl
can
also promote the extraction of metal ions (Torkaman et al.,
2017). Therefore, the existence of Cl
will not have a negative
influence on the separation and purification process. The accumu-
lation of sulphate in solution needs to be considered for the com-
mon ion effect, which will reduce the solubility of valuable metal
ions in solution. As a traditional technology, Ca(OH)2 is used to
removed SO2- 4 from raffinate. After that, the reductant will be
reused. Fig. 10(b) shows the possible process of chlorine circulation
in this leaching process. The chlorine circulation mainly depends
on the self-circulation of Cl among Cl
, Cl2, and HClO. Of course,
a little part of Cl2 also needs to be absorbed by alkaline solution,
like ammonium hydroxide.
To further identify the potential of the reusing of Cl
, NaOH is
used to separate Ni, Co and Mn from leachate. After that, the con-
centration of Cl
in different liquid have also been analyzed
through ion chromatography. The result is shown in Table 2, which
Table 2
The amount of Cl
in liquid in different process.
Liquid Cl
(g)
Before leaching (100 mL) 2.871
After leaching (100 mL) 2.726
After precipitation (120 mL) 2.367

Fig. 10. (a) Schematic diagram of the process to sustainably use Cl
as reductant in the leaching system, (b) schematic diagram of reaction mechanism of the sustainable
utilize of Cl
.
552 W. Lv et al. / Waste Management 79 (2018) 545–553
Table 3
The leaching efficiencies of different metals in first leaching and second leaching.
Leaching efficiency, % Li Ni Co
First leaching 99.11 97.49 97.55
Second leaching 97.23 94.12 94.45
indicates that the Cl
is mainly lost in precipitation process. How-
ever, the remaining Cl
in solution is possible to be reused in the
next leaching. 13.6 mL concentrated H2SO4 was added in the into
100 mL solution obtained from the leachate after precipitation
with 0.8 g NH4Cl added. The new leaching reagent can still leach
out nearly 95% of valuable metals from scraps in the second leach-
ing process (Table 3). Therefore, the reusing of Cl
is possible.
Meanwhile, the release of Cl2 is so small that it is easy to be
absorbed with little pollution.
4. Conclusions
A stable (easy to transport and store) and cheap reductant was
adopted to enhance the recovering of recycling valuable metals
from spent lithium-ion batteries cathode scraps. Meanwhile, using
ammonia chloride, which has a large quantity storage waiting to be
treated, is a win-win solution to improve the recycling effective-
ness of spent LIBs and reduce the pollution of waste water. The fol-
lowing conclusions can be obtained based on the current
experiments:
(1) A range of relevant factors have been examined to optimize
the parameters of leaching process. Under the leaching con-
ditions of 2.5 M H2SO4, 0.8 M NH4Cl, 100 g/L, 400 rpm at
353 K, 99.11% of Li, 97.49% of Ni, 97.55% of Co, and 97.34%
of Mn could be leached out within 60 min.
(2) The kinetics analysis was carried out based on three com-
mon models. The results indicate that the leaching reaction
of scrap with H2SO4 and NH4Cl belongs to the chemical reac-
tion control model. Meanwhile, the leaching process of Ni,
Co, Mn is similar to each other and is more difficult than
Li. The change of crystal firstly occurs in the release of Li,
which does not break the crystal structure, but just makes
it easy to react with H+. With the dissolution of Ni, Co and
Mn, the structure of crystal will be gradually destroyed.
(3) Most of the Cl
in the leachate would remain in the solution
after the separation and purification procedures, and has
immense potential to be reused.
Acknowledgments
This work was financially supported by National Key
Research and Development Program of China (2017YFB0403300/
2017YFB043305), Beijing Science and Technology Program (No.
Z171100002217028), the National Natural Science Foundation of
China (No. 51425405 and L1624051), and the Key Program of
Chinese Academy of Science (KFZD-SW-315).
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