Waste Management 51 (2016) 227233

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

Leaching lithium from the anode electrode materials of spent

lithium-ion batteries by hydrochloric acid (HCl)
Yang Guo a,b, Feng Li a, Haochen Zhu a,b, Guangming Li a, Juwen Huang a, Wenzhi He a,
a
State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai, China
b
Shanghai Cooperative Centre for Waste Electrical and Electronic Equipment Recycling, Shanghai 200092, China

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

Article history: Spent lithium-ion batteries (LIBs) are considered as an important secondary resource for its high contents
Received 25 August 2015 of valuable components, such as lithium and cobalt. Currently, studies mainly focus on the recycling of
Revised 22 November 2015 cathode electrodes. There are few studies concentrating on the recovery of anode electrodes. In this work,
Accepted 23 November 2015
based on the analysis result of high amount of lithium contained in the anode electrode, the acid leaching
Available online 7 December 2015
process was applied to recycle lithium from anode electrodes of spent LIBs. Hydrochloric acid was intro-
duced as leaching reagent, and hydrogen peroxide as reducing agent. Within the range of experiment per-
Keywords:
formed, hydrogen peroxide was found to have little effect on lithium leaching process. The highest
Lithium-ion battery
Anode
leaching recovery of 99.4 wt% Li was obtained at leaching temperature of 80 C, 3 M hydrochloric acid
Lithium and S/L ratio of 1:50 g/ml for 90 min. The graphite configuration with a better crystal structure obtained
Recycle after the leaching process can also be recycled.
Hydrochloric acid 2015 Elsevier Ltd. All rights reserved.

1. Introduction
In view of their distinctive advantages of higher operating volt-
age, smaller volume, lighter weight, longer cycling life, wider oper-
ating temperature range and low self-discharge (Dewulf et al.,
2010; Jha et al., 2013; Zhang et al., 2014), lithium-ion batteries
(LIBs) have been widely used as the power source in portable elec-
tronic applications, including mobile phones, computers, digital
cameras (Nan et al., 2005, 2006). In addition, they are also
expanding their potential application in electric vehicles and
hybrid electric vehicles (Zhang et al., 2014). It is reported that
the total world production in 2014 was about 36,000 tons, and
lithium prices have nearly tripled over the last 10 years (Baike,
2015). The widespread and constantly increasing use of LIBs also
leads to an increased battery scrap generation. Therefore, the
recycling treatment of spent LIBs by proper methods has attracted
worldwide concerns (Provazi et al., 2011; Mishra et al., 2008; Lee
and Pandey, 2012).
Reasonable management and recycling of LIBs is appropriate for
at least two important reasons (Chagnes and Pospiech, 2013; Shin
et al., 2005): (1) batteries have been identified as a fundamental
source of cobalt, lithium and other rare earth elements in WEEE,
at least one-third of the production costs for a portable LIBs cell
Corresponding author.
E-mail address: hithwz@163.com (W. He).
are related to the materials. (2) There contains many hazardous
materials such as toxic and flammable electrolyte in spent LIBs,
which are considered as environmental contaminant, it is manda-
tory to recycle LIBs for the sake of environmental sustainability and
safety hazards. LIBs are composed of shell, cathode, anode, organic
separator and organic electrolyte. Stainless steel nickel-plated
metal or plastic is the main material of shell (Chagnes and
Pospiech, 2013; Paulino et al., 2008; Sun and Qiu, 2011). The cath-
ode is made of an aluminum plate coated with active materials. For
most commercialized LIBs, Lithium cobalt oxide (LiCoO2) is
commonly used in active cathode material mainly containing
90% Li2CoO3, 78% acetylene black and 34% organic binder.
Similarly, the anode consists of a copper plate coated with active
materials mainly containing 90% graphite, 45% acetylene black
and 67% organic blinder. The thickness of anode and cathode is
0.180.20 mm, separated by a 10 lm separator (Ping, 2013). Based
on the structure and compositions of LIBs, the current recycling
situation about the treatment of the spent LIBs mainly focused
on the recycling Co and Li from cathode materials, because Co
and Li in spent LIBs are not only rare metals, but also hazardous
to the environment, while rarely on anode active materials
(Suzuki et al., 2012).
Many studies report on the leaching of metal species in the
separated cathode materials by critic acid such as HCl, HNO3, and
H2SO4, with hydrogen peroxide (H2O2) as the reductant (Jha
et al., 2013; Chagnes and Pospiech, 2013; Zhang et al., 2013).

http://dx.doi.org/10.1016/j.wasman.2015.11.036
0956-053X/ 2015 Elsevier Ltd. All rights reserved.
228 Y. Guo et al. / Waste Management 51 (2016) 227233
And the main emphasis of most is on the recovery of lithium,
cobalt or nickel. Fouad et al. (2007) calcined cathode materials at
800900 C so as to react Aluminum plate and Li2CoO3. As a result,
Li was converted to LiMO2 and Co to CoO. Grinding Li2CoO3
together with PVC in the planetary ball mill for 30 min, Saeki
et al. (2004) found nearly 100% Li react with Cl coming from PVC
and generated inorganic chlorides. Experiment performed by Li
et al. (2010) showed that 90% of Co and near 100% of Li could be
separated from the cathode active materials by taking citric acid
and H2O2 as the leachate. Our research group has also done a lot
in resource recycling from LIBs, including recovery of Co and Li
from spent lithium-ion batteries by acid leaching and chemical
precipitation (Zhu et al., 2012), partition of the copper from the
anodes of spent LIBs by combination method of pulverization,
vibratory screening and pneumatic separation (Zhu Shu Guang,
2011), and renovating LiCoO2 crystal structure by ultrasonic
hydrothermal reaction (Zhang et al., 2013). In the experiment pro-
cess, it was found that the anode active materials of spent LIBs con-
tain comparatively high content of lithium, reaching 31.03 mg/g,
much higher than that of the environmental standards (Shu,
2013; Meshram et al., 2014).
Nowadays, recycling of lithium in the long-term would be
mainly for ecological benefits and for adherence to environmental
laws, because the current market price and content of lithium con-
tained in LIBs makes it less economically attractive. Thus, recycling
lithium from anode active materials is significantly important
mainly from environmental point of view (Chagnes and Pospiech,
2013; Wang et al., 2014). In the present work, HCl was employed
to leach lithium from the anode electrode materials of spent
lithium-ion batteries, with H2O2 as the reducing agent. The chem-
ical composition of anode active materials was analyzed, and the
effects of operating variables were investigated to optimize the
leaching process.
2. Experimental
2.1. Materials and agents
The powder samples used in this study are from the spent LIBs
produced by Sony Ericsson Mobile Communications (China) Co.,
Ltd. Hydrochloric acid was taken as the leachate; meanwhile
H2O2 was used as the reductant. Hydrochloric acid and nitric acid
were used to measure the concentration of metal in the anode
materials. All solutions were prepared by deionized water.
Reagents used in this study were all analytically reagent.
2.2. Preparation of powder samples
Procedures of the present work are illustrated in Fig. 1
(a) and (b). The spent LIBs were discharged firstly to prevent the
dangers of short-circuits and spontaneous combustion. Then they
were dismantled manually to different parts: cathode, anode,
organic separator and the plastic case. With aid of scraper and
tweezers, active materials were separated from the anode. These
partitioned black active materials were placed in a furnace and cal-
cined at 500 C for one hour to remove the organic components.
2.3. Metal leaching
In this study, hydrochloric acid was taken as leachate to recycle
lithium from the calcined powder materials. To increase the leach-
ing efficiency, reductive leaching was carried out with H2O2 as the
reducing agent. Leaching processes were conducted in a thermo-
static water bath. Powder samples were put into a beaker, and
hydrochloric acid and hydrogen peroxide were added into the bea-
ker in sequence. After reaction, liquid production and powder resi-
due were separated through vacuum filtration for further analysis.
Being a solidliquid reaction, the leaching process was mainly
influenced by the concentration of hydrochloric acid, HClH2O2
volume ratio, solidliquid ratio, leaching time, and temperature
and agitation rate. In this study, agitation rate was conducted man-
ually and constantly. Therefore, the effects of concentration of
hydrochloric acid, HClH2O2 volume ratio, solidliquid ratio, time
and temperature were investigated.
2.4. Analytical methods
The microwave digestion method, which was performed in
Milestone ETHOS 1 microwave digestion dissolver, was adopted
to dissolve powder materials. The solution for digestion was mix-
ture of nitric acid, hydrochloric acid and hydrogen peroxide. Tem-
perature increasing was made in three steps. Temperature was
firstly increased to 180 C from indoor temperature in 10 min, then
increased to 200 C in 5 min and ultimately maintained at 200 C
for 5 min. The digestion solution was quantitatively analyzed
by Inductively Coupled PlasmaAtomic Emission Spectrometry
(ICPAES, Agilent 720ES) to calculate the contents of metals. After
leaching reaction, the amounts of Li in the leach liquor were also
analyzed by ICPAES. The leaching efficiency of Li is defined as
the ratio of Li content in leach liquor to that in the materials. With
the purpose of accurate and dependable determination of metal
components, parallel experiments and blank experiments were
conducted simultaneously.
To determine the influence of leaching reaction on the structure
of graphite, the crystal phase of anode active materials was
characterized by X-ray Diffraction (XRD, D8 Advance) and scanning
electron microscopy (SEM). For XRD analysis, the power materials
before leaching and solid residues after leaching were scanned
from 5 to 90 using increment of 0.02 and scan speed of
0.15/s. In order to determine the proper degradation temperature
of organic matters in anode active materials, the thermos-
gravimetric analysis (TGA) and differential thermal analysis
(DTA) curves were performed using a TA Instruments Q600 under
a dry static air atmosphere.
3. Results and discussion
3.1. Characterization of the anode active materials in spent LIBs
The characterization of anode active materials in spent LIBs was
firstly analyzed with an X-ray diffractometer. As shown in Fig. 2,
the strong diffraction intensity of peaks appeared at 2h of 26.5,
in correspondence with the characteristic peaks of the hexagonal
structure (PDF#25-284), indicated that the main composition of
anode active materials was graphite with integrated graphite lay-
ered structure. And from the figure, it can be noted that the gra-
phite materials basically remain good crystallinity and the
complete layer structure after electrochemical processes.
Fig. 3 shows the SEM images of the anode active materials of
spent LIBs. It confirms that the structure of the graphite materials
has no change after the charge and discharge cycles. The graphite
particles were not smooth and covered with sticky substances.
Combined with the compositions and the characteristics of the
anode matter, it can be inferred that the sticky substances are com-
posed of organic electrolytes, plasticizer and the polyvinylidene
fluoride (PVDF) binders.
These adhesive agents, polyvinylidene fluoride (PVDF) binders
in this study, have good chemical stability and mechanical perfor-
mance, making it difficult to react with most of the strong acid,
that can cause some issues during solidliquid separation after
 Y. Guo et al. / Waste Management 51 (2016) 227233 229

Spent LIBs

Discharging & Manually

dismantling

Cathode Organic Anode

Shell
electrode seperator electrode

Steel or
plastic

Single factor experiment: Active

Copper
CHCl, S/L, t, T, HCl/H2O2 materials

Remove organic
Leaching with HCl+H2O2 Grinding Calcination for 1 h, 500
components

Analyze with
Suction filtration Filtrate
ICP-AES

Residues Analyze with

XRD
(a)

Spent LBs Anode electrodes Copper sheet

Leachate Residues Active materials

(b)
Fig. 1. The disassembly and recycling process of anode active material from spent LIBs.

the organic compounds in the electrodes, i.e. binder and carbon

Fig. 2. XRD patterns of anode active materials from a spent LIB.
leaching and lower the recovery efficiency of the process. There-
fore, it is usual to implement such pyrolysis pretreatment before
hydrometallurgical processes as the high temperature decomposes
(Sun and Qiu, 2011, 2012).
In order to decompose them effectively, thermogravimetric
analysis (DTG) and differential thermal analysis (DTA) of anode
were carried to determine the pyrolysis temperature range as
shown in Fig. 4. Initially is observed a weight decrease (115 C)
due to loss of water in the anode active materials. With the tem-
perature increase to 490 C, it happened significantly weight loss
and the maximum weight loss rate of anode active materials was
in 590 C. In the meantime, the oxycompound groups in organic
matters were degraded completely remaining the graphite with
stable chemical properties. Therefore, in the experiment, the anode
active powder materials separated from the spent batteries were
calcined at 600 C for 1 h in a muffle and then cooled to room tem-
perature to degrade organic compounds.
Table 1 shows the metal compositions of the anode active mate-
rials. From the table, it can be noted that except tiny amounts of
Co, Ni and Fe, the main metals contained in the powder materials
are Cu and Li. Especially Li, its content is 30.07 mg/g, much higher
230 Y. Guo et al. / Waste Management 51 (2016) 227233

Fig. 3. SEM images of the anode active materials of spent LIBs.

Fig. 4. The thermogravimetric properties of the anode active materials of spent LIBs.

Table 1 Theoretically, the leaching reaction of both steps can be repre-

Chemical analysis of active materials from spent LIBs. sented as follows
Element Li+ Cu2+ Co2+ Ni+ Fe3+
Content (mg/g) 30.07 2.87 0.34 0.03 0.07
(1) The hydrolysis of lithium salt

Li2 O H2 O ! 2LiOH 1
than that of the environmental standards. The high content of
lithium maybe come from two aspects. ROCO2 Li H2 O ! LiOH ROCOOH 2

(1) In the process of lithium-ion travelling between the anode CH3 OLi H2 O ! LiOH CH3 OH 3
electrode and cathode electrode for energy storage and
(2) The double decomposition reaction
release, parts of the lithium-ion were inserted into the pores
of graphite (Filso et al., 2013).
Li2 CO3 2H ! 2Li H2 O CO2 " 4
(2) The solid electrolyte interface (SEI) film was found to be
stuck to the interface of graphite and electrolyte by interfa-

cial reaction. The main compositions of the SEI film were Li2 O 2H ! 2Li H2 O 5
inorganic constituents (including Li2CO3, LiF, Li2O) and

organic constituents (including ROCO2Li, ROLi, (ROCO2Li)2) ROCO2 Li H ! Li ROCOOH 6
Xiaoxing, 2013.

CH3 OLi 2H ! 2Li CH3 OH 7
3.2. Leaching of lithium

LiF H ! Li HF 8
As described above, the main forms of Li in the anode active
material are Li2CO3, Li2O, LiF, ROCO2Li, CH3OLi. Because some of
them are water-soluble, such as ROCO2Li, CH3OLi, Li2O, in the 3.2.1. Effect of hydrochloric acid concentration on leaching
experiment performed it has a high leaching efficiency of lithium The effect of HCl concentration was investigated with the con-
(84%) only in deionized water. While others are almost insoluble centration varied from 2.5 to 4 M at a leaching temperature of
in water and inlaid in the anode active materials, such as ROCO2Li, 80 C, S/L ratio of 1:50 g/mL, HClH2O2 volume ratio of 10:1 and
LiF, and they will occur decomposition reaction in HCl solution. a leaching time of 90 min. The results are showed in Fig. 5, which
Therefore, the leaching reaction between anode materials and demonstrated that the leaching efficiency of lithium was signifi-
HCl solution is a multiple process (Aurbach et al., 2002; Jiangfeng cantly influenced by the concentration of HCl, in other words, by
et al., 2004): (1) the hydrolysis of lithium salt (2) double decompo- the concentration of proton and ion diffusion velocity. The higher
sition reaction between lithium salt and HCl solution. the concentration is, the faster the reaction will be.
 Y. Guo et al. / Waste Management 51 (2016) 227233
Fig. 5. Effects of HCl concentration on the leaching efficiency of lithium (Leaching
temperature: 80 C, S/L: 1:50 g/mL, HClH2O2 volume ratio: 10:1, Leaching time:
90 min).
As shown in Fig. 5, leaching efficiency was firstly increasing and
then decreasing with the continuous increasing of acid concentra-
tion. At the first stage, the hydrolysis of lithium salt was dominated
that caused leaching efficiency can reach 83.6% when only using
deionized water as the leachate merely (see Eqs. (1)(3)). After
adding HCl, it increased from 84% to 98% with HCl concentration
increasing from 2.5 to 3 M. This is because that the increasing acid
concentration brings incremental amount of proton which can
replace more Li+. On the other hand, when HCl was consumed at
the solid liquid interphase, the concentration gradient of H+
between solidliquid interface and solution was gradually
increased. It leaded to a quicker diffusion velocity. Both of them
can promote the leaching process and bring higher leaching effi-
ciency. Henceforth, the leaching reaction reached equilibrium,
and the leaching efficiency of lithium reached its maximum. This
is because that the diffusion velocity would not change with fur-
ther increase of HCl concentration, and the Li+ had been replaced
sufficiently. From the figure, 3 M was employed as the optimum
acid concentration.
3.2.2. Effect of solidliquid ratio on leaching
Fig. 6 illustrated the influence of the S/L ratio on the leaching
efficiency of lithium from 1:30 to 1:70 g/ml by employing HCl at
a concentration of 3 M under experimental conditions of 80 C,
HClH2O2 ratio of 10:1 and 90 min leaching time. From the Fig, it
can be observed that the leaching efficiency reached to 99.4% with
S/L rate decreasing from 1:30 to 1:50. With the decreasing of S/L
rate, the concentration gradient of H+ between solidliquid inter-
face and solution increased, it promoted the ion transfer in the
solution, leading to the increasing leaching efficiency. While with
the further adding of HCl thereafter, the effect of diffusion velocity
and viscosity became weaker and weaker, that the leaching effi-
ciency didnt change significantly.
Fig. 6. Effects of S/L on the leaching efficiency of lithium (Leaching temperature:
80 C, 3 mol/L HCl, HClH2O2 volume ratio: 10:1, Leaching time: 90 min).
231
Considering the lower chemical consumption and a relatively
high efficiency, 1:50 g/ml was recommended as the suitable
solidliquid ratio for further study.
3.2.3. Effect of time on leaching
To examine the effect of reaction time on leaching efficiency,
the experiments were performed from 50 to 130 min. Other reac-
tion parameters were held at HCl with a concentration of 3 M,
solidliquid ratio of 1:50 g/mL, HClH2O2 ratio of 10:1 and leach-
ing temperature of 80 C. As observed in Fig. 7, before 70 min,
the leaching efficiency basically maintained at 95%, and then it
increased rapidly and reached the highest leaching efficiency of
99.5% with the leaching time increased from 70 to 90 min,
Because the graphite materials were covered by SEI film, the
leaching reaction was separated into two steps: SEI film dissolu-
tion, chemical reactions for lithium salt inside graphite. At the first
stage, the double decomposition reaction between SEI film and H+
occurred. After that, with the dissolution of SEI film, graphite mate-
rials gradually exposed into the solution. Then H+ went into the
pores of graphite and reacted with the lithium salt inside of it lead-
ing to the marked increase of the Li leaching efficiency with time.
When all the Li was leached out, the leaching efficiency reached a
stable status. Leaching time of 90 min, therefore, considered to be
suitable to leach lithium from the view point of economy.
3.2.4. Effect of temperature on leaching
The effect of reaction temperature was studied with a range of
temperature from 20 C to 100 C. During the leaching process,
concentration of HCl was maintained at 3 M, S/L at 1:50 g/ml, time
at 90 min, HClH2O2 ratio at 10:1. Fig. 8 exhibited that the temper-
ature can significantly influence the leaching process. The leaching
efficiency of Li increased from 89.7% to 99% with temperature from
20 C to 75 C, then the curve maintain stable with the increasing
temperature. Namely, nearly all the lithium was leached out at
80 C.
A reasonable explanation for this phenomenon was that both
the ionization reaction of HCl and the leaching reaction were
endothermic reaction. On one hand, the protons used for leaching
lithium came from the ionization of HCl. Therefore, with the
increasing of temperature, the ionization velocity of proton
increased which can accelerate the reaction velocity. On the other
hand, as an endothermic reaction, the leaching process could also
be promoted by the increasing temperature. Considering all the sit-
uation, 80 C was chosen as the optimum temperature for leaching.
3.2.5. Effect of HCl/H2O2 on leaching
Fig. 9 shows the alteration of the leaching efficiency of Li as a
function of HClH2O2 ratio in the range of 1:025:1 by using HCl
concentration of 3 M, S/L of 1:50, leaching time of 90 min and
leaching temperature of 80 C. It can be observed from Fig. 7 that
Fig. 7. Effects of time on the leaching efficiency of lithium (Leaching temperature:
80 C, 3 mol/L HCl, S/L: 1:50 g/mL, HClH2O2 volume ratio: 10:1).
232 Y. Guo et al. / Waste Management 51 (2016) 227233
Fig. 8. Effects of temperature on the leaching efficiency of lithium (S/L: 1:50 g/mL,
3 mol/L HCl, HClH2O2 volume ratio: 10:1, Leaching time: 90 min).
Fig. 9. Effects of HClH2O2 ratio on the leaching efficiency of lithium (Leaching
temperature: 80 C, S/L: 1:50 g/mL, 3 mol/L HCl, Leaching time: 90 min).
the leaching efficiency of Li was 97.1% without H2O2. And it
reached to 99.4% with HClH2O2 ration being 10:1. A conclusion
can be drawn from the experiment that H2O2 had a slight role in
the leaching process of Li. In the leaching process for Hydrometal-
lurgy, H2O2 was added as reductant to convert undissolved high
valence ions to soluble low ones to promote the reaction process.
Because of the absence of intermediate valence of Li, H2O2 can
reduce Co(III) to Co(II) and thus facilitate the forward reaction.
The result shows that the amount of H2O2 was sufficient for the
complete dissolution of lithium, as further increasing the concen-
tration of H2O2 did not show a significant effect in the recovery
efficiency compared to consumption of expensive of lithium. Con-
sidering lower energy consumption and relatively better leaching
efficiency, the suitable leaching agent was HCl without H2O2.
3.3. Effects of leaching process on graphite materials of anode
electrodes
In order to investigate the effects of leaching process on gra-
phite materials of anode electrodes, the powder materials before
and after its leaching were clearly identified by XRD analysis, see
Figs. 2 and 10. Compared to the XRD pattern of the materials before
leaching,
XRD analysis indicates that the main components of the anode
active material is hexagonal graphite as shown in Fig. 3. As we
know, the narrower and sharper the diffraction peak is, the better
the crystal structure will be. The diffracted intensity of character-
istics diffraction peak in Fig. 2 was 55,281, which increased to
96,014 after leaching. Therefore, the XRD pattern conclusively
demonstrated that the leaching process aiming at recycling lithium
in anode electrode was clearly essential for maintaining the integ-
rity of the hexagonal structure of graphite. Namely, the residues
after leaching could be recycled as graphite.
Fig. 10. XRD patterns for anode residues after leaching.
4. Conclusions
The experimental results indicated that because of the SEI film
deposited on the surface of anode active materials, high content of
Li (about 30.07 mg/g Li) could exist in the anode of spent LIBs.
Based on the existence form of Li, it occurred simultaneously
hydrolysis and double decomposition reaction between lithium
salt and HCl solution. Thus, the hydrochloric acid leaching process
was firstly proposed, and it can successfully separate the valuable
elements and leach out lithium. In this investigation, hydrogen
peroxide was found to have no significant effects on lithium leach-
ing. With the increase of concentration of HCl and temperature, the
leaching efficiency increased firstly and then decreased. And the
increase of leaching time and the decrease of S/L would improve
the leaching rate of lithium and finally maintained at a high leach-
ing efficiency. In the experimental condition of leaching tempera-
ture of 80 C, 3 M HCl, S/L ratio of 1:50 and reaction time of
90 min, the leaching efficiency reached its maximum of 99.4%.
According to the XRD pattern, the graphite which was the main
component of anode electrodes was found to keep the original
characteristics and configuration with a better crystal structure
after leaching, and was fit for recycling.
Acknowledgements
This work is supported by Shanghai Cooperative Centre for
Waste Electrical and Electronic Equipment Recycling. The authors
would like to thank the anonymous reviewers for supplying their
valuable comments.
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