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Waste Management 51 (2016) 227233

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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,
State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai, China
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-
formed, hydrogen peroxide was found to have little effect on lithium leaching process. The highest
Lithium-ion battery
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 are related to the materials. (2) There contains many hazardous
materials such as toxic and flammable electrolyte in spent LIBs,
In view of their distinctive advantages of higher operating volt- which are considered as environmental contaminant, it is manda-
age, smaller volume, lighter weight, longer cycling life, wider oper- tory to recycle LIBs for the sake of environmental sustainability and
ating temperature range and low self-discharge (Dewulf et al., safety hazards. LIBs are composed of shell, cathode, anode, organic
2010; Jha et al., 2013; Zhang et al., 2014), lithium-ion batteries separator and organic electrolyte. Stainless steel nickel-plated
(LIBs) have been widely used as the power source in portable elec- metal or plastic is the main material of shell (Chagnes and
tronic applications, including mobile phones, computers, digital Pospiech, 2013; Paulino et al., 2008; Sun and Qiu, 2011). The cath-
cameras (Nan et al., 2005, 2006). In addition, they are also ode is made of an aluminum plate coated with active materials. For
expanding their potential application in electric vehicles and most commercialized LIBs, Lithium cobalt oxide (LiCoO2) is
hybrid electric vehicles (Zhang et al., 2014). It is reported that commonly used in active cathode material mainly containing
the total world production in 2014 was about 36,000 tons, and 90% Li2CoO3, 78% acetylene black and 34% organic binder.
lithium prices have nearly tripled over the last 10 years (Baike, Similarly, the anode consists of a copper plate coated with active
2015). The widespread and constantly increasing use of LIBs also materials mainly containing 90% graphite, 45% acetylene black
leads to an increased battery scrap generation. Therefore, the and 67% organic blinder. The thickness of anode and cathode is
recycling treatment of spent LIBs by proper methods has attracted 0.180.20 mm, separated by a 10 lm separator (Ping, 2013). Based
worldwide concerns (Provazi et al., 2011; Mishra et al., 2008; Lee on the structure and compositions of LIBs, the current recycling
and Pandey, 2012). situation about the treatment of the spent LIBs mainly focused
Reasonable management and recycling of LIBs is appropriate for on the recycling Co and Li from cathode materials, because Co
at least two important reasons (Chagnes and Pospiech, 2013; Shin and Li in spent LIBs are not only rare metals, but also hazardous
et al., 2005): (1) batteries have been identified as a fundamental to the environment, while rarely on anode active materials
source of cobalt, lithium and other rare earth elements in WEEE, (Suzuki et al., 2012).
at least one-third of the production costs for a portable LIBs cell Many studies report on the leaching of metal species in the
separated cathode materials by critic acid such as HCl, HNO3, and
Corresponding author. H2SO4, with hydrogen peroxide (H2O2) as the reductant (Jha
E-mail address: (W. He).
et al., 2013; Chagnes and Pospiech, 2013; Zhang et al., 2013).
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, ker in sequence. After reaction, liquid production and powder resi-
cobalt or nickel. Fouad et al. (2007) calcined cathode materials at due were separated through vacuum filtration for further analysis.
800900 C so as to react Aluminum plate and Li2CoO3. As a result, Being a solidliquid reaction, the leaching process was mainly
Li was converted to LiMO2 and Co to CoO. Grinding Li2CoO3 influenced by the concentration of hydrochloric acid, HClH2O2
together with PVC in the planetary ball mill for 30 min, Saeki volume ratio, solidliquid ratio, leaching time, and temperature
et al. (2004) found nearly 100% Li react with Cl coming from PVC and agitation rate. In this study, agitation rate was conducted man-
and generated inorganic chlorides. Experiment performed by Li ually and constantly. Therefore, the effects of concentration of
et al. (2010) showed that 90% of Co and near 100% of Li could be hydrochloric acid, HClH2O2 volume ratio, solidliquid ratio, time
separated from the cathode active materials by taking citric acid and temperature were investigated.
and H2O2 as the leachate. Our research group has also done a lot
in resource recycling from LIBs, including recovery of Co and Li
2.4. Analytical methods
from spent lithium-ion batteries by acid leaching and chemical
precipitation (Zhu et al., 2012), partition of the copper from the
The microwave digestion method, which was performed in
anodes of spent LIBs by combination method of pulverization,
Milestone ETHOS 1 microwave digestion dissolver, was adopted
vibratory screening and pneumatic separation (Zhu Shu Guang,
to dissolve powder materials. The solution for digestion was mix-
2011), and renovating LiCoO2 crystal structure by ultrasonic
ture of nitric acid, hydrochloric acid and hydrogen peroxide. Tem-
hydrothermal reaction (Zhang et al., 2013). In the experiment pro-
perature increasing was made in three steps. Temperature was
cess, it was found that the anode active materials of spent LIBs con-
firstly increased to 180 C from indoor temperature in 10 min, then
tain comparatively high content of lithium, reaching 31.03 mg/g,
increased to 200 C in 5 min and ultimately maintained at 200 C
much higher than that of the environmental standards (Shu,
for 5 min. The digestion solution was quantitatively analyzed
2013; Meshram et al., 2014).
by Inductively Coupled PlasmaAtomic Emission Spectrometry
Nowadays, recycling of lithium in the long-term would be
(ICPAES, Agilent 720ES) to calculate the contents of metals. After
mainly for ecological benefits and for adherence to environmental
leaching reaction, the amounts of Li in the leach liquor were also
laws, because the current market price and content of lithium con-
analyzed by ICPAES. The leaching efficiency of Li is defined as
tained in LIBs makes it less economically attractive. Thus, recycling
the ratio of Li content in leach liquor to that in the materials. With
lithium from anode active materials is significantly important
the purpose of accurate and dependable determination of metal
mainly from environmental point of view (Chagnes and Pospiech,
components, parallel experiments and blank experiments were
2013; Wang et al., 2014). In the present work, HCl was employed
conducted simultaneously.
to leach lithium from the anode electrode materials of spent
To determine the influence of leaching reaction on the structure
lithium-ion batteries, with H2O2 as the reducing agent. The chem-
of graphite, the crystal phase of anode active materials was
ical composition of anode active materials was analyzed, and the
characterized by X-ray Diffraction (XRD, D8 Advance) and scanning
effects of operating variables were investigated to optimize the
electron microscopy (SEM). For XRD analysis, the power materials
leaching process.
before leaching and solid residues after leaching were scanned
from 5 to 90 using increment of 0.02 and scan speed of
2. Experimental 0.15/s. In order to determine the proper degradation temperature
of organic matters in anode active materials, the thermos-
2.1. Materials and agents gravimetric analysis (TGA) and differential thermal analysis
(DTA) curves were performed using a TA Instruments Q600 under
The powder samples used in this study are from the spent LIBs a dry static air atmosphere.
produced by Sony Ericsson Mobile Communications (China) Co.,
Ltd. Hydrochloric acid was taken as the leachate; meanwhile
3. Results and discussion
H2O2 was used as the reductant. Hydrochloric acid and nitric acid
were used to measure the concentration of metal in the anode
3.1. Characterization of the anode active materials in spent LIBs
materials. All solutions were prepared by deionized water.
Reagents used in this study were all analytically reagent.
The characterization of anode active materials in spent LIBs was
firstly analyzed with an X-ray diffractometer. As shown in Fig. 2,
2.2. Preparation of powder samples the strong diffraction intensity of peaks appeared at 2h of 26.5,
in correspondence with the characteristic peaks of the hexagonal
Procedures of the present work are illustrated in Fig. 1 structure (PDF#25-284), indicated that the main composition of
(a) and (b). The spent LIBs were discharged firstly to prevent the anode active materials was graphite with integrated graphite lay-
dangers of short-circuits and spontaneous combustion. Then they ered structure. And from the figure, it can be noted that the gra-
were dismantled manually to different parts: cathode, anode, phite materials basically remain good crystallinity and the
organic separator and the plastic case. With aid of scraper and complete layer structure after electrochemical processes.
tweezers, active materials were separated from the anode. These Fig. 3 shows the SEM images of the anode active materials of
partitioned black active materials were placed in a furnace and cal- spent LIBs. It confirms that the structure of the graphite materials
cined at 500 C for one hour to remove the organic components. has no change after the charge and discharge cycles. The graphite
particles were not smooth and covered with sticky substances.
2.3. Metal leaching Combined with the compositions and the characteristics of the
anode matter, it can be inferred that the sticky substances are com-
In this study, hydrochloric acid was taken as leachate to recycle posed of organic electrolytes, plasticizer and the polyvinylidene
lithium from the calcined powder materials. To increase the leach- fluoride (PVDF) binders.
ing efficiency, reductive leaching was carried out with H2O2 as the These adhesive agents, polyvinylidene fluoride (PVDF) binders
reducing agent. Leaching processes were conducted in a thermo- in this study, have good chemical stability and mechanical perfor-
static water bath. Powder samples were put into a beaker, and mance, making it difficult to react with most of the strong acid,
hydrochloric acid and hydrogen peroxide were added into the bea- that can cause some issues during solidliquid separation after
Y. Guo et al. / Waste Management 51 (2016) 227233 229

Spent LIBs

Discharging & Manually


Cathode Organic Anode

electrode seperator electrode

Steel or

Single factor experiment: Active

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

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

Analyze with
Suction filtration Filtrate

Residues Analyze with


Spent LBs Anode electrodes Copper sheet

Leachate Residues Active materials

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

(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-
Fig. 2. XRD patterns of anode active materials from a spent LIB. perature to degrade organic compounds.
Table 1 shows the metal compositions of the anode active mate-
leaching and lower the recovery efficiency of the process. There- rials. From the table, it can be noted that except tiny amounts of
fore, it is usual to implement such pyrolysis pretreatment before Co, Ni and Fe, the main metals contained in the powder materials
hydrometallurgical processes as the high temperature decomposes 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 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,
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: Because the graphite materials were covered by SEI film, the
90 min). 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+
As shown in Fig. 5, leaching efficiency was firstly increasing and occurred. After that, with the dissolution of SEI film, graphite mate-
then decreasing with the continuous increasing of acid concentra- rials gradually exposed into the solution. Then H+ went into the
tion. At the first stage, the hydrolysis of lithium salt was dominated pores of graphite and reacted with the lithium salt inside of it lead-
that caused leaching efficiency can reach 83.6% when only using ing to the marked increase of the Li leaching efficiency with time.
deionized water as the leachate merely (see Eqs. (1)(3)). After When all the Li was leached out, the leaching efficiency reached a
adding HCl, it increased from 84% to 98% with HCl concentration stable status. Leaching time of 90 min, therefore, considered to be
increasing from 2.5 to 3 M. This is because that the increasing acid suitable to leach lithium from the view point of economy.
concentration brings incremental amount of proton which can
replace more Li+. On the other hand, when HCl was consumed at 3.2.4. Effect of temperature on leaching
the solid liquid interphase, the concentration gradient of H+ The effect of reaction temperature was studied with a range of
between solidliquid interface and solution was gradually temperature from 20 C to 100 C. During the leaching process,
increased. It leaded to a quicker diffusion velocity. Both of them concentration of HCl was maintained at 3 M, S/L at 1:50 g/ml, time
can promote the leaching process and bring higher leaching effi- at 90 min, HClH2O2 ratio at 10:1. Fig. 8 exhibited that the temper-
ciency. Henceforth, the leaching reaction reached equilibrium, ature can significantly influence the leaching process. The leaching
and the leaching efficiency of lithium reached its maximum. This efficiency of Li increased from 89.7% to 99% with temperature from
is because that the diffusion velocity would not change with fur- 20 C to 75 C, then the curve maintain stable with the increasing
ther increase of HCl concentration, and the Li+ had been replaced temperature. Namely, nearly all the lithium was leached out at
sufficiently. From the figure, 3 M was employed as the optimum 80 C.
acid concentration. A reasonable explanation for this phenomenon was that both
the ionization reaction of HCl and the leaching reaction were
3.2.2. Effect of solidliquid ratio on leaching endothermic reaction. On one hand, the protons used for leaching
Fig. 6 illustrated the influence of the S/L ratio on the leaching lithium came from the ionization of HCl. Therefore, with the
efficiency of lithium from 1:30 to 1:70 g/ml by employing HCl at increasing of temperature, the ionization velocity of proton
a concentration of 3 M under experimental conditions of 80 C, increased which can accelerate the reaction velocity. On the other
HClH2O2 ratio of 10:1 and 90 min leaching time. From the Fig, it hand, as an endothermic reaction, the leaching process could also
can be observed that the leaching efficiency reached to 99.4% with be promoted by the increasing temperature. Considering all the sit-
S/L rate decreasing from 1:30 to 1:50. With the decreasing of S/L uation, 80 C was chosen as the optimum temperature for leaching.
rate, the concentration gradient of H+ between solidliquid inter-
face and solution increased, it promoted the ion transfer in the 3.2.5. Effect of HCl/H2O2 on leaching
solution, leading to the increasing leaching efficiency. While with Fig. 9 shows the alteration of the leaching efficiency of Li as a
the further adding of HCl thereafter, the effect of diffusion velocity function of HClH2O2 ratio in the range of 1:025:1 by using HCl
and viscosity became weaker and weaker, that the leaching effi- concentration of 3 M, S/L of 1:50, leaching time of 90 min and
ciency didnt change significantly. leaching temperature of 80 C. It can be observed from Fig. 7 that

Fig. 6. Effects of S/L on the leaching efficiency of lithium (Leaching temperature: Fig. 7. Effects of time on the leaching efficiency of lithium (Leaching temperature:
80 C, 3 mol/L HCl, HClH2O2 volume ratio: 10:1, Leaching time: 90 min). 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. 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
Fig. 9. Effects of HClH2O2 ratio on the leaching efficiency of lithium (Leaching leaching efficiency increased firstly and then decreased. And the
temperature: 80 C, S/L: 1:50 g/mL, 3 mol/L HCl, Leaching time: 90 min). 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-
the leaching efficiency of Li was 97.1% without H2O2. And it ture of 80 C, 3 M HCl, S/L ratio of 1:50 and reaction time of
reached to 99.4% with HClH2O2 ration being 10:1. A conclusion 90 min, the leaching efficiency reached its maximum of 99.4%.
can be drawn from the experiment that H2O2 had a slight role in According to the XRD pattern, the graphite which was the main
the leaching process of Li. In the leaching process for Hydrometal- component of anode electrodes was found to keep the original
lurgy, H2O2 was added as reductant to convert undissolved high characteristics and configuration with a better crystal structure
valence ions to soluble low ones to promote the reaction process. after leaching, and was fit for recycling.
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-
This work is supported by Shanghai Cooperative Centre for
tration of H2O2 did not show a significant effect in the recovery
Waste Electrical and Electronic Equipment Recycling. The authors
efficiency compared to consumption of expensive of lithium. Con-
would like to thank the anonymous reviewers for supplying their
sidering lower energy consumption and relatively better leaching
valuable comments.
efficiency, the suitable leaching agent was HCl without H2O2.

3.3. Effects of leaching process on graphite materials of anode
electrodes Aurbach, D., Zinigrad, E., Cohen, Y., Teller, H., 2002. A short review of failure
mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte
solutions. Solid State Ionics 148, 405416.
In order to investigate the effects of leaching process on gra- Baike,, (accessed
phite materials of anode electrodes, the powder materials before date: 2015).
and after its leaching were clearly identified by XRD analysis, see Chagnes, A., Pospiech, B., 2013. A brief review on hydrometallurgical technologies
for recycling spent lithium-ion batteries. J. Chem. Technol. Biotechnol. 88,
Figs. 2 and 10. Compared to the XRD pattern of the materials before 11911199.
leaching, Dewulf, J., Van der Vorst, G., Denturck, K., Van Langenhove, H., Ghyoot, W., Tytgat, J.,
XRD analysis indicates that the main components of the anode Vandeputte, K., 2010. Recycling rechargeable lithium ion batteries: critical
analysis of natural resource savings. Resour. Conserv. Recycl. 54, 229234.
active material is hexagonal graphite as shown in Fig. 3. As we Filso, M.O., Turner, M.J., Gibbs, G.V., Adams, S., Spackman, M.A., Iversen, B.B., 2013.
know, the narrower and sharper the diffraction peak is, the better Visualizing lithium-ion migration pathways in battery materials. Chem.-a Euro.
the crystal structure will be. The diffracted intensity of character- J. 19, 1553515544.
Fouad, O.A., Farghaly, F.I., Bahgat, M., 2007. A novel approach for synthesis of
istics diffraction peak in Fig. 2 was 55,281, which increased to
nanocrystalline gamma-LiAlO2 from spent lithium-ion batteries. J. Anal. Appl.
96,014 after leaching. Therefore, the XRD pattern conclusively Pyrol. 78, 6569.
demonstrated that the leaching process aiming at recycling lithium Jha, M.K., Kumari, A., Jha, A.K., Kumar, V., Hait, J., Pandey, B.D., 2013. Recovery of
in anode electrode was clearly essential for maintaining the integ- lithium and cobalt from waste lithium ion batteries of mobile phone. Waste
Manage. 33, 18901897.
rity of the hexagonal structure of graphite. Namely, the residues Jiangfeng, N., Henghui, Z., Jitao, C., Guangyao, S., 2004. Progress in solid electrolyte
after leaching could be recycled as graphite. interface in Lithium ion batteries (In Chinese). Progr. Chem. 16, 335342.
Y. Guo et al. / Waste Management 51 (2016) 227233 233

Lee, J.-C., Pandey, B.D., 2012. Bio-processing of solid wastes and secondary resources Sun, L., Qiu, K., 2011. Vacuum pyrolysis and hydrometallurgical process for the
for metal extractiona review. Waste Manage. 32, 318. recovery of valuable metals from spent lithium-ion batteries. J. Hazard. Mater.
Li, L., Ge, J., Wu, F., Chen, R.J., Chen, S., Wu, B.R., 2010. Recovery of cobalt and lithium 194, 378384.
from spent lithium ion batteries using organic citric acid as leachant. J. Hazard. Sun, L., Qiu, K., 2012. Organic oxalate as leachant and precipitant for the recovery of
Mater. 176, 288293. valuable metals from spent lithium-ion batteries. Waste Manage. 32, 1575
Meshram, P., Pandey, B., Mankhand, T., 2014. Extraction of lithium from primary 1582.
and secondary sources by pre-treatment, leaching and separation: a Suzuki, T., Nakamura, T., Inoue, Y., Niinae, M., Shibata, J., 2012. A hydrometallurgical
comprehensive review. Hydrometallurgy 150, 192208. process for the separation of aluminum, cobalt, copper and lithium in acidic
Mishra, D., Kim, D.-J., Ralph, D., Ahn, J.-G., Rhee, Y.-H., 2008. Bioleaching of metals sulfate media. Sep. Purif. Technol. 98, 396401.
from spent lithium ion secondary batteries using Acidithiobacillus ferrooxidans. Wang, X., Gaustad, G., Babbitt, C.W., Bailey, C., Ganter, M.J., Landi, B.J., 2014.
Waste Manage. 28, 333338. Economic and environmental characterization of an evolving Li-ion battery
Nan, J., Han, D., Zuo, X., 2005. Recovery of metal values from spent lithium-ion waste stream. J. Environ. Manage. 135, 126134.
batteries with chemical deposition and solvent extraction. J. Power Sources 152, Xiaoxing, W.K.Z.H.L.D.A.F.Z.Y.Z., 2013. Research survey on SEI film for electrode
278284. material of lithium ion batteries. Inorgan. Chem. Ind. 45, 4.
Nan, J., Han, D., Yang, M., Cui, M., Hou, X., 2006. Recovery of metal values from a Zhang, X.H., Xie, Y.B., Lin, X., Li, H.T., Cao, H.B., 2013. An overview on the processes
mixture of spent lithium-ion batteries and nickelmetal hydride batteries. and technologies for recycling cathodic active materials from spent lithium-ion
Hydrometallurgy 84, 7580. batteries. J. Mater. Cycles Waste Manage. 15, 420430.
Paulino, J.F., Busnardo, N.G., Afonso, J.C., 2008. Recovery of valuable elements from Zhang, W.H.Z., Li, G., Xia, J., Hu, H., Huang, J., 2013. Renovation of LiCoO2 crystal
spent Li-batteries. J. Hazard. Mater. 150, 843849. structure from spent lithium ion batteries by ultrasonic hydrothermal reaction.
Ping, W.Y.P.F.J.L.L.X.Z.W.L., 2013. Overview of recovery technique of valuable metals Res. Chem. Intermed. 8, 7.
from spent Lithium ion batteries. Chin. J. Rare Metals 37, 320329. Zhang, T., He, Y., Wang, F., Ge, L., Zhu, X., Li, H., 2014. Chemical and process
Provazi, K., Campos, B.A., Espinosa, D.C.R., Tenrio, J.A.S., 2011. Metal separation mineralogical characterizations of spent lithium-ion batteries: an approach by
from mixed types of batteries using selective precipitation and liquidliquid multi-analytical techniques. Waste Manage. 34, 10511058.
extraction techniques. Waste Manage. 31, 5964. Zhang, X., Xie, Y., Cao, H., Nawaz, F., Zhang, Y., 2014. A novel process for recycling
Saeki, S., Lee, J., Zhang, Q.W., Saito, F., 2004. Co-grinding LiCoO2 with PVC and water and resynthesizing LiNi 1/3 Co 1/3 Mn 1/3 O 2 from the cathode scraps intended
leaching of metal chlorides formed in ground product. Int. J. Miner. Process. 74, for lithium-ion batteries. Waste Manage. 34, 17151724.
S373S378. Zhu, S.G., He, W.Z., Li, G.M., Zhou, X., Zhang, X.J., Huang, J.W., 2012. Recovery of Co
Shin, S.M., Kim, N.H., Sohn, J.S., Yang, D.H., Kim, Y.H., 2005. Development of a metal and Li from spent lithium-ion batteries by combination method of acid leaching
recovery process from Li-ion battery wastes. Hydrometallurgy 79, 172181. and chemical precipitation. Trans. Nonferrous Metals Soc. China 22, 22742281.
Shu, X.J.Z.Z.H.W.L.G.L.X.W.Z.L., 2013. Characterization and analysis of the negative Zhu Shu Guang, H.W.Z., Ming, Li Guang, 2011. Recovering copper from spent
electrode active materials of spent lithium-ion secondary batteries. Chem. Ind. Lithium ion battery by a mechanical separation process. In: International
Eng. Progress 32, 4. Conference on Materials for Renewable Energy & Environment.
Sun, L., Qiu, K.Q., 2011. Vacuum pyrolysis and hydrometallurgical process for the
recovery of valuable metals from spent lithium-ion batteries. J. Hazard. Mater.
194, 378384.