Hydrometallurgy 79 (2005) 172 – 181

www.elsevier.com/locate/hydromet

Development of a metal recovery process from Li-ion

battery wastes
Shun Myung Shin a, Nak Hyoung Kim a, Jeong Soo Sohn a,
Dong Hyo Yang a, Young Han Kim b,*
a
Minerals and Materials Processing Division, Korea Institute of Geoscience and Mineral Resources, Taejon 305-350, South Korea
b
Dept. of Chemical Engineering, Dong-A University, Pusan 604-714, South Korea
Received 19 October 2004; received in revised form 16 May 2005; accepted 15 June 2005
Available online 18 July 2005

Abstract

A process for the recovery of lithium and cobalt from the waste of lithium ion batteries using sulfuric acid and hydrogen
peroxide was proposed, and metal leaching performance was investigated. The proposed procedure consisted of mechanical
separation of metal-containing particles and a chemical leaching process. The effects of leaching agent, of the size of metal-
bearing particles, and of incineration as a pretreatment for the leaching, were examined here.
Two stages of crushing and sieving resulted in satisfactory separation of the metal-bearing particles from the waste. Sulfuric
acid leaching with hydrogen peroxide in a concentration of 15 vol.% gave a full recovery of the metals within 10 min of
processing time. The leaching was carried out at a temperature of 75 8C and with an agitation of 300 rpm for a pulp
concentration of 50 g/L in a batch extractor. It was also found that incineration of lithium cobalt oxide particles to remove
carbon and organic binder before chemical leaching significantly reduces the leaching efficiency.
D 2005 Elsevier B.V. All rights reserved.

1. Introduction tandem with their applications. In consequence, the

Demand for secondary batteries has steadily in-
creased in recent times as portable electronic appli-
ances such as cellular phones and laptop computers
have come into wide use. Along with the development
of such portable devices, the technology of secondary
batteries–their power source–has rapidly improved in
* Corresponding author. Tel.: +82 51 200 7723; fax: +82 51 200
7728.
E-mail address: yhkim@mail.donga.ac.kr (Y.H. Kim).
0304-386X/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2005.06.004
amount of secondary battery waste is increasing along
with the proliferation of the portable devices. With the
disposal of the spent batteries, mostly by landfill, soil
contamination follows from the leakage of organic
electrolyte as well as heavy metals such as copper
and nickel contained in the batteries.
Lithium ion batteries consist of heavy metals, or-
ganic chemicals and plastics in the proportion of 5–
20% cobalt, 5–10% nickel, 5–7% lithium, 15% or-
ganic chemicals and 7% plastics, the composition
varying slightly with different manufacturers. When
 S.M. Shin et al. / Hydrometallurgy 79 (2005) 172–181 173

the lithium battery wastes are properly processed, and incineration on acid leaching were investigated to
valuable metals such as cobalt and lithium can be find the optimum condition for metal recovery. The
recovered. From the viewpoints of environmental procedure includes a thoroughgoing process of me-
preservation and recovery of valuable resources, the chanical separation of lithium cobalt oxide particles,
recycling of spent lithium ion batteries is highly de- which can be applicable in commercial recycling of
sirable. The current status of the recycling process has lithium ion battery waste. Though the hydrometallur-
been reviewed in several studies (Bernardes et al., gical process of battery recycling has been well de-
2003, 2004; Espinosa et al., 2004). veloped, preprocessing by mechanical separation has
Unlike other batteries, lithium ion batteries often not been so deeply studied as to facilitate the scale-up
blow up during the recycling process due to radical of the laboratory process for commercialization.
oxidation when lithium metal produced from battery
overcharge sustains a mechanical shock from expo-
sure to the air (Contestabile et al., 1999). Therefore, a 2. Experimental
preliminary separation before recovery of the valuable
metals from the waste is necessary. The process also 2.1. Chemicals
reduces scrap volume, separates battery components
and enriches valuable metals. On the other hand, In this experiment two reagent grade chemicals
lithium cobalt oxide (LiCoO2)–an active material were used. Sulfuric acid (Junsei Chemical Co.,
used as a cathode–is not dissolved easily with com- Japan, Code No. 83010-1230) was utilized for leach-
mon leaching chemicals. Zhang et al. (1998) per-
formed a study of leaching the lithium cobalt oxide lithium ion battery wastes
with various leachants, and of the effect of leaching
condition such as leachant concentration, temperature,
leaching time and solid-to-liquid ratio, in hydromet- crushing
allurgical recoveries of lithium and cobalt. In that
study, hydrochloric acid gave the best performance
among the three leachants examined, and it has been
sieving Fe, Al, Cu, plastics
utilized in other leaching processes for lithium and
cobalt (Contestabile et al., 2001). Nitric acid has also
been employed instead of hydrochloric acid in other
lithium leaching processes (Catillo et al., 2002). A magnetic separation
commercial process was introduced and developed by
AEA Technology Batteries, though the leachant in
which metal lithium and Co(II) ion were electrochem-
ically generated was not specified (Lain, 2001). A fine crushing
new procedure for nitric acid leaching of lithium
and cobalt from lithium ion batteries was proposed
by Lee and Rhee (2003), and the procedure was
extended to regenerate lithium cobalt oxide electrode sieving Al
from the leachate and to examine the performance of
the electrode (Lee and Rhee, 2002). Recently, a pro-
cedure for the direct regeneration of lithium cobalt
acid leaching
oxide electrode from waste lithium ion batteries has
been published by Kim et al. (2004).
In this study, a sulfuric acid leaching process for
the recovery of lithium and cobalt from lithium ion lithium and cobalt solution
battery wastes was proposed and its performance was
evaluated. The effects of leaching agent, particle size Fig. 1. A flowchart of the proposed metal recovery process.
174 S.M. Shin et al. / Hydrometallurgy 79 (2005) 172–181
ing, and hydrogen peroxide (Junsei Chemical Co.,
Japan, Code No. 23150-0350) was employed as a
leaching agent.
2.2. Experimental procedure
A series of mechanical processes were carried out
to yield enriched particles of lithium cobalt oxide. The
procedure involves crushing, sieving, magnetic sepa-
ration, fine crushing and classification in sequence.
Because the majority of valuable metals such as cobalt
and lithium are contained in lithium cobalt oxide
particles, this study focused on a complete mechanical
separation of these particles. In addition, for the pur-
poses of commercialization, the separation has to be
conducted in an automated machine process. Though
fine crushing of the particles is not required for the
leaching process with a high concentration leaching
agent, it does help attain a complete removal of
aluminum foil from the lithium cobalt oxide particles.
The experimental procedure is illustrated in Fig. 1,
where removed components are also indicated on the
right hand side.
Condenser
Water
Stirrer
Water
Heater
Fig. 2. Experimental setup for acid leaching.
The sizes of crushed aluminum and copper elec-
trode plates and steel battery casing were adjusted for
easy classification of active material from the cath-
ode, lithium cobalt oxide particles. Vibration sieving
and magnetic separation were performed in order to
separate aluminum and copper electrodes, steel cas-
ing and plastic packaging. After large pieces of the
materials were separated with a vibrating sieve of 850
Am, a magnetic separator removed pieces of steel
casing. The active material of the cathode is
contained in the bulk of non-magnetic particles
from the magnetic separator. In order to eliminate
small pieces of aluminum foil attaching to the parti-
cles of lithium cobalt oxide, a fine crushing followed.
The second vibration sieving separates the pieces of
aluminum foil completely.
The leaching experiments were conducted in the
apparatus shown in Fig. 2. A glass extractor of 1 L
capacity was put into a thermostat, and the extractor
temperature was maintained at 75 8C. The leaching
mixture was agitated at a speed of 300 rpm. For the
enhancement of agitation, baffles of 5 cm width
were installed at the inner wall of the extractor,
Thermometer
Reactor
Bath
 S.M. Shin et al. / Hydrometallurgy 79 (2005) 172–181
and a condenser was used to minimize evaporation
loss of water.
The effect of hydrogen peroxide concentration on
the leaching of lithium and cobalt was investigated for
a given set of leaching variables: kind and concentra-
tion of leaching agent, leaching temperature and pulp
density. During the leaching experiment, samples
were taken at scheduled intervals. Each sample was
vacuum filtered and divided into filtrate and cake. The
amounts of cobalt and lithium in the filtrate were
measured to compute leaching efficiency. Chemical
analyses for leachate and cake were performed with
an atomic absorption spectrophotometer (Perkin-
Elmer, U.S.A., model M3100) and an inductively
coupled plasma spectrometer (Jobin Yvon, France,
model JY38Plus). Chemical analysis of particles was
carried out with an X-ray diffractometer (Rigaku,
Japan, model Ru-200). The leaching efficiency of
the metal components is defined as the ratio of the
amount of a component in the leachate to the total
amount in the mechanically separated particles of
lithium cobalt oxide.
3. Results and discussion
3.1. Separation of lithium cobalt oxide powder
Lithium ion battery wastes were crushed with a
crusher fitted with a set of rotational and fixed
blades. A primary crushing was performed with a
sieve of 20 mm hole size installed at the inner side
of the crusher, and fine crushing was done with a
sieve of 10 mm hole size. Materials from the primary
crushing were separated with three different sizes of
sieve, 106 Am, 200 Am and 850 Am, in order to
classify three different groups of particle size, and
then to examine the effect of particle size on the
performance of acid leaching. Undersized products
obtained from the 850 Am sieve consisted of lithium
cobalt oxide particles and carbon, while oversized
products were plastic packaging, steel casing, alumi-
num foil, copper foil and separator. Because the
oversized products include the plastic and steel cas-
ings of the batteries, no lithium cobalt oxide particles
are contained in them. The undersized products were
classified with two sieves of 106 Am and 200 Am to
investigate their lithium and cobalt content and the
175
effect of particle size on leaching. Their contents are
listed in Table 1, which shows that there is a signif-
icant amount of iron in the particles, and this was
therefore separated with a magnet. After the magnet-
ic separation, the particles were crushed again and
sieved with a 10 mm sieve installed in the crusher, in
order to eliminate aluminum foil. Mechanical sepa-
ration before the metal leaching process is empha-
sized here because it improves the recovery
efficiency of target metals and eliminates the need
for a purification process of the leachate. This sub-
ject has not been thoroughly examined in most
previous lithium recycling studies.
3.2. Effect of hydrogen peroxide on leaching
The dissolution of cobalt oxides in acid solution
was studied by Vu et al. (1980). Because the chem-
ical bond between cobalt and oxygen is extremely
strong, acid leaching of lithium cobalt oxide is dif-
ficult. When hydrogen peroxide is added, the
evolved oxygen from the decomposition of the hy-
drogen peroxide converts Co(III) to Co(II) to help
the dissolution (Lain, 2001; Lee and Rhee, 2002).
The role of hydrogen peroxide is exhibited in Fig. 3a
for cobalt and Fig. 3b for lithium. The higher the
concentration of hydrogen peroxide, the more effi-
cient the leaching is. While the hydrogen peroxide
helps the dissolution of cobalt, the dissolution of
lithium is promoted because the two metals are
contained in the same oxide compound. In addition,
the dissolution of lithium with sulfuric acid is much
easier than that of cobalt. In these experiments, the
concentration of sulfuric acid was 2 mol/L, and pulp
density was 50 g/L. High pulp density is desirable to
raise processing throughput. Yet a density higher
than 50 g/L yields lower leaching efficiency, as
illustrated in Fig. 4a for cobalt leaching and Fig.
Table 1
Chemical compositions of different sizes of particles from the first
crushing
Size Co Li Fe Al Cu Ni Remainder
Smaller than 23.16 2.33 5.54 0.14 0.23 0.89 67.71
106 Am
106 Am–199 Am 22.70 2.34 6.15 0.23 0.29 0.78 67.51
200 Am–850 Am 28.32 2.67 6.45 0.45 0.83 0.82 60.46
Units are in wt.%.
176 S.M. Shin et al. / Hydrometallurgy 79 (2005) 172–181

Fig. 3. Effect of leaching agent concentration on cobalt (a) and lithium (b) leaching.

4b for lithium. The leaching temperature was 75 8C
with an agitation of 300 rpm. The leaching rate was
fast in the initial stage regardless of the hydrogen
peroxide concentration, whereas leaching efficiency
depends upon the amount of hydrogen peroxide. A
concentration of 15 vol.% was enough for the full
leaching of both metal components.
Because polyvinylidene fluoride (PVDF) binder
does not dissolve in acid solution, it remains in the
cake after filtration. Also, carbon does not dissolve in
acid solution, and instead it floats on the solution;
from filtration it is separated in the cake. The electro-
lyte lithium hexafluorophosphate (LiPF6) decomposes
into lithium fluoride and phosphor pentafluoride in the
 S.M. Shin et al. / Hydrometallurgy 79 (2005) 172–181 177

Fig. 4. Effect of pulp density on cobalt (a) and lithium (b) leaching.

crushing process, and the lithium dissolves in the acid
solution during leaching. The organic solvents pro-
pylene carbonate (PC) and diethyl carbonate (DEC)
were evaporated in the crushing process. The concen-
trations of copper and aluminum in the leachate were
0.46 g/L and 0.79 g/L, respectively, and the amounts
in the cake were less than 0.01 g.
3.3. Effect of particle size on leaching
To investigate the effect of particle size on leach-
ing, tests were performed with three different sizes
of particles. The initial pulp density, sulfuric acid
concentration and amount of hydrogen peroxide
were 50 g/L, 2 mol/L, and 10 vol.%, respectively.
178 S.M. Shin et al. / Hydrometallurgy 79 (2005) 172–181

Leaching temperature was 75 8C with an agitation
of 300 rpm. The leaching efficiency of cobalt for
particles with over 200 Am diameter was as low as
80%, as illustrated in Fig. 5a, though lithium leach-
ing was satisfactory for all sizes of particles, as
shown in Fig. 5b. In order to increase the leaching
efficiency of cobalt for particles of over 200 Am
diameter, the amount of hydrogen peroxide was
raised from 10 vol.% to 15 vol.% while other
leaching conditions were maintained; complete
leaching of both metals was obtained as demonstrat-
ed in Fig. 6.

Fig. 5. Effect of particle size on acid leaching of cobalt (a) and lithium (b).
 S.M. Shin et al. / Hydrometallurgy 79 (2005) 172–181 179

Fig. 6. Leaching rate of cobalt and lithium at the optimum condition.

This outcome indicates that an acid leaching with when a leaching temperature of 75 8C with an agita-
sulfuric acid at a concentration of 2 mol/L and 15 tion of 300 rpm is applied to the leaching at a pulp
vol.% of hydrogen peroxide gives full recovery of density of 50 g/L. The smaller the particle size, the
lithium and cobalt from lithium ion battery wastes easier the dissolution is and the greater is the leaching

Fig. 7. Spectra of X-ray diffraction analysis before and after incineration.

180 S.M. Shin et al. / Hydrometallurgy 79 (2005) 172–181
Fig. 8. Effect of incineration on metal leaching.
efficiency. Yet a high concentration of hydrogen per-
oxide helps the leaching of large particles, to give
complete leaching by converting less dissolvable
Co(III) into more dissolvable Co(II) with evolved
oxygen from hydrogen peroxide. However, fine
crushing is necessary to eliminate aluminum foil
contained in the lithium cobalt oxide particles from
the primary crushing.
3.4. Effect of incineration
The particles from crushing and mechanical sepa-
ration include carbon and organic binder, which cause
a problem in the filtration process of leachate after
acid leaching. Incineration of the particles was carried
out at 900 8C in a furnace for an hour. The removal of
the carbon and organic binder was observed from the
results of X-ray diffraction analysis as seen in Fig. 7.
The difference between two spectra at the carbon
peak indicates complete elimination of the carbon
powder and binder by the incineration. However,
the leaching efficiency of cobalt after incineration is
significantly lower compared with that obtained with-
out this high temperature treatment, as shown in Fig.
8. Following incineration the surface of lithium cobalt
oxide particles is covered with molten aluminum,
which obstructs cobalt leaching. Therefore, incinera-
tion is not recommended for inclusion in the metal
recovery process.
4. Conclusion
A novel process for the recovery of metal from
spent lithium ion batteries was proposed for possible
application to a commercial scale plant. The process
includes mechanical separation of lithium cobalt
oxide particles and a hydrometallurgical procedure
for lithium and cobalt recovery. The performance of
the proposed process was examined by an evalua-
tion of leaching efficiency. The effects of leaching
agent concentration, particle size and incineration
were examined to find an optimum condition for
metal recovery.
The experimental outcome indicates that a con-
centration of 15 vol.% of hydrogen peroxide in sul-
furic acid leaching is enough for full recovery of
lithium and cobalt, with fast leaching. Though parti-
cle size does not affect the leaching efficiency as
long as the concentration of leaching agent is high
enough, fine crushing helps to remove aluminum foil
attached to the lithium cobalt oxide particles. Incin-
eration for the removal of carbon and organic binder
from the separated lithium cobalt oxide particles
 S.M. Shin et al. / Hydrometallurgy 79 (2005) 172–181
significantly reduces leaching efficiency, suggesting
that the treatment should not be included in the metal
recovery process.
Acknowledgment
Financial support from the Ministry of Commerce,
Industry and Energy of Korea through the CANSMC
is gratefully acknowledged.
References
Bernardes, A.M., Espinosa, D.C.R., Tenorio, J.A.S., 2003. Collec-
tion and recycling of portable batteries: a worldwide overview
compared to the Brazilian situation. J. Power Sources 124 (2),
586 – 592.
Bernardes, A.M., Espinosa, D.C.R., Tenorio, J.A.S., 2004. Recy-
cling of batteries: a review of current processes and technolo-
gies. J. Power Sources 130 (1–2), 291 – 298.
Contestabile, M., Panero, S., Scrosati, B., 1999. A laboratory-scale
lithium battery recycling process. J. Power Sources 83 (1–2),
75 – 78.
181
Contestabile, M., Panero, S., Scrosati, B., 2001. A laboratory-
scale lithium-ion battery recycling process. J. Power Sources
92 (1–2), 65 – 69.
Catillo, S., Ansart, F., Laberty-Robert, C., Portal, J., 2002.
Advances in the recovering of spent lithium battery compounds.
J. Power Sources 112 (1), 247 – 254.
Espinosa, D.C.R., Bernardes, A.M., Tenorio, J.A.S., 2004. An
overview on the current processes for the recycling of batteries.
J. Power Sources 135 (1–2), 311 – 319.
Kim, D.-S., Sohn, J.-S., Lee, C.-K., Lee, J.-H., Han, K.-S., Lee, Y.-
I., 2004. Simultaneous separation and renovation of lithium
cobalt oxide from the cathode of spent lithium-ion rechargeable
batteries. J. Power Sources 132 (1–2), 145 – 149.
Lain, M.J., 2001. Recycling of lithium ion cells and batteries. J.
Power Sources 97–98, 736 – 738.
Lee, C.K., Rhee, K.-I., 2002. Preparation of LiCoO2 from spent
lithium-ion batteries. J. Power Sources 109 (1), 17 – 21.
Lee, C.K., Rhee, K.-I., 2003. Reductive leaching of cathodic active
materials from lithium ion battery wastes. Hydrometallurgy 68
(1–3), 5 – 10.
Vu, C., Han, K.N., Lawson, F., 1980. Leaching behavior of cobal-
tous and cobalto-cobaltic oxides in ammonia and in acid solu-
tions. Hydrometallurgy 6 (1–2), 75 – 87.
Zhang, P., Yokoyama, T., Itabashi, O., Suzuki, T.M., Inoue, K.,
1998. Hydrometallurgical process for recovery of metal values
from spent lithium-ion secondary batteries. Hydrometallurgy 47
(2–3), 259 – 271.