SME Annual Meeting

Feb. 28-Mar. 03, 2010, Phoenix, AZ

Preprint 10-061

PHYSICAL AND CHEMICAL TREATMENT ON SPENT ELECTRICAL VEHICLE MODULE OF LITHIUM SECONDARY BATTERY

J. Sohn, Korea Institute of Geoscience and Mineral Resources, Daejeon, Republic of Korea
J. Kang, Korea Univ. of Science and Technology, Daejeon, Republic of Korea
S. M. Shin, Korea Institute of Geoscience and Mineral Resources, Daejeon, Republic of Korea
S. Kim, Korea Institute of Geoscience and Mineral Resources, Daejeon, Republic of Korea

INTRODUCTION
The most promising near-term alternative to fuel cell driven
vehicles is probably Hybrid Electric Vehicle (HEV or EV) technology.
HEV technology combines the best characteristics of fuel-driven
engines, electric motor drives, and energy storage components. It is
designed with a combustion engine that functions as the primary power
source, and an electric power storage system that functions as the
secondary power source. The presence of the secondary power source
allows designers to size the combustion engine for cruising power
requirements.
A new energy source for HEV or EV market will become lithium
ion batteries (LIBs) in the near future. LIBs for HEV or EV has large
scale about more 10,000 times than small size one for IT devices in
order to achieve high electric density/capacity and high efficiency, etc.
In those reasons, physical treatment of the batteries is more difficult for
stable dismantling in comparison with the smaller one. Hybrid vehicle
sales will grow by nearly 400 percent during the next seven years,
according to a new report from analyst firm ABI Research. By 2013
hybrids will make up 6 percent of annual U.S. auto sales. The traction
battery pack will become air-cooled LIBs which consists of several
modules of Li ion battery and connected in series/parallel configuration
to provide about >450 VDC, >150 kW peak power, and >80 Ah
capacity.
As the use of these batteries tends to increase significantly for the
next years, it is relevant issues that development of new recycling
methods as well as optimization of existing processes to treat spent
LIBs for HEV have being addressed in order to obtain sustainability. Figure 1. Flow sheet of physical treatment for spent battery pack for
In this study, physical treatment containing stable electrical HEV.
discharge of spent LIBs for HEV was carried out for recovery of Methods
valuable metals from the batteries. Also In order to increase the yield In order to characterize the metal content of the spent LIBs, each
of valuable metals through physical treatments such as electric fraction samples were submitted to aqua regia (3:1 HCl:HNO3 ratio).
discharge of spent batteries, crushing, and classification, we also The quantitative metal content for Co, Li, Al, Cu, Ni, and Mn as well as
focused on the recovery of cobalt from +8 mesh fraction due to its large electric discharging solutions was assessed by inductive coupling
portion in crushed intermediates. plasma (ICP, JEOL, JY-38) after dissolving classified samples in aqua
o
EXPERIMENTS regia for 6 h at 70 C.

Physical treatment method RESULTS AND DISCUSSIONS

The battery samples were obtained from domestic manufacturer Concentration of valuable metals in the electric discharging
as a prototype which will be sold to the automobile market. A battery solution for the battery cell
module which are series with 8 unit cells are composed of 18% frame Table 1 shows the concentration of the electric discharging
body, 12% heat-reduce plate, 70% battery cells. solution for battery cell after electric discharging test. The main
The waste LIBs pack was prepared by physical treatment, element in the solution was Li of which the concentration was 1g/L. A
including hand disassembly, electric discharging, drying, and crushing little amount of Co and Cu were also observed. Other metal ions,
in Figure 1. Spent LIBs module was firstly treated by hand disassembly however, were not detected.
to frame, each battery cell, and Al cooling plate. The frame and Al Table 1. Concentration of metal ions in the electric discharging
cooling plate can be reused at manufacturing step. Battery cell was solution after electric discharging test for the battery cell.
treated by hand disassembly with scissors, of which it was separated
with Al laminate casing, cathode & anode materials, and separator. Components Co Li Cu Al Fe Ni Mn pH
The cathode & anode materials were soaked in distilled water for mg/L 5.6 1000 5.6 - - - - 8.4
o
electric discharging for 1 h at 25 C. After dehydration and drying,
electric discharged cathode & anode materials were subjected to In the case of Li, it is easily dissolved by water. Therefore, metallic
crushing and screening. After screening, the crushed battery cell was Li which was generated by charge reaction in the anode might be
classified into each fraction.

1 Copyright © 2010 by SME

 SME Annual Meeting
Feb. 28-Mar. 03, 2010, Phoenix, AZ

dissolved. Also the pH of the solution was 8.4. The reason why LiOH fractions were similar to Co and Li. Co was concentrated 36.4% in -8
was generated according Eq.1 in the solution. mesh as well as Li, Ni, Al, Cu also have same manner. Therefore it is
needed that further physical treatment such as calcination and
2 Li + 2 H2O • H2 + 2 LiOH (1) classification etc for increasing yield of valuable metals in -8 mesh by
Electric discharging of cathode & anode materials means of chemical process.
For investigation of the more detail electric discharge reaction of CONCLUSIONS
each anode and cathode, the battery cell was disassembly by hand to
each part: cathode materials, anode materials, and separators. The Spent LIBs were physically treated for hand assembly, electric
anode and cathode samples were soaked in each deionized water, discharged, crushed and classified. The following conclusions can be
respectively. During electric discharging experiments, we found out a drawn based on the experimental results: A battery module which are
gas generating reaction from the solution of anode, but in the case of series with 8 unit cells are composed of 18% frame body, 12% heat-
cathode, there was not found any reaction. reduce plate, 70% battery cells. In this battery cell, Li(Co1-x-yNixMny)O2
as a cathode active material is used. By the physical treatment process
Table 2 shows the concentration of electric discharging solution already developed in our previous study, we could get the crushed and
after the reaction finished. The main element in the solution was Li of concentrated powders containing metallic valuables such as Li, Co, Ni,
which 111 mg/L Li was in the anode discharged solution and 33.5 mg/L Mn, Cu, and Al. It will be performed on leaching-separation/purification-
Li was in the cathode discharged solution. The pH in the anode recovery tests and also on possibility of reuse for the cathode active
discharged solution and the cathode discharged solution was 12.2 and material of LIBs.
5.8, respectively. In the case of anode discharged solution, it is
considered that pH was raised by Eq. 1. Whereas pH in the cathode ACKNOWLEDGEMENT
discharged solution was not changed.
This study was supported by a grant operated by Ministry of
Table 2. Chemical composition of spent lithium ion polymer battery. Knowledge Economy (MKE) of Korea. The authors would like to thank
(mg/L) MKE for the financial support.
Components Co Li Ni Mn Al Cu Fe pH
REFERENCES
The solution for
discharging of <1 111 <1 <1 1.3 <1 <1 12.2 1. ABI Research, “http://www.abiresearch.com/research/ 1003272-
anode Consumer+Hybrid+Vehicles”
The solution for
discharging of <1 33.5 <1 <1 1.6 <1 <1 5.8 2. Shin, S.M., Kim, N.H., Sohn, J.S., Yang, D.H. and Kim, Y.H.
cathode (2005), Hydrometallurgy 79, 172-181.
3. Sohn, J.S., Shin, S.M., Yang, D.H., Kim, S.K., Lee, C.K. (2006),
Table 3 shows the contents of metal components in anode active Geosystem Engineering 9, 1-6.
material and cathode active material recovered from anode and
cathode after electric discharging and drying. The anode active 4. Shin, S.M., Sohn, J.S., Yang, D.H., Kim, T.H., Kang, J.G., and
material was graphite containing a little Li, Al, and Cu. The cathode Park, J.H. (2008), Patent KR 10-0860972.
active material was contained with 4.9% Co, 2.0% Li, 4.9% Ni, 24.8%
Mn, and 1.1% Al. 5. Xu, J., Thomas, H.R., Francis, R.W., Lum, K.R., Wang, J., Liang,
B. (2008), Journal of Power Sources 177, 512–527.
Table 3. Chemical composition of spent lithium ion polymer battery.
(%) 6. Zhang, P., Yokoyama, T., Itabashi, O., Suzuki, T.M., Inoue, K.
Anode active (1998), Hydrometallurgy 44, 259–271.
- 0.2 - - 0.02 0.05 -
material (graphite) 7. Shin, S.M., Kim, N.H., Sohn, J.S., Yang, D.H. and Kim, Y.H.
Cathode active (2005), Hydrometallurgy 79, 172-181.
material 4.9 2.0 4.9 24.8 1.1 - -
(Li(Co1-x-yNixMny)O2) 8. Swain, B., Sarangi, K., Das, R.P. (2004), Sep. Sci. Tech. 39 (9),
2171–2188.
Physical Treatment of discharged battery cells
Table 4 shows the result of the crushing and classification for an
electric discharged battery cell. As shown in Table 1, +8 mesh, -8+10
mesh, -10+16 mesh, -16+20 mesh, -20+40 mesh, and -40 mesh
fractions accounted for 63%, 6%, 4%, 6%, 14%, and 7%, respectively.
Especially, total -8 mesh fraction was quit lower than +8 mesh fraction.
Table 4. Chemical composition according to classification of
discharged battery cell crushed sample. (%)
Components Co Li Ni Mn Al Cu Fe Mass
+8 mesh 1.1 1.0 1.1 9.4 7.3 10.6 0.03 63.3
-8+10 mesh 0.1 0.1 0.1 0.5 0.8 1.6 0.02 6.3
-10+16
0.1 0.0 0.1 0.3 0.5 1.0 0.01 3.7
mesh
-16+20
0.1 0.1 0.1 0.4 0.8 1.4 0.02 5.7
mesh
-20+40
0.2 0.2 0.1 1.2 1.7 3.0 0.03 13.7
mesh
-40 mesh 0.2 0.1 0.2 0.9 0.2 0.5 0.01 7.2

After sampling from each fraction, the contents of valuable metals

were analyzed. The contents of valuable metals in each fraction were
that Co accounted for 1.1% in +8 mesh and 0.7% in -8 mesh. In case
of Li, it accounted for less than 0.5% in -8 mesh fractions. In case of Cu,
it accounted for 10.7%, 7.5% in +8 mesh, -8 mesh, respectively. Mn
accounts for 9.4% in +8 mesh and 3.3% in -8 mesh. Other metal
2 Copyright © 2010 by SME