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IME Process Metallurgy and Metal Recycling, RWTH Aachen University, D-52056 Aachen, Germany
ACCUREC Recycling GmbH, D-45472 Mlheim an der Ruhr, Germany
c
UVR-FIA GmbH, D-09599 Freiberg, Germany
b
a r t i c l e
i n f o
Article history:
Received 18 August 2011
Received in revised form
22 December 2011
Accepted 25 January 2012
Available online 7 February 2012
Keywords:
Li-ion batteries
Battery recycling
Cobalt recovery
Lithium recovery
a b s t r a c t
In cooperation with the industrial project partners ACCUREC Recycling and UVR-FIA a recycling process
specially dedicated to portable Li-ion batteries was developed combining a mechanical pretreatment
with hydro- and pyrometallurgical process steps. Therefore not only the recovery of cobalt but also the
recovery of all other battery components, especially of lithium was of interest. Besides the characterization and evaluation of all generated metallic material fractions, the focus of the research work was
the development of a pyrometallurgical process step in an electric arc furnace for the carbo-reductive
melting of the ne fraction extracted from spent Li-ion batteries. This ne fraction mainly consists of the
cobalt and lithium containing electrode material. Since a selective pyrometallurgical treatment of the
ne fraction for producing a cobalt alloy has not been done before, the proof of feasibility was the main
aim.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Within the last two decades the requirements for batteries as
mobile energy sources have constantly increased and have become
more and more complex. The trend towards improved mobility in
the rapidly developing elds of portable computer, communication,
video and audio technology has strongly pushed the development
of batteries. As supplier of the communications technology industry
the battery industry shows an annual double-digit growth rate [1].
At the beginning of the 1990s Li-ion batteries have been regarded as
the most promising energy sources for mobile applications. This has
been proven true today; for instance, Li-ion batteries have totally
replaced NiCd batteries as well as NiMH batteries in mobile phones
as they offer a lot of advantages compared to other rechargeable battery systems, such as high operating voltage, high specic
energy and long life-time.
The widespread and constantly increasing use of Li-ion batteries
also leads to an increased battery scrap generation (in both production as a well as end-of-life), which has to be recycled with
regard to environmental and economical sustainability. Ideally a
closed-loop recycling should allow for returning back the recycling products to the production of new batteries. Li-ion batteries
contain high amounts of valuable metals, such as aluminium, iron,
copper, lithium, cobalt, nickel and manganese. The most valuable
174
Table 1
EU sales gures, return ows and collection rates of Li-ion batteries (20022007)
(source: ACCUREC Recycling).
Sales in tonnes
Return in tonnes
Collection in %
2002
2003
2004
2005
2006
2007
3771
17
0.5
4977
54
1.1
6712
170
2.5
8210
175
2.1
9138
418
4.6
13,181
354
2.7
Fig. 1. Sales gures, return ows and collection rates of Li-ion batteries in Germany
(20002009) [7].
Table 2
Average material content of portable Li-ion batteries.
Battery component
Self-determined
Casing
Cathode material (LiCoO2 )
Anode material (graphite)
Electrolyte
Copper electrode foil
Aluminium electrode foil
Separator
Others
2025
2530
1419
1015
59
57
Balance
25
25
17
10
8
5
4
Balance
Since all battery producers sell their own specic types of Liion batteries it is difcult to specify exact numbers for the material
content of a Li-ion battery scrap mixture. In order to give some
numbers a study of various product data sheets from different battery producers has been done. Also, Li-ion batteries from a typical
production scrap charge have been disassembled by hand and the
battery components were separated and weighed. The results are
listed in Table 2.
Based on the assumptions that the metal content (selfdetermined gures) can completely be recovered in metallic form
and that the lithium content can completely be recovered in the
form of lithium carbonate the monetary value of 1 tonne Li-ion
battery scrap is approximately US$ 8500 taking current raw material prices into account. The monetary value of the cobalt content
is already about US$ 7200.
2.2. Industrial recycling processes
Various battery recycling processes exist which can basically be
divided into pyrometallurgical and hydrometallurgical processes.
Some recycling processes combine pyro- and hydrometallurgical
steps and often have integrated pre-treatment steps like pyrolysis or mechanical processing, i.e. crushing and material separation.
Besides utilisation of specialised battery recycling processes the
addition of spent batteries to existing large-scale processes, which
are not dedicated to battery recycling (e.g. extractive cobalt or
nickel metallurgy) is common practice and very often an economical advantage. Process examples for each category are given as
follows.
The company Batrec mainly runs a mechanical processing plant
for Li-ion battery cells. The batteries are crushed in CO2 gas atmosphere. Thereby the volatile organic electrolyte evaporates and is
collected as non-usable condensate. A subsequent material separation is done and the different material fractions are sold and
represent feedstock materials in other processes [1017].
Originally the hydrometallurgical Toxco process was developed
for the safe recycling of spent lithium primary batteries. Todays
facility processes lithium secondary battery scrap as well. The scrap
is stored in earth covered concrete storage bunkers. Residual electrical energy is removed from larger and more reactive batteries. If
necessary the batteries are treated by Toxcos patented cryogenic
process, i.e. they are cooled to about 200 C. Lithium, although
normally explosively reactive at room temperature, behaves almost
inert at this temperature. The batteries are then safely shredded and
the materials are separated. Metals from the batteries are collected
and sold. The lithium components are separated and converted to
lithium carbonate for resale. If the batteries contain cobalt it is
also recovered for production of LiCoO2 as new battery electrode
material [9,11,12,1820].
The pyrometallurgical Inmetco process was developed for
the recycling of spent NiCd, NiMH as well as Li-ion batteries.
Thereby only a small amount of Li-ion battery scrap is charged
into an electric arc furnace as secondary feedstock besides iron
175
176
Fig. 3. Metal containing material fractions after crushing and material separation (from left to right: iron-nickel fraction, aluminium fraction, electrode foil fraction).
177
Table 3
Composition of metal containing material fractions.
Fraction
Content in mass-%
Iron-nickel
Aluminium
Electrode foil
Al
Co
Cr
Cu
Fe
Li
Mn
Ni
Si
0.1
97.80
25.0
0.8
0.01
1.0
1.8
0.30
60.0
89.7
0.50
0.3
0.2
1.10
3.9
0.02
0.3
0.20
1.9
S1
S2
S3
a
b
c
At T = 1500 C.
At T = 1600 C.
At T = 1650 C.
Al2 O3
CaO
MgO
SiO2
Tm
Density
3
in mass-%
in C
in g cm
17.5
50.0
1460
1450
1350
2.8
2.6a
3.0a
54.5
45.0
45.0
5.0
45.5
37.5
Viscosity
1
in g cm
a
<2
5a
3a
Electr. conductivity
1
in 1 cm1
0.5b
0.6c
0.9b
178
Fig. 5. Metal alloy (left) and slag (right) produced in lab-scale tests.
Table 5
Input and output masses of lab-scale test series.
Test no.
Tholding ( C)
V1a
V1b
V2a
V2b
V3a
V3b
V4a
V4b
V5a
V5b
V6a
V6b
V7a
V7b
1760
1750
1750
1740
1760
1730
1720
1700
1730
1760
1740
1720
Input (g)
Output (g)
EM pellets
Slag
Metal
3500 (LM)
3500 (LM)
3500 (LM)
3500 (LM)
3500 (LM)
3500 (LM)
5500 (HM)
5500 (HM)
5500 (HM)
5500 (HM)
5500 (ZM)
5500 (ZM)
5500 (ZM)
5500 (ZM)
1500 (S1)
1500 (S1)
1500 (S2)
1500 (S2)
1500 (S3)
1500 (S3)
1500 (S1)
1500 (S1)
1500 (S3)
1500 (S3)
1500 (S1)
1500 (S1)
1500 (S3)
1500 (S3)
1130
1360
1330
680
No melting phase
No melting phase
2450
2660
2060
2080
2480
2540
1780
1730
Slag
1000
1000
1000
1000
1000
1000
2110
2110
2110
2110
1740
1740
1740
1740
690
490
750
700
730
850
1110
1640
740
670
1430
1580
In case of 100% cobalt and copper reduction and 50% manganese reduction.
Table 6
Range of metal alloy composition generated during lab-scale test series.
Co
in mass-%
Mn
Si
Al
Cu
5381
022
022
57
14
05
179
Table 7
Test campaign in technical-scale electric arc furnace.
Tapping
Slag (kg)
Othersa (kg)
Tholding ( C)
tcharge (h)
tholding (h)
1
2
3
4
50
100
100
100
350
130
100
50
50
330
12
12
12
12
48
1750
1750
1750
1750
4.0
3.5
2.5
2.5
0.5
1.0
0.5
0.5
551
689
481
430
2151
Fig. 7. Metal alloy (left), slag (middle) and ue dust (right) produced in technical-scale test.
Table 8
Output masses of test campaign in technical-scale.
Tapping
Metalout (kg)
Slagout (kg)
1
2
3
4
13
32
37
66 + 25a
173
96
83
60
70
309
47b
a
b
Table 9
Mass balance of single elements.
Input (kg)
Ca
Co
Cr
Cu
Fe
Li
Mn
Ni
Si
C
a
b
c
Output (kg)
EM
Slag
108.2
2.2
13.7
2.7
53.6
373.6c
128.7
70.1
Others
48.0a
Metal
Slag
95.7
0.7
1.9
39.5
2.4
3.7
27.1
378.4c
118.3
3.4
3.9
4.3
48.3
22.8
Flue dust
10.4
9.1
0.3
9.4
6.2
Difference
(mass-%)
Error value
(mass-%)
128.7
108.2
0.7
2.2
43.4
13.7
2.4
3.7
75.4
29.0
4.8c
0.0
0.0
0.7
0.0
4.6
0.0
2.4
1.0
5.3
24.6b
14.1c
0.1
0.0
0.7
0.0
4.6
0.0
2.4
1.0
5.3
3.8c
Relative error
(mass-%)
0.0
0.0
100.0
0.0
9.6
0.0
100.0
37.0
7.6
Estimated.
Output as CO resp. CO2 .
Without C.
Table 10
Metal slag and ue dust analysis of test campaign in technical-scale.
Metala
Slag
Flue dustc
Al
in mass-%
Ca
Co
Cr
Cu
Fe
Li
Mn
Ni
Si
0.4b
n.d.
n.v.
38.3
22.3
55.3
1.1
19.4
0.4
n.d.
1.1
n.v.
0.7
22.9
1.3
n.v.
1.4
20.1
1.4
n.v.
2.1
n.v.
15.7
15.6
n.v.
7.3
13.2
0.6
0.1
180
Table 11
Lithium yields of different leaching methods (results from UVR-FIA).
Leaching agent
Hydrochloric acid
Sodium hydroxide
Calcium carbonate
Sulphuric acid
45.8
7.5
2.9
76.7 resp. >90.0
Yield (up to
marketable
product)
Product
1.04
9.16
0.43
18.38
4.39
100
100
100
>90
>90
1.04
9.16
0.43
>16.54
>3.95
10.53
>90
>9.48
2.51
46.44
11.49
>90
>90
>2.26
>42.86
10.34
1.64
>90
1.48
62.85
>54.68
in mass-%
Li in Li2 CO3
Co in alloy
Al, Cu, Ni. . . in alloy
Fe-Ni fraction
Al in electrode foil fraction (25
mass-%)
Cu in electrode foil fraction (60
mass-%)
Al fraction
EMC in electrolyte condensate
(70 mass-%)
EC in electrolyte condensate (10
mass-%)
total
181
182
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