Advanced Materials Research Vols 113-116 (2010) pp 1688-1692 Online: 2010-06-07

© (2010) Trans Tech Publications, Switzerland

doi:10.4028/www.scientific.net/AMR.113-116.1688

Hydrometallurgical process for recovery of lithium and cobalt from spent

lithium–ion secondary batteries

Lung-Chang Tsai1,a, Fang-Chang Tsai2,b,*, Ning Ma2,c and Chi-Min Shu3,d

1
Doctoral Program of Engineering Science and Technology, National Yunlin University of Science
and Technology (NYUST), #123, Sec. 3, University Rd., Douliou, Yunlin, Taiwan 64002, R.O.C.
2*
Ministry of Education, Key Laboratory for the Green Preparation and Application of Functional
Materials, Faculty of Materials Science and Engineering, Hubei University, Wuhan 430062, China
3*
Department of Engineering Science and Technology, NYUST, #123, Sec. 3, University Rd.,
Douliou, Yunlin, Taiwan 64002, R.O.C.
a
g9410816@yuntech.edu.tw, b*tfc0323@gmail.com, cning.ning.999@163.com,
d
shucm@yuntech.edu.tw

Keywords: hydrometallurgical; recovery; lithium; cobalt; solvent extraction

Abstract. Hydrometallurgical process for recovery of aluminum, lithium and cobalt from the spent
secondary lithium–ion batteries of Yun–lin battery recycle corporation was investigated. The
recovery efficiency of spent lithium–ion secondary batteries on the hydrometallurgical process of
their leachant concentration, temperature (T), time (t), solid–to–liquid ratio (S:L) were investigated.
The experimental procedure include the following three major steps: (1) solvent extraction separation
of aluminum by NaOH, (2) solvent extraction separation of lithium and cobalt by 3 mol/L H2SO4
(4.76 % (v/v) 35% (v/v) H2O2) from the final solution after aluminum removal. Finally, (3) cobalt are
precipitated by ammonium oxalate ((NH4)2C2O4) from the final solutions after aluminum removal.
The experimental results for treating 3 g of anode plus in the battery by this new technique were
reported, and some evaluation were also carried out. In the processing, the percent removal of
impurities, such as aluminum could reach 90.6% or more, and that of lithium and cobalt were all more
than 90.0%.

Introduction
For environmental and efficiency reasons, lithium batteries have been a preferred portable source
energy for small electronic devices [1], and tend to replace Ni–Cd and Ni–MH (nickel metal–hydride)
batteries. In practice, there are two basic lithium batteries: Li/MnO2 and lithium–ion systems.
The last decades have seen an increasing motivation to recover and recycle as much waste
material as is possible because of rapidly deleting primary metal resources (e.g., ores) and ever
increasing demand for energy. Lithium–ion batteries (LIBs) and nickel–metal hydride (NiMH)
batteries have played a leading role in the portable secondary battery market since their
commercialization [2, 3]. In order to promote battery–recycling, it is necessary to know its
composition. In the authors' earlier publications [4–12] processes for the recycling of spent
lithium–ion secondary batteries (SLISBs) have been proposed, and cobalt, lithium and copper are
usually recovered. The present paper deals with the separation and recovery of cobalt and lithium
from another secondary raw material, namely SLIBs. Recycling of these batteries after use has thus
become an urgent matter. The objective of the present work was to develop an effective mining
treatment, pyrometallurgy and hydrometallurgical process for the separation and recovery of metal
values like cobalt and lithium from SLISBs [13].
In our opinions, the cost of treatment process must be given particular consideration to a
large–scale recycling of spent batteries. The recovery efficiency of SLISBs on the hydrometallurgical

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 Advanced Materials Research Vols. 113-114 1689

process of their leachant concentration, temperature (T), time (t), solid–to–liquid ratio (S:L) were
investigated. In fact, by using proper leachant concentration, T, t and S:L to recovery of metal values
from SLISBs by possible solvent extraction (SX) separation techniques.

Samples and chemical reagents

The SLISBs specimens were obtained from cylinder–shaped batteries (Yun–lin battery recycle
corporation). The compositions of SLISBs specimens prepared by aqua–regia method (ISO 15587) in
this study are summarized in Tables 1. The NaOH, HCl, H2O2, H2SO4 and HNO3 are all analytical
pure grade reagents.

Table 1 Average composition of SLISBs

Anode elements Cathode elements
Speries no.
Al Cu* Co Ni Li C** Al* Cu Co* Ni* Li C**

1 14.5 ND 42.6 2.5 4.5 35.9 ND 37.5 ND ND 0.2 62.3

2 15.1 ND 38.7 2.4 4.7 39.1 ND 37.1 ND ND 0.2 62.7

3 14.7 ND 42.5 2.9 4.5 35.4 ND 38.2 ND ND 0.3 61.5

4 14.1 ND 42.9 2.4 4.5 36.1 ND 37.4 ND ND 0.2 62.4

5 14.3 ND 39.5 2.3 4.5 39.4 ND 37.6 ND ND 0.2 62.2

6 15.6 ND 42.4 2.6 4.5 34.9 ND 36.2 ND ND 0.1 63.7

7 14.2 ND 42.1 3.1 4.5 36.1 ND 36.4 ND ND 0.2 63.4

8 14.7 ND 42.0 2.7 4.6 36.0 ND 36.3 ND ND 0.2 63.5

9 12.6 ND 39.1 2.8 4.5 41.0 ND 37.4 ND ND 0.5 62.1

14.8 ND 42.3 2.5 4.5 35.9 ND 37.8 ND ND 0.2 62.0
10
Average contents 14.5 ND 41.4 2.6 4.5 37.0 ND 37.2 ND ND 0.2 62.6
(% m/m)
*ND: ≤0.1 ppm
** Contents of C% = 100% − Contents of total metal%

Testing procedures
The experimental procedure includes the following three major steps: (1) SX separation of aluminum
by NaOH, and then stripped from the loaded organic phase by H2SO4 solution for aluminum recovery.
(2) SX separation of lithium and cobalt by 3 mol/L H2SO4 (4.76 % (v/v) 35% (v/v) H2O2) from the
final solution after aluminum removal. Finally, (3) cobalt are precipitated by ammonium oxalate
((NH4)2C2O4) from the final solutions after aluminum removal. For steps (1), (2) and (3), carefully
controlled the reaction conditions are needed for selective removal of Al and precipitation of Li and
Co.
1690 Environment Materials and Environment Management, EMEM2010

Analysis methods and calculation of metal recovery

This research of ISO 15587 specifies a method for extracting trace elements from SLISBs using
aqua–regia as a digestion agent. For measuring the amount of heavy metals, electrochemistry
possesses advantages different from those of flame type atom absorption spectroscope (FLAA,
(Thermo Elemental SOLAAR M Series)) and inductively coupled plasma optical emission
spectrometry (ICP–OES, (PerkinElmer Optima 5100 DV)) analysis.

Results and Discussion

Analysis of metal contents Content of the positive electrode partial metal of the SLISBs are the
aluminum 14.5% (v/v), the cobalt 41.4% (v/v), the nickel 2.6% (v/v), the lithium 4.5% (v/v), content
of the cathode partial metal is the copper 37.2% (v/v), the nickel 0.2% (v/v). After additive alkali (2
mol/L NaOH) of leaching of the positive electrode is also the liquid–solid compare when 0.15 leaches
for 3 h under the room temperature, this time leaching rate of the aluminum approximately may reach
90.6% (v/v), as shown in Figure 1. Further urges the aluminum ion 3 mol/L sulfuric acid solution
adjustment alkali leaching solution pH of by to precipitate, when finally pH obtains weight of the
white settling aluminum hydroxide in the neutrality for seriously, the precipitation quantity may
achieve 10.7 g also this time precipitation coefficients also achieve 93.8% (v/v), the aluminum purity
is 50.7% (v/v).

100
The leaching ratio of aluminum (wt%)

90

80

70

60

50

40
0
10
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Time (h)

Fig. 1 Leaching with 2 mol/L NaOH of SLISBs determined liquid–solid at 3 g/100 mL (○), 10 g/100
mL (○) and 15 g/100 mL (○). (The temperature is 25oC and reaction time 3 h)

SX separation of copper and lithium

The positive electrode best acid dissolves the condition is sulfuric acid of increase density 4.76% (v/v)
35% (v/v) H2O2 3 mol/L, the liquid–solid ratio is 3 g/100 mL, 70oC under dissolves for 2.5 h in the
temperature, may result in the cobalt to dissolve rate is 90.7% (v/v), the lithium is 90.6% (v/v) , as
shown in Figures 2 and 3.
 Advanced Materials Research Vols. 113-114 1691

100
The dissolves ratio of cobalt (wt%)

90
80
70
60
50
40
30
20
10
0
10
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Time (h)

Fig. 2 Different temperatures of 25 oC (○), 50 oC (○), 70 oC (○) and 90 oC ( ○) of 3 mol/L H2SO4 (4.76
% (v/v) 35% (v/v) H2O2) to the cobalt rate

100
The dissolves ratio of lithium (wt%)

90
80
70
60
50
40
30
20
10
0
10
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Time (h)

Fig. 3 Different temperatures of 25 oC (○), 50 oC (○), 70 oC (○) and 90 oC ( ○) of 3 mol/L H2SO4 (4.76
% (v/v) 35% (v/v) H2O2) dissolves to the lithium rate

Summary
Both processing flow sheets reported for SLISBs present the following merits: (i) higher recovery of
cobalt, manganese and lithium than in most studies in the literature; (ii) partial recovery of electrolyte
components that are usually lost in conventional processes. Previous separation of the battery
components allowed selective processing of the “active mass” (cathode + anode + electrolyte), thus
saving chemicals and energy with respect to the processing of the full battery.
1692 Environment Materials and Environment Management, EMEM2010

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Environment Materials and Environment Management, EMEM2010
10.4028/www.scientific.net/AMR.113-116

Hydrometallurgical Process for Recovery of Lithium and Cobalt from Spent Lithium-Ion Secondary
Batteries
10.4028/www.scientific.net/AMR.113-116.1688

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