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Separation by Thermal Treatment and Cobalt
Separation by Thermal Treatment and Cobalt
Deying Mu
Solvent extraction separation of nickel and cobalt from a sulfate solution containing iron(II)
and magnesium using versatic 10
AIP Conference Proceedings 1805, 030003 (2017); https://doi.org/10.1063/1.4974414
Effect of key parameters on the selective acid leach of nickel from mixed nickel-cobalt
hydroxide
AIP Conference Proceedings 1805, 030001 (2017); https://doi.org/10.1063/1.4974412
© 2017 Author(s).
One-Step Separation by Thermal Treatment and Cobalt
Acid-Leaching from Spent Lithium-ion Batteries
Deying Mu1, 2, a)
1
School of Food Engineering, Harbin University of Commerce, Harbin 150076, China.
2
School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001, China.
a)
Corresponding author: mudeying2004@163.com
Abstract. Lithium-ion batteries are extensively used in portable storage devices and automobiles, therefore the
environment and resource problems caused by spent lithium ion batteries have become increasingly severe. This paper
focuses on the recovery process of spent lithium cobalt oxide active material and comes up with reasonable processes and
the best conditions for cobalt leaching ultimately.
Key words: Lithium-ion battery; Cathode material; Lithium cobalt oxide; Recovery.
INTRODUCTION
New power technologies develop toward greater specific capacity, higher power and more convenience and
safety; on the other hand, protecting the environment and rationally using the limited resources on the earth adhere
to the national strategy of sustainable development and have become the first considerable factor of the new power
technology development[1,2]. Lithium ion batteries (LIBs) contain certain amount of cobalt, nickel, other toxic
heavy metal salts and the electrolyte, so they are not really complete "green batteries" as we were told before[3,4].
Without the effective recycling of waste batteries, the emissions will cause serious damage to the environment [5].
But if we can effectively deal with the spent batteries, the shift from trash to treasure will turn out to harvest a large
number of precious metals. These precious metals in China belong to the scarce resources, and the price on the
global market today is rising constantly. The recycling of valuable metals such as lithium, cobalt and nickel known
as scarce metals has high economic value [6]. Existing technologies of the recycling process mainly include split
pieces, the separation of each part and the enrichment of valuable metals, to eliminate or reduce the environmental
pollution caused by harmful substances, at the same time, the valuable metals are recycled in the form of primary
products [7, 8]. As the single operation process does not reach the purpose of effective separation and recycling the
battery components, the current recovery is the combination of several methods, such as a combination of (a)
crushing, acid leaching, heat treatment and chemical precipitation; (b) leaching, solvent extraction, and electro
winning; (c) mechanical dismantling, thermal, hydrometallurgical, and cobalt electrochemical reduction, which stays
mostly in the laboratory research stage [9, 10]. The large-scale industrialization of recycling spent LIBs is still in its
infancy. In view of the waste LIB recycling, our paper focuses on the recovery of cobalt and the main research work
presents as follows: Via pretreatment, the aluminum foil and cathode active materials were effectively separated; to
increase the cobalt leaching rate, the method of hydrochloric acid leaching was used to guarantee the purified
primary product.
2nd International Conference on Materials Science, Resource and Environmental Engineering (MSREE 2017)
AIP Conf. Proc. 1890, 040083-1–040083-5; https://doi.org/10.1063/1.5005285
Published by AIP Publishing. 978-0-7354-1568-3/$30.00
040083-1
MATERIALS AND METHODS
The spent lithium cobalt oxide batteries used in the experiments were supplied by Guanyin Co., Ltd. (Harbin,
China). Other chemicals were purchased from Sino pharm Chemical Reagent Co., Ltd. (Guangzhou, China) and
used as received (analytical reagent). The whole methodology adopted for collector separation and acid-leaching
analysis was divided into number of steps which were shown in Fig. 1. First of all, we first discharged and
dismantled the spent LIBs to get the aluminum alloy shell, separator, copper foil, aluminum foil, and other
substances respectively. The organic binder combined the aluminum foil and active materials with solid structure
and stable performance, so generally the rectangular pieces of cathode electrode were adopt thermal treatment from
400 to 600 ć to remove the electrolyte, organic binder and conductive carbon black and also make the collector
separated. After sieving separation, the sintered materials were taken into hydrochloric acid-leaching process. The
efficient recovery of cobalt was finally realized by adjusting the different concentration of hydrochloric acid, dosage
of reluctant, solid-liquid ratio and other conditions.
FIGURE 1.Flow chart adopted for collector separation and acid-leaching analysis.
Analytical Procedures
With reference to the literature, spectrophotometric method was used to detect the cobalt content in the test
solution. With cobalt chloride as standard solution and 5% diluted hydrochloric acid as the reference, the absorbance
of each concentration solution were measured under the wavelength of 510 mm. The standard curve according to the
experiment was fitted. The correlation coefficient values (R2) of 0.99136 represented a satisfactory correlation
between the absorbance value and the amount of substances. The micro-morphological features and particle sizes of
the samples were observed with a scanning electron microscope (SEM, HITACHI S -4700, and Japan). A D/max-¤
£ X-ray diffract meter (Rigaku, Japan) was applied to get the component identification of the sintered products.
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only partially off; when the sintering temperature was up to 600 ć, the edge of the aluminum foil became crisp and
fell off, so it was easy to introduce more aluminum impurities. When the sintering temperature was 500 ć and the
sintering time was 2 hours, the aluminum foil maintained complete and the recovery rate was much higher at
77.45%. The morphology of the cathode material after the calcination showed uniform particle size (see Fig.2a) that
the distribution of the samples concentrated with the average particle size of about 10 m. With the analysis of
XRD in Figure.2b, the spectra of lithium cobalt oxide corresponded well with the characteristic peaks of the
standard PDF card. Less impurity peak existed.
TABLE 1. Effect of temperature on the separation of aluminum foil and cathode active materials.
Temperature(ć
ć) Current collector(g) Cathode materials(g) Other loss (g) Recovery rate (%)
400 12.3 5.62 6.68 45.69
500 11.8 9.14 2.66 77.45
600 11.6 9.06 2.54 78.10
FIGURE 2. SEM image (a) and XRD pattern (b) of the recycled LiCoO2 active material.
The experimental results show that thermal treatment is effective to remove adhesive binder and conductive
carbon black and also can effectively separate the cathode material from aluminum foil. What we should pay more
attention is that the high temperature consumes more energy and the organic binder and other additives would be
transformed into other harmful ingredients, so special gas collecting purification treatments are in need.
The Optimization of Acid Leaching for Cobalt from Spent Lithium Ion Batteries
Active materials lithium cobalt oxide can be dissolved for the chemical reaction with inorganic acid. Hydrogen
peroxide used as reducing agent would change trivalent cobalt into bivalent one, thereby it can enhance cobalt’s
dissolution in acid solution. The main conditional factors are hydrochloric acid concentration, dosage of hydrogen
peroxide, reaction temperature and time. We filtered the above-mentioned experimental conditions, respectively,
and the results were as shown in Fig.3.Dissolving performance improved constantly with the increase of
concentration of HCl, while after the concentration increased to above 3 mol/L, the increase trend sloped gently, so
we selected 2.5 mol/L HCl for the following experiments. The influence of the amount of H2O2 was similar to that
of the concentration of HCl. It is also the case that hydrogen peroxide can promote the reductive dissolution of
cobalt. In the presence of hydrogen peroxide, trivalent cobalt is easy to be shifted into bivalent cobalt, but with the
increase of H2O2, the concentrations of HCl and lithium cobalt oxide were the limiting steps for the reductive
dissolution, so it didn’t mean the more H2O2 added, the better the dissolving effect took place.
As temperatures rose, the solubility of cobalt in the HCl solution increased due to the accelerating diffusion of
solution and the enhanced dissolution reaction. As you can see, when the temperature exceeded 70 ć , the
dissolution rate of active material was the maximum. But higher temperature can also accelerate the decomposition
of H2O2, resulting in the reduction of reducing reagent. That is why there was a fall when the temperature was
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increased to 80 ć. With the increase of time, the effect of acid leaching improved, but the leaching speed decreased.
In the comprehensive consideration of various factors, 60 minutes showed more practical and economic significance
for industrial applications.
FIGURE 3. Effects of (a) HCl concentration, (b) H2O2 concentration, (c) Temperature and (d) Time on the leaching
efficiency of cobalt (S/L:1:50g/mL, 2.5 mol/L HCl, H202 4.5%, temperature 60 ć and time 60 min)
CONCLUSION
On the pretreatment stage, the separation method of high-temperature calcination was applied to fulfill the
falling-off of the active material from the aluminum foil. The calcination at 500ćfor 2 hours was the best condition
to obtain relatively pure LiCoO2 material; the hydrochloric acid leaching experiment analyzed the effect of
hydrochloric acid concentration, the dosage of reductive reagent H2O2, temperature and time. The optimum
leaching conditions were as follows: HCl concentration is 2.5 mol/L, H2O2 dosage 4.5%, temperature 60 ćand
time 60min. The cobalt leaching rate was 98.5% under the optimized conditions.
ACKNOWLEDGMENTS
This work was sponsored by Youth Innovation Talents Support Project (2016QN073) from Harbin University of
Commerce.
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