Recycling of Electrode Materials from Spent Lithium-ion Batteries

Xu Zhou 1, Wen-zhi He 1*, Guang-ming Li 1, Xiao-jun Zhang 1, Ju-wen Huang 1, Shu-guang Zhu 1,2
1.Tongji University, College of Environmental Science and Engineering, the State Key Laboratory of Pollution Control and Resource Reuse, Shanghai, China;
AbstractIn this paper, based on the structure of lithium-ion batteries, the electrode materials were separated from spent lithiumion batteries (LIBs) with aim to recycle all valuable components as possible. The spent LIBs were dismantled first, then the mechanical pulverization and sieving process was adopted in the separation of anodes, and dissolution method was used to partition active components from cathodes. Owing to low bonding force between graphite carbon particles and copper foil, graphite carbon can easily drop off and be separated when anode materials were struck. The results showed that after shredding and sieving, most copper was concentrated in the size range above 0.30 mm at the condition of 3 min pulverization, which led to a favorite recovery rate for copper, reaching 95.9%. The selected organic solvent N, Ndimethylformamide (DMF) could be successfully applied to dissolve the polyvinylidene fluoride (PVDF) adhesive that the cathode active materials LiCoO2 be effectively separated from the aluminum current collector. Keywords- spent lithium-ion batteries; recycling; copper

Shu-guang Zhu 1,2

2. School of Environment and Energy Engineering, Anhui University of Architecture, Hefei, China

focus on the recycling of them. For example, Contestabile et al[6]. developed a laboratory-scale lithium ion battery recycling process consisting of crushing of spent batteries, selective separation of lithium cobalt oxide, dissolution using hydrochloric acid, and precipitation of cobalt hydroxide. Swain et al[7]. successfully separated cobalt and lithium from mixed solution of cobalt and lithium sulfate by solvent extraction using saponified Cyanex 272 as an extractant for cobalt. Considering the ever aggravated global problems of resource shortage and environment pollution with rapid economic growth and population increase, all valuable components in spent LIBs should be recovered besides Co or Li. In the present work, based on the structure of LIBs, the spent LIBs were dismantled first and then the components of anode and cathode were separated with aim to recycle all valuable components from spent Li-ion batteries as possible. II. EXPERIMENTAL

I.

INTRODUCTION

Lithium-ion secondary rechargeable batteries (LIBs) were firstly produced by Sony in early 1990s. Because of their high energy density, low auto-discharge rate, excellent cycle life and acceptable properties in environmental terms, LIBs have substituted Ni-Cd and Ni-MH batteries in many applications, and been extensively used as electrochemical power sources in mobile telephones, personal computers, video cameras and other modern life appliances[1]. The life-span of LIBs is about 1-3 years. The tremendous growth in the use of LIBs has resulted in a great amount of spent LIBs. Spent LIBs, if not properly treated, can cause serious environmental problems due to the hazardous components such as heavy metal, electrolyte, etc. On the other hand, spent LIBs also have high residual values. Co, Li, Cu, Al and other metals, shell plastic and graphite carbon in spent LIBs can all be recycled. Especially Co (515 wt.%) [2], a rare and precious metal, is an admittedly strategic resource. With the recognition on environmental risk and the values of the reusable materials, many technologies have been developed to recycle spent LIBs, including thermal treatment[3], mechanochemical process[4], acid (or base) leaching[5,6], solvent extraction[7], chemical precipitation[8] and electrochemical process[9,10], etc. Because the cobalt is the most valuable component in LIBs and lithium is also important in many industrial applications, most of the established technologies

A. Materials and reagents The materials used in this work are discarded lithium-ion batteries for mobile-phones. N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC) and N-methylpyrrolidone (NMP), are used as organic solvents for separation of active materials from cathodes. All reagents are utilized as received without any further purification. B. Equipments and Devices FW-400A hammer swing pulverizer is applied to pulverize the anode of spent LIBs. The content of copper is analyzed by Optima 2100 DV coupled plasma atomic emission spectroscopy, which has the detectability of ppb to ppm. C. Methods A LIB comprises an anode, a cathode, organic electrolyte and a separator. The anode is a copper plate coated with a mixture of graphite carbon, acetylene black electric conductor and additives through PVDF binder. Similar to anode, the cathode is composed of aluminum foil, active cathode materials, PVDF binder, electric conductor and additives[1,2]. In the experiment, it was discovered that the bonding force between copper foils and adhered graphite carbon is loose, and the mixture coating easily dropped off from their support

1*

corresponding author phone: +86 1356 475 3913; fax: +86 21 65989215e-mail: hithwz@163.com

978-1-4244-4713-8/10/$25.00 2010 IEEE

substrate when anodes were struck. Compared to anode, the mixture of LiCoO2 and acetylene black electric conductor are well-knit to the aluminum foil. It is difficult for the mixture coating to be dropped off from the aluminum foil when cathodes are pulverized. However, with the physicochemical property of PVDF, the active materials could be successfully separated from cathodes by dissolution of PVDF in organic solvent. Based on the fact above and the structure of the LIBs, the strategy of recycling the spent LIBs is as follows (see Fig.1).

III.

RESULTS AND DISCUSSIONS

A. Partition of copper and carbon powder by pulverization and sieving process Tab.- showed the results of pulverization and sieving process of anodes at different times. R refers to the mass percent of crushed aggregates within one size range. ( i.e. the ratio of the mass of crushed aggregates within one size range to the mass of initial anode materials.)
TABLE I. Mesh 30 30-50 50-60 60-80 80-120 120-160 160-200 TABLE II. Mesh 30 30-50 50-60 60-80 80-120 120-160 160-200 TABLE III. Mesh 30 30-50 50-60 60-80 80-120 120-160 160-200 TABLE IV. Mesh 30 SIEVING RESULTS AT 1 MIN PULVERIZATION TIME Content of copper% 86.42 29.30 3.39 1.56 1.33 1.24 1.44 R % 94.21 2.79 0.96 0.73 0.97 0.26 0.07

Size rangemm >0.59 0.30-0.59 0.25-0.30 0.18-0.25 0.12-0.18 0.10-0.12 0.07-0.10

Figure 1. Flow-sheet of the recycling of spent lithium-ion batteries.

SIEVING RESULTS AT 3 MIN PULVERIZATION TIME Content of copper% 95.39 61.25 4.63 2.12 1.59 1.50 1.44 R % 93.12 2.80 1.34 0.70 1.10 0.48 0.47

After discharged, the spent LIBs were first dismantled with screwdrivers, pliers, or other mechanical tools, and then the partitioned shell, separator, anode and cathode were further treated separately. Because of the complicated components of electrode materials, a separation process of different materials was carried out to simplify the recovery procedure. However, the separator and shell could be reused directly thanks to their single components. Anode was first cut to small plates with sizes about 1.5cm1.5cm, and then treated by the hammer swing pulverizer. The crumbled anode particles were sieved to reclaim copper particles. In the experiment performed, the pulverization time was separately 1 min, 3 min, 6 min, 9 min and 12 min. The solubility of PVDF in DMF, DMAC and NMP was tested at different temperature to determine the optimal operating condition for recovering LiCoO2 from cathodes by dissolution method. The test temperature was controlled at 30, 40, 50, 60 and 70 respectively. D. Analysis of copper contents in crumbled anode particles The contents of copper in crushed particles were determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES).

Size rangemm >0.59 0.30-0.59 0.25-0.30 0.18-0.25 0.12-0.18 0.10-0.12 0.07-0.10

SIEVING RESULTS AT 6 MIN PULVERIZATION TIME Content of copper% 98.64 82.82 6.07 6.31 3.84 2.44 2.51 R% 85.13 6.77 4.30 0.46 1.74 0.89 0.70

Size rangemm >0.59 0.30-0.59 0.25-0.30 0.18-0.25 0.12-0.18 0.10-0.12 0.07-0.10

SIEVING RESULTS AT 9MIN PULVERIZATION TIME Content of copper% 98.79 R % 89.47

Size rangemm >0.59

30-50 50-60 60-80 80-120 120-160 160-200 TABLE V. Mesh 30 30-50 50-60 60-80 80-120 120-160 160-200

0.30-0.59 0.25-0.30 0.18-0.25 0.12-0.18 0.10-0.12 0.07-0.10

91.55 48.44 18.68 5.95 3.45 1.37

5.70 0.96 0.53 0.74 0.41 2.19

SIEVING RESULTS AT 12 MIN PULVERIZATION TIME Content of copper% 99.84 97.62 15.61 9.07 6.03 5.02 3.22 R % 81.85 8.19 2.71 0.28 1.41 0.93 4.63 Figure 3. Influence of pulverization time on the content of copper and R of crushed aggredates with particle sizes above 0.59 mm and 0.30-0.59 mm

Size rangemm >0.59 0.30-0.59 0.25-0.30 0.18-0.25 0.12-0.18 0.10-0.12 0.07-0.10

Within the experiment condition, most crushed copper aggregates were concentrated in two bigger size ranges ( particle size above 0.30 mm ). Furthermore, with the increasing of the pulverization time, the mass percent (R) of crushed aggregates with particle sizes above 0.30 mm declines. The mass percent (R) is 96.9% at 1 min, while when the pulverization time is raised to 12 min, it drops to 90.0%. So increasing pulverization time is beneficial to the content of copper, but it is not always favorable to the recovery of copper. It mainly results from that when the pulverization time is short (1 min) , anode materials are not fully struck with each other, and graphite carbon cant effectively get rid of the copper substrate, leading to low content of copper. When the pulverization time ascends, copper plate has more chance to be shocked with each other. Therefore, more carbon powder falls off, going into smaller size ranges through sieving, and the copper contents of crushed aggregates with particle sizes above 0.59 mm and 0.30-0.59 mm are both improved. On the other hand, with the increase of pulverization time, it is unavoidable for more anode materials to be crushed into small particles, then go into smaller size ranges, which reduces the mass percent (R) of crushed aggregates with particle size above 0.30 mm. Due to the fact that most crushed aggregates are concentrated in the sizes above 0.30 mm, and the content of copper of the crushed aggregates in that two size ranges is also high. Therefore, the total mass percent (R) of crushed aggregates with particle size above 0.30 mm was regarded as the recovery rate of copper for the separation of anodes. Taking all factors into consideration, including recovery rate, operation time and energy consuming as well, pulverization time is determined at 3 min when most copper is concentrated in the particle size above 0.30 mm, and the copper recovery rate reaches 95.9%. B. Separation of aluminum foil and LiCoO2 mixture by dissolution process Dissolution process was adopted to separate aluminum foil and LiCoO2 mixture on cathodes. The solubility of PVDF in the selected organic solvents was shown in Fig.4.

It can be noted from the tables that the content of copper with particle size above 0.59 mm is pretty high at all pulverization times, even the lowest one reaches 86.42%. Fig.2 showed the effect of partition of copper and carbon powder, which indicated an effective separation of copper and carbon graphite through pulverization and sieving process.

copper

copper

carbon powder

Figure 2. Partition products of anodes by pulverization and sieving

The process of separation between copper and carbon powder can be explained in terms of the characteristics of copper. Due to the fact that copper is malleable, only a small part of copper will be crushed into fine particles. Generally, it will strike together, then curl and finally twist into copper cube with some shape. Such shape is in favor of crushing and knocking in the progress of pulverization. As a result, graphite carbon dropped off and separated from the copper substrate. Fig.3 showed the influence of pulverization time on the content of copper and R of crushed aggregates with particle sizes above 0.59 mm and 0.30-0.59 mm. From the Fig, it can be observed that the copper contents of crushed aggregates increase with the time. For example, the copper contents of crushed aggregates with the size above 0.59 mm and within size range between 0.30 mm and 0.59 mm are 86.4% and 29.3% at 1 min pulverization. However, when the pulverization time rises to 12 min, the contents of copper of above two sizes reach 99.8% and 97.6%, respectively.

Before dissolution

After dissolution

Figure 6. Aluminum foil and LiCoO2 mixture separated by dissolution Figure 4. Solubility of PVDF in three solvents at different temperatures

From the Fig.4, it can be noted that all of selected organic solvents can dissolve PVDF, and the solubility increases with the increasing of temperature. Among them, DMAC showed the highest solubility for PVDF. Its solubility for PVDF reaches 96g/L at 30, and increases to 214g/L at 70. NMP shows low solubility below 50, which is only 64g/L, but when the temperature is above 50, the solubility is close to DMAC. For example, at 70, the solubility of PVDF in NMP is 210g/L. As for DMF, more PVDF could solve in it than in NMP when the temperature is below 50, for example, 86g/L at 30. The performance of three solvents could be explained as the principle of similarity and intermiscibility. For solute A and solvent B, when the gravitation KAB between A and B is higher than the gravitation KAA or KBB between internal molecules, solute A can dissolve in solvent B. The interaction force between molecules A and B is related with the polarity of A and B. PVDF resin is polymerized of VDF or VDF with small quantities of fluoridebearing vinyls, and repeated unit is CH2CF2-[11]. From Fig.5, carbonyl group can be found in all three solvents DMAC, NMP and DMF, the polarization of which results to strong polarity of them, making PVDF easy to dissolve in them.
CH3 N

IV.

CONCLUSION

Mechanical pulverization and sieving process was used to separate graphite carbon and copper foil on anodes. The results showed that at a pulverization time of 3 min, most copper was concentrated in the size range above 0.30 mm, which led to a favorite recovery rate for copper, reaching 95.9%. Organic solvent DMF could be used to separate cathodic active materials LiCoO2 from the aluminum current collector effectively. The results showed that the solubility of DMF for PVDF could reach 176g/L at 60. ACKNOWLEDGMENT The authors gratefully acknowledge the financial support from the Key Research Project of Shanghai in China (07dz12029) and the National Key Technology R&D Program of China (2008BAC46B02). REFERENCES
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O
O

CH3 N CH3 H

O C N

CH3

H3C

CH3

NMP

DMAC

DMF

Figure 5. Molecular structure of three organic solvents

The current prices of three solvents available in the market respectively are 11000 to 14000 yuan per ton for DMAC, about 25000 yuan per ton for NMP and 6000 to 8000 yuan per ton for DMF. Considering the solubility and costs, DMF is chosen as the proper solvent for separating active material LiCoO2 from cathode materials. In the experiment, cathodes are immersed into DMF for 2h at 60 because of the low boiling point of DMF. Then the LiCoO2 mixture was filtered out from DMF solution and be dried for further purifying. Fig. 6 showed that the LiCoO2 mixture could be completely separated from the aluminum foil by the dissolution method.