APPLICATION OF DIGITAL CELLULAR RADIO FOR MOBILE LOCATION ESTIMATION IIUM Engineering Journal, Vol. 18, No. 2, 2017 Rahman et al. 238 RECYCLING AND DISPOSAL OF LITHIUM BATTERIES: AN ECONOMICAL AND ENVIRONMENTAL APPROACH ATAUR RAHMAN 1* , RAFIA AFROZ 2 AND MOHD SAFRIN 1 1 Department of Mechanical Engineering, Faculty of Engineering, 2 Department of Economics, Faculty of Economics and Management Sciences, International Islamic University Malaysia, Jalan Gombak, 53100 Kuala Lumpur, Malaysia. *Corresponding author: arat@iium.edu.my (Received: 28 th Nov. 2016; Accepted: 30 th Oct. 2017; Published on-line: 1 st Dec. 2017) ABSTRACT: The adoption of lithium-ion battery technology for electric vehicles/hybrid electric vehicles (EV/HEV) has recently received attention worldwide. The price of cobalt (Co) and lithium (Li) has increased due to the production of EV/HEV. A used lithium battery is a valuable source of active metals (Co, Li, and Al) and the optimal way of extracting these metals from this waste is still studied. The focus of this paper is to recover active metals using the hydrometallurgical method on a laboratory scale with a 48.8 Wh battery to reveal economic and environmental benefits. Calcination of extracted active metals as pre-thermal treatment has been conducted at 700°C to remove the organic compounds from the surface of active metals. The experiment has been conducted and the result shows that the recovery of active metals (cathode) is 41% of the cell cathode and 8.5% of the cell anode materials, which represent 48.8% and 23.4% of the cathode and anode cell material price, respectively. By recycling about 47.34% of the battery active metals, emissions can be reduced by 47.61% for battery metal production and 60.7% for disposal transportation of the used battery. The total emission can be reduced by about 52.85% by recycling the active metals in used batteries. ABSTRAK: Adaptasi teknologi bateri Litium-ion ke dalam kenderaan elektrik/ kenderaan elektrik hibrid (EV/HEV) telah memdapat perhatian seluruh dunia baru-baru ini. Harga kobalt (Co) dan litium telah bertambah hasil daripada EV/HEV. Perggunaan bateri litium adalah sumber berharga kepada logam-logam aktif (Co, Li dan Al) dan cara terbaik untuk mengekstrak logam-logam ini daripada sisa ini masih dipelajari. Fokus kertas ini adalah untuk mendapatkan logam aktif dengan menggunakan kaedah hidrometalurgikal dalam skala makmal dengan bateri 48.8 Wh untuk mendedahkan faedah ekonomi dan alam sekitar. Proses penulenan pada logam aktif yang diekstrak sebagai rawatan pre-haba telah dijalankan pada suhu 700 o C untuk membuang kompoun organik daripada permukaan logam aktif. Eksperimen telah dijalankan dan keputusan menunjukkan logam aktif didapati pada (katod) adalah 41% daripada sel katod dan anod adalah 8.5% daripada bahan sel anod, di mana 48.8% dan 23.4% daripada sel katod dan harga bahan sel anod, masing-masing. Dengan kitar semula logam aktif bateri sebanyak 47.43%, pelepasan boleh dikurangkan sebanyak 47.61% bagi penghasilan logam bateri dan 60.7% bagi pengangkutan pelupusan bateri terpakai. Pelepasan total boleh dikawal sebanyak 52.85% dengan mengitar semula logam aktif pada pengeluaran bateri. KEYWORDS: Li-ion battery; electro-chemistry; calcination; recycling;economics and environmental values IIUM Engineering Journal, Vol. 18, No. 2, 2017 Rahman et al. 239 1. INTRODUCTION Demand for electric vehicles (EVs) is growing around the world fairly rapidly. The EV/HEV sales share will represent at least 50% of light-duty vehicle sales worldwide by 2050. The aim of EVs/HVs is to contribute greenhouse-gas emission reductions and deliver substantial benefits in terms of improved oil security, reduced urban area pollution, and noise. The actual penetration of EVs has been seen as a key factor in material demand because these vehicles require larger batteries [1]. Lithium-ion batteries play a major role in powering electric vehicles by meeting their torque and speed demands. However, there is a threat regarding the availability of the lithium needed for battery production. This threat has shifted focus towards ensuring a continuous supply of materials needed for the green revolution through reuse and recycling. The dominant chemistry used in electronics batteries of active metals like Ni, Co., and Al for LCA battery, Li, Fe and phosphate (P) for LFP and Li, manganese (M) and sulfate (S) for LMS battery electrochemistry, as shown in Table 1. The battery contains a weight percentage (wt%) of lithium carbonate that is less expensive compared to cobalt (Co) or nickel (Ni). The average lithium cost associated with Li-ion battery production is less than 3% of the production cost while the battery metal production cost is about 200% higher than the battery metal‟s recycle cost [2]. Intrinsic value for the Li-ion recycling business currently comes from valuable metals such as Co and Ni that are more highly priced than Li. Table 1: Battery materials System /Electrodes LCA LFP LMS Graphite Graphite MS TiO Cathode LiNi0.8Co0.15Al0.05O2 LiFePO4 LiMn2O4 LiMn2O4 Anode Graphite Graphite Graphite Li4Ti5O12 Note: NCA: nickel, cobalt and aluminum; LFP: lithium iron phosphate; LMO: lithium manganese oxide; LMS: lithium manganese salt General Motor‟s claim that “one million tons of lithium is enough to produce 395 million Chevrolet Volts each with the power capacity of 16 kWh and battery electrochemistry chemistry LiFePO4”, i.e. 158 g of lithium metal required per kWh battery and hence the lithium needs are in the range of 113-246 g per kWh lithium-ion battery development. In addition, the theoretical charge density of lithium metal from fundamental electrochemistry is 3.8 Ah/g, representing 1 g of lithium, could supply 3.8 A of electric current for 1 hour [3]. Recycled lithium is as much as five times the cost of lithium produced from the least costly brine-based process [4,5]. However, with the increasing number of EVs entering the market in the future, and with a significant supply crunch, recycling is expected to be an important factor for consideration in effective material supply for battery production. Metal compositions of Li-ion batteries are mainly Al, Cu, Co, Fe, and Li, as shown in Table 2. The anode typically consists of Cu foil covered by a fine layer of carbon while the cathode contains Al, Co, and Li metals. It is particularly interesting to focus research on the recycling of cathodes as the active material. Such components represent 41%, by weight, of the cell components or 48.8% of the cell price. The price of Al, Cu, Ni, Co and Li per kilogram are USD1.58, USD5.3, USD10.57, USD27.5 and USD9.5, respectively [1]. IIUM Engineering Journal, Vol. 18, No. 2, 2017 Rahman et al. 240 Research has been reviewed to identify an economical and easy recycling process [6, 7]. Several methods could be preferred to recycle used Li-ion batteries for metal recovery; hydrometallurgical-based and pyro-metallurgical-based processes are the most predominant. As the pyro-metallurgical process is expensive and consumes too much energy, most of the previous literature prefers the hydrometallurgical process for metal recovery. In this study, the recovery of Al, Co, Fe, and Li metals from the cathode of the used Li-ion battery is focused using hydrometallurgical processes [8]. The steps are associated with the hydrometallurgical processes: physical separation of the battery (dismantling), manual separation of anode and cathode, acid leaching for the cathode, and crystallization testing for recovery of the Co metal. The global EV market will represent more than 7% of the light-duty vehicle market by 2020 and 70% of EVs are powered by Li-ion batteries. The green revolution, through reuse and recycling of batteries, has become a crucial topic in the automotive industry ensuring the availability of lithium needed for battery production. Recycling of used lithium batteries is the primary focuses of this work to extract active valuable metals such as cobalt (Co) and lithium (Li). Table 2: Composition of lithium battery [6] Components Amount (wt%) Cathode, Anode, and Electrode 40  1.5% Plastic case 22  1 Steel case 11  1.5 Copper foil 9  0.5 Aluminum foil 6.5  0.5 Electrolyte 5  1.5 Solvent 5.5  1 Electrical board and circuit 1.5 0.5 2. MATERIALS AND METHODS Recycling batteries is beneficial to the environment. It keeps them out of landfill, where heavy metals may leak into ground when the battery casing corrodes, causing soil and water pollution. The composition of an Li-ion battery is shown in Table 2. 2.1 Recycling and Disposal The author [9] has developed a „hydrometallurgy‟ process (Fig. 1) by modifying the hydrometallurgy process to recover the LiCoO2 battery metals. Mechanical pre-treatment (Calcination) and physical separation are applied to recover the battery materials such as plastic, metal casings, Co, Li, Cu, Al, and Fe [7]. In the hydrometallurgical process, lithium batteries are first dismantled to separate plastic and iron scraps from the active electrode materials by physical separation using crushing, sieving, and magnetic separation. The leaching method involves a model to separate the battery electrodes by dissolving them into an aqueous solution HCl, and H2SO4 with and without H2O2. The used LiCoO2 battery of 48.8 Wh capacity and 302 g weight has been used in this study to recover the metals. Mechanical treatment, breaking apart plastic and cells, and some physical separations have been performed by means of gravity and magnetism. Crushed plastics from shells can be separated by flotation. Using magnetism the steel parts of the containers are separated. IIUM Engineering Journal, Vol. 18, No. 2, 2017 Rahman et al. 241 Fig. 1: Lithium battery recycling model (A) metallurgy process, (B) precipation process by using Na2CO3 solution, (C) solvent extraction process by Cyanex 272 agent, (D) electrolysis process by using current density 200-250 A/m 2 , (E) crystalization process. 2.2 Leaching Process Leaching is a liquid-solid operation. Two phases are intimately in contact; the anode of the battery is diffused from the electrolyte to the liquid phase, which causes a separation of the components originally in the solid. The rate of mass transfer of the cathode can be estimated by, (1) where, is the mass rate of cathode materials dissolved into the solution, A is the surface area of chop particles of cathode in m 2 , km is the mass transfer coefficient of cathode into the acid solution in m/s, Scm(s) is the saturation solubility of the battery active materials (Li, Co, Al) in the aqueous solution (HCl and H2SO4 with and without H2O2) in kg∙mol/m 3 , and ca is the concentration of the aqueous soluble compounds of cathode materials at time t sec in kg∙mol/m 3 . The rate of accumulation of Li in the solution is equal to the dissolving beaker: dc a S li s( ) -c ac a i( ) c a f( ) ò = k m V A dt ti t f ò (2) If the dissolving time (t) of the cathode material into the solution between time, t= ti to tf and concentration, ca = ca(i) to ca(f), by integrating Eq. (2), the saturation solubility of Li can be modelled as, IIUM Engineering Journal, Vol. 18, No. 2, 2017 Rahman et al. 242 S cm s( ) = c a f( ) -c a i( )( )+e kmADt V (3) with Dt = t f -t i( ). where, Scm(s) is the rate of cathode material accumulation in the solution kg∙mol/m 3 . The 3 M of HCl solution has been prepared by mixing 75 ml of HCl with 300 ml of distilled water based on reported work [8]. The cathode of the battery was cut into small pieces of 2g each and put into acid solution and stirred with a magnetic stirrer for 1 hr. The temperature of the solution was varied to identify the changes in leaching rate. The leaching test was performed at room temperature of 30 o C and by varying the temperature in the range of 60 o C - 80 o C with the inorganic acid solutions of HCl and H2SO4 with and without H2O2. The effect of H2O2 on the percentage of metal obtained from the leaching process was studied. From observation, the presence of H2O2 as the reducing agent of H2SO4 makes a „Piranha‟ solution (H2SO5) and separates lithium and Co metal. 2.3 Physical Separation The composition of the LiCoO2 battery after physical separation is presented in Table 3. The peeled cobalt lithium oxide from aluminum foil is gained by the vacuum pyrolysis process, which is leached with inorganic acids such hydrochloric acid (HCl), and sulfuric acid (H2SO4). Hydrochloric acid can leach Co and Li more efficiently and economically. By adding H2O2 with H2SO4, the Co and Li leaching efficiencies have been increased. The optimal volume percentage of H2O2 is in the range of 1-10% and can be used in the leaching process [8, 9]. In this study, 2 vol% of H2O2 with 4 M H2SO4 were used. After leaching, the leaching solution and insoluble residue were separated by filtration for the precipitation, solvent extraction, and electrolysis processes to recover Co and crystallization test to identify the intensity of Cu, Li, CoSO4 using the established X-ray diffraction (XRD) method. Table 3: Battery (48.8 Wh LiCoO2) materials composition Components Amount (%) Cathode, Anode, and Electrode 46.2 Plastic case 18.63 Steel case 10.56 Copper barrel 7.5 Aluminum foil 1.8 Electrical board and circuit 2.75 Others 12.56 2.4 Precipitation The chemical precipitation method has been conducted for recovering Co and Li. The precipitation of the leaching processes was collected to recover Li. The ammonium oxalate [(NH4)2C2O4] 2 M was used with the precipitate for further precipitation of Co. The precipitation was then collected and treated with Na2CO3 to recover Li and Co. The Li was recovered about 82% with the Co impurities about 0.90%. The result can be supported by the findings [10-12]. While the Co was extracted to 84%. 2.5 Solvent Extraction Solvent extractant Cyanex 272 (a dialkyl phosphine acid extractant) was used to IIUM Engineering Journal, Vol. 18, No. 2, 2017 Rahman et al. 243 recover cobalt after leaching with H2SO4 without H2O2 based on the study with H2O2 [13,14]. The Co was recovered 81.78% by using of 1.5 M Cyanex 272 with the organics/aqueous ratio and 85.42% by using of 1.5 M Cyanex 272 with the organics/aqueous ratio (O/A) of 1.6. By using 0.5 M of Cyanex 272 with the O/A of 1, the 99% of the rest Co (14.58%) was recovered. 2.6 Electrolysis The authors [14] have used the electrolysis process for Ni recovery from a leaching solution using H2SO4 with an H2O2 after-solvent extraction of Co with Cyanex 272. Nickel electrowinning was performed at 250 A/m 2 current density at 50 o C, pH 3–3.2, with an electrolyte having about 50 g/l Ni and 20 g/l H3BO3, produces a good aspect Ni deposit with a current efficiency of 87% and a specific energy consumption of 2.96 kWh/kg [15]. In this study, we have used the electrolysis process to recover Co from a leaching solution using H2SO4 with H2O2 after solvent extraction of Co with Cyanex 272. The Co electrowinning extraction was conducted with the current density of 240 A/m 2 at temperature 60 o C. The pure Co was extracted about 92.01%. Fig. 2: Procedure of cathode separation. 2.7 Crystallization Test A crystallization test was conducted to separate the cathode and the intensity of the cathode was identified using an X-ray diffraction test. A crystallization model (Fig. 2) has been developed from this study to analyze the cobalt sulphate (CoSO4) electrolyte. The pure solution from the acid leaching process has been reheated with temperature in the range of 100-150 o C for 3-4 hours to obtain high pure CoSO4. The CoSO4 was washed with acetone and filtered. The CoSO4 was left dried and weighed and processed the sample for metal detection and analyzed by X-ray diffraction (XRD). The atomic plane of ! ! ! ! ! ! Wash the CoSo4 with acetone Filter!to! obtain! salt! powder! Wight!the!salt! powder!CoSo4! Reheat the CoSo4 solution obtained from acid leaching test !at 100-150C By using X-Ray Diffraction (XRD) Analysis CoSo4 CoSo4 dry salt IIUM Engineering Journal, Vol. 18, No. 2, 2017 Rahman et al. 244 CoSO4 causes an incident beam of X-rays to interfere with one another. The phenomenon is called X-ray diffraction (XRD). It is a rapid analytical technique used for phase identification of a crystalline material. 2.8 Emission Estimation Transportation is essential for battery collection prior to recycling or disposal in a landfill. When fuel is burned in an engine combustion chamber, most of the carbon is eventually oxidized to CO2 and emitted to the atmosphere. The emission of CO2 can be improved drastically if the battery is processed for recycling rather than disposal. The emission of carbon can be estimated using equation [16]: C emission =M c  ´ (FC) oxidized (4) with Mc =Qfuel ´ sfcc(coeff ) and Qfuel =Vfuel ´Hvfuel where, Mc is the mass of carbon content in fuel in kg, sfcc(coeff) is the coefficient of carbon content in fuel in kg/J, Qfuel is the fuel combustion energy in J, Vfuel is the volume of fuel in l, Hvfuel is the heating value of fuel in J/l. Equation (4) can be rewritten: C emission =V fuel  ´Hv fuel ´ sf cc(coeff ) ´ (FC) oxidized (5) where, (FC)oxidized is the fraction of carbon oxidized in percentage. CO 2 emission( ) =C emission ´ CO 2 (m.w) C m.w( ) (6) where, m.w represents molecular weight and Cemission is the amount of carbon emission in kg. Equation (6) can be re-written by using Eqs. (5) and (6): CO 2 emission( ) =V fuel  ´Hv fuel ´ sf cc(coeff ) ´ (FC) oxidized  ´ CO 2 (m.w) C m.w( ) (7) where, Vfuel is the volume of fuel in liters. The amount of fuel (volume) can be estimated directly from the vehicle mobile source. 3. RESULTS AND DISCUSSION The separation of Co metal by leaching with 4 M of HCl and H2SO4 with and without H2O2 has been studied for the temperature of 60-80°C and is presented in Table 5. The leaching rate of Co metal extraction has increased 45% for the leaching with HCL and increased 21% for changing temperature from 60 to 70 o C and decreased 6% due to the removal of the impurities from the surface of Co metal. The leaching rate of Co metal extraction has increased 7% for changing temperature from 60 to 70 o C and decreased 2.5% for changing temperature from 70 to 80 o C. Overall, the Co leaching rate was lower than the leaching rate for the acid HCl and H2SO4 without H2O2. This could be the decomposition of H2O2 resulting in the evolution of oxygen onto the Co. The conclusion can be supported by the research work of the authors [18]. Furthermore, the weight of Co extraction by using HCl and H2SO4 without H2O2 is more than by using H2SO4 with H2O2. This is due to the formation of Caro acid (H2SO5). Caro acid has an acidic property and a higher oxidizing potential, which has the high potentiality to remove impurities and residue from the surface of Co. The conclusion can be supported by the authors„ published research work [17-18]. Based on the results exhibited in Table 5, it is concluded that the leaching rate of the Co by HCl is more than the H2SO4 without H2O2 and H2SO4 with IIUM Engineering Journal, Vol. 18, No. 2, 2017 Rahman et al. 245 H2O2 because of the boiling temperature in the range of 60-80 o C. In this case, the H2SO4 with and without H2O2 are stronger than the HCl. Fewer impurities remained on the surface of the Co when it was leached by H2SO4, with and without H2O2. Table 4: Leaching of the Co for temperature of 30 o C Acid solution Concentration (M) Leaching rate (%) HCl 1 37.5 2 47.6 3 55.7 4 60.5 H2SO4 1 48.6 2 71.8 3 85.3 4 99.0 H2SO4 with 2% vol. of H2O2 1 40.2 2 67.8 3 78.9 4 83.0 Table 5: Temperature effect on acidic leaching process Acid Solution Temp. ( o C) Weight of Co (g) Leaching Rate (%) Initial Final Difference 4 M HCl 60 2.00 1.10 0.90 55.0 70 2.00 1.43 0.57 71.5 80 2.00 1.58 0.42 79.0 H2SO4 60 2.00 0.98 1.02 49.0 70 2.00 1.4 0.60 70.0 80 2.00 1.45 0.55 64.0 H2SO4 with 2% vol. of H2O2 60 2.00 0.74 1.26 37.0 70 2.00 0.88 1.12 44.0 80 2.00 0.83 1.17 41.5 Table 6: Metal extraction Metal Extracted Purity of metal extracted (%) Precipitation Solvent extraction with H2SO4 Electrolysis (electro-winning) (NH4)2C2O4 Na2CO3 with H2O2 without H2O2 Lithium (%) - 82 - - - Cobalt (%) 84 - 85.42 81.78 92.01 Table 6 shows the lithium and Cobalt extraction from the leached solution by three different processes with the leached solution, which was made with 4 M H2SO4 + 2% H2O2. The electrowinning process is a promising process of the hydrometallurgy family of techniques. Table 7 shows the composition of the powder of Li-ion battery, which was found from the recycling of a 48.8 Wh battery (weight 302.7 g). The amount of Cobalt (Co) 9.11% (27.85 g) in the battery mass (or 13.8% the total amount of anode, cathode and IIUM Engineering Journal, Vol. 18, No. 2, 2017 Rahman et al. 246 electrolyte mass) is greater than the other anode and cathode materials. The amount of total recycled active metals (Co, Li, Cu and Al) is 29.78%. Table 7: Battery‟s metal obtained after recycling Components Weight (g) Amount (wt%) Plastic 56.27 18.63 Steel (battery pack cover) 12.56 3.98 Lithium 8.58 4.03 Anode and Cathode extracted 24.82% Cobalt 27.85 13.08 Aluminum 7.45 2.46 Copper 15.84 5.25 Electrical board and circuit 8.32 2.75 Others (including electrolyte) 55.14 18.25 Table 8 shows the metal obtained from recycling for the equivalent of a 1000 Wh battery. The economic value of Co obtained from the 48.8 Wh battery is USD 0.77 while for the 1000 Wh battery it is approximately USD 15.7. The economic values of the recycled LiCoO2 battery of a 48.8 Wh is USD 0.91 while for the 1000 Wh battery, it is approximately USD 20.29. If an electric vehicle is equipped with a LiCoO2 battery with a capacity of 33 kWh (standard power pack for an electric car), the recycled value of anode and cathode materials is USD 669.57; where the value of Co is USD 528.00. For 100 EV batteries, each with 33 kWh of electrochemistry LiCoO2, the recycled values of Co is only USD 52800.00. Fig. 3 shows that the cleavage faces of the anode, cathode, and crystalline electrolyte appear to reflect X-ray beams at certain angles of incidence (theta, θ). Results show the cleavage faces 111, 200, 220, 222, 311, and 511 for the atoms of an anode, cathode, and electrolyte. The shape of the incident beam or counts depends on the focal projection of the filament onto and from the anode material. Cu (atomic number 29) is suitable for most diffraction examinations and is the most widely used anode material. Co (atomic number 27) is often used with ferrous samples, Fe (atomic number 26) fluorescence radiation would cause interference and cannot be eliminated by other measures. Li (atomic number 3) is the lightest metal and the least dense solid element. Table 8: Economic values of recycled cathode and anode materials Materials Materials extracted (g) International Price (USD/kg) Values of extracted materials (USD) 48.8 Wh 1000 Wh 48.8 Wh 1000 Wh Lithium 8.58 175.82 9.5 0.082 3.41 Cobalt 27.85 570.65 27.5 0.77 15.7 Aluminum 7.45 152.65 1.58 0.012 0.24 Copper 15.84 324.56 5.3 0.046 0.94 Total price of extracted materials of battery (USD) 0.91 20.29 IIUM Engineering Journal, Vol. 18, No. 2, 2017 Rahman et al. 247 (a) Cathode (Li) (b) Anode (Cu) Crystal (CoSO4) Fig. 3: X-ray analysis for LiCoO2 battery. Fig. 4: Overall cost breakdown of battery production [18]. 3.1 Economic Benefit of Recycling Recycling of automotive batteries has economic benefit. Recycling means saving natural resources and energy, generating income, and reducing imports. In addition, the biological activities of Co are largely confined to its role in the vitamin B12 series of coenzymes and the Cu presents in a variety of proteins and enzymes, including cytochrome oxides, an enzyme in respiratory chains [19]. Therefore, battery recycling is a much better option than disposal in landfills. The recycling cost can be limited by the steps involved in the metallurgical process. Stewardship Ontario program pays USD1.24 per kg of batteries for recycling, compensating recyclers USD1,240. The estimated cost to Detection of DiffractedX-rays by a Diffractometer Photon counter Detector Amplifier C Circle of Diffractometer Recording Focalization Circle Bragg - Brentano Focus Geometry, Cullity Figure : Bragg’s-Bretano Focus Geometry : detection of diffracted X-ray by a diffractometer. 54 other acid solutions. Leaching process at temperature of 80 o C using 4M HCl solution will be selected as its leaching rate was the highest (79%). 4.5 XRD Analysis Fig. 4- 5 X-ray patterns of the metal obtained after leaching process After conducting the leaching process, the metal obtained was dried before being analyzed using X-ray diffraction (XRD). The dried sample was tested in order to characterize the metal content. The peak of the graph showed the metal available from the sample. Based on Fig. 4-5, the metal obtained from leaching process mostly lithium metal. It can be concluded that the leaching process separates lithium metal from other metal which available at the cathode. Data can be obtained from Appendix A. Li Li Li 0 20 40 60 80 100 120 140 0 10 20 30 40 50 60 70 c o u n ts / s 2 Theta XRD analysis for cathode peak Figure : X-ray analysis for cathode. (200 (220) (111) Li(311) Li (331) (2 Theta) (Theta) Text Intensity IIUM Engineering Journal, Vol. 18, No. 2, 2017 Rahman et al. 248 recycle batteries is about USD2,000 per ton, while the cost for the hydrometallurgical process is about USD1,500 per ton [20]. Fig. 5: Reproduce energy for battery production [2]. Table 9: Battery pack for EV and its baseline cost [24]. Battery Parameter Baseline Electric vehicle range, km 50 Number of battery pack 1 Number of cells per pack 52 Battery system total energy, kWh 8.7 Cell capacity, Ah 43 Module (2S2P) capacity, Ah 86 Battery system capacity, Ah 86 Battery Nominal voltage, V (OCV at 50% SOC) 100 Cost for baseline battery with total price to OEM: USD 2528 The recycled metal is USD 20.03/kWh, which will reduce the material cost. Electrode cost is USD 140 per kWh battery. It is calculated that the recycled metal can save 14% of the total cost of active metal per kWh battery. If an EV battery power pack equivalent to 33 kWh is recycled, its production cost can be reduced USD 660 by using the recycled materials. Figure 4 shows the breakdown of unit costs for baseline battery with total price to OEM of USD 2,528. The total battery cost to the OEM, including pack integration components but excluding thermal management external to the pack USD 2,923 [21-22]. Figure 5 shows that the metal production for the battery is 3 times more than the battery production while it is 300 times more than the recycling process. By recycling, the cathode and anode are obtained by 41% and 8.5% by weight of the cell components respectively, which is USD 20.03/kWh of the battery. Table 9 shows the capacity of a 8.7 kWh battery for the short travelling range of an electric vehicle (about 50 km), which has been developed and tested [22]. The total cost of 52 Table 4- 2 Data from the leaching process with different temperature Acid solution Temperature ( o C) Initial weight (g) Final weight (g) 𝚫m (g) Leaching rate (%) 4M HCl 60 2.0 1.10 0.90 55.0 70 2.0 1.43 0.57 71.5 80 2.0 1.58 0.42 79.0 4M H2SO4 60 2.0 0.98 1.02 49.0 70 2.0 1.40 0.60 70.0 80 2.0 1.28 0.72 64.0 4M H2SO4 + 2 vol% H2O2 60 2.0 0.74 1.26 37.0 70 2.0 0.88 1.12 44.0 80 2.0 0.83 1.17 41.5 4.4.1 Sample calculations To calculate the leaching rate for different temperature, the same equation to be used as follows: Leaching rate; xB=    x  100% Sample calculations: Initial weight of cathode used = 2.0 g Weight of the filter paper = 0.56 g Weight of metal after filtration + weight of filter paper = 2.14 g Final weight = (2.14-0.56) = 1.58 g Leaching rate = (1.58) / (2.0) x 100% = 79% 30 40 50 60 70 80 90 55 IIUM Engineering Journal, Vol. 18, No. 2, 2017 Rahman et al. 249 the battery was USD 2528. The battery lifespan was considered as 5 years based on the OEM. The recycled materials value for 8.7 kWh batteries is 14% of the active cost and 8% of the battery OEM baseline price. The battery electrodes values are estimated as 0.49 × USD 2528 or USD 1238 and the recycled material values as USD 20.03×8.7 or USD 174.26. Table 10: Emission on battery metal production and transportation Note: Wo-RC = without recycling; Wi-RC = with recycling Assumption (i) *Fuel consumption of a pick-up van with 500 kg payload = 0.121 liter/km. (ii) Source of energy = Diesel (iii) Standard battery capacity for an EV= 33 kWh (iv) 33 kWh battery mass = 264 kg (v) CO2 emission = 2.2 kg/liter (vi) Distance:  EV battery exchanging workshop to landfill = 20 km  Battery exchanging workshop to recycling plant = 0 km  Recycling plant to landfill = 8 km It is also estimated that the if the battery capacity of 34 kWh for an EV with a range of 117 km (AEO recommended), the recycled material values of the battery materials (cathodes and anodes) would be USD 681. If the 100,000 EVs each of battery capacity 34 kWh will be under recycled (i.e, 3400,000 kWh battery), the material would save 833.77 g/kWh battery and its values would be USD68102 which is very much profitable for a small scale company. The recycled values of the material of batteries 41 % and 48.8% price of the cathode and anode are 8.5% and 23.4% price of the anode. It shows that by recycling the electrodes of the battery, consisting mainly of cobalt, nickel, and lithium, will save up to 48.8% of new battery manufacturing cost. This indicates that in a lithium- ion battery recycled component values can be higher and would encourage people to set up recycling plants to recycle large-scale batteries. This not only contributes economically but also environmentally. ! Metal Production Description Energy Required Emission (CO2) (g) (MCal/kWh) Gasoline (Litre) 1 kWh 33 kWh Metal Production Wo-RC (need 100% materials) 290 0.042 92.4 3049 Wi-RC (Reduces 47.43% metals production) 153.7 0.022 48.4 1597.2 Transportation *Transportation (used battery) Fuel consumption for each 33 kWh battery pack (litre) Emission (CO2) (g) Wo-RC 0.26 572 Wi-RC 0.05 110 IIUM Engineering Journal, Vol. 18, No. 2, 2017 Rahman et al. 250 3.2 Environmental Benefit of Recycling The battery powered EV is increasing significantly to improve the environment for living planets. Furthermore, batteries in the modern day world have become universal. They make available energy for a wide range of products that are used across all sections of economic activity, from households to large industrial enterprises. They also provide backup power for activities that involve an uninterruptible power supply (UPS). The battery is categorized as hazardous waste at the end of its life as it can damage human health or the environment [23]. Furthermore, mining and processing ores (e.g., SOx emissions from smelting of sulfide ores, such as those that yield copper, nickel, and cobalt) creates significant negative environmental impacts. These are avoided if the materials can be recycled [24]. If usable materials used batteries can be recovered, excessive battery materials production cost can be avoided, which could be 200% more than the battery production, as shown in Fig. 5. It should be mentioned that the higher input on the material production causes more CO2 emission than the battery production as the motorized system uses for the material production, which is powered by the IC engine or electrical motor. Table 10 shows the amount of emission (CO2) on battery metal production and transportation. Table 6 shows that the valuable anode and cathode metals can be recycled by 24.82% while total metal recycled, including plastic and steel, is 47.43%. The result indicates that the metal production decreases by about 47.43%, which reduces the energy consumption. Fig. 5 shows the energy required for metal production is 290 Mcal per kWh of LiCoO2 battery. It is considered that the energy required also decreases by 47.43%, which causes the CO2 reduction by 47.61%. Furthermore, if the battery is disposed of in a landfill some distance away from the recycling center, the emission of CO2 will be increased, as the CO2 emission is directly proportional with the engine fuel consumption. The emission of CO2 is estimated at about 2.2 kg per liter of diesel using Eq. (9). A diesel pick-up van (engine capacity of 2.4 liter) is considered for transportation, which reduces fuel by 1 liter for every 8 km. The van is considered to go to & from the disposal point. It is estimated that the CO2 reduction from transportation with recycling is 80.7% lower than that of without recycling. Total emission (CO2) can be controlled by recycling is about 52.85%. 7. CONCLUDING REMARKS The cobalt and lithium recovery from used lithium batteries is discussed in this work. The hydrometallurgical method is used for the extraction of materials from the waste. Calcination was chosen for thermal pretreatment of Co, Li, and Cu black masses from the used portable lithium batteries. Calcination was conducted at 700 o C for 60 minutes to remove the organic impurities before leaching process. The leaching process has been conducted mainly with different concentrations, mainly of acid H2SO4 , with and without an H2O2 reducing agent at varying temperature 60 o C - 80 o C. The electrolysis process can be considered as it could achieve the cobalt compound of very high purity from lithium battery since it does not introduce other substances and avoid impurities. This process has the disadvantage of consuming too much electricity and the safety. The recovery of the cathode (Li, Co and Al) is 41% of cell cathode and anode (Cu) is 8.5% of the cell anode materials, which are 48.8% and 23.4% of the cathode and anode cell material price, respectively. This could be considered as the motivation and encouragement to recycle large-scale used batteries. IIUM Engineering Journal, Vol. 18, No. 2, 2017 Rahman et al. 251 Based on the recycled metals, it is found that the emission reduced by 47.61% for metal production of battery and 80.7% for transportation of used battery disposal. In overall, emission for the metal production and transportation can be controlled by 52.85% if the battery active materials will be recycled and used in battery production. ACKNOWLEDGEMENT The authors are grateful to the Ministry of Higher Education, Malaysia and Research Management Center, International Islamic University Malaysia for financing this project by MyRA grant. 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