• Resources Recycling
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• v.24 no.6
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• pp.9-16
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• 2015

In a recycling scheme of spent lithium ion batteries, a co-precipitation process for the re-synthesis of precursor is essential after the leaching of lithium ion battery scraps. In this study, the effect of ammonia as impurity during the co-precipitation process was investigated in order to re-synthesize a precursor of Ni-rich cathode active material $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ (NCM 622). As ammonia concentration increases from 1 M (the optimum condition for synthesis of the precursors based on 2 M of metal salt solution) to 4 M, the composition of obtained precursors deviates from the designed composition, most notably for Ni. The Ni co-precipitation efficiency gradually decreases from 100% to 87% when the concentration of ammonia solution increases from 1 M to 4 M. Meanwhile, the morphological properties of the obtained precursors such as sphericity, homogeneity and size distribution of particles were also investigated.

• Resources Recycling
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• v.31 no.3
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• pp.73-80
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• 2022

Reduction smelting of spent lithium-ion batteries at high temperature produces metallic alloys. Following solvent extraction of the leaching solutions of these metallic alloys with either sulfuric or hydrochloric acid, the raffinate is found to contain Ni(II), Co(II), Mn(II), and Si(IV). In this study, two cationic exchange resins (Diphonix and P204) were employed to investigate the loading behavior of these ions from synthetic sulfate and chloride solutions. Experimental results showed that Ni(II), Co(II), and Mn(II) could be selectively loaded onto the Diphonix resin from a sulfate solution of pH 3.0. With a chloride solution of pH 6.0, Mn(II) was selectively loaded onto the P204 resin, leaving Ni(II) and Si(IV) in the effluent. Elution experiments with H₂SO₄ and/or HCl resulted in the complete recovery of metal ions from the loaded resin.

• Proceedings of the Korean Institute of Resources Recycling Conference
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• 2005.10a
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• pp.173-177
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• 2005

리튬이온 2차전지(Lithium ion battery, LIB)는 기존에 사용되던 전지에 비해 에너지 밀도가 높고 충방전 사이클이 우수하다. 이 때문에 휴대전화와 노트북 등에 수요가 급속하게 증가하고 있으며 1995년 LIB의 생산량은 4천만 개에서 2004년에는 약 8억 개로 20배 이상 증가하였다. 이에 따라 폐LIB도 급속하게 증가하게 되어 전국적인 재활용 시스템의 확보가 필요한 실정이다. 본 연구에서는 폐LIB에 함유되어 있는 유가금속 중에서 리튬코발트옥사이드(이하 $LiCoO_2$)를 회수하기 위하여 분쇄기(orient vertical cutting mill)와 진동 Screen을 사용하여 유기분리막, 금속류(Aluminium foil, Copper foil, case 등) 그리고 전극물질(lithium cobalt oxide와 graphite 등의 혼합 분말)로 분리하였다. 전극물질에서 $LiCoO_2$와 graphite 분리를 위한 전처리 단계로서 $500^{\circ}C$ 정도의 열처리를 하여 $LiCoO_2$의 표면 성질을 변화시켜 부유선별에 의해 $LiCoO_2$와 graphite의 분리가 가능하도록 하였다. 부유선별 실험 결과 93% 이상의 순도를 가지는 $LiCoO_2$를 92% 이상 회수할 수 있었다.

• Resources Recycling
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• v.28 no.4
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• pp.51-58
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• 2019

Dismantlement of lithium primary batteries without explosion is required to recycle the lithium primary batteries which could be exploded by heating too much or crushing. In the present study, the optimum discharging condition was investigated to dismantle the batteries without explosion. When the batteries were discharged with $0.5kmol{\cdot}m^{-3}$ sulfuric acid, the reactivity of the batteries decreased after 4 days at $35^{\circ}C$ and after 1 day at $50^{\circ}C$, respectively. This result shows that higher temperature removed the high reactivity of the batteries. Because loss of metals recycled increases when the batteries are discharged only with the sulfuric acid, discharging process using acid solution and water was newly proposed. When the batteries were discharged with water during 24 hours after discharging with $0.5kmol{\cdot}m^{-3}$ sulfuric acid during 6 hours, the batteries discharged were dismantled without explosion. Because decrease in loss of metals was accomplished by new process, the recycling process of the batteries could become economic by the 2-step discharging process.

• Resources Recycling
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• v.28 no.6
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• pp.79-86
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• 2019

Recently, the use of lithium ion battery(LIB) has increased. As a result, the price of lithium and the amount spent lithium on ion battery has increased. For this reason, research on recycling lithium in waste LIBs has been conducted1). In this study, the effect of roasting for the selective lithium leaching from the spent LIBs is studied. Chemical transformation is required for selective lithium leaching in NCM LiNi_xCo_yMn_zO₂) of the spent LIBs. The carbon in the waste EV cell powder reacts with the oxygen of the oxide at high temperature. After roasting at 550 ~ 850 ℃ in the Air/N₂ atmosphere, the chemical transformation is analysed by XRD. The heat treated powders are leached at a ratio of 1:10 in D.I water for ICP analysis. As a result of XRD analysis, Li₂CO₃ peak is observed at 700 ℃. After the heat treatment at 850 ℃, a peak of Li₂O was confirmed because Li₂CO₃ is decomposed into Li₂O and CO₂ over 723 ℃. The produced Li₂O reacted with Al at high temperature to form LiAlO₂, which does not leach in D.I water, leading to a decrease in lithium leaching ratio. As a result of lithium leaching in water after heat treatment, lithium leaching ratio was the highest after heat treatment at 700 ℃. After the solid-liquid separation, over 45 % of lithium leaching was confirmed by ICP analysis. After evaporation of the leached solution, peak of Li₂CO₃ was detected by XRD.

• Resources Recycling
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• v.31 no.5
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• pp.34-41
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• 2022

Smelting reduction of spent lithium-ion batteries results in metallic alloys, slag, and dust containing Li(I). Precipitation of Li₂CO₃ was performed using the synthetic leachate of the dust. Herein, the effects of the precipitant and addition of non-aqueous solvents on the precipitation of Li(I) were investigated. Na₂CO₃ was a more effective precipitating agent than (NH₄)₂CO₃ owing to the hydrolysis reaction of dissolved ammonium and carbonate. The addition of acetone or ethanol improved the Li(I) precipitation percentage for both the precipitants. When using (NH₄)₂CO₃, the Li(I) precipitation percentage increased at a solution pH of 12. Under the same conditions, the Li(I) precipitation percentage using Na₂CO₃ was much higher than that using (NH₄)₂CO₃.

• Resources Recycling
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• v.32 no.3
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• pp.9-17
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• 2023

Efforts are currently underway to develop a method for efficiently recovering lithium from the cathode material of waste lithium iron phosphate batteries (LFP). The successful application of lithium battery recycling can address the regional ubiquity and price volatility of lithium resources, while also mitigating the environmental impact associated with both waste battery material and lithium production processes. The isomorphic substitution leaching process was used to recover lithium from spent lithium iron phosphate batteries. Lithium was leached by the isomorphic substitution of Fe²⁺ in LFP using a relatively inexpensive ferric chloride etching solution as a leaching agent. In the study, the leaching rate of lithium was compared using the ferric chloride etching solution at various multiples of the LFP molar ratio: 0.7, 1.0, 1.3, and 1.6 times. The highest lithium leaching rate was shown at about 98% when using 1.3 times the LFP molar ratio. Subsequently, to eliminate Fe, the leachate was treated with NaOH. The Fe-free solution was then used to synthesize lithium carbonate, and the harvested powder was characterized and validated. The surface shape and crystal phase were analyzed using SEM and XRD analysis, and impurities and purity were confirmed using ICP analysis.

• Resources Recycling
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• v.30 no.6
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• pp.43-52
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• 2021

In this study, the optimal nitration process for selective lithium leaching from powder of a spent battery cell (LiNi_xCo_yMn_zO₂, LiCoO₂) was studied using Taguchi method. The nitration process is a method of selective lithium leaching that involves converting non-lithium nitric compounds into oxides via nitric acid leaching and roasting. The influence of pretreatment temperature, nitric acid concentration, amount of nitric acid, and roasting temperature were evaluated. The signal-to-noise ratio and analysis of variance of the results were determined using L₁₆(4⁴) orthogonal arrays. The findings indicated that the roasting temperature followed by the nitric acid concentration, pretreatment temperature, and amount of nitric acid used had the greatest impact on the lithium leaching ratio. Following detailed experiments, the optimal conditions were found to be 10 h of pretreatment at 700℃ with 2 ml/g of 10 M nitric acid leaching followed by 10 h of roasting at 275℃. Under these conditions, the overall recovery of lithium exceeded 80%. X-ray diffraction (XRD) analysis of the leaching residue in deionized water after roasting of lithium nitrate and other nitrate compounds was performed. This was done to determine the cause of rapid decrease in lithium leaching rate above a roasting temperature of 400℃. The results confirmed that lithium manganese oxide was formed from lithium nitrate and manganese nitrate at these temperatures, and that it did not leach in deionized water. XRD analysis was also used to confirm the recovery of pure LiNO₃ from the solution that was leached during the nitration process. This was carried out by evaporating and concentrating the leached solution through solid-liquid separation.

• Resources Recycling
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• v.17 no.1
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• pp.59-65
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• 2008

The adsorption features of nickel ion in wastewater on manganese dioxide from spent batteries were investigated for its usage as an adsorbent. The aquatic behavior of nickel ion was characterized by MINTEQ program and the considered influential variables on the adsorption of nickel ion were its initial concentration, reaction temperature, the amount of adsorbent, and pH. The adsorption ratio of nickel ion decreased with increasing its initial concentration and thermodynamic estimation has been carried out based on the adsorption characteristics of nickel ion depending on temperature. In addition, the adsorption of nickel ion was shown to be promoted according to the amount of manganese dioxide and a lot of nickel ions were adsorbed as the solution pH was raised.

• Resources Recycling
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• v.20 no.4
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• pp.65-70
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• 2011

Environmental friendly leaching process for the recovery of cobalt and lithium from the $LiCoO_2$ was investigated by organic acids as a leaching reagent. The experimental parameters, such as organic acid type, concentrations of leachant and hydrogen peroxide, reaction time and temperature as well as the pulp density were tested to obtain the most effective conditions for the leaching of cobalt and lithium. The results showed that the latic acid was the most effective leaching reagent for cobalt and lithium among the organic acids and was reached about 99.9% of leaching percentage respectively. With the increase of the concentration of citric acid, hydrogen peroxide and temperature, the leaching rate of cobalt and lithium increased. But the increase of pulp density decreased the leaching rate of cobalt and lithium.