• Applied Chemistry for Engineering
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• v.17 no.2
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• pp.163-169
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• 2006

A Life Cycle Assessment (LCA) study was carried out to identify and improve the environmental aspects associated with the present incineration system of spent Li-ion batteries (LIBs) in Korea. The environmental impact associated with the landfill of the incineration ash was also assessed in this study, while so far it was excluded in most studies. It was found out that the $CO_{2}$ emission from the electricity generation as well as the incineration process and heavy metals emissions to air and water accounted for about 90% of total environmental impacts. In particular, the effect of the emission of heavy metals were dominant. In oder to improve the current incineration system environmentally, it is needed to incinerate the wastes like spent LIBs which contained relatively high portion of heavy metals separately from other combustible wastes. On the other hand, the effect of the landfill of ash after incineration was insignificant since the ash from the incineration process was chemically stable.

• Resources Recycling
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• v.9 no.4
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• pp.37-43
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• 2000

Leaching of $LiCoO_2$ as a cathodic active materials for recovering Li and Co from spent lithium ion battery was investigated in terms of reaction variables. At the optimum condition determined in the previous work, Li and Co in a $H_2SO_4$ and $HNO_3$ solution were dissolved 70~80% and 40%, respectively. Li and Co were leached over 95% with the addition of a reductant such as $Na_2S_2O_3$ or $H_2O_2$. This behavior is probably due to the reduction of $Co^{3+}$ to $Co^{2+}$. Leaching of $LiCoCo_2$ powder obtained by calcination of an electrode materials from spent batteries was also carried out. Leaching efficiency of Li and Co were over 99% at the optimum condition with $H_2O_2$ addition of 1.7 vol.%. It seems to be due to the activation of $LiCoO_2$ by repeated charging and discharging or an imperfect crystal structure by deintercalation of Li.

• Resources Recycling
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• v.29 no.5
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• pp.73-80
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• 2020

In order to develop a process for the recovery of valuable metals from spent LiBs, solvent extraction experiments were performed to separate Cu(II) and/or Co(II) from synthetic hydrochloric acid solutions containing Li(I), Mn(II), and Ni(II). Commercial amines (Alamine 336 and Aliquat 336) were employed and the extraction behavior of the metals was investigated as a function of the concentration of HCl and extractants. The results indicate that HCl concentration affected remarkably the extraction efficiency of the metals. Only Cu(II) was selectively at 1 M HCl concentration, while both Co(II) and Cu(II) was extracted by the amines when HCl concentration was higher than 5 M, leaving the other metal ions in the raffinate. Therefore, it was possible to selectively extract either Cu(II) or Co(II)/Cu(II) by adjusting the HCl concentration.

• Resources Recycling
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• v.11 no.3
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• pp.10-16
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• 2002

In the leaching of $LiCoO_2$with a strong acid such as sulfuric and nitric acid, an additional step was needed to recover cobalt and lithium separately from spent lithium ion batteries (LIBs). The leaching of $LiCoO_2$in an oxalic acid solution was investigated to recover cobalt selectively using a low solubility of cobalt oxalate at low pH. Leaching efficiency of 95% of lithium and less than 1% of cobalt were obtained when pure $LiCoO_2$powder was leached in 3M oxalic acid at $80^{\circ}C$ and 50 g/L pulpdensity. Under the above leaching conditions, complete dissolution of lithium was accomplished with mere 0.25% of cobalt in the solution when the cathodic active material collected from spent LIBs was employed. The lithium in the leaching solution can be recovered as a form of carbonate or hydroxide depending on the addition of $Na_2$$CO_3$or LiOH.

• 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.

• Journal of the Korean Electrochemical Society
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• v.26 no.1
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• pp.11-18
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• 2023

As the use of lithium-ion secondary batteries is rapidly increasing due to the rapid growth of the electric vehicle market, the disposal and recycling of spent batteries after use has been raised as a serious problem. Since stored energy must be removed in order to recycle the spent batteries, an effective discharging process is required. In this study, graphite and NCM622 were used as active materials to manufacture coin-type half cells and full cells, and the electrochemical behavior occurring during overdischarge was analyzed. When the positive and negative electrodes are overdischarged respectively using a half-cell, a conversion reaction in which transition metal oxide is reduced to metal occurs first in the positive electrode, and a side reaction in which Cu, the current collector, is corroded following decomposition of the SEI film occurs in the negative electrode. In addition, a side reaction during overdischarge is difficult to occur because a large polarization at the initial stage is required. When the full cell is overdischarged, the cell reaches 0 V and the overdischarge ends with almost no side reaction due to this large polarization. However, if the full cell whose capacity is degraded due to the cycle is overdischarged, corrosion of the Cu current collector occurs in the negative electrode. Therefore, cycled cell requires an appropriate treatment process because its electrochemical behavior during overdischarge is different from that of a fresh cell.

• Journal of Powder Materials
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• v.25 no.4
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• pp.296-301
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• 2018

In this study, an experiment is performed to recover the Li in $Li_2CO_3$ phase from the cathode active material NMC ($LiNiCoMnO_2$) in waste lithium ion batteries. Firstly, carbonation is performed to convert the LiNiO, LiCoO, and $Li_2MnO_3$ phases within the powder to $Li_2CO_3$ and NiO, CoO, and MnO. The carbonation for phase separation proceeds at a temperature range of $600^{\circ}C{\sim}800^{\circ}C$ in a $CO_2$ gas (300 cc/min) atmosphere. At $600{\sim}700^{\circ}C$, $Li_2CO_3$ and NiO, CoO, and MnO are not completely separated, while Li and other metallic compounds remain. At $800^{\circ}C$, we can confirm that LiNiO, LiCoO, and $Li_2MnO_3$ phases are separated into $Li_2CO_3$ and NiO, CoO, and MnO phases. After completing the phase separation, by using the solubility difference of $Li_2CO_3$ and NiO, CoO, and MnO, we set the ratio of solution (distilled water) to powder after carbonation as 30:1. Subsequently, water leaching is carried out. Then, the $Li_2CO_3$ within the solution melts and concentrates, while NiO, MnO, and CoO phases remain after filtering. Thus, $Li_2CO_3$ can be recovered.

• Resources Recycling
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• v.23 no.4
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• pp.21-29
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• 2014

Nickel, cobalt and manganese-based(NCM, $Li(Ni_xCo_yMn_z)O_2$) cathode active materials of spent lithium-ion batteries contained valuable metals such as cobalt(15 ~ 20%), nickel(25 ~ 30%), manganese(10 ~ 15%) and lithium(5 ~ 10%). It was investigated the eco-friendly leaching process for the recovery of valuable metal from spent lithium-ion battery NCM cathode active materials by DL-malic acid($C_4H_5O_6$) as an organic leachant in this research. The experiments were carried out to optimize the process parameters for the recovery of cobalt, nickel and lithium by varying the concentration of lixivant, reductant concentration, solid/liquid ratio and temperature. The leaching solution was analyzed using ICP-OES(Inductively Coupled Plasma Optic Emission Spectrometer). Cathode active materials of 5 wt. % were introduced into the leaching solution which was 2 M DL-malic acid in addition of 5 vol. % $H_2O_2$ at $80^{\circ}C$ and it resulted in the recovery of 99.10% cobalt, 99.80% nickel and 99.75% lithium in 120 min. $H_2O_2$ in DL-malic acid solution acts as an effective reducing agents, which enhance the leaching of metals.

• Korean Chemical Engineering Research
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• v.53 no.2
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• pp.137-144
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• 2015

The present paper deals with the extractive separation and selective recovery of nickel and lithium from the sulfate leachate of cathode scrap generated during the manufacture of LIBs. The conditions for extraction, scrubbing and stripping of nickel from lithium were optimized with an aqueous feed containing $2.54kg{\cdot}m^{-3}$ Ni and $4.82kg{\cdot}m^{-3}$ Li using PC-88A. Over 99.6% nickel was extracted with $0.15kmol{\cdot}m^{-3}$ PC-88A in two counter-current stages at O/A=1 and pH=6.5. Effective scrubbing Li from loaded organic was systematically studied with a dilute $Na_2CO_3$ solution ($0.10kmol{\cdot}m^{-3}$). The McCabe-Thiele diagram suggests two counter-current scrubbing stages are required at O/A=2/3 to yield lithium-scrubbing efficiency of 99.6%. The proposed process showed advantages of simplicity, and high purity (99.9%) nickel sulfate recovery along with lithium to ensure the complete recycling of the waste from LIBs manufacturing process.

• 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.