• Resources Recycling
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• v.16 no.6
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• pp.10-19
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• 2007

The mechanical process followed by hydrometallurgical treatment has been developed in order to recover cobalt and lithium from spent lithium ion battery. In the previous study, a citrate precursor combustion process to prepare cathodic active materials from the leaching solution was elucidated. Resynthesis of electrode materials should be more valuable in spent battery recycling. Conventional slurry mixing of $LiCoO_2$ and carbon cannot make uniform distribution, and therefore the cathode cannot reach the theoretical charge-discharge capacity and is easily degraded during the charge-discharge cycling. In this study, ultra-fine $LiCoO_2$ powders has been prepared by modification of the combustion process and fabricated the enhanced cathode by modification of mixing method of $LiCoO_2$ and carbon added.

• Proceedings of the IEEK Conference
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• 2001.10a
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• pp.240-244
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• 2001

Recycling process involving mechanical, thermal, hydrometallurgical, and sol-gel step has been applied to recover cobalt and lithium from spent lithium ion batteries and to synthesize LiCoO$_2$from leach liquor as cathodic active materials. Electrode materials containing lithium and cobalt could be concentrated with 2-step thermal and mechanical treatment. Leaching behaviors of the lithium and cobalt in nitric acid media was investigated in terms of reaction variables. Hydrogen peroxide in 1 M HNO$_3$solution turned out to be an effective reducing agent by enhancing the leaching efficiency. O f many possible processes to produce LiCoO$_2$, the amorphous citrate precursor process (ACP) has been applied to synthesize powders with a large specific surface area and an exact stoichiometry. After leaching used LiCoO$_2$with nitric acid, the molar ratio of Li/Co in the leach liquor was adjusted at 1.1 by adding a fresh LiNO$_3$solution. Then, 1 M citric acid solution at a 100% stoichiometry was also added to prepare a gelatinous precursor. When the precursor was calcined at 95$0^{\circ}C$ for 24 hr, purely crystalline LiCoO$_2$was successfully obtained. The particle size and specific surface area of the resulting crystalline powders were 20 пm and 30 $\textrm{cm}^2$/g, respectively The LiCoO$_2$powder was proved to have good characteristics as cathode active materials in charge/discharge capacity and cyclic performance.

• 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.14 no.6 s.68
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• pp.37-43
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• 2005

[ $LiCoO_{2}$ ] nanoparticles were synthesized from leach liquor of lithium ion battery waste using flame spray pyrolysis. Electrode Materials containing lithium and cobalt could be concentrated with thermal and mechanical treatment. After dissolution of used cathode materials of the lithium battery with nitric acid, the molar ratio of Li/Co in the leach liquor was adjusted at 1.0 by adding a fresh $LiNO_{3}$ solution. The nanoparticles synthesized by the flame spray pyrolysis showed clear crystallinity and were nearly spherical, and their average primary particle diameters ranged from 11 to 35 nm. The average particle diameter increased with an increase in the molar concentration of the precursor. Raising the maximum flame temperature by controlling the gas flow rates also led to an increase in the average diameter of the particles. The $LiCoO_{2}$ powder was proved to have good characteristics as cathode active materials in charge/discharge capacity and cyclic performance.

• 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.10 no.6
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• pp.9-14
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• 2001

A sulfuric acid leaching of $LiCoO_2$as cathodic active materials of lithium ion secondary batteries was investigated in terms of reaction variables. In the absence of a reducing agent, the extraction of cobalt was less than 40% in 2 M sulfuric acid at $75^{\circ}C$ instead of that of lithium could be almost 100% in the same conditions. To improve the Co extraction, hydrogen peroxide was used as a reducing agent in the range 2~20 vol%. When over 10vo1% hydrogen peroxide was added, the extractions of both metals were improved to about 95%. It seems to be due to the reduction of Co(III) to Co(II) that can be readily dissolved. The extractions of Co and Li were increased with increasing $H_2$$SO_4$concentration and temperature, and amount of hydrogen peroxide and with decreasing of pulp density. The optimum leaching conditions were determined at $2 M H_2$$SO_4$concentration, $75^{\circ}C$ operating temperature, 100 g/L. initial pulp density, 20 vol% $H_2$$O_2$addition and 30 min.

• Resources Recycling
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• v.31 no.4
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• pp.26-33
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• 2022

Owing to the demand for lithium-ion batteries, the recovery of valuable metals from waste lithium-ion batteries is required in future. A pyrometallurgical treatment is appropriate for recycling a large number of waste lithium-ion batteries, but Li loss to slag and dust present a significant challenge. This research investigated carbonation roasting and water leaching behaviors in Li-ion batteries by graphite addition to recover Li from the NCM-based cathode materials of waste Li-ion batteries. When 10 wt% of graphite was added, CO and CO₂ gases were emitted with a rapid weight reduction at apporoximately 850 K, when heated in Ar and CO₂ atmosphere. After the rapid weight reduction, NCM was decomposed and reduced to metal oxides and pure metals. In the carbonation roasting of black powder (NCM+graphite), O₂ is generated via the decomposition of NCM, and an oxides, such as Li₂O and NiO were were also generated. Subsequently, Li₂O reacts with CO₂ to generate Li₂CO₃, and a part of NiO was reduced by graphite to produce metal Ni. In addition, up to 94.5 % Li₂CO₃ with ~99.95 % purity was recovered via water leaching after carbonation roasting.

• 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.19 no.1
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• pp.27-32
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• 2010

To improve electronic conductivity of cathodic active materials of lithium ion battery, carbonaceous materials is usually added. New mixing method of abrasive milling has been investigated in mixing of graphite and $LiCoO_2$ powders. It would be expected that uniform mixing of graphite reduces capacity fading of cathode of lithium battery. Abrasion milled $LiCoO_2$ composite showed the best electrochemical performance as a cathode material with 1 wt% of graphite content, 300 rpm of milling speed, and 10 min of milling time. The improvement of the electrochemical performances such as cycleability and charge/discharge capacity retention would be mainly attributed to increase of the electronic conductivity and/or prevention of the active materials by uniform dispersion and coating of graphite on $LiCoO_2$.

• Journal of Powder Materials
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• v.21 no.4
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• pp.286-293
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• 2014

The electrochemical properties of cells assembled with the $LiNiO_2$ (LNO) recycled from cathode materials of waste lithium secondary batteries ($Li[Ni,Co,Mn]O_2$), were evaluated in this study. The leaching, neutralization and solvent extraction process were applied to produce high-purity $NiSO_4$ solution from waste lithium secondary batteries. High-purity NiO powder was then fabricated by the heat-treatment and mixing of the $NiSO_4$ solution and $H_2C_2O_4$. Finally, $LiNiO_2$ as a cathode material for lithium ion secondary batteries was synthesized by heat treatment and mixing of the NiO and $Li_2CO_3$ powders. We assembled the cells using the $LiNiO_2$ powders and evaluated the electrochemical properties. Subsequently, we evaluated the recycling possibility of the cathode materials for waste lithium secondary battery using the processes applied in this work.