• Resources Recycling
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• v.32 no.1
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• pp.13-20
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• 2023

The objective of this article is to summarize the commercial lithium ion battery (LIB) recycling processes in Korea and to suggest new direction for LIB recycling. A representative LIB recycler, SungEel Hitech Co. has successfully operated the LIB recycling process for over 10 years, and new recycling processes were recently proposed or developed by many recycling companies and battery manufacturers. In the new recycling processes, lithium is recovered before nickel and cobalt due to the rapid rise in lithium prices, and metal sulfate solution as final product of recycling process can be supplied to manufacturers. The main problem that the new recycling process will face is impurities, which will mainly come from end-of-life electric vehicles or new additives in LIB, although the conventional processes must be improved for mass processing.

• Resources Recycling
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• v.33 no.1
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• pp.58-68
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• 2024

Critical minerals such as nickel, cobalt and lithium, are known as materials for cathodic active materials of lithium ion batteries. The consumption of the minerals is expected to grow with increasing the demands of electric vehicles, resulting from carbon neutrality. Especially, the demand for LIB (lithium ion battery) recycling is expected to increase to meet the supply of nickel, cobalt and lithium for LIB. The recycling of EOL (end-of-life) LIB can be achieved by leaching EOL LIB using inorganic acid such as HCl, HNO₃ and H₂SO₄, which are regarded as hazardous materials. In the present study, the potential use of MSA (Methanesulfonic acid), as an alternative lixiviant replacing sulfuric acid was investigated. In addition, leaching behaviors of NCM black mass leaching with MSA was also investigated by studying various leaching factors such as chemical concentration, leaching time, pulp density (P/D) and temperatures. The leaching efficiency of nickel (Ni), cobalt (Co), lithium (Li), and manganese (Mn) from LIB was enhanced by increasing concentration of lixiviant and reductant, leaching time and temperature. The maximum leaching of the metals was above 99% at 80℃. In addition, MSA can replace sulfuric acid to recover Ni, Co, Li, Mn from NCM black mass.

• 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.5
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• pp.60-67
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• 2019

A valuable metal recovery from waste resources such as spent rechargeable secondary batteries is of critical issues because of a sharp increase in the amount of waste resources. In this context, it is necessary to research not only recycling waste lithium-ion batteries (LIBs), but also reusing valuable metals (e.g., Li, Co, Ni, Mn etc.) recovered from waste LIBs. In particular, the lithium hydroxide ($LiOH{\cdot}xH_2O$), which is of precursors that can be prepared by the recovery of Li in waste LIBs, can be reused as a catalyst, a carbon dioxide absorbent, and again as a precursor for cathode materials of LIB. However, most studies of recycling the waste LIBs have been focused on the preparation of lithium carbonate with a recovery of Li. Herein, we show the preparation of high purity lithium hydroxide powder along with the precipitation process, and the systematic study to find an optimum condition is also carried out. The lithium carbonate, which is recovered from waste LIBs, was used as starting materials for synthesis of lithium hydroxide. The optimum precipitation conditions for the preparation of LiOH were found as follows: based on stirring, reaction temperature $90^{\circ}C$, reaction time 3 hr, precursor ratio 1:1. To synthesize uniform and high purity lithium hydroxide, 2-step precipitation process was additionally performed, and consequently, high purity $LiOH{\cdot}xH_2O$ powder was obtained.

• Resources Recycling
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• v.19 no.6
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• pp.51-60
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• 2010

A study on the recovery of cobalt and lithium from Lithium Ion Battery(LIB) scraps has been carried out by a physical treatment - leaching - solvent extraction process. The cathode scraps of LIB in production were used as a material of this experiment. The best condition for recovering cobalt from the anode scraps was acquired in each process. The cathode scraps are dissolved in 2M sulfuric acid solution with hydrogen peroxide at $95^{\circ}C$, 700 rpm. The cobalt is concentrated from the leaching solution by means of a solvent extraction circuit with bis(2-ethylhexyl) phosphoric acid(D2EHPA) and PC88A in kerosene, and then cobalt and lithium are recovered as cobalt hydroxide and lithium carbonate by precipitation technology. The purity of cobalt oxide powder was over 99.98% and the average particle size after milling was about 10 lim. The over all recoveries are over 95% for cobalt and lithium. The pilot test of mechanical separation was carried out for the recovery of cobalt from the scraps. The $Co_3O_4$ powder was made by the heat treatment of $Co(OH)_2$ and the average particle size was about 10 ${\mu}m$ after grinding. The recovery was over 99% for cobalt and lithium each other and the purity of cobalt oxide was over 99.98%.

• Resources Recycling
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• v.30 no.1
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• pp.44-52
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• 2021

This study investigated the effect of the type of alkaline precipitant used on the synthesis of lithium hydroxide by examining the behavior of lithium hydroxide produced using lithium sulfate recovered from a waste lithium secondary battery as a raw material. The double-replacement reaction (DRR) process was used to remove the impurities contained in the lithium salt precursor of lithium sulfate and to improve the efficiency of the synthesis of lithium hydroxide. The experiment was conducted by control the molar ratio of the precursor ([Li]/[OH]), the reaction temperature, and the composition of the alkaline precipitant (KOH, Ca(OH)2, Ba(OH)2) used for the production of highly-crystalline lithium hydroxide. A secondary solid-liquid separation was performed following the reaction to remove the impurities generated, and the purified aqueous solution of lithium hydroxide was evaporated to remove the moisture and obtain the product as a powder. The crystallinity and synthesis behavior of the product were examined.

• Resources Recycling
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• v.32 no.1
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• pp.21-32
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• 2023

Because the application of lithium has gradually increased for the production of lithium ion batteries (LIBs), more research studies about recycling using solvent extraction (SX) should focus on Li⁺ recovery from the waste solution obtained after the removal of the valuable metals nickel, cobalt and manganese (NCM). The raffinate obtained after the removal of NCM metal contains lithium ions and other impurities such as Na ions. In this study, we optimized a selective SX system using di-(2-ethylhexyl) phosphoric acid (D2EHPA) as the extractant and tri-n-butyl phosphate (TBP) as a modifier in kerosene for the recovery of lithium from a waste solution containing lithium and a high concentration of sodium (Li⁺ = 0.5 ~ 1 wt%, Na⁺ = 3 ~6.5 wt%). The extraction of lithium was tested in different solvent compositions and the most effective extraction occurred in the solution composed of 20% D2EHPA + 20% TBP + and 60% kerosene. In this SX system with added NaOH for saponification, more than 95% lithium was selectively extracted in four extraction steps using an organic to aqueous ratio of 5:1 and an equilibrium pH of 4 ~ 4.5. Additionally, most of the Na⁺ (92% by weight) remained in the raffinate. The extracted lithium is stripped using 8 wt% HCl to yield pure lithium chloride with negligible Na content. The lithium chloride is subsequently treated with high purity ammonium bicarbonate to afford lithium carbonate powder. Finally the lithium carbonate is washed with an adequate amount of water to remove trace amounts of sodium resulting in highly pure lithium carbonate powder (purity > 99.2%).

• Resources Recycling
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• v.26 no.6
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• pp.73-83
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• 2017

Used small household appliances have a wide variety of product types and component materials, and contain high percentage of black plastics. However, they are not being recycled efficiently as conventional sensors such as near-infrared ray (NIR), etc. are not able to detect black plastic by types. In the present study, an automatic sorting system was developed based on laser-induced breakdown spectroscopy (LIBS) to promote the recycling of waste plastics. The system we developed mainly consists of sample feeder, automatic position recognition system, LIBS device, separator and control unit. By applying laser pulse on the target sample, characteristic spectral data can be obtained and analyzed by using CCD detectors. The obtained data was then treated by using a classifier, which was developed based on artificial intelligent algorithm. The separation tests on waste plastics also were carried out by using a lab-scale automatic sorting system and the test results will be discussed. The classification rate of the radial basis neural network (RBFNNs) classifier developed in this study was about > 97%. The recognition rate of the black plastic by types with the automatic sorting system was more than 94.0% and the sorting efficiency was more than 80.0%. Automatic sorting system based on LIBS technology is in its infant stage and it has a high potential for utilization in and outside Korea due to its excellent economic efficiency.

• Resources Recycling
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• v.24 no.3
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• pp.44-50
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• 2015

Recycling technologies would be required in consideration of increasing demand in lithium ion batteries (LIBs). In this study, the leaching behavior of Ni, Co and Mn is investigated with ammoniacal medium for spent cathode active materials, which are separated from a commercial LIB pack in hybrid electric vehicles. The leaching behavior of each metal is analyzed in the presence of reducing agent and pH buffering agent. The existence of reducing agent is necessary to increase the leaching efficiency of Ni and Co. The leaching of Mn is insignificant even with the existence of reducing agent in contrast to Ni and Co. The most conspicuous difference between acid and ammoniacal leaching would be the selective leaching behavior between Ni/Co and Mn. The ammoniacal leaching can reduce the cost of basic reagent that makes the pH of leachate higher for the precipitation of leached metals in the acid leaching.

• 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.