• 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.

• Journal of Korean Society of Environmental Engineers
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• v.38 no.11
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• pp.603-610
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• 2016

This work studies the synthesis of birnessite (${\delta}-MnO_2$), a catalyst of oxidative-coupling reactions, from the powder of spent alkaline manganese batteries (SABP, <8 mesh) and evaluate its reactivity for 1-naphthol (1-NP) removals. Manganese oxides using commercial reagents ($MnSO_4$, $MnCl_2$) and the acid birnessite (A-Bir) by McKenzie method were also synthesized, and their crystallinity and reactivity for 1-NP were compared with one another. 96% Mn and 98% Zn were extracted from SABP by acid leaching at the condition of solid/liquid (S/L) ratio 1:10 in $1.0M\;H_2SO_4+10.5%\;H_2O_2$ at $60^{\circ}C$. From the acid leaching solution, 69% (at pH 8) and 94.3% (pH>13) of Mn were separated by hydroxide precipitation. Optimal OH/Mn mixing ratio (mol/mol) for the manganese oxide (MO) synthesis by alkaline (NaOH) hydrothermal techniques was 6.0. Under this condition, the best 1-NP removal efficiency was observed and XRD analysis confirmed that the MOs are corresponding to birnessite. Kinetic constants (k, at pH 6) for the 1-NP removals of the birnessites obtained from Mn recovered at pH 8 (${Mn^{2+}}_{(aq)}$) and pH>13 ($Mn(OH)_{2(s)}$) are 0.112 and $0.106min^{-1}$, respectively, which are similar to that from $MnSO_4$ reagent ($0.117min^{-1}$). The results indicated that the birnessite prepared from the SABP as a raw material could be used as an oxidative-coupling catalyst for removals of trace phenolic compounds in soil and water, and propose the recycle scheme of SAB for the birnessite synthesis.

• 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.

• 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.17 no.2
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• pp.3-15
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• 2008

Different toxic wastes are disposed of in our surroundings and these will ultimately threaten the existence of living organisms. Biohydrometallurgy, which includes the processes of bioleaching and bioremediation through the activities of microorganisms such as bacterial or fungal species, is a technology that has the potential to overcome many environmental problems at a reasonable economic cost. Bioleaching were carried out for dissolution of metals from different materials using most important metal mobilizing bacteria such as Thiobacillus ferrooxidans, Thiobacillus thiooxidans and Laptospirillum ferrooxidans. According to the reaction, bioleaching is parted as direct and indirect mechanism. In direct mechanism the bacteria oxidize the sulphides minerals by accepting electron and producing sulphuric acid in leaching media for their growth and metabolism. In other hand the indirect bioleaching is demonstrated as the oxidation of sulphides mineral by the oxidant like $Fe^{3+}$ produced by the iron oxidizing bacteria. Through this process, substantial amount of metal can be recovered from low-grade ores, concentrates, industrial wastes like sludge, tailings, fly ash, slag, electronic scrap, spent batteries and spent catalysts. This may be alternative technology to solve the high deposition of waste, which moves toward a healthy environment and green world.

• 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.

• Applied Chemistry for Engineering
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• v.17 no.5
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• pp.517-520
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• 2006

The leaching behaviors of zinc and manganese oxides of spent alkaline manganeses battery in sulfuric acid solution by using $H_{2}O_{2}$ as a reducing agent were investigated according to the concentration of $H_{2}SO_{4}$, temperature, reaction time, and the amount of $H_{2}O_{2}$. The experimental results of zinc and manganeses dissolution rates obtained without a reducing agent at 100 g/L solid/liquid ratio, 3.0 M $H_{2}SO_{4}$, $60^{\circ}C$ and 200 r.p.m. were 97.7% and 43.5%, respectively. On the other hand, zinc and manganeses dissolution rates obtained by adding 30 mL reducing agent at $60^{\circ}C$ were 99.6% and 97.1%, respectively. The addition of the reducing agent increased the leaching of manganese by two-fold compared to the absence of a reducing agent. In case of adding over 30 mL $H_{2}O_{2}$, however, the leaching rates of zinc and manganeses were independent of reducing agent amounts.

• Resources Recycling
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• v.21 no.6
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• pp.58-64
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• 2012

A study on the solvent extraction for the separation and recovery of Ni and Li from the leaching solution of active cathode materials of Li-ion batteries was investigated using PC88A(2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester). The experimental parameters, such as the pH of the solution, concentration of extractant and phase ratio were observed. Experimental results showed that the extraction percent of Ni and Li and separation factor of Ni/Li were increased with increasing the equilibrium pH. More than 99.4% of Ni and 28.7% of Li were extracted in eq. pH 8.5 by 25% PC88A and the separation factor of Ni/Li was 411.6. From the analysis of McCabe-Thiele diagram, 99% of Ni was extracted by three extraction stages at phase ratio(A/O) of 1.5. Stripping of Ni and Li from the loaded organic phases can be accomplished by sulfuric acid as a stripping reagent and 50-60g/L of $H_2SO_4$ was effective for the stripping of Ni.

• 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.28 no.6
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• pp.18-25
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• 2019

In order to recover the cerium contained in the spent nickel metal hydride batteries (NiMH battery), the recovered rare earth complex precipitates from NIMH were converted into rare earth hydroxides through ion exchange reaction to react with NaOH aqueous solution at a reaction temperature of 70 ℃, for 4 hours. Rare earth hydroxides were oxidized by injecting air at 80 ℃ for 4 hours to oxidize Ce³⁺ to Ce⁴⁺. The oxidation rate of cerium was confirmed to be about 25 % through XPS, and the oxidized powder was separated from the rest of the rare earth using the difference in solubility in dilute sulfuric acid. The finally recovered powder has a crystal phase of cerium hydroxide (Ce(OH)₄). The cerium purity of the final product was about 94.6 %, and the recovery rate was 97.3 %.