• 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.31 no.1
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• pp.12-20
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• 2022

The smelting reduction of spent lithium-ion batteries results in metallic alloys containing Co, Cu, Fe, Mn, Ni, and Si. A process to separate metal ions from the sulfuric acid leaching solution of these metallic alloys has been reported. In this process, ionic liquids are employed to separate Fe(III) and Cu(II). In this study, D2EHPA and Cyanex 301 were employed to replace these ionic liquids. Fe(III) and Cu(II) from the sulfate solution were sequentially extracted using 0.5 M D2EHPA with three stages of cross-current and 0.3 M Cyanex 301. The stripping of Fe(III) and Cu(II) from the loaded phases was performed using 50% (v/v) and 60% (v/v) aqua regia solutions, respectively. The mass balance results from this process indicated that the recovery and purity percentages of the metals were greater than 99%.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.32 no.2
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• pp.61-67
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• 2022

A metal salt solution was prepared from valuable metals (Ni, Co, Mn) recovered from a scrap of waste lithium secondary batteries, and an NCM811 precursor was synthesized from the solution. The effect on precursor formation according to reaction time was confirmed by SEM, PSA, and ICP analysis. Based on the analysis results, the electrochemical properties of the synthesized NCM811 precursor and the commercial NCM811 precursor were investigated. The Galvano charge-discharge cycle, rate performance, and Cycle performance were compared, and as a result, there was no significant difference from commercial precursors.

• Resources Recycling
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• v.21 no.2
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• pp.3-8
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• 2012

In the points of the environmental conservation and the recirculating utilization of limited resources, it is very important to recover valuable metals like Au, Ag, Pd, Cu, Sn, Ni, Co, and Li used as industrial raw materials from urban ores. From now, many processes have been developed for recovering the valuable metals contained in urban ores and some of them have been operated commercially. In the paper, pyrometallurgical processes developed for reclaiming valuable metals from urban ores will be briefly introduced.

• Clean Technology
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• v.27 no.1
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• pp.33-38
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• 2021

Demand for lithium-based secondary batteries is greatly increasing with the explosive growth of related industries, such as mobile devices and electric vehicles. In Korea, there are several top-rated global lithium-ion battery manufacturers accounting for 40% of the global secondary battery business. Most discarded lithium secondary batteries are recycled as scrap to recover valuable metals, such as Nickel and Cobalt, but residual wastes are disposed of according to the residual lithium-ion concentration. Furthermore, there has not been an attempt on the possibility of water discharge system contamination due to the concentration of lithium ions, and the effluent water quality standards of public sewage treatment facilities are becoming stricter year after year. In this study, the as-received waste water generated from the cathode electrode coating process in the manufacturing of high-nickel-based NCM cathode material used for high-performance and long-term purposes was analyzed. We suggested a facile recycling process chart for waste water treatment. We revealed a correlation between lithium-ion concentration and pH effect according to the proposed waste water of each recycling process through analyzing standard water quality tests and daphnia ecological toxicity. We proposed a realistic waste water treatment plan for lithium electrode manufacturing plants via comparison with other industries' ecotoxicology.

• 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%).

• Analytical Science and Technology
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• v.9 no.4
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• pp.336-344
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• 1996

The extraction of trace cobalt, copper, nickel, cadmium, lead and zinc in urine samples of organic and alkali metal matrix into chloroform by the complex with a dithizone was studied for graphite furnace AAS determination. Various experimental conditions such as the pretreatment of urine, the pH of sample solution, and dithizone concentration in a solvent were optimized for the effective extraction, and some essential conditions were also studied for the back-extraction and digestion as well. All organic materials in 100 mL urine were destructed by the digestion with conc. $HNO_3$ 30 mL and 30% $H_2O_2$ 50 mL. Here, $H_2O_2$ was added dropwise with each 5.0 mL, serially. Analytes were extracted into 15.0 mL chloroform of 0.1% dithizone from the digested urine at pH 8.0 by shaking for 90 minutes. The pH was adjusted with a commercial buffer solution. Among analytes, cadmium, lead and zinc were back-extracted to 10.00 mL of 0.2 M $HNO_3$ from the solvent for the determination, and after the organic solvent was evaporated, others were dissolved with $HNO_3-H_2O_2$ and diluted to 10.00 mL with a deionized water. Synthetic digested urines were used to obtain optimum conditions and to plot calibration-eurves. Average recoveries of 77 to 109% for each element were obtained in sample solutions in which given amounts of analytes were added, and detection limits were Cd 0.09, Pb 0.59, Zn 0.18, Co 0.24, Cu 1.3 and Ni 1.7 ng/mL, respectively. It was concluded that this method could be applied for the determination of heavy elements in urine samples without any interferences of organic materials and major alkaline elements.

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.6 no.1
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• pp.13-26
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• 2001

Six ferromanganese crusts from the Lomilik and Litatfooki seamounts in the Marshall Islands were analyzed for texture, geochemistry and stratigraphy to delineate the paleoceanographic conditions. The crusts can be divided into three layers; 1) outermost massive layer (Layer 1), 2) middle porous Fe-oxides rich layer infllled with biointemal clasts (Layer 2), and 3) innermost massive layer cemented and/or replaced by carbonate fluoapatite (CFA) (Layer 3). The Layer 1 contains higher Mn, Co, Ni, and Mg than other two layers, and the Layer 2 was relatively more enriched in Fe, Al, Ti, Ba, Cu, and Zn. However, the Layer 3 shows higher Ca and P and lower Mn, Fe, Co, and Ni contents than overlying two layers. Based on the Co-chronometry, the crusts are postulated to have begun to grow from 56-31 Ma (early Eocene to Oligocene). The boundaries between layers 1 and 2, and layers 2 and 3 are dated to be 7-3 Ma and 26-14 Ma, respectively. High contents of Ca and P in Layer 3 clearly indicate that the layer had been phosphatized prior to the formation of Layer 2. Considering the well-preserved mjcrostructures in Layer 3, it is unlike that the crusts themselves were recrystallized in suboxic condition. Also, the lower Co concentrations in Layer 3 may imply that the Co supply was not constant during the formation of Layer 3. Layer 2, characterized by the porous texture, grew over Layer 3 during 26-9 Ma. Internal biogenic sediments including foraminifera within the original cavities and the enrichment of organophillic elements such as Ba, Cu, and Zn, suggest that Layer 2 have below high production regions. Also, high content of allumino silicate components may indicate increased terrigeneous input during the formation of Layer 2. The Layer 2. The Layer 1 has been subjected to little diagenetic influence since the Pliocene.

• 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.

• Journal of the Korean Chemical Society
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• v.38 no.9
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• pp.667-675
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• 1994

The precipitate flotation using $La(OH)_3$ as a coprecipitant was studied for the simultaneous determination of trace three elements in a sea water. Several experimental conditions such as pH, coprecipitant and surfactant were investigated with an artificial sea water. To remove the influence of Cr(VI) the Cr(VI) was reduced to Cr(III) using $NaBH_4$ prior to the flotation. Trace amounts of Cu(II), Co(II) and total Cr in 1.0 l sea water was coprecipitated together with the precipitation of $La(OH)_3$ in the solution of pH 9.8 adjusted with 3.OM NaOH solution. The precipitate was floated by using a mixed surfactant (1 to 8 of each 0.5% ethanolic sodium oleate and sodium dodecylsulfate solution) by bubbling a nitrogen gas. The floats was separated and filtrated from the mother liquor by suction. The precipitate was dissolved in 7.0 M $HNO_3$ solution and then marked to 25.0 ml with a deionized water. These elements were determined by graphite fumace atomic absorption spectrophotometry. This method was applied to determine the elements in the sea water of the Eastern and Western coasts. And the recoveries were over 90.0% in the samples into which given amounts of the analyte elements were spiked.