• Environmental Engineering Research
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• v.25 no.1
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• pp.88-95
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• 2020

An investigation of rare metals recovery from LiNi_xCo_yMn_zO₂ cathode material of the end-of-life lithium-ion batteries is presented. To determine the influence of reductant on the leach process, the cathode material (containing Li 7.6%, Co 20.4%, Mn 19.4%, and Ni 19.3%) was leached in H₂SO₄ solutions either with or without H₂O₂. The optimal process parameters with respect to acid concentration, addition dosage of H₂O₂, temperature, and the leaching time were found to be 2.0 M H₂SO₄, 4 vol.% H₂O₂, 70℃, and 150 min, respectively. The yield of metal values in the leach liquor was > 99%. The leach liquor was subsequently treated by precipitation techniques to recover nickel as Ni(C₄H₇N₂O₂)₂ and lithium as Li₂CO₃ with stoichiometric ratios of 2:1 and 1.2:1 of dimethylglyoxime:Ni and Na₂CO₃:Li, respectively. Cobalt was recovered by solvent extraction following a 3-stage process using Na-Cyanex 272 at pH_eq ~5.0 with an organic-to-aqueous phase ratio (O/A) of 2/3. The loaded organic phase was stripped with 2.0 M H₂SO₄ at an O/A ratio of 8/1 to yield a solution of 114 g/L CoSO₄; finally recovered CoSO₄.xH₂O by crystallization. The process economics were analyzed and found to be viable with a margin of $476 per ton of the cathode material.

• Resources Recycling
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• v.30 no.6
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• pp.28-35
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• 2021

An experiment was conducted to separate or recover Co and Ni using Cyanex 301 from process by-products and waste resources containing Co and Ni. To separate and recover Co and Ni from simulated leaching solutions, 10 v/v% Cyanex 301 was used as an extractant in this study; Li was not extracted. At equilibrium pH 1.5 and a phase ratio (A/O) of 1.0, 0.44% of Mg and 11.57% of Mn were extracted, and more than 99% of Co and Ni were extracted. McCabe-Thiele diagram analysis confirmed that more than 99.9% of Co and Ni could be extracted simultaneously through two-stage extraction with an extraction phase ratio (A/O) of 2. It was possible to extract Mg and Mn simultaneously through the scrubbing process. In the scrubbing process, more than 99% of Mg and 87% of Mn were scrubbed using 0.05 M of H₂SO₄, and 99.9% of Mg and more than 80% of Mn were scrubbed using 0.05 M of HCl. In the stripping process, 93% of Co and 5% of Ni were stripped selectively by 3.0 M of H₂SO₄. However, when 8.0 M of HCl was used as a stripping solution, more than 99.9% of Co and more than 90% of Ni were stripped simultaneously.

• Journal of the Korean Electrochemical Society
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• v.17 no.2
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• pp.111-118
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• 2014

The electrochemical properties using the cells assembled with the synthesized $LiCoO_2$(LCO) were evaluated in this study. The LCO was synthesized from high-purity cobalt sulfate($CoSO_4$) which is recovered from the cathode scrap in the wastes lithium ion secondary battery(LIB). The leaching process for dissolving the metallic elements from the LCO scrap was controlled by the quantities of the sulfuric acid and hydrogen peroxide. The metal precipitation to remove the impurities was controlled by the pH value using the caustic soda. And also, D2EHPA and $CYANEX^{(R)}272$ were used in the solvent extraction process in order to remove the impurities again. The high-purity $CoSO_4$ solution was recovered by the processes mentioned above. We made the 6 wt.% $CoSO_4$ solution mixed with distilled water. And the 6 wt.% $CoSO_4$ solution was mixed with oxalic acid by the stirring method and dried in oven. $LiCoO_2$ as a cathode material for LIB was formed by the calcination after the drying and synthesis with the $Li_2CO_3$ powder. We assembled the cells using the $LiCoO_2$ powders and evaluated the electrochemical properties. And then, we confirmed possibility of the recyclability about the cathode materials for LIBs.

• Korean Chemical Engineering Research
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• v.43 no.2
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• pp.206-214
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• 2005

Heterogeneously-catalyzed oxidation of aqueous phase trichloroethylene (TCE) over supported metal oxides has been conducted to establish an approach to eliminate ppm levels of organic compounds in water. A continuous flow reactor system was designed to effect predominant reaction parameters in determining catalytic activity of the catalysts for wet TCE decomposition as a model reaction. 5 wt.% $CoO_x/TiO_2$ catalyst exhibited a transient period in activity vs. on-stream time behavior, suggesting that the surface structure of the $CoO_x$ might be altered with on-stream hours; regardless, it is probable to be the most promising catalyst. Not only could the bare support be inactive for the wet decomposition reaction at $36^{\circ}C$, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. Very low TCE conversion appeared for $TiO_2$-supported $NiO_x$ and $CrO_x$ catalysts. Wet oxidation performance of supported Cu and Fe catalysts, obtained through an incipient wetness and ion exchange technique, was dependent primarily on the kinds of the metal oxides, in addition to the acidic solid supports and the preparation routes. 5 wt.% $FeO_x/TiO_2$ catalyst gave no activity in the oxidation reaction at $36^{\circ}C$, while 1.2 wt.% Fe-MFI was active for the wet decomposition depending on time on-stream. The noticeable difference in activity of the both catalysts suggests that the Fe oxidation states involved to catalytic redox cycle during the course of reaction play a significant role in catalyzing the wet decomposition as well as in maintaining the time on-stream activity. Based on the results of different $CoO_x$ loadings and reaction temperatures for the decomposition reaction at $36^{\circ}C$ with $CoO_x/TiO_2$, the catalyst possessed an optimal $CoO_x$ amount at which higher reaction temperatures facilitated the catalytic TCE conversion. Small amounts of the active ingredient could be dissolved by acidic leaching but such a process gave no appreciable activity loss of the $CoO_x$ catalyst.