• Clean Technology
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• v.27 no.2
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• pp.139-145
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• 2021

The purpose of this study is to recover valuable metals from spent batteries using a dry process. We focused on the effect of the smelting temperature on the composition of recovered solid and liquid products and collected gaseous products. After removal of the cover, the spent battery was left in NaCl solution and discharged. Then, the spent battery was made into a powder form through a crushing process. The smelting of the spent battery was performed in a tubular electric furnace in an oxygen atmosphere. For spent lithium-ion batteries, the recovery yield of the solid product was 80.1 wt% at a reaction temperature of 850 ℃, and the final product had 27.2 wt% of cobalt as well as other metals such as lithium, copper, and aluminum. Spent nickel-hydrogen batteries had a recovery yield of 99.2 wt% at a reaction temperature of 850 ℃ with about 37.6 wt% of nickel and other metals including iron. For spent nickel-cadmium batteries, the yield decreased to 65.4 wt% because of evaporation with increasing temperature. At 1050 ℃, the recovered metals were nickel (41 wt%) and cadmium (12.9 wt%). Benzene and toluene, which were not detected with the other secondary waste batteries, were detected in the gaseous product. The results of this study can be used as basic data for future research on the dry recycling process of spent secondary batteries.

• 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%).

• Korean Journal of Crystallography
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• v.15 no.2
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• pp.59-68
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• 2004

Three crystal structures of dehydrated partially $Co^{2+}-exchanged$ zeolite A treated with 0.6 Torr of K at $300^{\circ}C$ (for 12 hrs, 6 hrs, and 2 hrs) vapor have been determined by single-crystal X-ray diffraction techniques in the cubic space group Pm3m at 21(1)$^{\circ}C(a=12.181(1)\;{\AA},\;a=12.184(1)\;{\AA},\;and\;a=12.215(1)\;{\AA})\;respectively)$. Their structures were refined to the final error indices, R(weight) of 0.090 with 10 reflections, 0.091 with 82 reflections, and 0.090 with 80 reflections, respectively, for which $1>\sigma(I)$. In each structure, all four $Co^{2+}$ and four $Na^+$ ions to be reduced by K atoms. The cobalt and sodium atoms produced are no longer found in the zeolite. K species are found at five different crystallographic sites: three $K^+$ ions lie at the planes of 8-rings, filling that position, ca. 11.5 K^+$ ions lie on threefold axes, ca. 4.0 in the large cavity and ca. 4.0 in the sodalite cavity, and ca. 0.5 $K^+$ ion is found near a 4-ring. ca. three $K^0$ atoms are found deep into the large cavity on threefold axes. In these structures, crystallographic results show that cationic tetrahedral $K_4$ (and/or triangular $K_3$) clusters have formed in the sodalites of zeolite A. The $K_4$ and/or $K_3$ clusters coordinate trigonally to three oxygens of a six-oxygen ring. The partially reduced ions of these clusters interact primarily with oxygen atoms of the zeolite structure rather than with each other. ca. 14.5K species are found per unit cell, more than the twelve $K^+$ ions needed to balance the anionic charge of zeolite framework, indicating that sorption of $K^0$ has occurred. The three $K^0$ atoms in the large cavity are closely associated with three out of four $K^+$ ions in the large cavity to form $K_7^{4+}$ clusters. The $K_7^{4+}$ cluster not interacts primarily with framework oxygens.

• 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.

• Korean Journal of Crystallography
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• v.6 no.2
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• pp.125-133
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• 1995

The crystal structure of dehydrated, partially Co(II)-exchanged zeolite X, stoichiometry Co2+Na+-X (Co41+Na10Si100Al92O384) per unit cell, has been determined from three-dimensional X-ray diffraction data gathered by counter methods. The structure was solved and refined in the cubic space group Fd3:α=24.544(1)Å at 21(1)℃. The crystal was prepared by ion exchange in a flowing stream using a solution 0.025 M each in Co(NO3)2 and Co(O2CCH3)2. The crystal was then dehydrated at 380℃ and 2×10-6 Torr for two days. The structure was refined to the final error indices, R1=0.059 and R2=0.046 with 211 reflections for which I > 3σ(I). Co2+ ions and Na+ ions are located at the four different crystallographic sites. Co2+ ions are located at two different sites of high occupancies. Sixteen Co2+ ions are located at the center of the double six-ring (site I; Co-O = 2.21(1)Å, O-Co-O = 90.0(4)°) and twenty-five Co2+ ions are located at site II in the supercage. Twenty-five Co2+ ions are recessed 0.09Å into the supercage from its three oxygen plane (Co-O = 2.05(1)Å, O-Co-O = 119.8(7)°). Na+ ions are located at two different sites of occupandies. Seven Na+ ions are located at site II in the supercage (Na-O = 2.29(1)Å, O-Na-O = 102(1)°). Three Na+ ions are statistically distribyted over site III, a 48-fold equipoint in the supercages on twofold axes (Na-O = 2.59(10)Å, O-Na-O = 69.0(3)°). Seven Na+ ions are recessed 1.02Å into the supercage from the three oxygen plane. It appears that Co2+ ions prefer sites I and II in order, and that Na+ ions occupy the remaining sites, II and III.

• Journal of the Korean Electrochemical Society
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• v.24 no.4
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• pp.120-132
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• 2021

Although the development of high-Nickel is being actively carried out to solve the capacity limitation and the high price of raw cobalt due to the limitation of high voltage use of the existing LiCoO₂, the deterioration of the battery characteristics due to the decrease in structural stability and increase of the Ni content. It is an important cause of delaying commercialization. Therefore, in order to increase the high stability of the Ni-rich ternary cathod material LiNi_0.6Co_0.2Mn_0.2O₂, precursor Ni_0.6Co_0.2Mn_0.2-x(OH)₂/xTiO₂ was prepared using a nanosized TiO₂ suspension type source for uniform Ti substitution in the precursor. It was mixed with Li₂CO₃, and after heating, the cathode active material LiNi_0.6Co_0.2Mn_0.2-xTi_xO₂ was synthesized, and the physical properties according to the Ti content were compared. Through FE-SEM and EDS mapping analysis, it was confirmed that a positive electrode active material having a uniform particle size was prepared through Ti-substituted spherical precursor and Particle Size Analyzer and internal density and strength were increased, XRD structure analysis and ICP-MS quantitative analysis confirmed that the capacity was effectively maintained even when the Ti-substituted positive electrode active material was manufactured and charging and discharging were continued at high temperature and high voltage.