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Temperature-Dependent Mn Substitution Effect on LiNiO2

  • Seungjae Jeon;Sk. Khaja Hussain;Jin Ho Bang
    • Journal of Electrochemical Science and Technology
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    • v.15 no.1
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    • pp.161-167
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    • 2024
  • Despite the important role of manganese (Mn) in cobalt-free, Ni-rich cathode materials, existing reports on the effects of Mn as a substitute for cobalt are not consistent. In this work, we analyzed the performance of cathodes comprised of Li(Ni1-xMnx)O2 (LNMO). Both beneficial and detrimental results occurred as a result of the Mn substitution. We found that a complex interplay of effects (Li/Ni mixing driven by magnetic frustration, grain growth suppression, and retarded lithium insertion/extraction kinetics) influenced the performance and was intimately related to calcination temperature. This indicates the importance of establishing an optimal reaction temperature for the development of high-performance LNMO.

Behavior of Cobalt Extraction from Cobalt Sulphate solution using Supercritical 2 (황산코발트용액(溶液)으로부터 초임계(超臨界CO2에 의한 코발트 추출거동(抽出擧動))

  • Shin, Shun-Myung;Joo, Sung-Ho;Sohn, Jeong-Soo;Kang, Jin-Gu
    • Resources Recycling
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    • v.20 no.6
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    • pp.78-82
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    • 2011
  • Supercritical $CO_2$($scCO_2$) extraction has a great possibility to be a new process to recover metal and to replace the existing leaching/solvent extraction processes. The cobalt extraction was carried out using $scCO_2$ from cobalt sulphate solution. The bis (2,4,4-trimethylpentyl) phosphinic acid and diethylamine ligands were used to extract cobalt ion in $scCO_2$. The recommended method consists of $scCO_2$/extractants complexation process and metal extraction process at 60, 200bar. Experimental results showed that the extraction efficiency of Co was increased by 16-99% with increasing the ligand amount.

Chemical Leaching of Cobalt and Lithium from the Cathode Active Materials of Spent Lithium-ion Batteries by Organic Acid (폐(廢)리튬이온전지(電池) 양극활물질(陽極活物質)에서 유기산(有機廳)을 이용(利用)한 코발트 및 리튬의 화학적(化學的) 침출(浸出))

  • Ahn, Jae-Woo;Ahn, Hyo-Jin
    • Resources Recycling
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    • v.20 no.4
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    • pp.65-70
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    • 2011
  • Environmental friendly leaching process for the recovery of cobalt and lithium from the $LiCoO_2$ was investigated by organic acids as a leaching reagent. The experimental parameters, such as organic acid type, concentrations of leachant and hydrogen peroxide, reaction time and temperature as well as the pulp density were tested to obtain the most effective conditions for the leaching of cobalt and lithium. The results showed that the latic acid was the most effective leaching reagent for cobalt and lithium among the organic acids and was reached about 99.9% of leaching percentage respectively. With the increase of the concentration of citric acid, hydrogen peroxide and temperature, the leaching rate of cobalt and lithium increased. But the increase of pulp density decreased the leaching rate of cobalt and lithium.

A Study on the Cobalt and Lithium Recovery from the Production Scraps of Lithium Secondary Battery by High Efficient and Eco-friendly Method (이차전지(二次電池) 제조공정(製造工程)스크랩으로부터 고효율(高效率) 親環境(친환경) 코발트(Co)와 리튬(Li)의 회수(回收)에 관(關)한 연구(硏究))

  • Lee, Jeong-Joo;Chung, Jin-Do
    • 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%.

Quantitative Analysis of SO2 and NO2 Adsorption and Desorption on Quartz Crystal Microbalance Coated with Cobalt Gallate Metal-Organic Framework

  • Junhyuck Ahn;Taewook Kim;Sunghwan Park;Young-Sei Lee;Changyong Yim
    • Journal of Sensor Science and Technology
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    • v.32 no.3
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    • pp.147-153
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    • 2023
  • Metal-organic frameworks (MOFs) of cobalt gallate were synthesized and deposited on gold electrodes using self-assembly monolayers (SAMs) and hydrothermal processing. These MOF films exhibit strong adsorption capabilities for gaseous particulates, and the use of SAMs allows the synthesis and deposition processes to be completed in a single step. When cobalt gallate is mixed with SAMs, a coordination bond is formed between the cobalt ion and the carboxylate or hydroxyl groups of the SAMs, particularly under hydrothermal conditions. Additionally, the quartz crystal microbalance (QCM) gas sensor accurately measures the number of particulates adsorbed on the MOF films in real-time. Thus, the QCM gas sensor is a valuable tool for quantitatively measuring gases, such as SO2, NO2, and CO2. Furthermore, the QCM MOF film gas sensor was more effective for gas adsorption than the MOF particles alone and allowed the accurate modeling of gas adsorption. Moreover, the QCM MOF films accurately detect the adsorption-desorption mechanisms of SO2 and NO2, which exist as gaseous particulate matter, at specific gas concentrations.

Leaching of Cobalt and Nickel from Metallic Mixtures by Inorganic and Organic Acid Solutions (코발트와 니켈 금속혼합물로부터 무기산 및 유기산에 의한 침출)

  • Moon, Hyun Seung;Song, Si Jeong;Tran, Thanh Tuan;Lee, Man Seung
    • Resources Recycling
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    • v.30 no.2
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    • pp.53-60
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    • 2021
  • Leaching experiments from single metal and metallic mixtures were conducted to develop a process for the recovery of cobalt, copper, and nickel in spent lithium ion batteries. Inorganic and organic acid solutions without oxidizing agents were employed. No copper was dissolved in the absence of an oxidizing agent in the leaching solutions. The leaching condition to completely dissolve single metal of cobalt and nickel was determined based on acid concentration, reaction temperature and time, and pulp density. The leaching condition to dissolve all of cobalt and nickel from the metallic mixtures was also obtained. Leaching of the metallic mixture with methanesulfonic acid led to selective dissolution of cobalt at low temperatures.

Cobalt Recovery by Oxalic Acid and Hydroxide Precipitation from Waste Cemented Carbide Scrap Cobalt Leaching Solution (폐초경 스크랩 코발트 침출용액으로부터 옥살산 및 수산화물 침전에 의한 코발트 분말 회수)

  • Lee, Jaesung;Kim, Mingoo;Kim, Seulgi;Lee, Dongju
    • Journal of Powder Materials
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    • v.28 no.6
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    • pp.497-501
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    • 2021
  • Cobalt (Co) is mainly used to prepare cathode materials for lithium-ion batteries (LIBs) and binder metals for WC-Co hard metals. Developing an effective method for recovering Co from WC-Co waste sludge is of immense significance. In this study, Co is extracted from waste cemented carbide soft scrap via mechanochemical milling. The leaching ratio of Co reaches approximately 93%, and the leached solution, from which impurities except nickel are removed by pH titration, exhibits a purity of approximately 97%. The titrated aqueous Co salts are precipitated using oxalic acid and hydroxide precipitation, and the effects of the precipitating agent (oxalic acid and hydroxide) on the cobalt microstructure are investigated. It is confirmed that the type of Co compound and the crystal growth direction change according to the precipitation method, both of which affect the microstructure of the cobalt powders. This novel mechanochemical process is of significant importance for the recovery of Co from waste WC-Co hard metal. The recycled Co can be applied as a cemented carbide binder or a cathode material for lithium secondary batteries.

Methanol-to-Olefin Conversion over UZM-9 Zeolite: Effect of Transition Metal Ion Exchange on its Deactivation (UZM-9 제올라이트에서 메탄올의 올레핀으로 전환반응: 전이금속 이온 교환이 촉매의 활성저하에 미치는 영향)

  • Kim, Sun Jung;Jang, Hoi-Gu;Seo, Gon
    • Korean Chemical Engineering Research
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    • v.51 no.2
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    • pp.181-188
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    • 2013
  • The effect of transition metal ion exchange into UZM-9 zeolite with LTA framework on its deactivation in methanol-to-olefin (MTO) conversion was discussed. The ion exchange of copper, cobalt, nickel, and iron did not induce any notable change in the crystallinity, crystal morphology, and acidity of UZM-9. The small cage entrance of UZM-9 caused the high selectivity to lower olefins in the MTO conversion, while its large cages allowed the rapid further cyclecondensation of active intermediates, polymethylbenzenes including hexamethylbenzene, resulting in a rapid deactivation. The UZM-9 containing copper and cobalt ions showed considerably slow deactivations. The interaction between transition metal ions and polymethylbenzene cation radicals, the active intermediates, generated in the MTO conversion stabilized the radicals and slowed down the deactivation of UZM-9.

Solvent Effects on the Isotropic NMR Shifts in Quinuclidine and Pyridine-Type Ligands Coordinated to the Paramagnetic Polyomometalate, $[SiW_{11}Co^{II}o_{39}]^{6-}$

  • Hyun, Jaewon;Park, Suk-Min;So, Hyunsoo
    • Bulletin of the Korean Chemical Society
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    • v.18 no.10
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    • pp.1090-1093
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    • 1997
  • The solvent effects on the isotropic NMR shifts in conformationally rigid ligands such as quinuclidine, pyridine, and 4-aminopyridine coordinated to the paramagnetic polyoxometalate, [SiW11CoⅡO39]6- (SiW11Co), are reported. For these complexes the ligand exchange is slow on the NMR time scale and pure 1H NMR signals have been observed at room temperature. The signals for the SiW11Co complexes are shifted upfield whe dimethyl sulfoxide-d6 (DMSO) is added to a D2O solution. The isotropic shifts are separated into contact and pseudocontact contributions by assuming that the contact shifts are proportional to the isotropic shifts of the same ligands coordinated to [SiW11NiⅡO39]6-. It is shown that both the contact and pseudocontact shifts decrease (the absolute values of the pseudocontact shifts increase), when D2O is replaced by DMSO. It is suggested that D2O, a strong hydrogen bond donor, withdraws electron density from [SiW11CoⅡO39]6-, increasing the acidity of the cobalt ion toward the axial ligand. When D2O is replaced by DMSO, the acidity of the cobalt ion in SiW11Co decreases, weakening the Co-N bond. Then both the contact and pseudocontact shifts are expected to decrease in agreement with the observed solvent effects.

Electrokinetic Remediation of Cobalt Contaminated Soil Using Ethanoic Buffer

  • Kim, Gye-Nam;Won, Hui-Jun;Oh, Won-Zin;Shim, Jun-Bo
    • Nuclear Engineering and Technology
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    • v.34 no.1
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    • pp.1-8
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    • 2002
  • After kaolin clay was artificially contaminated with Co$^{2+}$ ion, the remediation characteristics were analyzed by the electrokinetic method. Ethanoic buffer was injected in the soil column and $CH_3$COOH was continuously inputted to the cathode reservoir to restrain the pH increase. Since the pH of the cathode side of the soil column was 4.0 initially and increased to only 6.5 after remediation for 43.6 hours, precipitate, Co(OH)$_2$, was not formed in the column. The effluent rate increased with the passage of time and Co$^{2+}$ removal in the column at the initial time were mainly controlled by ion migration. 13.1% of the total amount of Co$^{2+}$ in the soil column was removed in 10 hours, 46.8% of the total Co$^{2+}$ in 20.8 hours, 71.7% of the total Co$^{2+}$ in 30.1 hours, and 94.6% of the total Co$^{2+}$ in 43.6 hours. Meanwhile, residual concentrations in the column calculated by the developed model were similar to those by experiment. experiment.