• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.18 no.4
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• pp.421-437
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• 2020

This study provides an assessment on a proposed method for separation of cesium, strontium, and barium using electrochemical reduction at a liquid bismuth cathode in LiCl-KCl eutectic salt, investigated via cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDS). CV studies were performed at temperatures of 723-823 K and concentrations of the target species up to 4.0wt%. Redox reactions occurring during potential sweeps were observed. Concentration of BaCl2 in the salt did not seem to influence the diffusivity in the studied concentration range up to 4.0wt%. The presence of strontium in the system affected the redox reaction of lithium; however, there were no distinguishable redox peaks that could be measured. Impedance spectra obtained from EIS methods were used to calculate the exchange current densities of the electroactive active redox couple at the bismuth cathode. Results show the rate-controlling step in deposition to be the mass transport of Cs+ ions from the bulk salt to the cathode surface layer. Results from SEM-EDS suggest that Cs-Bi and Sr-Bi intermetallics from LiCl-KCl salt are not thermodynamically favorable.

• Bulletin of the Korean Chemical Society
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• v.27 no.9
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• pp.1310-1314
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• 2006

Sulfur-substituted $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$ $(0\;\leq\;x\;\leq\;0.1)$ layered oxides have been prepared by solid state reaction under inert atmosphere. From powder X-ray diffraction analyses, all the present lithium manganates were found to be crystallized with monoclinic-layered structure. Electrochemical measurements clearly demonstrated that, in comparison with the pristine $LiMn_{0.9}Cr_{0.1}O_2$, the sulfur-substituted derivatives exhibit smaller discharge capacities for the entire cycle range but the recovery of discharge capacity after the initial several cycles becomes faster upon sulfur substitution. The effect of the sulfur substitution on the chemical bonding nature of $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$has been investigated using X-ray absorption spectroscopic (XAS) analyses at Mn and Cr K-edges. According to Mn K-edge XAS results, the trivalent oxidation state of manganese ion remains unchanged before and after the substitution whereas the local structure around manganese ions becomes more distorted with increasing the substitution rate of sulfur. On the other hand, the replacement of oxygen with sulfur has negligible influence on the local atomic arrangement around chromium ions, which is surely due to the high octahedral stabilization energy of $Cr^{+III} $ ions. Based on the present experimental findings, we have suggested that the decrease of discharge capacity upon sulfur substitution is ascribable to the enhanced structural distortion of $MnO_6$ octahedra and/or to the formation of covalent Li-S bonds, and the accompanying improvement of cyclability would be related to the depression of Mn migration and/or to the pillaring effect of larger sulfur anion.

• Korean Chemical Engineering Research
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• v.58 no.1
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• pp.142-149
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• 2020

In this study, the electrochemical performance of Graphite/Silicon/Pitch composites as anode material was investigated to improve the low theoretical capacity of artificial graphite. Spherical artificial graphite surface was coated with polyvinylpyrrolidone (PVP) amphiphiles material to synthesize Graphite/Silica material by silica islands growth. The Graphite/Silicon/Pitch composites were prepared by petroleum pitch coating and magnesiothermic reduction. The Graphite/Silicon/Pitch composite electrodes manufactured using poly(vinylidene fluoride) (PVDF), carboxymethyl cellulose (CMC) and polyacrylic acid (PAA) binders. The coin type half cell was assembled using various electrolytes and additives. The Graphite/Silicon/Pitch composites were analysed by X-ray diffraction (XRD), scanning electron microscope (SEM) and a thermogravimetric analyzer (TGA). The electrochemical characteristics of Graphite/Silicon/Pitch composite were investigated by constant current charge/discharge, rate performance, cyclic voltammetry and electrochemical impedance spectroscopy. The Graphite/Silicon/Pitch composites showed high cycle stability at a graphite/silica/pitch ratio (1:4:8 wt%). When the electrode is prepared using PAA binder, the high capacity and stability is obtained. The coin type half cell assembled using EC: DMC: EMC electrolyte showed high initial capacity (719 mAh/g) and excellent cycle stability. The rate performance has an capacity retention (77%) at 2 C/0.1 C and an capacity recovery (88%) at 0.1 C / 0.1 C when the vinylene carbonate (VC) was added.

• 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.

• Journal of Electrical Engineering and Technology
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• v.13 no.1
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• pp.143-151
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• 2018

In this paper, a novel hybrid configuration combining a phase-shift full-bridge (PSFB) and a half-bridge resonant LLC converter is proposed for the On-Board Charger of Electric Vehicles (EVs). In the proposed converter, the PSFB converter shares the lagging-leg switches with half-bridge resonant converter to achieve the wide ZVS range for the switches and to improve the efficiency. The output voltage is modulated by the effective-duty-cycle of the PSFB converter. The proposed converter employs an active reset circuit composed of an active switch and a diode for the transformer which makes it possible to achieve zero circulating current and the soft switching characteristic of the primary switches and rectifier diodes regardless of the load, thereby making the converter highly efficient and eliminating the reverse recovery problem of the diodes. In addition an optimal power sharing strategy is proposed to meet the specification of the charger and to optimize the efficiency of the converter. The operation principle the proposed converter and design considerations for high efficiency are presented. A 6.6 kW prototype converter is fabricated and tested to evaluate its performance at different conditions. The peak efficiency achieved with the proposed converter is 97.7%.

• 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.

• Journal of the Korean Electrochemical Society
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• v.14 no.1
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• pp.27-32
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• 2011

The electorchemical properties of $Li_4Ti_5O_{12}$ added with Cr was tested. The addition or substitution of atoms to $Li_4Ti_5O_{12}$ are expected to modify the crystal structure, and therefore to change the electrochemical performances of $Li_4Ti_5O_{12}$. After the spinel structure $Li_4Ti_{5-x}Cr_xO_{12}$ (x = 0~0.2) were obtained via sol-gel method, the gel was heated in a muffle furnace at $800{\sim}850^{\circ}C$ for 12 h in air. The physical properties of the samples were characterized by TG-DTA, XRD, SEM, FT-IR, and the electrochemical properties were tested with battery cycler at 0.01~2.0 V range. The $Li_4Ti_5O_{12}$ exhibited 169.9 mAh/g at 1C and capacity recovery was 97.5% of the initial capacity at 0.1C. $Li_4Ti_{4.9}Cr_{0.1}O_{12}$ (Cr 1% added) showed best performance of 193.8 mAh/g at 1C and the capacity recovery was increased to 98.8% of the initial capacity at 0.1C.

• Resources Recycling
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• v.31 no.6
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• pp.81-91
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• 2022

The use of lithium-ion batteries increases significantly with the rapid spread of electronic devices and electric vehicle and thereby an increase in the amount of waste batteries is expected in the near future. Therefore, studies are continuously being conducted to recover various resources of cathode active material (Ni, Co, Mn, Li) from waste battery. In order to recover the cathode active material, black mass is generally recovered from waste battery. The general process of recovering black mass is a waste battery collection - discharge - dismantling - crushing - classification process. This study focus on the crushing/classification process among the processes. Specifically, the particle size distribution of various samples at each crushing/classification step were evaluated, and the particle shape of each particle fraction was analyzed with a microscope and SEM (Scanning Electron Microscopy)-EDS(Energy Dispersive Spectrometer). As a result, among the black mass particle, fine particle less than 74 ㎛ was the mixture of cathode and anode active material which are properly liberated from the current metals. However, coarse particle larger than 100 ㎛ was present in a form in which the current metal and active material were combined. In addition, this study developed a PBM(Population Balance Model) system that can simulate two-species mixture sample with two different crushing properties. Using developed model, the breakage parameters of two species was derived and predictive performance of breakage distribution was verified.

• Economic and Environmental Geology
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• v.12 no.1
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• pp.41-49
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• 1979

A literature review is made on the physical and chemical characteristics of clay minerals in acidic solutions from the mineralogical and hydrometallurgical viewpoints. Some of the important characteristics of clays are their ability to cation exchange, swelling, and incongruent dissolution in acidic solutions. Various clay minerals can take up metallic ions from solution via cation exchange mechanism. Generally, cation exchange capacity increases in the following order : kaolinite, halloysite, illite, vermiculite, and montmorillonite. In acidic solutions, the cation uptake such as copper by clay minerals is strongly inhibited by hydrogen and aluminum ions and thus is not economically significant factor for recovery of metals such as uranium and copper. In acidic solutions, the cation uptake is substial. Swelling is minimal at lower pH, possibly due to lattice collapse. Swelling may be controllable with montmorillonite type clays by exchanging interlayer sodium with lithium and/or hydroxylated aluminum species. The effect of add on clay minerals are : 1. Division of aggregates into smaller plates with increase in surface area and porosity. 2. Clay-acid reactions occur in the following order: (i) $H^+$ replacement of interlayer cations, (ii) removal of octahedral cations, such as Al, Fe, and Mg, and (iii) removal of tetrahedral Al ions. Acid attack initiates, around the edges of the clay particles and continued inward, leaving hydrated silica gel residue around the edges. 3. Reaction rates of (ii) and (iii) are pseudo-1st order and proportional to acid concentration. Rate doubles for every temperature increment of $10^{\circ}C$. Implications in in-situ leaching of copper or uranium with acid are : 1. Over the life span of the operation for a year or more, clays attacked by acid will leave silica gel. If such gel covers the surface of valuable mineral surfaces being leached, recovery could be substantially delayed. 2. For a copper deposit containing 0.5% each of clay minerals and recoverable copper, the added cost due to clay-acid reaction is about 1.5c/lb of copper (or 0.93 lbs of $H_2SO_4/1b$ of copper). This acid consumption by clay may be a factor for economic evaluation of in-situ leaching of an oxide copper deposit.

• 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.