• 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%).

• Resources Recycling
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• v.32 no.6
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• pp.25-33
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• 2023

With the growth of the battery industry, a rapid increase in the production and usage of lithium-ion batteries is expected, and in line with this, much interest and effort is being paid to recycle waste batteries, including production scrap. Although much effort has been made to recycle cathode material, much attention has begun to recycle anode material to secure the supply chain of critical minerals and improve recycling rates. The proximate analysis that measures the content of coal can be used to analyze graphite in anode material, but it cannot accurately analyze due to the interaction between the components of the black mass. Therefore, in this study, thermogravimetric analysis of each component of black mass was measured as the temperature increased up to 950℃ in an oxygen atmosphere. As a result, in the case of cathode material, no change in mass was measured other than a mass reduction of about 5% due to oxidation of the binder and conductive material. In the case of anode material, except for a mass reduction of about 2% due to the binder, all mass reduction were due to the graphite(fixed carbon). In addition, metal conductors (Al, Cu) were oxidized and their mass increased as the temperature increased. Thermal analysis results of mixed samples of cathode/anode show similar results to the predictive values that can be calculated through each cathode and anode analysis results.

• Resources Recycling
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• v.28 no.5
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• pp.60-67
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• 2019

A valuable metal recovery from waste resources such as spent rechargeable secondary batteries is of critical issues because of a sharp increase in the amount of waste resources. In this context, it is necessary to research not only recycling waste lithium-ion batteries (LIBs), but also reusing valuable metals (e.g., Li, Co, Ni, Mn etc.) recovered from waste LIBs. In particular, the lithium hydroxide ($LiOH{\cdot}xH_2O$), which is of precursors that can be prepared by the recovery of Li in waste LIBs, can be reused as a catalyst, a carbon dioxide absorbent, and again as a precursor for cathode materials of LIB. However, most studies of recycling the waste LIBs have been focused on the preparation of lithium carbonate with a recovery of Li. Herein, we show the preparation of high purity lithium hydroxide powder along with the precipitation process, and the systematic study to find an optimum condition is also carried out. The lithium carbonate, which is recovered from waste LIBs, was used as starting materials for synthesis of lithium hydroxide. The optimum precipitation conditions for the preparation of LiOH were found as follows: based on stirring, reaction temperature $90^{\circ}C$, reaction time 3 hr, precursor ratio 1:1. To synthesize uniform and high purity lithium hydroxide, 2-step precipitation process was additionally performed, and consequently, high purity $LiOH{\cdot}xH_2O$ powder was obtained.

• Clean Technology
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• v.24 no.1
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• pp.77-84
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• 2018

In this study, $Li_4Ti_5O_{12}$ anode materials for lithium ion battery were synthesized by dry ball-mill method. Polyvinyl chloride (PVC) as a carbon source was added to improve electrochemical properties. When the PVC was added after $Li_4Ti_5O_{12}$ formation, the spinel structure was well synthesized and it was confirmed by X-ray diffraction (XRD) experiments. When the carbon material was added before the synthesis and the heat treatment was performed, it was confirmed that a material having a different crystal structure was synthesized even when a small amount of carbon material was added. In the case of $Li_4Ti_5O_{12}$ without the carbon material, the electrical conductivity value was about $10{\mu}S\;m^{-1}$, which was very small and similar to that of the nonconductor. As the carbon was added, the electrical conductivity was greatly improved and increased up to 10,000 times. Electrochemical impedance spectroscopy (EIS) analysis showed that the size of semicircle corresponding to the resistance decreased with the carbon addition. This indicates that the resistance inside the electrode is reduced. According to the Cyclic voltammetry (CV) analysis, the potential difference between the oxidation peak and the reduction peak was reduced with carbon addition. This means that the rate of lithium ion insertion and deinsertion was increased. $Li_4Ti_5O_{12}$ with 9.5 wt% PVC added sample showed the best properties in rate capabilities of $180mA\;h\;g^{-1}$ at 0.2 C-rate, $165mA\;h\;g^{-1}$ at 0.5 C-rate, and $95.8mA\;h\;g^{-1}$ at 5 C-rate.

• KEPCO Journal on Electric Power and Energy
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• v.6 no.2
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• pp.173-179
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• 2020

Electric vehicles (EVs) using lithium secondary batteries (LIBs) with excellent power and long-term cycle performance are gaining interest as the successors of internal combustion engine (ICE) vehicles. However, there are few systematic researches for fast charging to satisfy customers' needs. In this study, we compare the degradation of LIB where its composition is LiNi_0.5Co_0.2Mn_0.3/Graphite with the constant current and constant power-charging method. The charging speed was set to 1C, 2C, 3C and 4C in the constant current mode and the value of constant power was calculated based on the energy at each charging speed. Therefore, by analyzing the battery degradation based on the same charging energy but different charging method; CP charging method can slow down the battery degradation at a high rate of 3C through the voltage curve, capacity retention and DC-IR. However, when the charging rate was increased by 4C or more, the deviation between the LIBs dominated the degradation than the charging method.

• Journal of the Korean Electrochemical Society
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• v.12 no.2
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• pp.189-195
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• 2009

$\beta-Ga_{2}O_{3}$ nanorods were synthesized by chemical vapor deposition method using nickel-oxide nanoparticle as a catalyst and gallium metal powder as a source material. The average diameter of nanorods was around 160 nm and the average length was $4{\mu}m$. Also, we confirmed that the synthesis of nanorods follows the vapor-solid growth mechanism. From the results of X-ray diffraction and HR-TEM observation, it can be found that the synthesized nanorods consisted of a typical core-shell structure with single-crystalline $\beta-Ga_{2}O_{3}$ core with a monoclinic crystal structure and an outer amorphous gallium oxide layer. Li/$\beta-Ga_{2}O_{3}$ nanorods cell delivered capacity of 867 mAh/g-$\beta-Ga_{2}O_{3}$ at first discharge. Although the Li/$\beta-Ga_{2}O_{3}$ nanorods cell showed low coulombic efficiency at first cycle, the cell exhibited stable cycle life property after fifth cycle.

• Journal of Radiation Protection and Research
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• v.39 no.4
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• pp.199-205
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• 2014

In the field of neutron detections, $^3He$ gas, the so-called "the gold standard," is the most widely used material for neutron detections because of its high efficiency in neutron capturing. However, from variable causes since early 2009, $^3He$ is being depleted, which has maintained an upward pressure on its cost. For this reason, the demands for $^3He$ replacements are rising sharply. Research into neutron converting materials, which has not been used well due to a neutron detection efficiency lower than the efficiency of $^3He$, although it can be chosen for use in a neutron detector, has been highlighted again. $^{10}B$, which is one of the $^3He$ replacements, such as $BF_3$, $^6Li$, $^{10}B$, $Gd_2O_2S$, is being researched by various detector development groups owing to a number of advantages such as easy gamma-ray discrimination, non-toxicity, low cost, etc. One of the possible techniques for the detection is an indirect neutron detection method measuring secondary radiation generated by interactions between neutrons and $^{10}B$. Because of the mean free path of alpha particle from interactions that are very short in a solid material, the thickness of $^{10}B$ should be thin. Therefore, to increase the neutron detection efficiency, it is important to make a $^{10}B$ thin film. In this study, we fabricated a $^{10}B$ thin film that is about 60 um in thickness for neutron detection using well-known technology for the manufacturing of a thin electrode for use in lithium ion batteries. In addition, by performing simple physical tests on the conductivity, dispersion, adhesion, and flexibility, we confirmed that the physical characteristics of the fabricated $^{10}B$ thin film are good. Using the fabricated $^{10}B$ thin film, we made a proportional counter for neutron monitoring and measured the neutron pulse height spectrum at a neutron facility at KAERI. Furthermore, we calculated using the Monte Carlo simulation the change of neutron detection efficiency according to the number of thin film layers. In conclusion, we suggest a fabrication method of a $^{10}B$ thin film using the technology used in making a thin electrode of lithium ion batteries and made the $^{10}B$ thin film for neutron detection using suggested method.

• Economic and Environmental Geology
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• v.56 no.6
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• pp.781-797
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• 2023

Recently, there has been a rapid response from mineral-demanding countries for securing critical minerals in a high tech industries. Graphite, while overwhelmingly dominated by China in production, is changing in global supply due to the exponential growth in EV battery sector, with active exploration in East Africa. Rare earth elements are essential raw materials widely used in advanced industries. Globally, there are ongoing developments in the production of REEs from three main deposit types: carbonatite, laterite, and ion-adsorption clay types. While China's production has decreased somewhat, it still maintains overwhelming dominance in this sector. Recent changes over the past few years include the rapid emergence of Myanmar and increased production in Vietnam. Nickel has been used in various chemical and metal industries for a long time, but recently, its significance in the market has been increasing, particularly in the battery sector. Worldwide, nickel deposits can be broadly classified into two types: laterite-type, which are derived from ultramafic rocks, and ultramafic hosted sulfide-type. It is predicted that the development of sulfide-type, primarily in Australia, will continue to grow, while the development of laterite-type is expected to be promoted in Indonesia. This is largely driven by the growing demand for nickel in response to the demand for lithium-ion batteries. The global lithium ores are produced in three main types: brine lake (78%), rock/mineral (19%), and clay types (3%). Rock/mineral type has a slightly higher grade compared to brine lake type, but they are less abundant. Chile, Argentina, and the United States primarily produce lithium from brine lake deposits, while Australia and China extract lithium from both brine lake and rock/mineral sources. Canada, on the other hand, exclusively produces lithium from rock/mineral type. Vanadium has traditionally been used in steel alloys, accounting for approximately 90% of its usage. However, there is a growing trend in the use for vanadium redox flow batteries, particularly for large-scale energy storage applications. The global sources of vanadium can be broadly categorized into two main types: vanadium contained in iron ore (81%) produced from mines and vanadium recovered from by-products (secondary sources, 18%). The primary source, accounting for 81%, is vanadium-iron ores, with 70% derived from vanadium slag in the steel making process and 30% from ore mined in primary sources. Intermediate vanadium oxides are manufactured from these sources. Vanadium deposits are classified into four types: vanadiferous titanomagnetite (VTM), sandstone-hosted, shale-hosted, and vanadate types. Currently, only the VTM-type ore is being produced.

• Journal of the Korean Electrochemical Society
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• v.15 no.4
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• pp.222-229
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• 2012

We studied the electrochemical phenomena and increase of capacity according to the polymer composite electrode of two different polymeric materials with different the voltage range and capacity. Polyaniline (PANI) with relatively high voltage and small capacity and poly [1,2] bis-thio[1,8]-naphthylidine (PTND) with slightly low voltage and large capacity were used as polymer composite electrode materials. After PTND was synthesized, PANI was synthesized on the surface of PTND. The synthesis and the fine structure were analyzed by FT-IR, XPS, FE-SEM, and FE-TEM. Charge/discharge capacity and cyclic voltammetry measurements were carried out for the electrochemical performance as a polymer cathode active material for lithium secondary batteries. The discharge capacities of PANI/PTND after 1,5, and 10 cycles at 1.3~4.0 V voltage range and room temperature 167 mAh/g, 90 mAh/g, and 81 mAh/g. When we compared with PANI (80, 67, and 62 mAh/g), the discharge capacity after 10 cycles was improved about 30%. After 50 cycles, the discharge capacity of PANI/PTND was 67 mAh/g.