• 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.

• Journal of the Korean Electrochemical Society
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• v.22 no.1
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• pp.36-42
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• 2019

A macroporous Sn thick film as a high capacity negative electrode for a lithium ion secondary battery was prepared by using a chemical etching method using nitric acid for a Sn film having a thickness of $52{\mu}m$. The porous Sn thick film greatly reduced the over-voltage for the alloying reaction with lithium by the increased reaction area. At the same time. The porous structure of active Sn film plays a part in the buffer and reduces the damage by the volume change during cycles. Since the porous Sn thick film electrode does not require the use of the binder and the conductive carbon black, it has substantially larger energy density. As the concentration of nitric acid in etching solution increased, the degree of the etching increased. The etching of the Sn film effectively proceeded with nitric acid of 3 M concentration or more. The porous Sn film could not be recovered because the most of Sn was eluted within 60 seconds by the rapid etching rate in the 5 M nitric acid. In the case of etching with 4 M nitric acid for 60 seconds, the appropriate porous Sn film was formed with 48.9% of weight loss and 40.3% of thickness change during chemical acid etching process. As the degree of etching of Sn film increased, the electrochemical activity and the reversible capacity for the lithium storage of the Sn film electrode were increased. The highest reversible specific capacity of 650 mAh/g was achieved at the etching condition with 4 M nitric acid. The porous Sn film electrode showed better cycle performance than the conventional electrode using a Sn powder.

• 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.

• Korean Journal of Mineralogy and Petrology
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• v.37 no.2
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• pp.77-85
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• 2024

Recently, the world has been declaring global carbon neutrality to curb carbon emissions, a major factor in global warming. Therfore, high-tech and clean energy industries such as renewable energy, electric vehicles, batteries, and semiconductors are rapidly developing. The Korean government selected total 33 critical minerals on based of evaluating the supply risk and economic impact of raw minerals essential for national high-tech industries (semiconductors, secondary battery, etc). Among these critical minerals, Copper, Zinc and lead have been used as basic materials in human life from the past to the present and in addition, they are currently used as an essential material for mobile phones, electric vehicles, and batteries. So, I would like to introduce the Las Bambas copper mine within Apurimac porphyry copper metallogenic belt of Peru, which have the world's 2^nd (copper), 4^th (zinc) and 5^th (lead) largest reserves of these critical minerals. Las Bambas copper mine is the world's largest mine with copper reserves of more than 1 billion tons and is joint venture project mine invested by MMG (Minerals and Metals Group, 62.5%), Guoxin international investment company (22.5%) and CITIC metal company (15.0%). This mine mainly produces copper and also produces gold, silver and molybdenum as a by-product. The ore grade of this mine has 0.77% Cu, 0.06 g/t Au, 3.93 g/t Ag and 178 ppm Mo. Mineral resource and ore reserve of this mine have 10.5 million ton Cu (0.61% Cu) and 6.9 million ton Cu (0.73% Cu). So, this mine life is about more than 20 years. The copper mineralization of this mine occurs as skarn type and vein type related with lower limestone of Ferrobamba formation and Cenozoic monzonites.

• Journal of the Korean Electrochemical Society
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• v.16 no.2
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• pp.85-90
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• 2013

Graphite is a commercial anode material to have the specific capacity of 372 mAh/g and the true density of 2.2 g/ml. Many effort had been pouring to find out the better material than graphite. Good candidates are silicon, tin, etc. Zinc is also a plausible candidate to have the specific capacity of 412 mAh/g and the true density of 7.14 g/ml. In this study, the Zn based anode material including indium and nickel as minor additives was synthesised. In order to get the homogeneouly mixed Zn-In-Ni composite material, the sol-gel method was used. The anode prepared by Zn-In-Ni composite material has the $1^{st}$ specific capacity of 910 mAh/g. Through prolonged charge-discharge cycling, the specific capacities were reduced to 365 (at $31^{st}$ cycle) and 378 mAh/g (at $62^{th}$ cycle). The $1^{st}$ Ah efficiency was 45% and Ah efficiencies were exhibited at the prolonged cycle.

• Journal of the Korean Electrochemical Society
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• v.20 no.2
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• pp.34-40
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• 2017

Electric double layer capacitors (EDLC: electric double layer capacitors) have drew attention as an energy storage device for the next generation because of their outstanding power capability and durability. But their usage is somewhat limited due to low energy density over secondary batteries. One of methods to improve the energy of EDLC is expanding the voltage window of cell operation by increasing the charge cut-off voltage. In this study, $SBP-BF_4$ (spirobipyrrolidinium tetrafluoroborate), $TEA-BF_4$ (tetraethylammonium tetraflouroborate) and $EMI-BF_4$ (1-ethyl-3-methylimidazolium tetrafluoroborate) in AN (acetonitrile) were selected to evaluate the possibility of application at high voltage environment. The LSV (linear sweep voltammetry) measurements showed that the 1.5M SBP-BF4/AN electrolyte was stable over a wide potential window and showed the best electrochemical performance compared to other combinations of electrolytes at high voltage environments (over 3.0 V). Furthermore, TMSP (tris(trimethylsilyl) phosphite) was applied to 1.5M SBP-BF4/AN in order to maintain stable performance at high voltage for the long period of time. The electrolyte with TMSP additive showed the capacity retention of 93% after 10,000 cycles at 3.3 V.

• Journal of the Korean Ceramic Society
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• v.42 no.4
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• pp.292-297
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• 2005

$LiMO_{2}(M=Co,Ni)$ samples were synthesized with $Li_{2}CO_{3},\;Co_{3}O_{4}$, and NiO by the solid-state reaction method. In the case of $LiCoO_{2}$, at low temperature$(T=400^{\circ}C)$ spinel structure was synthesized and the obtained spinel phase was transformed to layered phase at high temperature$(T\ge600^{\circ}C)$. The phase transition behaviors of $LiCoO_{2}$ were investigated with various heating temperature and time. The rate of transition was directly proportional to the concentrations of reactant, and activation energy of reaction was around 6.76 kcal/mol. When CoO(rock salt structure) was used as a starting material instead of $Co_{3}O_{4}$(spinel structure), layered structure of $LiCoO_{2}$ was obtained at low temperature. In the case of $LiNiO_{2}$ the transition from layered structure to rock salt structure occurred easily by disordering/ordering reaction, but did not occur in $LiCoO_{2}$. The difference in metal ion radii in $LiCoO_{2}$ and $LiNiO_{2}$ results in different behaviors of phase transitions.

• 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.

• Korean Journal of Materials Research
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• v.20 no.12
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• pp.669-675
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• 2010

One of the greatest challenges for our society is providing powerful electrochemical energy conversion and storage devices. Rechargeable lithium-ion batteries and fuel cells are among the most promising candidates in terms of energy and power density. As the starting material, $TiCl_4{\cdot}YCl_3$ solution and dispersing agent (HCP) were mixed and synthesized using ammonia as the precipitation agent, in order to prepare the nano size Y doped spherical $TiO_2$ precursor. Then, the $Li_4Ti_5O_{12}$ was synthesized using solid state reaction method through the stoichiometric mixture of Y doped spherical $TiO_2$ precursor and LiOH. The Ti mole increased the concentration of the spherical particle size due to the addition of HPC with a similar particle size distribution in a well in which $Li_4Ti_5O_{12}$ spherical particles could be obtained. The optimal synthesis conditions and the molar ratio of the Ti 0.05 mol reaction at $50^{\circ}C$ for 30 minutes and at $850^{\circ}C$ for 6 hours heat treatment time were optimized. $Li_4Ti_5O_{12}$ was prepared by the above conditions as a working electrode after generating the Coin cell; then, electrochemical properties were evaluated when the voltage range of 1.5V was flat, the initial capacity was 141 mAh/g, and cycle retention rate was 86%; also, redox reactions between 1.5 and 1.7V, which arose from the insertion and deintercalation of 0.005 mole of Y doping is not a case of doping because the C-rate characteristics were significantly better.

• Journal of Surface Science and Engineering
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• v.42 no.1
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• pp.8-12
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• 2009

Electronic structures and chemical bonding of Li-intercalated $LiTiS_2$ and $LiTiO_2$ were investigated by using discrete variational $X{\alpha}$ method as a first-principles molecular-orbital method. ${\alpha}-NaFeO_2$ structure is the equilibrium structure for $LiCoO_2$, which is widely used as a commercial cathode material for lithium secondary battery. The study especially focused on the charge state of Li ions and the magnitude of covalency around Li ions. The average voltage of lithium intercalation was calculated using pseudopotential method and the average intercalation voltage of $LiTiO_2$ was higher than that of $LiTiS_2$. It can be explained by the differences in Mulliken charge of lithium and the bond overlap population between the intercalated Li ions and anions in $LiTiO_2$ as well as $LiTiS_2$. The Mulliken charge, which means the ionicity of Li atom, was approximately 0.12 in $LiTiS_2$ and the bond overlap population (BOP) indicating the covalency between Ti and S was about 0.339. One the other hands, the Mulliken charge of lithium was about 0.79, which means that Li is fully ionized. The BOP, the covalency between Ti and O, was 0.181 in $LiTiO_2$. Because of high ionicity of Li and the weak covalency between Ti and the nearest anion, $LiTiO_2$ has a higher intercalation voltage than that of $LiTiS_2$.