• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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• pp.277-277
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• 2010

The capacity of the carbonaceous materials reached ca. $350\;mAhg^{-1}$ which is close to theorestical value of the carbon intercalation composition $LiC_6$, resulting in a relatively low volumetric Li capacity. Notwithstanding the capacities of carbon, it will not adjust well to the need so future devices. Silicon shows the highest gravimetric capacities (up to $4000\;mAhg^{-1}$ for $Li_{21}Si_5$). Although Si is the most promising of the next generation anodes, it undergoes a large volume change during lithium insertion and extraction. It results in pulverization of the Si and loss of electrical contact between the Si and the current collector during the lithiation and delithiation. Thus, its capacity fades rapidly during cycling. We focused on electrode materials in the multiphase form which were composed of two metal compounds to reduce the volume change in material design. A combination of electrochemically amorphous active material in an inert matrix (Si-M) has been investigated for use as negative electrode materials in lithium ion batteries. The matrix composited of Si-M alloys system that; active material (Si)-inactive material (M) with Li; M is a transition metal that does not alloy with Li with Li such as Ti, V or Mo. We fabricated and tested a broad range of Si-M compositions. The electrodes were sputter-deposited on rough Cu foil. Electrochemical, structural, and compositional characterization was performed using various techniques. The structure of Si-M alloys was investigated using X-ray Diffractometer (XRD) and transmission electron microscopy (TEM). Surface morphologies of the electrodes are observed using a field emission scanning electron microscopy (FESEM). The electrochemical properties of the electrodes are studied using the cycling test and electrochemical impedance spectroscopy (EIS). It is found that the capacity is strongly dependent on Si content and cycle retention is also changed according to M contents. It may be beneficial to find materials with high capacity, low irreversible capacity and that do not pulverize, and that combine Si-M to improve capacity retention.

• Journal of Soil and Groundwater Environment
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• v.23 no.2
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• pp.1-14
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• 2018

The recent increase in demand for lithium has led to the development of new brine prospects, The brines are hosted in closed salar basin aquifers of two types that are mature halite salars and immature clastic salars. Salar brines also contain other elements of commercial interest, most notably potassium and boron. As a result, there has been a plethora of new exploration projects focused on the brines hosted in the aquifers of the intermontane-closed basins. The estimate of lithium resources and reserves in these salars depends on a detailed knowledge of aquifer geometry, porosity, and brine grade. Because the resource is in a fluid state, it has the propensity to move, mix, rearrange itself relatively rapidly during the course of a project lifetime, and lower recovery factors compared with most metalliferous and industrial mineral deposits due to reliance on pumping of the brine from wells for extraction. This is unlike any other type of metallic mineral resource and hence a different approach specially focusing on hydrogeology and brine hydrology is required for these prospects.

• Resources Recycling
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• v.31 no.1
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• pp.12-20
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• 2022

The smelting reduction of spent lithium-ion batteries results in metallic alloys containing Co, Cu, Fe, Mn, Ni, and Si. A process to separate metal ions from the sulfuric acid leaching solution of these metallic alloys has been reported. In this process, ionic liquids are employed to separate Fe(III) and Cu(II). In this study, D2EHPA and Cyanex 301 were employed to replace these ionic liquids. Fe(III) and Cu(II) from the sulfate solution were sequentially extracted using 0.5 M D2EHPA with three stages of cross-current and 0.3 M Cyanex 301. The stripping of Fe(III) and Cu(II) from the loaded phases was performed using 50% (v/v) and 60% (v/v) aqua regia solutions, respectively. The mass balance results from this process indicated that the recovery and purity percentages of the metals were greater than 99%.

• Environmental Engineering Research
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• v.25 no.1
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• pp.88-95
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• 2020

An investigation of rare metals recovery from LiNi_xCo_yMn_zO₂ cathode material of the end-of-life lithium-ion batteries is presented. To determine the influence of reductant on the leach process, the cathode material (containing Li 7.6%, Co 20.4%, Mn 19.4%, and Ni 19.3%) was leached in H₂SO₄ solutions either with or without H₂O₂. The optimal process parameters with respect to acid concentration, addition dosage of H₂O₂, temperature, and the leaching time were found to be 2.0 M H₂SO₄, 4 vol.% H₂O₂, 70℃, and 150 min, respectively. The yield of metal values in the leach liquor was > 99%. The leach liquor was subsequently treated by precipitation techniques to recover nickel as Ni(C₄H₇N₂O₂)₂ and lithium as Li₂CO₃ with stoichiometric ratios of 2:1 and 1.2:1 of dimethylglyoxime:Ni and Na₂CO₃:Li, respectively. Cobalt was recovered by solvent extraction following a 3-stage process using Na-Cyanex 272 at pH_eq ~5.0 with an organic-to-aqueous phase ratio (O/A) of 2/3. The loaded organic phase was stripped with 2.0 M H₂SO₄ at an O/A ratio of 8/1 to yield a solution of 114 g/L CoSO₄; finally recovered CoSO₄.xH₂O by crystallization. The process economics were analyzed and found to be viable with a margin of $476 per ton of the cathode material.

• Korean Chemical Engineering Research
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• v.60 no.4
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• pp.473-477
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• 2022

In this study, candidate technologies for lithium recovery from the process waste liquid generated in the waste battery recycling process were reviewed, and technologies applicable to the process from the commercialization point of view were reviewed from a qualitative point of view. The evaporation method is difficult to apply because it requires a large-scale land and shows a low recovery rate due to the loss of Li during the concentration process. In the case of precipitation, a commercially available technology shows a high recovery rate due to the high Li/Na selectivity of phosphoric acid, but there are disadvantages in that the process is complicated due to the use of expensive phosphoric acid, requiring a recovery step, and continuous operation is impossible because solids are handled in the Li concentration process. In the case of solvent extraction, if we find an inexpensive extractant with high Li/Na selectivity, continuous operation is possible with the method used in extraction of other metals in the previous step, and when Li is concentrated, continuous operation is possible because it is in a liquid state. If it shows a similar recovery rate compared to precipitation technology, commercialization will be the most likely.

• Applied Chemistry for Engineering
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• v.25 no.1
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• pp.1-13
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• 2014

Lithium ion batteries (LIBs) are the state-of-the-art technology among electrochemical energy storage and conversion cells, and are still considered the most attractive class of battery in the future due to their high specific energy density, high efficiency, and long cycle life. Rapid development of power-hungry commercial electronics and large-scale energy storage applications (e.g. off-peak electrical energy storage), however, requires novel anode materials that have higher energy densities to replace conventional graphite electrodes. Germanium (Ge) and silicon (Si) are thought to be ideal prospect candidates for next generation LIB anodes due to their extremely high theoretical energy capacities. For instance, Ge offers relatively lower volume change during cycling, better Li insertion/extraction kinetics, and higher electronic conductivity than Si. In this focused review, we briefly describe the basic concepts of LIBs and then look at the characteristics of ideal anode materials that can provide greatly improved electrochemical performance, including high capacity, better cycling behavior, and rate capability. We then discuss how, in the future, Ge anode materials (Ge and Ge oxides, Ge-carbon composites, and other Ge-based composites) could increase the capacity of today's Li batteries. In recent years, considerable efforts have been made to fulfill the requirements of excellent anode materials, especially using these materials at the nanoscale. This article shall serve as a handy reference, as well as starting point, for future research related to high capacity LIB anodes, especially based on semiconductor Ge and Si.

• Journal of the Korean institute of surface engineering
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• v.30 no.2
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• pp.121-127
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• 1997

Vanadium tungsten oxide thin films were formed by RF magnetron sputtering and the effects of tungsten addition on the crystallinity and on the electrochemical behavior were investigated. X-ray analysis revealed that amorphized films could be obtained by tungase addition. In order to investigate the electrochemical behavior of the vanadium tungsten oxide films, electrochemical insertion and extraction of lithium were out in 1m $LiCIO_4$-PC-DME electrolyte using litium metal as a counter electrode. When the tungsten was added to the $V_2O_5$ films, cycling reversibility was considerably improved. Electrochemical test showed the cell capacity of about $70\mu\;Ah/\textrm{cm}^2-\mu\textrm{m}$ when the amount of additive tungseten reached 30 atomic percent. No appreciable degradation of the cell capacity could be observed after hundred cycles of insertion and extration od Li.

• Journal of Industrial Technology
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• v.42 no.1
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• pp.19-27
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• 2022

This review will discuss the effort to understand the interfacial reactions at the anode and cathode sides of all-solid-state batteries. Antiperovskite solid electrolytes have received increasing attention due to their low melting points and anion tunability which allow controlling microstructure and crystallographic structures of this material system. Antiperovskite solid electrolytes pave the way for the understanding relationship between critical current density and mechanical properties of solid electrolytes. Microstructure engineering of cathode materials has been introduced to mitigate the volume change of cathode materials in solid-state batteries. The hollow microstructure coupled with a robust outer oxide layer effectively mitigates both volume change and stress level of cathode materials induced by lithium insertion and extraction, thus improving the structural stability of the cathode and outer oxide layer, which results in stable cycling performance of all-solid-state batteries.

• Resources Recycling
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• v.27 no.6
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• pp.53-58
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• 2018

Solvent extraction of Li(I) from weak HCl solution was investigated by the mixture of TBP/MIBK with other neutral extractants such as Cyanex 923, TOPO and TOP. The TBP/MIBK organic phase was loaded with 0.1 M $FeCl_3$ at different HCl concentrations (1-9 M). Extraction of Li(I) from weak HCl solution is related to the stability of $FeCl_3$ in the organic mixture. As HCl concentration increased in preparing the loaded TBP phase, the stripping percentage of Fe(III) during the extraction of Li(I) became reduced and thus Li(I) could be extracted by ion exchange reaction with hydrogen ion in the organic. The concentration of TBP in the extractant mixture affected the stability of $FeCl_3$. Compared to TBP, Fe(III) was easily stripped from the loaded MIBK and thus no Li(I) was extracted by the mixture with MIBK. The nature of neutral extractant with TBP/MIBK showed little difference in the extraction of Li(I) and stripping of Fe(III).

• Proceedings of the Materials Research Society of Korea Conference
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• 2010.05a
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• pp.37.2-37.2
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• 2010

Recently $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$ has been consistently examined and investigated by scientists because of its high lithium storage capacity, which exceeds beyond the conventional theoretical capacity based on conventional chemical concepts. Consequently, $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$ is considered as one of the most promising cathode candidates for next generation in Li rechargeable batteries. Yet the mechanism and the origin of the overcapacity have not been clarified. Previously, many authors have demonstrated simultaneous oxygen evolution during the first delithiation. However, it may only explain the high capacity of the first charge process, and not of the subsequent cycles. In this work, we report a clarified interpretation of the structural evolution of $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$, which is the key element in understanding its anomalously high capacity. We identify how the structural evolution of $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$ occurs upon the electrochemical cycling through careful study of electrochemical profiles, ex-situ X-ray diffraction (XRD), HR-TEM, Raman spectroscopy, and first principles calculation. Moreover, we successfully separated the structural change at subsequent cycles (mainly cation rearrangement) from the first charge process (mainly oxygen evolution with Li extraction) by intentionally synthesizing sample with large particle size. Consequently, the intermediate states of structural evolution could be well resolved. All observations made through various tools lead to the result that spinel-like cation arrangement and lithium environment are created and embedded in layered framework during repeated electrochemical cycling.