• 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.

• Journal of Electrochemical Science and Technology
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• v.10 no.2
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• pp.196-205
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• 2019

Ni-rich layered oxides $Li(Ni_xCo_yMn_z)O_2$ (x + y + z = 1) have been extensively studied in recent times owing to their high capacity and low cost and can possibly replace $LiCoO_2$ in the near future. However, these layered oxides suffer from problems related to the capacity fading, thermal stability, and safety at high voltages. In this study, we use surface coating as a strategy to improve the thermal stability at higher voltages. The uniform and conformal $Al_2O_3$ coating on prefabricated electrodes using atomic layer deposition significantly prevented surface degradation over prolonged cycling. Initial capacity of 190, 199, 188 and $166mAh\;g^{-1}$ is obtained for pristine, 2, 5 and 10 cycles of ALD coated samples at 0.2C and maintains 145, 158, 151 and $130mAh\;g^{-1}$ for high current rate of 2C in room temperature. The two-cycle $Al_2O_3$ modified cathode retained 75% of its capacity after 500 cycles at 5C with 0.05% capacity decay per cycle, compared with 46.5% retention for a pristine electrode, at an elevated temperature. Despite the insulating nature of the $Al_2O_3$ coating, a thin layer is sufficient to improve the capacity retention at a high temperature. The $Al_2O_3$ coating can prevent the detrimental surface reactions at a high temperature. Thus, the morphology of the active material is well-maintained even after extensive cycling, whereas the bare electrode undergoes severe degradation.

• Journal of the Korean Ceramic Society
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• v.53 no.3
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• pp.306-311
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• 2016

Li-air batteries have received much attention due to their superior theoretical energy density. However, their sluggish kinetics on the cathode side is considered the main barrier to high performance. The rational design of electrode catalysts with high activity is therefore an important challenge. To solve this issue, we performed density functional theory (DFT) calculations to analyze the adsorption behavior of the $LiO_2$ molecule, which is considered to be a key intermediate in both the Li-oxygen reduction reaction (ORR) and the evolution reaction (OER). Specifically, to use the activity descriptor approach, the $LiO_2$ adsorption energy, which has previously been demonstrated to be a reliable descriptor of the cathode reaction in Li-air batteries, was calculated on $LaB_{1-x}B^{\prime}_xO_3$(001) (B, B' = Mn, Fe, Co, and Ni, x = 0.0, 0.5). Our fast screening results showed that $LaMnO_3$, $LaMn_{0.5}Fe_{0.5}O_3$, or $LaFeO_3$ would be good candidate catalysts. We believe that our results will provide a way to more efficiently develop new cathode materials for Li-air batteries.

• Journal of Electrochemical Science and Technology
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• v.12 no.2
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• pp.272-278
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• 2021

In this study, high nickel layered LiNi_0.8Co_0.1Mn_0.1O₂ cathode materials for lithium-ion batteries were modified by yttrium doping and poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) coating. The effects of yttrium doping and PEDOT:PSS coating on the structural and electrochemical properties of the LiNi_0.8Co_0.1Mn_0.1O₂ cathode material were investigated and compared. The substitution of nickel with an electrochemically inert yttrium was confirmed to be successful in stabilizing the layered structure framework. Moreover, coating the surfaces of the LiNi_0.8Co_0.1Mn_0.1O₂ particles with a conductive polymer, PEDOT:PSS, improved the capacity retention, thermal stability, and impedance of the cathode material by increasing its ionic and electric conductivities.

• Journal of the Korean Electrochemical Society
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• v.19 no.4
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• pp.123-128
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• 2016

In this study, poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP)-based gel polymer electrolyte incorporating nano-size $Al_2O_3$ ceramic particle was prepared by electrospinning. The gel polymer electrolyte (GPE) incorporated with $Al_2O_3$ ceramic particle showed higher ionic conductivity of $9.5{\times}10^{-2}Scm^{-1}$ than pure PVdF-HFP GPE without ceramic particle and improved the electrochemical stability up to 5.2 V. The GPEs were assembled with $LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ (NMC) cathode for electrochemical test. The GPE batteries at 0.1 C-rate delivered $168.2mAh\;g^{-1}$ for pure GPE and $189.6mAh\;g^{-1}$ for hybrid GPE, respectively. Therefore, the incorporation of high dielectric constant ceramic particle will be good strategy to enhance the stability and electrochemical properties of lithium ion gel polymer batteries.

• Journal of the Korean Electrochemical Society
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• v.21 no.3
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• pp.47-54
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• 2018

To maximize the areal capacity($mAh\;cm^{-2}$) of $LiNi_{0.5}Co_{0.2}Mn_{0.3}O_2$(NCM523) electrode with the same loading level of $15mg\;cm^{-2}$, three NCM523 electrodes with 4, 2, and 1 wt% poly(vinylidene fluoride)(PVdF) binder content are fabricated. Due to the delamination issue of electrode composite at the edge during punching process, the 1 wt% electrode is excluded for further evaluation. When the PVdF binder content decreases from 4 to 2 wt%, both adhesion strength and shear stress decrease from 0.4846 to $0.2627kN\;m^{-1}$ by -46% and from 3.847 to 2.013 MPa by -48%, respectively. Regardless of these substantial decline of mechanical properties, their initial electrochemical properties such as initial coulombic efficiency and voltage profile are almost the same. However, owing to high loading level, the 2 wt% electrode not only exhibits worse cycle performance than the 4 wt% electrode, but also cannot maintain its mechanical integrity only after 80 cycles. Therefore, if the binder content is reduced to increase the area capacity, the mechanical properties as well as the cycle performance must be carefully evaluated.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.19 no.1
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• pp.35-39
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• 2006

In this study, in order to develop the multilayer piezoelectric actuator and ultrasonic resonator, PMN-PNN-PZT ceramics were fabricated by sintering with $Li_2CO_3-Na_2CO_3$ as sintering aids at $950^{\circ}C$ and their piezoelectric and dielectric characteristics were investigated as a function of PNN substitution. With increasing PNN substitution, dielectric constant(${\epsilon}_r$), electromechanical coupling factor(kp), and piezoelectric d constant($d_{33}$) were increased to $12 mol\%$ PNN substitution and then showed a tendency to decrease rapidly With increasing PNN substitution, crystal structure changed from tetragonal to rhombohedral at $12 mol\%$ PNN substitution and then secondary phase was appeared and its intensity was increased. At the $12 mol\%$ PNN substituted PMN-PZT composition ceramic sintered at $950^{\circ}C$, density, kp, $d_{33}$ and Qm showed the optimum value of $7.79 g/cm^3$, 0.599, 419 pC/N, and 894, respectively for multilayer piezoelectric actuator application.

• Journal of Powder Materials
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• v.26 no.1
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• pp.49-57
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• 2019

Layered $LiNi_{0.83}Co_{0.11}Mn_{0.06}O_2$ cathode materials single- and dual-doped by the rare-earth elements Ce and Nd are successfully fabricated by using a coprecipitation-assisted solid-phase method. For comparison purposes, non-doping pristine $LiNi_{0.83}Co_{0.11}Mn_{0.06}O_2$ cathode material is also prepared using the same method. The crystal structure, morphology, and electrochemical performances are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) mapping, and electrochemical techniques. The XRD data demonstrates that all prepared samples maintain a typical ${\alpha}-NaFeO_2$-layered structure with the R-3m space group, and that the doped samples with Ce and/or Nd have lower cation mixing than that of pristine samples without doping. The results of SEM and EDS show that doped elements are uniformly distributed in all samples. The electrochemical performances of all doped samples are better than those of pristine samples without doping. In addition, the Ce/Nd dual-doped cathode material shows the best cycling performance and the least capacity loss. At a 10 C-rate, the electrodes of Ce/Nd dual-doped cathode material exhibit good capacity retention of 72.7, 58.5, and 45.2% after 100, 200, and 300 cycles, respectively, compared to those of pristine samples without doping (24.4, 11.1, and 8.0%).

• Journal of the Korean earth science society
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• v.27 no.1
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• pp.49-60
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• 2006

The purpose of this study is to investigate geochemical characteristics for stream sediments in the Naju area. We collected 139 stream sediments samples from primary channels. Samples were dried slowly in the laboratory and chemical analysis was carried out using XRF. ICP-AES and NAA. In order to investigate geochemical characteristics, the geological groups categorized into granitic gneiss area, schist area, granite area, arenaceous rock area, tuff area, andesite area, and rhyolite area. Average contents of major elements for geological groups are $SiO_2\;58.37{\sim}66.06wt.%,\;Al_2O_3\;13.98{\sim}18.41wt.%,\;Fe_2O_3\;4.09{\sim}6.10wt.%,\;CaO\;0.54{\sim}1.33wt.%,\;MgO\;0.86{\sim}1.34wt.%,\;K_2O\;2.38{\sim}4.01wt.%,\;Na_2O\;0.90{\sim}1.32wt.%,\;TiO_2\;0.82{\sim}1.03wt.%,\;MnO\;0.09{\sim}0.15wt.%,\;P_2O_5\;0.11{\sim}0.18wt.%$. According to the comparison of average contents of major elements, $Al_2O_3\;and\;K_2O$ are higher in granitic gneiss area, $Fe_2O_3,\;CaO,\;P_2O_5$ are higher in tuff area, MgO and $TiO_2$ are higher in andesite area, $Na_2O_$ is higher in rhyolite area, $SiO_2$, and MnO are higher in arenaceous rock area. Average contents of minor and rare earth elements for geological groups are $Ba\;1278{\sim}1469ppm,\;Be\;1.1{\sim}1.5ppm,\;Cu\;18{\sim}25ppm,\;Nb\;25{\sim}37ppm,\;Ni\;16{\sim}25ppm,\;Pb\;21{\sim}28ppm,\;Sr\;83{\sim}155ppm,\;V\;64{\sim}98ppm,\;Zr\;83{\sim}146ppm,\;Li\;32{\sim}45ppm,\;Co\;7.2{\sim}12.7ppm,\;Cr\;37{\sim}76ppm,\;Cs\;4.8{\sim}9.1ppm,\;Hf\;7.5{\sim}25ppm,\;Rb\;88{\sim}178ppm,\;Sc\;7.7{\sim}12.6ppm,\;Zn\;83{\sim}143ppm,\;Pa\;11.3{\sim}37ppm,\;Ce\;69{\sim}206ppm,\;Eu\;1.1{\sim}1.5ppm,\;Yb\;1.8{\sim}4.4ppm$. According to the comparison of average contents of minor and rare earth elements for geological groups, Pb, Li, Cs, Hf, Rb, Sb, Pa, Ce, Eu, and Yb are higher in granitic gneiss area; Ba, Co, and Cr in schist area; Nb, Ni, and Zr in arenaceous rock area; Sr in tuff area: and Be, Cu, V, Sc, and Zn are such in andesite area.

• Applied Chemistry for Engineering
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• v.31 no.1
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• pp.97-102
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• 2020

Recently, various degradation mechanisms of lithium secondary battery cathode materials have been revealed. As a result, many studies on overcoming the limitation of cathode materials and realizing new electrochemical properties by controlling the degradation mechanism have been reported. Li-rich layered oxide is one of the most promising cathode materials due to its high reversible capacity. However, the utilization of Li-rich layered oxide has been restricted, because it undergoes a unique atomic structure change during the cycle, in turn resulting in unwanted electrochemical degradations. To understand an atomic structure deterioration mechanism and suggest a research direction of Li-rich layered oxide, we deeply evaluated the atomic structure of 0.4Li₂MnO₃_0.6LiNi_1/3Co_1/3Mn_1/3O₂ Li-rich layered oxide during electrochemical cycles, by using an atomic-resolution analysis tool. During a charge process, Li-rich materials undergo a cation migration of transition metal ions from transition metal slab to lithium slab due to the structural instability from lithium vacancies. As a result, the partial structural degradation leads to discharge voltage drop, which is the biggest drawback of Li-rich materials.