• Applied Chemistry for Engineering
• /
• v.23 no.2
• /
• pp.131-137
• /
• 2012

Polyaniline (PANI) and polypyrrole (Ppy) hollow sphere structures with controlled shell thicknesses can be easily synthesized than those of using a layer-by-layer method for cathode active material of lithium-ion batteries. Polystyrene (PS) core was synthesized by emulsion polymerization using an anion surfactant. The shell thicknesses of PANI and Ppy were controlled by amounts of aniline and pyrrole monomers. PS was removed by an organic solution. This structure increased in contact with an electrolyte and a specific capacity in lithium-ion batteries. But polymers have disadvantages such as the difficult control of molecular weights and low densities. These disadvantages were completed by controlled shell thicknesses. The amount of aniline monomer increased from 1.2, 2.4, 3.6, 4.8 to 6.0 mL, and the shell thicknesses were 30.2, 38.0, 42.2, 48.2, and 52.4 nm, respectively. And the amount of pyrrole monomer was 0.6, 1.2, 2.4 and 3.6 mL, the shell thicknesses were 16.0, 22.0, 27.0 and 34.0 nm, respectively. In the cathode materials with controlled shell thicknesses, shell thicknesses of the PANI hollow spheres were 30.2, 42.2, and 52.4 nm, and discharge specific capacities of after 10 cycle were ~18, ~29, and ~62 mAh/g, respectively. The shell thicknesses of the Ppy hollow spheres were 16.0, 22.0, 27.0 and 34.0 nm, and discharge specific capacities of after 15 cycle were ~15, ~36, ~56, and ~77 mAh/g, respectively. Thus, shell thicknesses of PANI and Ppy increased, the specific capacities increased.

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

• Transactions of the Korean hydrogen and new energy society
• /
• v.26 no.2
• /
• pp.170-178
• /
• 2015

In this study, we carry out a study on how to improve performance of vanadium redox flow battery (VRFB) through promoting reaction rate of rate determining vanadium reaction ($[VO]^{2+}/[VO_2]^+$). In order to do that, three different carbons like Vulcan (XC-72), CMK3 and MSU-F-C are adopted as the catalysts, while their catalytic activity and reaction reversibility are evaluated using half-cell tests. Their topological images are also measured by TEM. For estimation of the VRFB performance, multiple charge-discharge curves of VRFBs including the catalysts are measured by single cell tests. As a result of that, MSU-F-C shows relatively excellent catalytic activity and reaction reversibility as well as large surface area compared to those of Vulcan (XC-72) and CMK3. Also, in terms of the performance of VRFBs including the catalysts, VRFB including MSU-F-C indicates (i) low charging/discharging overpotentials and low internal resistance, (ii) high charge/discharge capacities and (iii) high energy efficiency. These VRFB performance data are well agreed with results on catalytic activity and reaction reversibility. The reason that MSU-F-C induces superior VRFB performances is attributed to (i) its large surface area and (ii) its hydrophilic surface functional groups that mainly consist of hydroxyl bonds that are supposed to play active surface site role for facilitaing $[VO]^{2+}/[VO_2]^+$ redox reaction. Based on the above results, it is found that adoption of MSU-F-C as catalyst for VRFB results in improvement in VRFB performance by promoting the languid $[VO]^{2+}/[VO_2]^+$ redox reaction.

• KSCE Journal of Civil and Environmental Engineering Research
• /
• v.36 no.4
• /
• pp.637-644
• /
• 2016

This study sought to reevaluate the water supply capacities of the Nakdong river dams, and identify measures to remedy any shortages using weirs, focusing on 5 multipurpose dams and 8 weirs. The reevaluation of the dams was performed by the HEC-5 program using the original design criteria and inflow data recorded for each dam. The results show that the capacities of the 3 dams has decreased to 73~87%. Three simulations were performed to determine the effect of coordinating the dams and weirs. The first simulation was based on individual operation of the dams; the second on coordinated operation of the dams; and the third on coordinated operation of the dams and weirs. To obtain a water supply reliability of 95%, the annual water shortage was calculated for a 20-year period (1992~2011). In addition, long-term runoff simulation data used in the national river basin investigation by the Ministry of Land, Infrastructure and Transportation were used with the dam discharge data, because long-term inflow data for the weirs were not available. The simulations were performed by the HEC-ResSim program, with the reservoir network divided into 2 groups based on the Waegwan water station. The results show that water supply capacity for the 3 simulations to be $2424Mm^3/yr$, $2612Mm^3/yr$ and $2734Mm^3/yr$, respectively. This indicates that coordinated operation of the dams and weirs could provide an additional water supply of $122Mm^3/yr$.

• Transactions of the Korean hydrogen and new energy society
• /
• v.31 no.1
• /
• pp.132-137
• /
• 2020

Lithium secondary batteries have become an important power source for portable electronic devices such as cellular phones, laptop computers. Presently, commercialized lithium-ion batteries use a LiCoO₂ cathode. However, due to the high cost and environmental problems resulting from cobalt, an intensive search for new electrode materials is being actively conducted. Recently, solid solution LiMn_1-xNi_xO₂ have become attractive because of high capacity and enhanced safety at high voltages over 4.5 V. The Li_1.6Ni_0.35Mn_0.65O₂ compounds were conventionally prepared by a sol-gel method, which can produce the layered Li-Ni-Mn-O compounds with a high homogeneity. And by adding a graphene 2wt% the first charge-discharge voltage profiles was increased over Li_1.6Ni_0.35Mn_0.65O₂ compound. Also, the variation s of the discharge capacities with cycling showed a higher capacity retention rater. In this study, material lifecycle evaluation was performed to analyze the environmental impact characteristics of Li_1.6Ni_0.35Mn_0.65O₂ & graphene 2wt% half-cell manufacturing process. The software of material life cycle assessment was Gabi. Through this, environmental impact assessment was performed for each process. The environmental loads induced by Li_1.6Ni_0.35Mn_0.65O₂ & graphene 2wt% synthesis process were quantified and analyzed, and the results showed that the amount of power had the greatest impact on the environment.

• Journal of Powder Materials
• /
• v.13 no.5 s.58
• /
• pp.327-335
• /
• 2006

In the development of new hydrogen absorbing materials for a next generation of metal hydride electrodes for rechargeable batteries, metastable Mg-Ni-based compounds find currently special attention. Amor phous-nanocrystalline $Mg_{63}Ni_{30}Y_7$ and $Mg_{50}Ni_{30}Y_{20}$ alloys were produced by mechanical alloying and melt-spinning and characterized by means of XRD, TEM and DSC. On basis of mechanically alloyed Mg-Ni-Y powders, complex hydride electrodes were fabricated and their electrochemical behaviour in 6M KOH (pH=14,8) was investigated. The electrodes made from $Mg_{63}Ni_{30}Y_7$ powders, which were prepared under use of a SPEX shaker mill, with a major fraction of nanocrystalline phase reveal a higher electrochemical activity far hydrogen reduction and a higher maximum discharge capacity (247 mAh/g) than the electrodes from alloy powder with predominantly amorphous microstructure (216 mAh/g) obtained when using a Retsch planetary ball mill at low temperatures. Those discharge capacities are higher that those fur nanocrystalline $Mg_2Ni$ electrodes. However, the cyclic stability of those alloy powder electrodes was low. Therefore, fundamental stability studies were performed on $Mg_{63}Ni_{30}Y_7$ and $Mg_{50}Ni_{30}Y_{20}$ ribbon samples in the as-quenched state and after cathodic hydrogen charging by means of anodic and cathodic polarisation measurements. Gradual oxidation and dissolution of nickel governs the anodic behaviour before a passive state is attained. A stabilizing effect of higher fractions of yttrium in the alloy on the passivation was detected. During the cathodic hydrogen charging process the alloys exhibit a change in the surface state chemistry, i.e. an enrichment of nickel-species, causing preferential oxidation and dissolution during subsequent anodization. The effect of chemical pre-treatments in 1% HF and in $10\;mg/l\;YCl_3/1%\;H_2O_2$ solution on the surface degradation processes was investigated. A HF treatment can improve their anodic passivation behavior by inhibiting a preferential nickel oxidation-dissolution at low polarisation, whereas a $YCl_3/H_2O_2$ treatment has the opposite effect. Both pre-treatment methods lead to an enhancement of cathodically induced surface degradation processes.

• Korean Chemical Engineering Research
• /
• v.58 no.1
• /
• pp.52-58
• /
• 2020

Electrochemical characterization and thermal stability were investigated for MgF₂ coated LiNi_0.8Co_0.15Al_0.05O₂ cathode. The ratio of MgF₂ was controlled by 0.5, 1, 3 wt%. Cyclic voltammetry, charge-discharge profiles, rate capability, cycle life were measured for electrochemical properties. DSC analysis was measured for thermal stability. The first discharge capacities of MgF₂ coated LiNi_0.8Co_0.15Al_0.05O₂ were decreased at 0.1C-rate compared to pristine LiNi_0.8Co_0.15Al_0.05O₂. But the rate capability and cycle life of MgF₂ coated LiNi_0.8Co_0.15Al_0.05O₂ were improved at 2C-rate. In DSC analysis result, the exothermic temperature of MgF₂ coated LiNi_0.8Co_0.15Al_0.05O₂ was increased and peak height was decreased.

• Journal of the Korean Electrochemical Society
• /
• v.9 no.2
• /
• pp.64-69
• /
• 2006

Cathode materials of Al-doped $Li(Ni_{1/3}Co_{1/3}Mn_{1/3-x}Al_x)O_2$ (x=0.0, 0.005, 0.01 0.05) for lithium ion batteries were synthesized with ultra-sonic spray pyrolysis method and single-step heat treatment. No secondary phases were found in all synthesized powders. The intensity ratio of $I_{003}\;to\;I_{104}$, however, slightly decreased and the particle size increased with the Al contents. The cells with bare, 0.5 and 1.0 at% Al-doped powders showed the initial discharge capacities of 182, 180 and $184mAhg^{-1}$ in a voltage range of $3.0\sim4.5V$ at 1C rate, and the capacity retentions of 81, 77 and 78% at the end of 30 cycles, respectively. But in the voltage range of $3.0\sim4.6V$, the Al-doping significantly enhanced the cycle stability. For example, the discharge capacity after 50 cycles was maintained to 70% in the 0.5 at% Al-doped sample compared to only 30% in no doped sample. The improvement of the cycle stability was thought to be due to $Mn^{3+}$ ion decrease as the Al doping from the XPS analysis results.

• Journal of the Korean Electrochemical Society
• /
• v.3 no.4
• /
• pp.224-231
• /
• 2000

The exfoliation of graphite (layer) was progressed due to the irreversible insertion of PC molecules between graphene layers, when propylene carbonate (PC) solvent was used as the organic solvents. The problem could be mitigated by the replacement of PC by ethylene carbonate (EC). But, the freezing point of EC-based electrolyte increased due to the high freezing point of $EC(36.2^{\circ}C)$. Therefore, EC+PC mixed electrolyte is expected as a good organic electrolyte for lithium ion battery. The EC-based organic electrolyte containing PC within pertinent quantity can be expected to have high molar conductivity and reduced exfoliation of graphite layer. The dielectric constant and molar conductivity of $LiPF_6/PC+EC+DEC$ electrolyte was investigated with a variation in the PC content. The electrochemical properties of carbon electrode in the electrolyte were also investigated. Molar conductivity and dielectric constant increased linearly by increasing the PC volume fraction in the electrolyte. The results of charge-discharge test for carbon/electrolyte/Li cell indicated that the initial irreversible specific capacity(IIC) of MCMB-6-28s and MPCF3000 decreased by the addition of $0.83 vol\%$ of PC, but increased with PC content over than $0.83 vol\%$. In the case of MPCF3000 and PCG100 having less than $10 vol\%$ PC, IIC was lower than 50 mAh/g. The discharge specific capacities varied with carbon material, but did not vary with PC content in the electrolyte.

• Korean Chemical Engineering Research
• /
• v.54 no.2
• /
• pp.157-162
• /
• 2016

Porous $Co(OH)_2$ nano-flake thin films were prepared by a potential-controlled electro-deposition technique at various deposition voltage (-0.75, -1.0, -1.2, and -1.4 V) on Ti-mesh substrates for supercapacitor application. The potential of electrode was controlled to regulate the film thickness and the amount of $Co(OH)_2$ nano-flake on the titanium substrate. The film thickness was shown to reach the maximum value of $34{\mu}m$ at -1.4 V of electrode potential, where 17.2 g of $Co(OH)_2$ was deposited on the substrate. The specific discharge capacitances were measured to be 226, 370, 720, and $1008mF\;cm^{-2}$ in the 1st cycle corresponding to the films which were formed at -0.75, -1.0, -1.2, and -1.4 V of electrode potentials, respectively. Then the discharge capacities were decreased to be 206, 349, 586 and $866mF/cm^{-2}$, where the persistency rates were 91, 94, 81, and 86%, respectively.