• Journal of the Korean Electrochemical Society
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• v.27 no.2
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• pp.55-72
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• 2024

Secondary batteries are used as an essential renewable energy source in our lives, such as electric vehicles and energy storage systems (ESS), as an alternative to fossil fuels due to global warming. However, cases of battery fires and explosions have been reported due to thermal runaway in secondary batteries due to various causes such as overdischarge, high-speed charging and discharging, and external short circuit, and great efforts are being made to find solutions suitable for each cause. In particular, as cases presumed to be caused by the overcharging process have been reported, this review will examine the chemical reactions of secondary batteries that can occur during the overcharging process and discuss risk investigation methods to check and prevent them.

• Korean Chemical Engineering Research
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• v.54 no.6
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• pp.734-745
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• 2016

This review article described the electrochemical Frumkin, Langmuir, and Temkin adsorption isotherms of over-potentially deposited hydrogen (OPD H) and deuterium (OPD D) for the cathodic $H_2$ and $D_2$ evolution reactions (HER, DER) at Pt, Ir, Pt-Ir alloy, Pd, Au, and Re/normal ($H_2O$) and heavy water ($D_2O$) solution interfaces. The Frumkin, Langmuir, and Temkin adsorption isotherms of intermediates (OPD H, OPD D, etc.) for sequential reactions (HER, DER, etc.) at electrode/solution interfaces are determined using the phase-shift method and correlation constants, which have been suggested and developed by Chun et al. The basic procedure of the phase-shift method, the Frumkin, Langmuir, and Temkin adsorption isotherms of OPD H and OPD D and related electrode kinetic and thermodynamic parameters, i.e., the fractional surface coverage ($0{\leq}{\theta}{\leq}1$) vs. potential (E) behavior (${\theta}$ vs. E), equilibrium constant (K), interaction parameter (g), standard Gibbs energy (${\Delta}G_{\theta}{^{\circ}}$) of adsorption, and rate (r) of change of ${\Delta}G_{\theta}{^{\circ}}$ with ${\theta}$ ($0{\leq}{\theta}{\leq}1$), at the interfaces are briefly interpreted and summarized. The phase-shift method and correlation constants are useful and effective techniques to determine the Frumkin, Langmuir, and Temkin adsorption isotherms and related electrode kinetic and thermodynamic parameters (${\theta}$ vs. E, K, g, ${\Delta}G_{\theta}{^{\circ}}$, r) at electrode/solution interfaces.

• Resources Recycling
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• v.26 no.4
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• pp.34-41
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• 2017

The effect of Mn(II) concentration on the anodic reactions occurring on a Pb-Ag electrode in sulfuric acid solutions has been studied by potentiostatic oxidation in the potential range of 1.8 to 2.0 V. High oxidation potentials and low initial concentrations of Mn(II) resulted in higher concentrations of soluble Mn(III) ions which were obtained from spectrophotometric analysis of the solution after oxidation. $MnO_2$ was deposited on the electrode by electrochemical oxidation of Mn(II) at 1.8 and 1.9 V, while it was formed by disproportionation of Mn(III) at 2.0 V. No $PbO_2$ was formed in the presence of Mn(II) during potentiostatic oxidation treatment for two hours at 1.8 V. Chemical reduction of $PbO_2$ with Mn(II) led to a decrease in the amount of $PbO_2$ as Mn(II) concentration increased at 1.9 and 2.0 V.

• Journal of the Microelectronics and Packaging Society
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• v.31 no.2
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• pp.54-62
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• 2024

SICM (Scanning Ion Conductivity Microscopy) is a technique for measuring surface topography in an environment where electrochemical reactions occur, by detecting changes in ion conductivity as a nanopipette tip approaches the sample. This study includes an investigation of the current response curve, known as the approach curve, according to the distance between the tip and the sample. First, a simulation analysis was conducted on the approach curves. Based on the simulation results, then, several measuring experiments were conducted concurrently to analyze the difference between the simulated and measured approach curves. The simulation analysis confirms that the current squeezing effect occurs as the distance between the tip and the sample approaches half the inner radius of the tip. However, through the calculations, the decrease in current density due to the simple reduction in ion channels was found to be much smaller compared to the current squeezing effect measured through actual experiments. This suggests that ion conductivity in nano-scale narrow channels does not simply follow the Nernst-Einstein relationship based on the diffusion coefficients, but also takes into account the fluidic hydrodynamic resistance at the interface created by the tip and the sample. It is expected that SICM can be combined with SECM (Scanning Electrochemical Microscopy) to overcome the limitations of SECM through consecutive measurement of the two techniques, thereby to strengthen the analysis of electrochemical surface reactivity. This could potentially provide groundbreaking help in understanding the local catalytic reactions in electroless plating and the behaviors of organic additives in electroplating for various kinds of patterns used in semiconductor damascene processes and packaging processes.

• Proceedings of the Materials Research Society of Korea Conference
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• 2011.05a
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• pp.45.1-45.1
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• 2011

Cobalt-free $La_xSr_{4-x}Fe_6O_{13}$ ($0{\leq}x{\leq}2$) oxide have been synthesized and investigated as a potential cathode material for solid oxide fuel cells (SOFCs). $Sr_4Fe_6O_{13}$ consists of alternating perovskite layers ($Sr_4Fe_2O_8$) containing iron cations in octahedral oxygen coordination and $Fe_4O_5$ layers where iron cations have 5-fold coordination of two types-square pyramids and trigonal bipyramids. Our preliminary electrochemical testes of pristine $Sr_4Fe_6O_{13}$ show a rather high area specific resistance ($0.47{\Omega}cm^2$ at $700^{\circ}C$) for ~20 ${\mu}m$ thick layers with CGO electrolyte. The electrochemical performances are improved by La addition up to x=1 ($La_1Sr_3Fe_6O_{13}$, $0.06{\Omega}cm^2$ at $700^{\circ}C$). In addition, thermal expansion coefficient (TEC) values of $La_1Sr_3Fe_6O_{13}$ specimen demonstrated $15.1{\times}10^{-6}\;^{\circ}C^{-1}$ in the range of 25-900$^{\circ}C$, which provides good thermal expansion compatibility with the CGO electrolyte. An electrolyte supported (300-${\mu}m$-thick) single-cell configuration of $La_1Sr_3Fe_6O_{13}$/CGO/Ni-CGO delivered a maximum power density of 584 $mWcm^{-2}$ at $700^{\circ}C$. In addition, an anode supported single cell by YSZ electrolyte (10-${\mu}m$-thick) with a porous CGO interlayer between the cathode and the electrolyte to avoid undesired interfacial reactions exhibited 1,517 $mWcm^{-2}$ at $800^{\circ}C$. The unique composition of $La_1Sr_3Fe_6O_{13}$ with low thermal expansion coefficient and higher electrochemical properties could be a good cathode candidate for intermediate temperature SOFCs with CGO and YSZ electrolyte.

• Journal of the Korean Electrochemical Society
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• v.9 no.1
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• pp.19-28
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• 2006

The phase-shift method for determining the Langmuir, Frumkin, and Temkin adsorption isotherms ($\theta_H\;vs.\;E$) of H for the cathodic $H_2$ evolution reaction (HER) at a Pt/0.1 M KOH solution interface has been proposed and verified using cyclic voltammetric, differential pulse voltammetric, and electrochemical impedance techniques. At the Pt/0.1 M KOH solution interface, the Langmuir and Temkin adsorption isotherms ($\theta_H\;vs.\;E$), the equilibrium constants ($K_H=2.9X10^{-4}mol^{-1}$ for the Langmuir and $K_H=2.9X10^{-3}\exp(-4.6\theta_H)mol^{-1}$ for the Temkin adsorption isotherm), the interaction parameters (g=0 far the Langmuir and g=4.6 for the Temkin adsorption isotherm), the rate of change of the standard free energy of $\theta_H\;with\;\theta_H$ (r=11.4 kJ $mol^{-1}$ for g=4.6), and the standard free energies (${\Delta}G_{ads}^{\circ}=20.2kJ\;mol^{-1}$ for $k_H=2.9\times10^{-4}mol^{-1}$, i.e., the Langmuir adsorption isotherm, and $16.7<{\Delta}G_\theta^{\circ}<23.6kJ\;mol^{-1}$ for $K_H=2.9\times10^{-3}\exp(-4.6\theta_H)mol^{-1}$ and $0.2<\theta_H<0.8$, i.e., the Temkin adsorption isotherm) of H for the cathodic HER are determined using the phase-shift method. At intermediate values of $\theta_H$, i.e., $0.2<\theta_H<0.8$, the Temkin adsorption isotherm ($\theta_H\;vs.\;E$) corresponding to the Langmuir adsorption isotherm ($\theta_H\;vs.\;E$), and vice versa, is readily determined using the constant conversion factors. The phase-shift method and constant conversion factors are useful and effective for determining the Langmuir, Frumkin, and Temkin adsorption isotherms of intermediates for sequential reactions and related electrode kinetic and thermodynamic data at electrode catalyst interfaces.

• Journal of the Korean Electrochemical Society
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• v.15 no.4
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• pp.230-235
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• 2012

Polymer electrolytes consisted of $BF_3LiMA$ and 300 (PEGMA300) or 1100 (PEGMA1100) g $mol^{-1}$ of PEGMA were prepared and the electrochemical properties were characterized. Interestingly, the AC-impedance measurement shows $1.22{\times}10^{-5}S\;cm^{-1}$ of room temperature ionic conductivity from PEGMA1100 based solid polymer electrolytes while $8.54{\times}10^{-7}S\;cm^{-1}$ was observed in PEGMA300 based liquid polymer electrolytes. The more suitable coordination between lithium ion and ethylene oxide (EO) unit might be the reason of higher ionic conductivity which can be possible in PEGMA1100 based electrolytes since it has 23 EO units in monomer. The lithium ion transference number was found to be 0.6 due to the side reactions between $BF_3$ and lithium metal expecially for longer time but 0.9 was observed within 3000 seconds of measuring time which is strong evidence of a single-ion conductor.

• 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.

• Ceramist
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• v.21 no.4
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• pp.378-387
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• 2018

The optimal fabrication conditions for $Gd_{0.1}Ce_{0.9}O_{2-{\delta}}$(GDC) buffer layer and $La_{0.6}Sr_{0.4}Co_{0.2}Fe_{0.8}O_{3-{\delta}}$ (LSCF) cathode on 1mol% $CeO_2-10mol%\;Sc_2O_3$ stabilized $ZrO_2$ (CeScSZ) electrolyte were investigated for application of IT-SOFCs. GDC buffer layer was used in order to prevent undesired chemical reactions between LSCF and CeScSZ. These experiments were carried out with $5{\times}5cm^2$ anode supported unit cells to investigate the tendencies of electrochemical performance, Microstructure development and interface reaction between LSCF/GDC/CeScSZ along with the variations of GDC buffer layer thickness, sintering temperatures of GDC and LSCF were checked, respectively. Electrochemical performance was analyzed by DC current-voltage measurement and AC impedance spectroscopy. Microstructure and interface reaction were investigated by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Although the interfacial reaction between these materials could not be perfectly inhibited, We found that the cell, in which $6{\mu}m$ GDC interlayer sintered at $1200^{\circ}C$ and LSCF sintered at $1000^{\circ}C$ were applied, showed good interfacial adhesions and effective suppression of Sr, thereby resulting in fairly good performance with power density of $0.71W/cm^2$ at $800^{\circ}C$ and 0.7V.

• Applied Chemistry for Engineering
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• v.33 no.2
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• pp.126-132
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• 2022

Alkaline fuel cells using liquid fuels such as hydrazine and ammonia are gaining great attention as a clean and renewable energy solution possibly owing to advantages such as excellent energy density, simple structure, compact size in fuel container, and ease of storage and transportation. However, common shortcomings including cathode flooding, fuel crossover, side yield reactions, and fuel security and toxicity are still challenging issues. Real time monitoring of fuel concentrations integrated into a fuel cell device can help improving fuel cell performance via predicting any loss of fuels used at a cathode for efficient energy production. There have been extensive research efforts made on developing real-time sensing platforms for hydrazine and ammonia. Among these, recent advancements in electrochemical sensors offering high sensitivity and selectivity, easy fabrication, and fast monitoring capability for analysis of hydrazine and ammonia concentrations will be introduced. In particular, research trend on the integration of metallic and metal oxide nanoparticles and also their hybrids with carbon-based nanomaterials into electrochemical sensing platforms for improvement in sensitivity and selectivity will be highlighted.