• Proceedings of the Materials Research Society of Korea Conference
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• 2011.10a
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• pp.30.1-30.1
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• 2011

Silicon is one of useful materials in various industry such as semiconductor, solar cell, and secondary battery. The metallic silicon produces generally melting process for ingot type or chemical vapor deposition (CVD) for thin film type. However, these methods have disadvantages of high cost, complicated process, and consumption of much energy. Electrodeposition has been known as a powerful synthesis method for obtaining metallic species by relatively simple operation with current and voltage control. Unfortunately, the electrodeposition of the silicon is impossible in aqueous electrolyte solution due to its low oxidation-reduction equilibrium potential. Ionic liquids are simply defined as ionic melts with a melting point below $100^{\circ}C$. Characteristics of the ionic liquids are high ionic conductivities, low vapour pressures, chemical stability, and wide electrochemical windows. The ionic liquids enable the electrochemically active elements, such as silicon, titanium, and aluminum, to be reduced to their metallic states without vigorous hydrogen gas evolution. In this study, the electrodeposion of silicon has been investigated in ionic liquid of 1-butyl-3-methylpyrolidinium bis (trifluoromethylsulfonyl) imide ([bmpy]$Tf_2N$) saturated with $SiCl_4$ at room temperature. Also, the effect of electrode materials on the electrodeposition and morphological characteristics of the silicon electrodeposited were analyzed The silicon electrodeposited on gold substrate was composed of the metallic Si with single crystalline size between 100~200nm. The silicon content by XPS analysis was detected in 31.3 wt% and the others were oxygen, gold, and carbon. The oxygen was detected much in edge area of th electrode due to $SiO_2$ from a partial oxidation of the metallic Si.

• Transactions of the Korean hydrogen and new energy society
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• v.7 no.1
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• pp.11-18
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• 1996

The Laves phase alloy hydrides have some promising properties as electrode materials in reversible metal hydride batteries. In this work, the hydrogen storage performance, crystallographic parameters, surface morphology, surface area and electrochemical characteristics of the non-stoichiometric $ZrMn_{0.3}V_{0.7}Ni_{1.4+{\alpha}}$, $ZrMn_{0.5}V_{0.5}Ni_{1.4+{\alpha}}$($\alpha$ =0.0, 0.2, 0.4, 0.6) alloys were examined. These as-cast alloys were found to have mainly a cubic C15-type Laves phase structure by X -ray diffraction analysis. The equilibrium pressure of the alloy were increased as $\alpha$ increased in both two types alloy. In case of $ZrMn_{0.5}V_{0.5}Ni_{1.4+{\alpha}}$ alloys, discharge efficiency and the rate capability of the alloy were decreased as $\alpha$ increased but, these values were increased in case of $ZrMn_{0.3}V_{0.7}Ni_{1.4+{\alpha}}$ alloys. The differences of these electrode properties observed were dependent on the reaction surface area and the catalytic activity of unit area of the each electrode.

• 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.

• Transactions of the Korean hydrogen and new energy society
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• v.10 no.4
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• pp.197-210
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• 1999

The hydrogen storage performance and electrochemical properties of $Zr_{1-X}Ti_X(Mn_{0.2}V_{0.2}Ni_{0.6})_{1.8}$(X=0.0, 0.2, 0.4, 0.6) alloys are investigated. The relationship between discharge performance and alloy characteristics such as P-C-T characteristics and crystallographic parameters is also discussed. All of these alloys are found to have mainly a C14-type Laves phase structure by X-ray diffraction analysis. As the mole fraction of Ti in the alloy increases, the reversible hydrogen storage capacity decreases while the equilibrium hydrogen pressure of alloy increases. Furthermore, the discharge capacity shows a maxima behavior and the rate-capability is increased, but the cycling durability is rapidly degraded with increasing Ti content in the alloy. In order to analyze the above phenomena, the phase distribution, surface composition, and dissolution amount of alloy constituting elements are examined by S.E.M., A.E.S. and I.C.P. respectively. The decrease of secondary phase amount with increasing Ti content in the alloy explains that the micro-galvanic corrosion by multiphase formation is little related with the degradation of the alloys. The analysis of surface composition shows that the rapid degradation of Ti-substituted Zr base alloy electrode is due to the growth of oxygen penetration layer. After comparing the radii of atoms and ions in the electrolyte, it is clear that the electrode surface becomes more porous, and that is the source of growth of oxygen penetration layer while accelerating the dissolution of alloy constituting elements with increasing Ti content. Consequently, the rapid degradation (fast growth of the oxygen-penetrated layer) with increasing Ti substitution in Zr-based alloy is ascribed to the formation of porous surface oxide through which the oxygen atom and hydroxyl ion with relatively large radius can easily transport into the electrode surface.

• Applied Chemistry for Engineering
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• v.7 no.3
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• pp.473-480
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• 1996

Synthesis of n-perfluorooctanesulfonyl fluoride(n-PFOSF), which is valuable precursor perfluoro-chemicals, was studied by electrochemical fluorination(ECF). Of prime concern was to investigate the cyclic voltamograms of Ni electrode in anhydrous hydrogen fluoride(AHF) with and without the reactants and to measure fluorine evolution potential. In a batch cell, chronoampherometric electrolysis and various chemical analysis such as GC, GC/MS and IR were used to understand the amphere change of electrode and the reaction paths. Fluorine equilibrium potential was found to be about 2.8V(vs. $Cu/CuF_2$) from the cyclic voltammograms and decay curves of anode potential in AHF. In batch processes, the ECF proceeded in two distinguished steps. The first step proceeded electrochemically and the second one chemically. Under 7V(vs. $Cu/CuF_2$), amount of crude products was proportional to the applied anode potential. Above 7V(vs. $Cu/CuF_2$), it had a hundred percentage with weight ratio of reactants and productivity of PFOSF was almost constant.

• Korean Chemical Engineering Research
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• v.50 no.1
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• pp.93-105
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• 2012

Activity coefficients and solubilities of L-Valine and L-Proline in aqueous solutions containing each of four electrolytes such as NaCl, KCl, $NaNO_3$ and $KNO_3$ were measured at 298.15 K. The measurements of activity coefficients were carried out in the electrochemical cell coupled with two ion-selective electrodes (cation and anion), and the solubilities were measured by the gravimetric analysis of saturated solutions in equilibrium with the solid phase of amino acid. The measured activity coefficients of electrolytes and amino acids were correlated with the theoretical thermodynamic model presented in the previous work [Korean Chem. Eng. Res. 48(4), 519(2010)]. It was found that the activity coefficients of amino acids and electrolytes described based on the our previous model were well agreeable with experimental data. Also the experimental solubility data of L-Valine and L-Proline were successfully correlated with the thermodynamic relation mentioned in the previous work.

• Korean Chemical Engineering Research
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• v.61 no.1
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• pp.155-161
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• 2023

Ion concentration polarization (ICP) is one of the essential important mechanisms for biomolecule preconcentration devices as well as a fundamental transport phenomenon found in electrodialysis, electrochemical cell, etc. The ICP triggered by externally applied voltage enables the biomolecular analyte to be preconcentrated at an arbitrary position by a locally amplified electric field inside the microchannel. Conventional preconcentration methodologies using the ICP have two limitations: uncertain equilibrium position and hydrodynamic instability of preconcentration plug. In this work, a new preconcentration method in the dead-end microchannel around cation exchange membrane was numerically studied to resolve the limitations. As a result, the numerical model showed that the analyte was concentrated at a shock front developed in a geometrically confined dead-end channel. Furthermore, the electrokinetic behaviors for preconcentration dynamics were analyzed by changing microchannel's applied voltage and volumetric charge concentration of microchannel as key parameters to describe the dynamics. This work would provide an effective means for a point-of-care platform that requires ultra-fast preconcentration method.

• Journal of the Korean Electrochemical Society
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• v.5 no.3
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• pp.131-142
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• 2002

The Langmuir adsorption isotherms of the under-potentially deposited hydrogen (UPD H) and the over-potentially deposited hydrogen (OPD H) at the poly-Pt/0.5M $H_2SO_4$ and 0.5 M LiOH aqueous electrolyte interfaces have been studied using cyclic voltammetric and ac impedance techniques. The behavior of the phase shift $(0^{\circ}{\leq}{-\phi}{\leq}90^{\circ})$ for the optimum intermediate frequency corresponds well to that of the fractional surface coverage $(1{\geq}{\theta}{\geq}0)$ at the interfaces. The phase-shift method, i.e., the phase-shift profile $({-\phi}\;vs.\;E)$ for the optimum intermediate frequency, can be used as a new electrochemical method to determine the Langmuir adsorption isotherms $({\theta}\;vs.\;E)$ of the UPD H and the OPD H for the cathodic $H_2$ evolution reactions at the interfaces. At the poly-Pt/0.5M $H_2SO_4$ aqueous electrolyte interface, the equilibrium constant (K) and the standard free energy $({\Delta}G_{ads})$ of the OPD H are $2.1\times10^{-4}$ and 21.0kJ/mol, respectively. At the poly-Pt/0.5M LiOH aqueous electrolyte interface, K transits from 2.7(UPD H) to $6.2\times10^{-6}$ (OPD H) depending on the cathode potential (E) and vice versa. Similarly, ${\Delta}G_{ads}$ transits from -2.5kJ/mol (UPD H) to 29.7kJ/mol (OPD H) depending on I and vice versa. The transition of K and ${\Delta}G_{ads}$ is attributed to the two distinct adsorption sites of the UPD H and the OPD H on the poly-Pt surface. The UPD H and the OPD H on the poly-Pt surface are the independent processes depending on the H adsorption sites themselves rather than the sequential processes for the cathodic $H_2$ evolution reactions. The criterion of the UPD H and the OPD H is the H adsorption sites and processes rather than the $H_2$ evolution reactions and potentials. The poly-Pt wire electrode is more efficient and useful than the Pt(100) disc electrode for the cathodic $H_2$ evolution reactions in the aqueous electrolytes. The phase-shift method is well complementary to the thermodynamic method rather than conflicting.

• Korean Chemical Engineering Research
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• v.48 no.4
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• pp.519-533
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• 2010

Activity oefficients and solubilities of L-Alanine in aqueous solutions containing each of four electrolytes(NaCl, KCl, $NaNO_3$ and $KNO_3$) were measured at 298.15 K. The measurements of activity coefficients were carried out in the electrochemical cell coupled with two ion-selective electrodes(cation and anion), and the solubilities were measured by the gravimetric analysis of saturated solutions in equilibrium with the solid phase of L-alanine. To model the activity coefficients and solubilities of amino acid in the amino acid/electrolyte aqueous solutions, thermodynamic relations of the residual Helmholtz free energy in the amino acid/electrolyte aqueous solutions were developed based on the perturbed-chain statistical associating fluid theory(PC-SAFT) combined with the primitive mean spherical approximation(primitive-MSA). In the present model, it is assumed that the zwitterions of L-alanine are associated with each other and cross-associated with water molecules, and also cross-associated with the cation and anion dissociated from an electrolyte(inorganic salt). The activity coefficients and solubilities of L-Alanine calculated from the theoretical model proposed in this work are found to be well agreeable with experimental data.

• Korean Chemical Engineering Research
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• v.45 no.5
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• pp.433-441
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• 2007

This work investigated the stability of a Sn-modified Pt electrode, which was used for reduction of nitrate, fabricated by an adsorption or electro-deposition of Sn on Pt. In order to find the causes for instability of the electrode, the effects of the solutions in which the electrode was used and the potential applied to the electrode on the electrochemical and metallurgical behaviors of Sn on Pt were studied. The Sn of freshly- prepared modified-Sn Pt electrode existed as Sn hydroxide form, which brought about an easy loss of the electro-activity of the electrode even staying in water, especially in acid solution. When the Sn-modified Pt electrode was used for the reduction of nitrate, the electro-activity of the electrode was affected depending on the potential applied to the electrode. When a more negative potential than the redox equilibrium potential between $Sn(OH)_2$ and Sn was applied to the electrode, the Sn hydroxide was converted to Sn that could diffused into Pt, which leaded to the loss of electro-activity of the electrode as well. The solid diffusion of Sn increased linearly with the applied potential. The Sn-electrodeposited Pt electrode which had more Sn on the electrode was more favorable to maintaining the integrity of the electrode during the reduction of nitrate than the Sn-adsorbed Pt electrode prepared in the under-potential deposition way.