• Title/Summary/Keyword: Electrochemical equilibrium

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Electrochemical Approach in Plasma Display Panel Glass Melts doped with Sulfate and Sulfide I. Oxygen Equilibrium Pressure

  • Kim, Ki-Dong;Kim, Hyo-Kwang
    • Journal of the Korean Ceramic Society
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    • v.45 no.2
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    • pp.90-93
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    • 2008
  • The oxygen gas behavior in PDP (plasma Display Panel) glass melts doped with sulfate ($SO_4^{-2}$) or blast furnace slag (BFS, $S^{2-}$) or both by means of yttria-stabilized zirconia (YSZ) electrodes was observed after the first fining. The temperature dependence of oxygen equilibrium pressure ($P_{O2}$) in each melt showed typical behavior, namely $P_{O2}$ decreased as temperature decreased. This suggests that an oxidation of $S^{4+}$ to $S^{6+}$ took place. However, the $P_{O2}$-value at constant temperature increased in the following order: BFS$P_{O2}$ of the melt doped with sulfate+BFS was much lower than that of the melt with only sulfate, although only 10% of sulfur was added by the BFS. This behavior can be explained by the redox reaction between sulfide ions in the BFS and dissolved oxygen ions in the melt during the first fining.

Determination of the Frumkin and Temkin Adsorption Isotherms of Hydrogen at Nickel/Acidic and Alkaline Aqueous Solution Interfaces Using the Phase-Shift Method and Correlation Constants

  • Chun, Jang-H.
    • Journal of the Korean Electrochemical Society
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    • v.15 no.1
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    • pp.54-66
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    • 2012
  • The phase-shift method and correlation constants, which are unique electrochemical impedance spectroscopy techniques for studying the linear relationship between the phase shift ($90^{\circ}{\geq}-{\varphi}{\geq}0^{\circ}$) vs. potential (E) behavior for the optimum intermediate frequency ($f_o$) and the fractional surface coverage ($0{\leq}{\theta}{\leq}1$) vs. E behavior, are proposed and verified to determine the Frumkin, Langmuir, and Temkin adsorption isotherms and the related electrode kinetic and thermodynamic parameters. At Ni/0.5 M $H_2SO_4$ and 0.1M LiOH aqueous solution interfaces, the Frumkin and Temkin adsorption isotherms (${\theta}$ vs. E) of H for the cathodic hydrogen ($H_2$) evolution, interaction parameters (g), equilibrium constants (K), standard Gibbs energies (${\Delta}G^0_{\theta}$) of H adsorption, and rates of change (r) of ${\Delta}G^0_{\theta}$ with ${\theta}$ have been determined using the phase-shift method and correlation constants. A lateral repulsive interaction (g>0) between the adsorbed H species appears. The value of K in the alkaline aqueous solution is much greater than that in the acidic aqueous solution.

Numerical model for local corrosion of steel reinforcement in reinforced concrete structure

  • Chen, Xuandong;Zhang, Qing;Chen, Ping;Liang, Qiuqun
    • Computers and Concrete
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    • v.27 no.4
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    • pp.385-393
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    • 2021
  • Reinforcement corrosion is the main cause of the durability failure of reinforced concrete (RC) structure. In this paper, a three-dimensional (3D) numerical model of macro-cell corrosion is established to reveal the corrosion mechanisms of steel reinforcement in RC structure. Modified Direct Iteration Method (MDIM) is employed to solve the system of partial differential equations for reinforcement corrosion. Through the sensitivity analysis of electrochemical parameters, it is found that the average corrosion current density is more sensitive to the change of cathodic Tafel slope and anodic equilibrium potential, compared with the other electrochemical parameters. Furthermore, both the anode-to-cathode (A/C) ratio and the anodic length have significant influences on the average corrosion current density, especially when A/C ratio is less than 0.5 and anodic length is less than 35 mm. More importantly, it is demonstrated that the corrosion rate of semi-circumferential corrosion is much larger than that of circumferential corrosion for the same A/C ratio value. The simulation results can give a unique insight into understanding the detailed electrochemical corrosion processes of steel reinforcement in RC structure for application in service life prediction of RC structures in actual civil engineer.

Electrochemical Stability of Co-Mo and Ni-Mo Intermetallic Compound Electrodes for Hydrogen Electrode of Alkaline Fuel Cell (알칼리형 연료전지의 수소극용 Co-Mo 및 Ni-Mo 금속간화합물 전극의 전기화학적 안정성)

  • Lee C. R.;Kang S. G.
    • Journal of the Korean Electrochemical Society
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    • v.2 no.3
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    • pp.150-155
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    • 1999
  • The Electrochemical stabilities of the Brewer-Engel type intermetallic compounds of Co-Mo $(35 wt\%)$ and Ni-Mo$(35 wt\%)$ manufactured by the arc-melting method for the hydrogen electrode of $H_2-O_2$ alkaline fuel cell were investigated. Effects of temperature and concentration on the electrochemical behavior of the electrodes in the $80^{\circ}C$ 6 N KOH solution deaerated with $N_2$ gas were studied by electrochemical methods. The effect of overpotential on the electrochemical stabilities of Co-Mo and Ni-Mo intermetallic compounds was also discussed under the normal operation condition of AFC. It was shown that Co-Mo electrode had lower electrochemical stability as compared to Ni-Mo. In the case of Co-Mo electrode, a simultaneous dissolution of cobalt and molybdenum has occurred at low anodic overpotential form equilibrium hydrogen electrode potential, but the dissolution of cobalt was serious, and Co(OH)l layer on the electrode surface formed at the high anodic overpotential. In contrast the Ni-Mo electrode had high electrochemical stability because formation of the dense and thin protective $Ni(OH)_2$ layer prevented the dissolution of molybdenum.

Function through Defects: Thermodynamic and Kinetics of Point Defects in Ionic Solids

  • Ko, Taegyung;Bang, Gyusuk;Shin, Jungmuk
    • The Korean Journal of Ceramics
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    • v.4 no.2
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    • pp.61-67
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    • 1998
  • The significance of point defects as relevant centers concerning electrochemical function is highlighted. Starting from the most simple case of dilute equilibrium bulk defect chemistry, influence of defect interaction and in particular the impact of interfaces on point defect redistribution are considered. Then recent progress in the field of kinetics in bulk and at boundaries is discussed. Finally, selected applications with emphasis on battery and sensor technology are presented.

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A Study on the Alloy Design of High Capacity Ti-Based Metal Hydride for Ni/MH Rechargeable Battery (Ni/MH 2차 전지용 고용량 Ti계 수소저장합금의 설계에 관한 연구)

  • Lee, Han-Ho;Lee, Jai-Young
    • Journal of Hydrogen and New Energy
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    • v.7 no.1
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    • pp.19-28
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    • 1996
  • Ti-Mn based hydrogen storage alloy were modified by substituting alloying elements such as Zr, V and Ni in order to design a high capacity MH electrode for Ni/MH rechargeable battery. When V was substituted in Ti-Mn binary system, the crystal structure was maintained as $Cl_4$ Laves phase at a composition of $Ti_{0.2}V_{0.4}Mn_{0.4}$ and $Ti_{0.4}V_{0.2}Mn_{0.4}$ and equilibrium pressure decreased below 1 atm without decreasing hydrogen storage capacity considerably. It was found that Ni should be included in Ti-V-Mn alloy in order to hydrogenate it electrochemically in KOH electrolyte. But substitution of Ni for Mn in Ti-V-Mn system caused the increase of equilibrium pressure above 1atm and decrease of hydrogen storage capacity. Zr was able to increase the reversible hydrogen storage capacity of Ti-V-Mn-Ni alloy without considerable change of hydrogenation properties. The electrochemical discharge capacity of Ti-Zr-V-Mn-Ni system were in the range of 350 - 464mAh/g and among them $Ti_{0.8}Zr_{0.2}V_{0.5}Mn_{0.5}Ni_{1.0}$ alloy had $Cl_4$ Laves single phase and very high electrochemical discharge capacity of 464mAh/g.

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Analysis on the Langmuir adsorption isotherm at the $Pt/H_2SO_4$ electrolyte interface using the ac impedance measurement and phase-shift method ($Pt/H_2SO_4$ 전해질 계면에서 교류임피던스 측정과 위상이동 방법에 의한 Langmuir 흡착등온식 해석)

  • Chun Jang Ho;Cho Sung Chil;Son Kwang Chul
    • Journal of the Korean Electrochemical Society
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    • v.2 no.1
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    • pp.23-26
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    • 1999
  • The Langmuir adsorption isotherm at the $(Pt)/0.1M\;H_2SO_4$ electrolyte interface has been qualitatively analyzed using the ac impedance measurement and phase-shift method. The phase shift $(\phi)$ depends on both the cathode potential (E<0) and frequency (f) and is inversely proportional to the factional surface coverage $(\theta)$. At an intermediate frequency band (ca. $1\~100$ Hz), the phase-shift profile $(\phi\;vs.\;E)$ can be related to the fractional surface coverage $(\theta\;vs.\;E)$. The phase-shift profile $(\phi\;vs.\;E)$ can be used as an experimental method to estimate and analyze the Langmuir adsorption isotherm $(\theta\;vs.\;E)$. The equilibrium constant (K) and the standard free energy $({\Delta}G_{ads})$ of the adsorbed hydrogen atom $(H_{ads})\;and\;3\times10^{-4}$ and 20.1 kJ/mol, respectively.

Structural Analysis of Species in NbCI5-EMIC Room-Temperature Molten Salt with Raman Spectroscopic Measurement and Ab Initio Molecular Orbital Calculation

  • Koura, Nobuyuki;Matsuzawa, Hidenori;Kato, Tomoki;Idemoto, Yasushi;Matsumoto, Futoshi
    • Journal of the Korean Electrochemical Society
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    • v.5 no.4
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    • pp.183-188
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    • 2002
  • The structure of species formed in $NbCI_5-I-ethyl-3-methylimidazolium$ chloride (EMIC) room-temperature molten salt (RTMS) was examined with the Raman spectroscopic measurement and ab initio molecular orbital calculation. The equilibrium structures of $NbCl_5,\;NbCl_6^-,\;Nb_2CI_{10},\;Nb_2CI_{11}^-,\;Nb_3CI_6^-,\;NbCI_6^--EMI^+\;(in\;which\;NbCI_6^-$ anion approaches $EMI^+$ cation with strong interaction) and $Nb_2CI_{11}^--EMI^+$ were obtained with the HF/LANL2DZ level of calculation. The harmonic frequencies at each equilibrium structure were compared with Raman spectra. The harmonic frequencies of $NbCI_6^--EMI^+,\; Nb_2CI_{11}^--EMI^+,\;and\;Nb_2CI_{10}$ were in good agreement with the Raman spectra of RTMS melts. In the $NbCI_5-EMIC RTMS$, the main species were $NbCI_6^-\;and\;EMI^+$. In the $NbCl_5-EMIC$ RTMS added $NbCl_5\;over\;50mol\%$, small amount of $Nb_2CI_{11}^-\;and\; Nb_2CI_{10}$ were also formed. The structures of anions and cation in the RTMS distorted from free ions with Coulomb force.

Electrochemical and Mechanical Characteristics of Covalently Cross-Linked SPEEK Polymer Electrolyte Membrane for Water Electrolysis (수전해용 공유가교 SPEEK 고분자 전해질 막의 전기 화학적 및 기계적 특성)

  • Kim, Kyung-Eon;Jang, In-Young;Kweon, Oh-Hwan;Hwang, Yong-Koo;Moon, Sang-Bong;Kang, An-Soo
    • Journal of Hydrogen and New Energy
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    • v.18 no.4
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    • pp.391-398
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    • 2007
  • The covalently cross-linked sulfonated polyetheretherketone (CL-SPEEK) membrane was prepared by four-step synthesis of sulfonation-sulfochlorination, partial reduction, lithiation, and cross-linking, and its electrochemical and mechanical properties were investigated for water electrolysis application. The prepared ion exchange membranes showed good electrochemical and mechanical properties; proton conductivity of 0.116 S/cm at $80^{\circ}C$, water uptake of 44.6%, ion exchange capacity of 1.75 meq/g-dry-memb., tensile strength of 64.25 MPa and elongation of 61.11%. The membrane electrode assembly (MEA) with homemade membranes were prepared by non-equilibrium impregnation-reduction (I-R) method. Especially, the electrochemical surface area (ESA) and roughness factor of CL-SPEEK electrolyte by cyclic voltammetry method were 23.46 $m^2/g$ and 307.3 $cm^2-Pt/cm^2$, respectively. The prepared MEA was used in the unit cell of water electrolysis and the cell voltage was 1.81 V at 1 A/$cm^2$ and $80^{\circ}C$, with platinum loadings of 1.31 mg/$cm^2$.

Strategic design for oxide-based anode materials and the dependence of their electrochemical properties on morphology and architecture

  • Gang, Yong-Muk
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2012.05a
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    • pp.73-73
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    • 2012
  • Modern technology-driven society largely relies on hybrid electric vehicles or electric vehicles for eco-friendly transportation and the use of high technology devices. Lithium rechargeable batteries are the most promising power sources because of its high energy density but still have a challenge. Graphite is the most widely used anode material in the field of lithium rechargeable batteries due to its many advantages such as good cyclic performances, and high charge/discharge efficiency in the initial cycle. However, it has an important safety issue associated with the dendritic lithium growth on the anode surface at high charging current because the conventional graphite approaches almost 0 V vs $Li/Li^+$ at the end of lithium insertion. Therefore, a fundamental solution is to use an electrochemical redox couple with higher equilibrium potentials, which suppresses lithium metal formation on the anode surface. Among the candidates, $Li_4Ti_5O_{12}$ is a very interesting intercalation compound with safe operation, high rate capability, no volume change, and excellent cycleability. But the insulating character of $Li_4Ti_5O_{12}$ has raised concerns about its electrochemical performance. The initial insulating character associated with Ti4+ in $Li_4Ti_5O_{12}$ limits the electronic transfer between particles and to the external circuit, thereby worsening its high rate performance. In order to overcome these weak points, several alternative synthetic methods are highly required. Hence, in this presentation, novel ways using a synergetic strategy based on 1D architecture and surface coating will be introduced to enhance the kinetic property of Ti-based electrode. In addition, first-principle calculation will prove its significance to design Ti-based electrode for the most optimized electrochemical performance.

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