• Title/Summary/Keyword: ion transfer reaction

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Modeling and Applications of Electrochemical Impedance Spectroscopy (EIS) for Lithium-ion Batteries

  • Choi, Woosung;Shin, Heon-Cheol;Kim, Ji Man;Choi, Jae-Young;Yoon, Won-Sub
    • Journal of Electrochemical Science and Technology
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    • v.11 no.1
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    • pp.1-13
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    • 2020
  • As research on secondary batteries becomes important, interest in analytical methods to examine the condition of secondary batteries is also increasing. Among these methods, the electrochemical impedance spectroscopy (EIS) method is one of the most attractive diagnostic techniques due to its convenience, quickness, accuracy, and low cost. However, since the obtained spectra are complicated signals representing several impedance elements, it is necessary to understand the whole electrochemical environment for a meaningful analysis. Based on the understanding of the whole system, the circuit elements constituting the cell can be obtained through construction of a physically sound circuit model. Therefore, this mini-review will explain how to construct a physically sound circuit model according to the characteristics of the battery cell system and then introduce the relationship between the obtained resistances of the bulk (Rb), charge transfer reaction (Rct), interface layer (RSEI), diffusion process (W) and battery characteristics, such as the state of charge (SOC), temperature, and state of health (SOH).

Kinetics and Mechanism of Azidolysis of Y-Substituted Phenyl Benzoates

  • Um, Ik-Hwan;Kim, Eun-Hee;Han, Hyun-Joo
    • Bulletin of the Korean Chemical Society
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    • v.29 no.3
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    • pp.580-584
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    • 2008
  • Second-order rate constants (kN) have been measured spectrophotometrically for reactions of Y-substituted phenyl benzoates (1a-h) with azide ion (N3) in 80 mol % H2O/20 mol % DMSO at 25.0 0.1 oC. The Brnsted-type plot for the azidolysis exhibits a downward curvature, i.e., the slope (b lg) changes from 0.97 to 0.20 as the basicity of the leaving group decreases. The pKao (defined as the pKa at the center of the Brnsted curvature) is 4.8, which is practically identical to the pKa of the conjugate acid of N3 ion (4.73). Hammett plots correlated with s o and s constants exhibit highly scattered points for the azidolysis. On the contrary, the corresponding Yukawa-Tsuno plot results in an excellent linear correlation with r = 2.45 and r = 0.40, indicating that the leaving group departs in the rate-determining step. The curved Brnsted-type plot has been interpreted as a change in the rate-determining step in a stepwise mechanism. The microscopic rate constants (k1 and k2/k1 ratio) have been calculated for the azidolysis and found to be consistent with the proposed mechanism.

The Thioacetate-Functionalized Self-Assembled Monolayers on Au: Toward High-Performance Ion-Selective Electrode for Ag+

  • Jin, Jian;Zhou, Wei-Jie;Chen, Ying;Liu, Yi-Long;Sun, Xiao-Qiang;Xi, Hai-Tao
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.601-604
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    • 2014
  • Two classes of morpholino-substitued thioacetate have been successfully synthesized and their electrochemical properties of self-assembled monolayers (SAMs) on Au electrode are measured by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The barrier property of the SAMs-modified surfaces is evaluated by using potassium ferro/ferri cyanide. The results suggest that the arenethioacetate forms higher-quality close-packed blocking monolayers in comparison with alkanethioacetate. Furthermore, it has shown that the barrier properties of these monolayers can be significantly improved by mixed SAMs formation with decanethiol. From our experimental results we find that the electron transfer reaction of $[Fe(CN)_6]^{3/4-}$ redox couple occurs predominantly through the pinholes and defects present in the SAM and both SAMs show a good and fast capacity in recognition for $Ag^+$. The morphological and elementary composition have also been examined by scanning electron microscope (SEM) and energy dispersive spectrometer (EDS).

Cathodoluminescence of $Mg_2$$SnO_4$:Mn,:Mn Green Phosphor under Low-Voltage Electron Excitation ($Mg_2$$SnO_4$:Mn 녹색 형광체의 저전압 음극선 발광 특성)

  • Kim, Gyeong-Nam;Jeong, Ha-Gyun;Park, Hui-Dong;Kim, Do-Jin
    • Korean Journal of Materials Research
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    • v.11 no.9
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    • pp.759-762
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    • 2001
  • Mg$_2$SnO$_4$having an inverse spinel structure was selected as a new host material of $Mn^{2+}$ activator. The luminescence of the $Mg_2$SnO$_4$:Mn phosphor prepared by the solid-state reaction were investigated under ultraviolet and low-voltage electron excitation. The Mn-doped magnesium tin oxide exhibited strong green emission with the spectrum centered at 500nm wavelength. It was explained that the green emission in $Mg_2$SnO$_4$:Mn phosphor is due to energy transfer from $^4T_1to ^6A_1\;of\; Mn^{2+}$ ion at tetrahedral site in the spinel structure. The optimum concentration of $Mn^{2+}$/ion exhibiting maximum emission intensity by the low-voltage electron excitation was 0.6mol%. ?

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Optical and Electrochemical Property of Self-Assembled Monolayers Containing Viologen Derivative by EQCM Study (EQCM법을 이용한 자기조립된 Viologen 유도체의 광학적 특성 및 전기화학적 특성 연구)

  • Lee, Dong-Yun;Park, Sang-Hyun;Park, Jae-Chul;Kwon, Young-Soo
    • Proceedings of the KIEE Conference
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    • 2006.07c
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    • pp.1305-1306
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    • 2006
  • A monolayer assembly of anthracene-viologen linked thiol ($AMVC_{8}SH$) was fabricated on a gold electrode by self-assembly method. Structural property of the self-assembled monolayers (SAMs) was carried out by optical and electrochemical method. Firstly, we investigated PL spectrum and UV/visible absorption for the optical properties in solution state. Secondly, we determined the characteristics of charge transfer in different electrolyte solutions by electrochemical quartz crystal microbalance (EQCM). From the data, the PL spectrum and UV/visible absorption were observed and the well-defined shape peaks were nearly equal charges during redox reactions and existed to an excellent linear relationship between the scan rates and existed to currents. The mass change was determined during redox reaction. The mass change behavior of SAMs was not only governed by the mobility of the ion in the viologen but the valence of the ion in the electrolyte solution.

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Ce $L_Ⅲ$-edge X-ray Absorption Spectroscopic Studies on the Tetrameric Ce-polyoxyhydroxy Cation Intercalated Aluminosilicate

  • Yun, Ju Byeong;Hwang, Seong Ho;Kim, Dong Guk;Gang, Seong Gu;Choe, Jin Ho
    • Bulletin of the Korean Chemical Society
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    • v.21 no.3
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    • pp.305-309
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    • 2000
  • The cerium ion intercalated aluminosilicate was prepared by ion exchange reaction between $Na^+$ in montmorillonite and $Ce^{+4}$ in aqueous solution. The X-ray absorption near edge structrure(XANES) analyses indicate that the $Ce^{+4}$ ions are partially reduced to the $Ce^{+3}$ ones during the intercalation into layered aluminosilicate due to a charge transfer between host and intercalant. From the EXAFS analysis, two different (Ce-O) bonding pairs could be characterized with the distances and coordination numbers of 2.31 $({\pm}0.02){\AA}$ ${\times}$ 8.2 $({\pm}1.5)$ and 2.66 $({\pm}0.02){\AA}$ ${\times}$ 2.7 $({\pm}1.0)$, respectively, with the oxygen atoms as the first nearest neighbor, and two (Ce-Ce) pairs at 3.78 ${\AA}$ as the second neighbor. It is therefore concluded that the most probable Ce-species stabilized in the interlayer space of aluminosilicate after the intercalation is the tetrameric Ce-polyoxy/hydorxy cations with the mixed valent state of 0.75 $Ce^{+4}$.0.25 $Ce^{+3}$.

Synthesis and Characterization of Tetrathiafulvalene (TTF) and 7,7,8,8-Tetracyanoquinodimethane (TCNQ) Compounds with PdX2(X=CI, NO3and Hexafluoroacetylacetonate)

  • Kim, Young-Inn;Jeong, Chan-Kyou;Lee, Yong-Min;Choi, Sung-Nak
    • Bulletin of the Korean Chemical Society
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    • v.23 no.12
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    • pp.1754-1758
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    • 2002
  • Tetrathiafulvalene(TTF) reacts with $PdCl_2,Pd(NO_3)_2$ and $Pd(hfacac)_2$(hexafluoroacetylacetonate) in ethanol to give $(TTF)_{1.5}PdCl_2$ (1a), $(TTF)_3Pd(NO_3)_2$ (1b) and $(TTF)_4Pd(hfacas)_2$ nd (1c), respectively. $PdCl(TCNQ)_{2.5}{\cdot}CH_3OH(2a)$was obtained from the reaction of $PdCl_2$ with LiTCNQ in methanol via the partial replacement of $Cl^-$ in $PdCl_2$ by $TCNQ^-$anion, whereas the total substitution of the labile $NO_3^-$ in $Pd(NO_3)_2$ yielded pd(TCNQ)·$CH_3OH$ (2b). $Pd(hfacac)_2(TCNQ)_2\cdot3CH_3OH$ (2c) was obtained from $Pd(hfacac)_2$ and LiTCNQ in methanol. The prepared compounds were characterized by spectroscopic (IR, UV, XPS) methods and magnetic (EPR, magnetic susceptibility) studies. The powdered electrical conductivities (${\sigma}_{rt}$) of the prepared compounds at room temperature were about~$10^{-7}S{\cdot}cm^{-1}$. The effective magnetic moments were lass than the spin-only value of one unpaired electron and no EPR signals from Pd metal ions were observed in any of the compounds, indicating that the Pd ions were diamagnetic and the magnetic moments arose from$(TTF)_n$ or $(TCNQ)_n$ moieties. The experimental evidences revealed that the charge transfer had occurred form $(TTF)_n$ moiety to the central Pd metal ion in 1a, 1b and 1c. Thus the TTF donors were ions in 2a and 2b were diamagnetic Pd(II) oxidation state. In contrast, the Pd metal ion was oxidized to Pd(IV) state in 2c as a result of an addition of $TCNQ^-$anion to $Pd(hfacac)_2$ in methanol. The oxidation states of the Pd metal ions were confirmed using the x-ray photoelectron spectroscopy.

A Study on the Electrochemical Kinetics of Electrowinning Process of Valuable Metals Recovered from Lithium-ion Batteries (폐리튬이온전지로부터 유가금속 회수를 위한 전해채취 공정 전기화학 반응속도론적 연구)

  • Park, Sung Cheol;Kim, Yong Hwan;Lee, Man Seung;Son, Seong Ho
    • Resources Recycling
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    • v.31 no.5
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    • pp.59-66
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    • 2022
  • To investigate the rate-determining step of nickel, cobalt and copper electrowinning, experiments were conducted by varying the electrolyte temperature and agitation speed using a rotating disc electrode. Analyzing the rate-determining step by calculating the activation energy in the electrowinning process, it was found that nickel electrowinning is controlled by a mixed mechanism (partly by chemical reaction and partly by mass transport), cobalt is controlled by chemical reaction, and copper is controlled by mass transfer. Electrowinning of nickel, cobalt and copper was performed by varying the electrolyte temperature and agitation speed, and the comparison of the current efficiencies was used the determine the rate-determining step.

Stereoselective Electron Transfer and Ionic Association between Λ$-[Co(EDDS)]^-and [Co(en)_3]^{2+}$ (광학활성인 Λ$-[Co(EDDS)]^-$$[Co(en)_3]^{2+}$간의 입체선택적 전자전달 및 이온회합)

  • Lee, Dong Jin;O, Chang Eon;Do, Myeong Gi
    • Journal of the Korean Chemical Society
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    • v.34 no.2
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    • pp.159-164
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    • 1990
  • Absolute configuration of optically active [Co(EDDS)]- (EDDS = ethylenediaminedisuccinate) complex was determined as Λ-form by octant rule and spectroscopic data, and the stereoselective ionic association of Λ-[Co(EDDS)]- and racemic-$[Co(en)^3]_{3+}$ occurs preferrentially between Λ$-[Co(EDDS)]-$ and Δ$-[Co(en)3]3+$. The stereoselective electron-transfer reaction between Λ-[Co(EDDS)]- and racemic-$[Co(en)_3]^{2+}$ has produced 14% e.e (e.e = enantiomeric excess) of Δ$[Co(en)_3]^{3+}$ through the stereoselective ion pairing.

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Studies on the Cd(II)-Flavonoid Chelation Reactions (카드뮴(II)-플라보노이드 킬레이트 반응에 관한 연구)

  • Lee, Jeong-Ho;Shin, Sun-Woo;Baek, Seung-Hwa
    • YAKHAK HOEJI
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    • v.54 no.1
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    • pp.13-21
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    • 2010
  • The interaction of cadmium (II) ion with quercetin, qurecitrin and (+)-catechin was investigated in aqueous solution at various pH. The flavonoid/cadmium stochiometries for cadmium (II) binding to flavonoid have been determined by UV-visible spectroscopy. 1:1 Cd(II)-Flavonoid complex had a maximum absorbance and showed the bathochromic shift of the long-wavelength band of the UV-vis spectra in the alkaline pH, that occurs upon complexation, is due to a ligand-tometal charge transfer. The optimal concentration of Cd(II)-flavonoid complexes showed that complexation reaction could be classified in the following way: 55.27 ${\mu}M$ catechin > 54.72 ${\mu}M$ quercetin > 53.52 ${\mu}M$ quercitrin at the chelating site level. These results suggest that Cd(II)-flavonoid complex has the optimal condition of chelation in 0.2 M $NH_3$ - 0.2 M $NH_4Cl$ (pH 8.0) solution.