• 제목/요약/키워드: transition metal ion

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Conversion-Alloying Anode Materials for Na-ion Batteries: Recent Progress, Challenges, and Perspective for the Future

  • Kim, Joo-Hyung;Kim, Do Kyung
    • 한국세라믹학회지
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    • 제55권4호
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    • pp.307-324
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    • 2018
  • Rechargeable lithium-ion batteries (LIBs) have been rapidly expanding from IT based applications to uses in electric vehicles (EVs), smart grids, and energy storage systems (ESSs), all of which require low cost, high energy density and high power density. The increasing demand for LIBs has resulted in increasing price of the lithium source, which is a major obstacle to wider application. To date, the possible depletion of lithium resources has become relevant, giving rise to the interest in Na-ion batteries (NIBs) as promising alternatives to LIBs. A lot of transition metal compounds based on conversion-alloying reaction have been extensively investigated to meet the requirement for the anodes with high energy density and long life-time. In-depth understanding the electrochemical reaction mechanisms for the transition metal compounds makes it promising negative anode for NIBs and provides feasible strategy for low cost and large-scale energy storage system in the near future.

An NMR Study of Solvent Interactions in a Paramagnetic System

  • Golding, R.M.;Pascual, R.O.;Suvanprakorn, C.;Dance, I.G.
    • Bulletin of the Korean Chemical Society
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    • 제27권11호
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    • pp.1752-1756
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    • 2006
  • This study explores and interprets in a new way the complex solvent and the temperature dependence of the NMR shifts for the N-$CH_2$ protons in tris(N,N-diethyldithiocarbamato) iron(III) in acetone, benzene, carbon disulfide, chloroform, dimethylformamide and pyridine. The NMR shifts are interpreted in terms of the Fermi contact interaction and the dipolar term from the multipole expansion of the interaction of the electron orbital angular momentum and the electron spin dipolar-nuclear spin angular momentum. This analysis yields a direct measure of the effect of the solvent system on the environment of the transition metal ion. The results are analysed in terms of the crystal field environment of the transition metal ion with contributions from (a) the dithiocarbamate ligand (b) the solvent molecules and (c) the interaction of the effective dipole moment of the polar solvent molecule with the transition metal ion complex.

Montmorilloint와 Cysteamin의 반응(점토의 효율적인 이용을 위한 기초연구-1) (On the Reaction of Montmorillonit with Cysteamin)

  • 신건철
    • 한국세라믹학회지
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    • 제20권4호
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    • pp.361-365
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    • 1983
  • The Cation Exchange Isotherm of $Na^+$ Montmorillonit with Cysteammonium ion is determined. It is shown that Cysteammonium ion is bonded relatively good on the silicate interlayer of Montmorilloint. And it is also shown that the bonded $HSCH_2CH_2NH_3^+$ ion on the Silicate interlayer reacts with the transition metal ion $Co^+$ in is SH group.

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전이 및 중금속이온과 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxa-cyclooctadecane과의 착물형성 (Complex Formation of Transition and Post-Transition Metal Ions with 1,15-Diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane)

  • 김시중;이명재;구창현;우경자
    • 대한화학회지
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    • 제35권6호
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    • pp.645-652
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    • 1991
  • 몇 가지 전이금속이온(Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ)) 및 후전이금속이온(Cd(Ⅱ), Hg(Ⅱ), Pb(Ⅱ))과 $N_2O_3$계 거대고리 리간드인 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane 사이에 형성되는 착물의 안정도 상수를 수용액에서 전위차 적정법으로 결정하였다. 각 착물의 안정도 상수$(logK_f)$$25^{\circ}$C에서 Co(Ⅱ): 3.83, Ni(Ⅱ) : 4.56, Cu(Ⅱ) : 7.74, Zn(Ⅱ) : 4.98, Cd(Ⅱ) : 3.91, Hg(II) : 14.87, Pb(Ⅱ) : 6.65이었다. 전이금속착물의 안정도 순위는 Williams-Irving 서열인 Co(Ⅱ) < Ni(Ⅱ) < Cu(Ⅱ) < Zn(Ⅱ)와 일치하였고, 후전이금속착물의 안정도는 Cd(Ⅱ) < Pb(Ⅱ) < Hg(Ⅱ)이 순위이었다. 한편 메탄올 용액에서 자외-가시선이온과 리간드가 1:1인 조성을 가졌으나, Ni(Ⅱ), 착물은 1:1과 1:2 두 가지 조성을 가질 수 있음을 알았으며, 또 디메틸술폭시드 용액에서 $^1H-$$^{13}C-$핵자기공명스펙트럼을 분석하여 후전이금속이온 착물은 주로 리간드의 질소원자가 결합에 기여함을 알았다. Cu(Ⅱ)와 Zn(Ⅱ)이 고체착물은 원소분석, 전기전도도, 자화율 측정, 자외-가시선 및 적외선 스펙트럼분석 등으로 Cu(Ⅱ) 착물은 일그러진 팔면체, 그리고 Zn(Ⅱ) 착물은 사면체 구조를 이루고 있는 것으로 예측되었다.

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아연의 대기부식에 미치는 주기적 침적/건조 효과 (Effect of wet/dry transition on the atmospheric corrosion of Zn)

  • Kim, Ki-Tae
    • 한국표면공학회:학술대회논문집
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    • 한국표면공학회 1998년도 춘계학술발표회 초록집
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    • pp.3-3
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    • 1998
  • The atmospheric corrosIOn properties of Zinc (Zn) under wet/dry transition of $H_20$ film were investigated in this study. The atmospheric corrosion of metal is usually occurred as a result of repetitious thickness transition (so called wet/dry transition) of liquid phase which is covering the metal surface. Corrosion potential and the polarization behaviour of Zn during liquid film thickness transition were measured by Kelvin probe method which IS using vibrating reference electrode without touching the liquid film. The oxidized states of Zn as a result of successive wet/dry transition were also investigated by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results show that the corrosion potential and the corrosIOn rate of Zn both are increasing during drying. However, the corrOSIon rate is decreasing again when the Zn surface is completely dried while the corrosion potential still remains high. This behaviour can be explained by the polarization behaviour change of Zn according to the $H_20$ film thickness change. The completely dried surface is consisted mostly with Zn and ZnO phases. After a number of cycles of wet/dry transition, however, the oxidized Zn phase of ${\varepsilon}-Zn(OH)_2$, which has rather voluminous and defected structure, were found.

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리튬 이차전지의 양극 내부 이온 확산 및 상변화 특성 연구 (Study of Li-Ion Diffusion and Phase Transition in Cathode of Li-Ion Battery)

  • 김수일;김동철
    • 대한기계학회논문집B
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    • 제37권7호
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    • pp.665-667
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    • 2013
  • 리튬이온 전지의 양극은 다양한 종류의 전이금속재료로 구성되며, 전지의 성능은 양극을 구성하는 금속재료에 의해 많은 영향을 받는다. 이는, 양극 내부에서 리튬이온의 확산 및 상전이 양상이 재료마다 서로 다르게 나타나기 때문이다. 따라서, 충방전 시 양극 내부 리튬이온의 확산 및 상전이를 이해하는 것은 고용량, 고전압 리튬 이차전지를 설계하기 위해 필수적이다. 본 연구에서는 phase field model을 바탕으로 양극 내부의 리튬이온 확산 및 상전이 과정을 분석한다.

A Thermodynamic Investigation into the Stabilization of Poly(dA).[poly(dT)]2 Triple Helical DNA by Various Divalent Metal Ions

  • Choi, Byung-Hoon;Yeo, Ga-Young;Jung, Jin-Ah;Lee, Bae-Wook;Han, Sung-Wook;Cho, Tae-Sub
    • Bulletin of the Korean Chemical Society
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    • 제30권11호
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    • pp.2691-2696
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    • 2009
  • Effects of representative group II and transition metal ions on the stability of the $poly(dA){\cdot}[poly(dT)]_2$ triplex were investigated by the van’t Hoff plot constructed from a thermal melting curve. The transition, $poly(dA){\cdot}[poly(dT)]_2\;{\rightarrow}\;poly(dA){\cdot}poly(dT)\;+\;poly(dT)$, was non-spontaneous with a positive Gibb’s free energy, endothermic (${\Delta}H^{\circ}$ > 0), and had a favorable entropy change (${\Delta}S^{\circ}$ > 0), as seen from the negative slope and positive y-intercept in the van’t Hoff plot. Therefore, the transition is driven by entropy change. The $Mg^{2+}$ ion was the most effective at stabilization of the triplex, with the effect decreasing in the order of $Mg^{2+}\;>\;Ca^{2+}\;>\;Sr^{2+}\;>\;Ba^{2+}$. A similar stabilization effect was found for the duplex to single strand transition: $poly(dA){\cdot}poly(dT)\;+\;poly(dT)\;→\;poly(dA)\;+\;2poly(dT)$, with a larger positive free energy. The transition metal ions, namely $Ni_{2+},\;Cu_{2+},\;and\;Zn_{2+}$, did not exhibit any effect on triplex stabilization, while showing little effect on duplex stabilization. The different effects on triplex stabilization between group II metal ions and the transition metal ions may be attributed to their difference in binding to DNA; transition metals are known to coordinate with DNA components, including phosphate groups, while group II metal ions conceivably bind DNA via electrostatic interactions. The $Cd_{2+}$ ion was an exception, effectively stabilizing the triplex and melting temperature of the third strand dissociation was higher than that observed in the presence of $Mg_{2+}$, even though it is in the same group with $Zn_{2+}$. The detailed behavior of the $Cd_{2+}$ ion is currently under investigation.

Alkali-Metal Ion Catalysis in Nucleophilic Substitution Reactions of 5-Nitro-8-quinolyl Picolinate with Alkali Metal Ethoxides: Effect of Modification of Nonleaving Group from Benzoyl to Picolinyl on Reactivity and Transition State Structure

  • Jeon, Seong Hoon;Yoon, Jung Hwan;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제35권5호
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    • pp.1506-1510
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    • 2014
  • A kinetic study on nucleophilic substitution reaction of 5-nitro-8-quinolyl picolinate (6) with alkali-metal ethoxides (EtOM; M = K, Na, and Li) in anhydrous ethanol is reported. The plot of $k_{obsd}$ vs. [EtOM] curves upward in the absence of crown ethers but is linear with significantly decreased reactivity in the presence of crown ethers. Dissection of $k_{obsd}$ into $k_{EtO}$- and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is significantly more reactive than the dissociated $EtO^-$ (e.g., $k_{EtOM}/k_{EtO^-}$ = 33.4-141). This indicates that the reaction of 6 is catalyzed by $M^+$ ions in the order $Na^+$ > $Li^+$ > $K^+$ and the catalytic effect disappears in the presence of a proper crown ether. Picolinate ester 6 is much more reactive and is more strongly catalyzed by $M^+$ ions than 5-nitro-8-quinolyl benzoate (5). It has been concluded that $M^+$ ions catalyze the reaction of 6 by increasing electrophilicity of the reaction center through a cyclic transition state, which is structurally not possible for the reaction of 5.

Alkali-Metal Ion Catalysis in Alkaline Ethanolysis of 2-Pyridyl Benzoate and Benzyl 2-Pyridyl Carbonate: Effect of Modification of Nonleaving Group from Benzoyl to Benzyloxycarbonyl

  • Um, Ik-Hwan;Kang, Ji-Sun;Kim, Chae-Won;Lee, Jae-In
    • Bulletin of the Korean Chemical Society
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    • 제33권2호
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    • pp.519-523
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    • 2012
  • A kinetic study is reported on nucleophilic displacement reactions of benzyl 2-pyridyl carbonate 6 with alkalimetal ethoxides, EtOM (M = Li, Na, and K), in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of pseudo-firstorder rate constant $k_{obsd}$ vs. [EtOM] curve upward, a typical phenomenon reported previously for alkaline ethanolysis of esters in which alkali-metal ions behave as a Lewis-acid catalyst. The kobsd value for the reaction of 6 with a fixed EtOK concentration decreases rapidly upon addition of 18-crown-6-ether (18C6), a complexing agent for $K^+$ ion up to [18C6]/[EtOK] = 1.0 and then remains constant thereafter, indicating that the catalytic effect exerted by K+ ion disappears in the presence of excess 18C6. The reactivity of EtOM towards 6 increases in the order $EtO^-$ < EtOLi < EtONa < EtOK, which is contrasting to the reactivity order reported for the corresponding reactions of 2-pyridyl benzoate 4, i.e., $EtO^-$ < EtOK < EtONa < EtOLi. Besides, 6 is 1.7 and 3.5 times more reactive than 4 towards dissociated $EtO^-$ and ion-paired EtOK, respectively. The reactivity difference and the contrasting metal-ion selectivity are discussed in terms of electronic effects and transition-state structures.