• 전기화학회지
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• 제14권2호
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• pp.92-97
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• 2011

In this study we have investigated the Li-ion coordination, thermal behavior and electrochemical stability of N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide ($Py_{14}TFSI$) with lithium bis(trifluoromethanesulfony)imide (LiTFSI) doping intended for use as electrolytes for lithium batteries. The ionic conductivity is reduced and glass transition temperature ($T_g$) increases with LiTFSI doping concentration. Also, the electrochemical stability increases with LiTFSI doping. A high LiTFSI doping could enhance the electrochemical stability of electrolytes for lithium batteries, whereas the decrease in the ionic conductivity limits the capacity of the battery.

• Bulletin of the Korean Chemical Society
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• 제34권12호
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• pp.3743-3748
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• 2013

A tetradentate ligand of 2-phenyl-4,6-di(pyridin-2-yl)pyrimidine (L) has been synthesized and its complexes with $ZnI_2$ and CuI have been obtained by hydrothermal method. single crystal X-ray diffraction analysis indicates that ligand L coordinates with Zn(II) ions to form a simple four-coordinate di-nuclear complex, while the complexation of L with Cu(I) constructs a one-dimensional chain polymer. The existence of $I^-$ ion hampers the L to assemble grid-type complexes with Zn(II) and Cu(I). Fluorescence spectra show that the L emits blue fluorescence while its Cu(I) polymer decrease the fluorescence intensity and Zn(II) complex quenches the fluorescence.

• Bulletin of the Korean Chemical Society
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• 제32권spc8호
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• pp.3031-3038
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• 2011

Ion-coordinating ruthenium complexes [cis-Ru(dcbpy)(L)(NCS)$_2$, where dcbpy is 4,4'-dicarboxylic acid-2,2'-bipyridine and L is 1,4,7,10-tetraoxa-13-azacyclopentadecane, JK-121, or bis(2-(2-methoxy-ethoxy)ethyl) amine, JK-122] have been synthesized and characterized using $^1H$ NMR, Fourier transform IR, UV/vis spectroscopy, and cyclic voltammetry. The effect of $Li^+$ in the electrolyte on the photovoltaic performance was investigated. With the stepwise addition of $Li^+$ to a liquid electrolyte, the device shows significant increase in the photo-current density, but a small decrease in the open circuit voltage. The solar cell with a hole conductor, the addition of $Li^+$ resulted in a 30% improvement in efficiency. The JK-121 sensitized cells in the liquid and solid-state electrolyte give power conversion efficiencies of 6.95% and 2.59%, respectively, under the simulated sunlight.

• Bulletin of the Korean Chemical Society
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• 제29권1호
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• pp.117-121
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• 2008

Pseudo-first-order rate constants (kobsd) have been measured spectrophotometrically for nucleophilic substitution reactions of 5-nitro-8-quinolyl benzoate (5) with alkali metal ethoxides, EtO?M+ (M+ = Li+, Na+ and K+) in anhydrous ethanol (EtOH) at 25.0 0.1 C. The plots of kobsd vs. [EtO?M+] exhibit upward curvatures, while the corresponding plots for the reactions of 5 with EtO?Na+ and EtO?K+ in the presence of complexing agents, 15-crown-5-ether and 18-crown-6-ether are linear with rate retardation. The reactions of 5 with EtO?Na+ and EtO?Li+ result in significant rate enhancements on additions of Na+ClO4, indicating that the M+ ions behave as a catalyst. The dissociated EtO and ion-paired EtOM+ have been proposed to react with 5. The second-order rate constants for the reactions with EtO (kEtO) and EtOM+ (kEtOM+) have been calculated from ion-pairing treatments. The kEtO and kEtOM+ values decrease in the order kEtONa+ > kEtOK+ > kEtOLi+ > kEtO, indicating that ion-paired EtOM+ species are more reactive than the dissociated EtO ion, and Na+ ion exhibits the largest catalytic effect. The M+ ions in this study form stronger complex with the transition state than with the ground state. Coordination of the M+ ions with the O and N atoms in the leaving group of 5 has been suggested to be responsible for the catalytic effect shown by the alkali metal ions in this study.

• Journal of Electrochemical Science and Technology
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• 제7권4호
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• pp.306-315
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• 2016

Amorphous vanadium titanates (aVTOs) are examined for use as a negative electrode in lithium-ion batteries. These amorphous mixed oxides are synthesized in nanosized particles (<100 nm) and flocculated to form secondary particles. The $V^{5+}$ ions in aVTO are found to occupy tetrahedral sites, whereas the $Ti^{4+}$ ions show fivefold coordination. Both are uniformly dispersed at the atomic scale in the amorphous oxide matrix, which has abundant structural defects. The first reversible capacity of an aVTO electrode ($295mAhg^{-1}$) is larger than that observed for a physically mixed electrode (1:2 $aV_2O_5$ | $aTiO_2$, $245mAhg^{-1}$). The discrepancy seems to be due to the unique four-coordinated $V^{5+}$ ions in aVTO, which either are more electron-accepting or generate more structural defects that serve as $Li^+$ storage sites. Coin-type Li/aVTO cells show a large irreversible capacity in the first cycle. When they are prepared under nitrogen (aVTO-N), the population of surface hydroxyl groups is greatly reduced. These groups irreversibly produce highly resistive inorganic compounds (LiOH and $Li_2O$), leading to increased irreversible capacity and electrode resistance. As a result, the material prepared under nitrogen shows higher Coulombic efficiency and rate capability.

• 전기화학회지
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• 제15권4호
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• pp.230-235
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• 2012

분자량이 각각 300(PEGMA300) 및 1100(PEGMA1100) g $mol^{-1}$인 PEGMA와 합성된 $BF_3LiMA$ 리튬염을 이용하여 다양한 조성의 고분자전해질을 제조하고 전기화학적 특성을 평가하였다. 흥미롭게도 AC-impedance 측정법에 의한 상온 이온전도도는 분자량 $300g\;mol^{-1}$로 합성된 액체 고분자전해질에서 $8.54{\times}10^{-7}S\;cm^{-1}$의 값이 얻어진 반면, PEGMA1100으로 합성된 고체상태의 고분자전해질에서 최대 14배 이상 높은 $1.22{\times}10^{-5}S\;cm^{-1}$가 관찰되었다. 이러한 결과는 PEGMA에 ethylene oxide 단위가 5개인 $300g\;mol^{-1}$보다 23개인 $1100g\;mol^{-1}$에서 리튬이온의 배위가 쉽게 일어나기 때문으로 해석된다. 또한 양이온 수율 측정결과 리튬메탈과 $BF_3$간의 반응으로 인해 0.6의 비교적 낮은 값이 나왔지만 초기 3000초 동안에는 0.9 이상의 값이 관찰되어 단일이온 전도체의 특징을 보여주었다.

• Bulletin of the Korean Chemical Society
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• 제31권2호
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• pp.303-308
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• 2010

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl benzoate (5a), 4-nitrophenyl 4-methoxybenzoate (5b), and 4-nitrophenyl 4-hydroxybenzoate (5c) with alkali metal ethoxides, $EtO^-M^+$ ($M^+=Li^+$, $Na^+$ and $K^+$) in anhydrous ethanol (EtOH) at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [$EtO^-M^+$] exhibit upward curvatures in all cases, indicating that $M^+$ ions catalyze the reactions and ionpaired $EtO^-M^+$ species are more reactive than dissociated $EtO^-$. Second-order rate constants for reactions with dissociated $EtO^-$ and ion-paired $EtO^-M^+$ (i.e., $k_{EtO^-}$ and $k_{EtO^-M^+}$, respectively) have been calculated from ion-pair treatment for the reactions of 5a and 5b. However, such ion-pair treatment has failed to determine $k_{EtO^-}$ and $k_{EtO^-M^+}$ values for the reactions of 5c. It has been concluded that reactions of 5a and 5b are catalyzed by one metal ion, which increases electrophilicity of the reaction center through coordination on the carbonyl oxygen. In contrast, reactions of 5c have been suggested to involve two metal ions, i.e., the one coordinated on the carbonyl oxygen increases the electrophilicity of the reaction center while the other one associated on the phenoxy oxygen decreases the charge repulsion between the anionic reagents (i.e., $EtO^-$ and deprotonated 5c). It has been found that the rate equation derived from the mechanism involving two metal ions fits nicely to the kinetic results obtained for the reactions of 5c.

• Bulletin of the Korean Chemical Society
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• 제32권3호
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• pp.894-898
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• 2011

The first example of lead compound from $Pb(NO_3)_2$ and $H_3L$ N-heterocyclic ligand $(H_3L\;=\;(HO_2C)_2(C_3N_2)(C_3H_7)CH_2(C_6H_4)(C_6H_3)CO_2H)$, $[Pb_4(L')_4]{\cdot}5H_2O$ 1 (L' = OOC$(C_3H_7)(C_3N_2)CH_2(C_6H_4)(C_6H_3)COO)$, has been obtained under hydrothermal condition by decarboxylation, and characterized by elemental analysis, IR, TGDTA, and single-crystal X-ray diffraction. Compound 1 possesses a rare two-dimensional upper-lower offset terrace-like layer structure. In 1, crystallographic distinct Pb(II) ion adopts five-coordination geometry, and two lattice water molecules occupy the voids between 2-D layers. Results of solid state fluorescence measurement indicate that the emission band 458 nm may be assigned to $\pi^*-n$ and $\pi^*-\pi$ electronic transitions within the aromatic systems of the ligand L', however, the emission bands centred at 555 nm, 600 nm and 719 nm may be derived from phosphorescent emission ($\lambda_{excitation}$ = 390 nm).

• Bulletin of the Korean Chemical Society
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• 제34권12호
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• pp.3749-3754
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• 2013

Two 3D isomorphous and isostructural complexes, namely, $[Zn(BDOA)(bpy)(H_2O)_2]_n$ (1) and $[Cd(BDOA)-(bpy)(H_2O)_2]_n$ (2); (BDOA = Benzene-1,4-dioxyacetic acid, bpy = 4,4'-bipyridine) were synthesized under hydrothermal conditions and characterized by means of elemental analyses, thermogravimetric (TG), infrared spectrometry, and single crystal X-ray diffraction. Complexes 1 and 2 crystallize in the triclinic system, space group P-1 and each metal ion in the complexes are six-coordinated with the same coordination environment. In the as-synthesized complexes, $BDOA^{2-}$ anions link central metal ions to form a 1D zigzag chain $[-BDOA^{2-}-Zn(Cd)-BDOA^{2-}-Zn(Cd)-]_{\infty}$, whereas bpy pillars connect metal ions to generate a 1D linear chain $[-bpy-Zn(Cd)-bpy-Zn(Cd)-]_{\infty}$. Both infinite chains are interweaved into 2D grid-like layers which are further constructed into a 3D open framework, where hydrogen bonds play as the bridges between the adjacent 2D layers. Luminescent properties of complex 1 showed selectivity for $Hg^{2+}$ ion.