• 전기화학회지
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• 제13권2호
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• pp.145-152
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• 2010

본 연구에서는 organophosphate를 기반으로 한 과불소화된 아크릴레이트 가교제를 사용하여 제조한겔 고분자 전해질의 이온 전도도 및 전기화학적 특성을 평가하였다. 과불소화된 아크릴레이트 가교제를 사용하여 만든 겔 고분자 전해질은 액체전해질의 함량이 최대 97 wt%까지 안정한 겔 상태를 유지하였다. 본 연구에서 제조한 겔 고분자 전해질의 이온전도도는 $30^{\circ}C$에서 $1.0\;{\times}\;10^{-2}\;S/cm$의 값을 가졌다. 또한 전기화학적 안정성 테스트에서도 약 4.5V로 이상까지 산화에 의한 열화가 없이 안정하였다. 합성된 겔고분자 전해질을 리튬이온 고분자 전지에 적용하여 그 활용성을 평가하였다. 양극으로는 $LiCoO_2$를 사용하였으며 음극으로는 카본을 사용하였다. 이렇게 만든 리튬이온 고분자 전지는 0.1C에서 136.11 mAh/g의 용량으로 이론용량과 거의 비슷한 값을 나타내었으며, 2C 방전에서도 초기 용량의 91%를 유지하였다. 또한 500번의 충방전 후에도 초기 용량의 70%정도의 용량을 유지하였다.

• 공업화학
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• 제16권5호
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• pp.689-692
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• 2005

스피넬계 $LiMn_2O_4$를 양극 활물질로 사용하는 리튬이온전지의 전기화학적 성능을 향상시키기 위하여 서로 상이한 입자크기를 가지는 Super P Black 및 $Vulcan^{(R)}$ XC-72R을 사용한 이성분계 전도성물질을 제조하였다. 이렇게 이성분계 전도성물질을 사용하여 제조되어진 $LiMn_2O_4$ 전지 시스템은 충 방전 동안의 비용량 및 사이클 수명의 관점에서 특성 평가되었다. 결과적으로 Super P Black 및 $Vulcan^{(R)}$ XC-72R이 3:7의 비율로 구성되어진 이성분계 전도성물질을 사용하였을 때의 전지가 우수한 전기화학적 성능을 보여주었으며 이는 적절한 조합의 ionic diffusion rate와 electric contact에 의해 제어되어졌기 때문인 것으로 여겨진다.

• Bulletin of the Korean Chemical Society
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• 제31권5호
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• pp.1199-1203
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• 2010

Second-order rate constants ($k_N$) have been measured spectrophotometrically for Michael-type reactions of 1-(X-substituted phenyl)-2-propyn-1-ones (2a-f) with a series of alicyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The $k_N$ value increases as the incoming amine becomes more basic and the substituent X changes form an electron-donating group (EDG) to an electron-withdrawing group (EWG). The Br${\o}$nsted-type plots are linear with ${\beta}_{nuc}$ = 0.48 - 0.51. The Hammett plots for the reactions of 2a-f exhibit poor correlations but the corresponding Yukawa-Tsuno plots result in much better linear correlations with ${\rho}$ = 1.57 and r = 0.46 for the reactions with piperidine while ${\rho}$ = 1.72 and r = 0.39 for those with morpholine. The amines employed in this study are less reactive in MeCN than in water for reactions with substrates possessing an EDG, although they are ca. 8 pKa units more basic in the aprotic solvent. This indicates that the transition state (TS) is significantly more destabilized than the ground state (GS) in the aprotic solvent. It has been concluded that the reactions proceed through a stepwise mechanism with a partially charged TS, since such TS would be destabilized in the aprotic solvent due to the electronic repulsion between the negative-dipole end of MeCN and the negative charge of the TS. The fact that primary deuterium kinetic effect is absent supports a stepwise mechanism in which proton transfer occurs after the rate-determining step.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2016년도 제50회 동계 정기학술대회 초록집
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• pp.427-427
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• 2016

Organic-inorganic hybrid perovskite have attracted significant attention as a new revolutionary light absorber for photovoltaic device due to its remarkable characteristics such as long charge diffusion lengths (100-1000nm), low recombination rate, and high extinction coefficient. Recently, power conversion efficiency of perovskite solar cell is above 20% that is approached to crystalline silicon solar cells. Planar heterojunction perovskite solar cells have simple device structure and can be fabricated low temperature process due to absence of mesoporous scaffold that should be annealed over 500 oC. However, in the planar structure, controlling perovskite film qualities such as crystallinity and coverage is important for high performances. Those controlling methods in one-step deposition have been reported such as adding additive, solvent-engineering, using anti-solvent, for pin-hole free perovskite layer to reduce shunting paths connecting between electron transport layer and hole transport layer. Here, we studied the effect of alkali metal halide to control the fabrication process of perovskite film. During the morphology determination step, alkali metal halides can affect film morphologies by intercalating with PbI2 layer and reducing $CH3NH3PbI3{\cdot}DMF$ intermediate phase resulting in needle shape morphology. As types of alkali metal ions, the diverse grain sizes of film were observed due to different crystallization rate depending on the size of alkali metal ions. The pin-hole free perovskite film was obtained with this method, and the resulting perovskite solar cells showed higher performance as > 10% of power conversion efficiency in large size perovskite solar cell as $5{\times}5cm$. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma optical emission spectrometry (ICP-OES) are analyzed to prove the mechanism of perovskite film formation with alkali metal halides.

• Journal of Photoscience
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• 제1권1호
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• pp.31-37
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• 1994

Photoirradiation at > 300 nm onto a suspension of platinized TiO$_2$ (TiO$_2$-Pt) particles in an aqueous solution. of N$_{\varepsilon}$-carbamyI-L-lysine (Lys(CONH)$_2$) induced the selective N-cyclization of Lys(CONH$_2$) into almost optically pure L-pipecolinic acid (PCA) under argon atmosphere at ambient temperature. Among various TiO$_2$-Pt catalysts, a P-25 (Degussa) powder platinized via impregnation from chloroplatinic acid followed by hydrogen reduction at 753 K exhibited the highest photocatalytic activity for Lys(CONH$_2$) consumption and L-PCA production. GC-MS analyses of L-PCA obtained photocatalytically from $^{15}$N$\alpha$-Lys(CONH$_2$) revealed the selective formation $^{15}$N-substituted L-PCA. This implies that the mechanism for L-PCA production contains selective cleavage of C$_{\varepsilon}$-N bond and intramolecular alkylation at $\alpha$-amino group. Effect of pH on the rate of this photocatalytic reaction was investigated in detail and compared with the pH-dependent charge distribution in Lys(CONH$_2$) molecule. It is clarified that protonation-deprotonation of $\alpha$-amino group gives marked influence on the rate and selectivity of the photocatalytic reaction. On the basis of these results, it is concluded that the selective production of optically pure L-PCA, especially in an acidic suspension of TiO$_2$-Pt, was attributed to the enhanced protonation of $\alpha$-amino group to prevent undesirable oxidation by photogenerated positive holes and blocking of $\varepsilon$-amino group to yield racemic Schiff base intermediate.

• Bulletin of the Korean Chemical Society
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• 제35권7호
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• pp.2135-2138
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• 2014

A kinetic study is reported for the SNAr reaction of 1-Y-substituted-phenoxy-2,4-dinitrobenzenes (1a-1h) with OH- in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The second-order rate constant ($k_{OH^-}$) increases as the substituent Y in the leaving group changes from an electron-donating group (EDG) to an electronwithdrawing group (EWG). The Br${\o}$nsted-type plot for the reactions of 1a-1h is linear with ${\beta}_{lg}$ = -0.16, indicating that the reactivity of substrates 1a-1h is little affected by the leaving-group basicity. A linear Br${\o}$nsted-type plot with ${\beta}_{lg}=-0.3{\pm}0.1$ is typical for reactions reported previously to proceed through a stepwise mechanism in which formation of a Meisenheimer complex is the rate-determining step (RDS). The Hammett plot correlated with ${\sigma}_Y{^{\circ}}$ constants results in a much better correlation than that correlated with ${\sigma}_Y{^-}$constants, implyng that no negative charge is developing on the O atom of the leaving group (or expulsion of the leaving group is not advanced at all in the TS). This excludes a possibility that the $S_NAr$ reaction of 1a-1h with $OH^-$ proceeds through a concerted mechanism or via a stepwise pathway with expulsion of the leaving group being the RDS. Thus, the current reactions have been concluded to proceed through a stepwise mechanism in which expulsion of the leaving group occurs rapidly after the RDS.

• Bulletin of the Korean Chemical Society
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• 제35권1호
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• pp.177-181
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• 2014

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the reactions of Y-substituted-phenyl benzoates (5a-j) with potassium ethoxide (EtOK) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [EtOK] curve upward regardless of the electronic nature of the substituent Y in the leaving group. Dissection of $k_{obsd}$ into the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOK (i.e., $k_{EtO^-}$ and $k_{EtOK}$, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. The Br${\phi}$nsted-type plots for the reactions with the dissociated $EtO^-$ and ion-paired EtOK exhibit highly scattered points with ${\beta}_{lg}$ = -$0.5{\pm}0.1$. The Hammett plots correlated with ${\sigma}^o$ constants result in excellent linear correlations, indicating that no negative charge develops on the O atom of the leaving Y-substituted-phenoxide ion in transition state. Thus, it has been concluded that the reactions with the dissociated $EtO^-$ and ion-paired EtOK proceed through a stepwise mechanism, in which departure of the leaving group occurs after the RDS, and that $K^+$ ion catalyzes the reactions by increasing the electrophilicity of the reaction center through a four-membered cyclic TS structure.

• Journal of Electrochemical Science and Technology
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• 제10권2호
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• pp.223-230
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• 2019

A facile method for surface coating with $Li_2TiF_6$ which has a high lithium-ion conductivity, on $LiMn_2O_4$ spinel cathode material for high performance lithium ion batteries. The surface coating is performed by using a co-precipitation method with $Li_2CO_3$ powder and $H_2TiF_6$ solution under room temperature and atmospheric pressure without special equipment. Total coating amount of $Li_2TiF_6$ is carefully controlled from 0 to 10 wt.% based on the active material of $LiMn_2O_4$. They are evaluated by a systematic combination of analyses comprising with XRD, SEM, TEM and ICP. It is found that the surface modification of $Li_2TiF_6$ is very beneficial to high cycle life and excellent rate capability by reducing surface failure and supporting lithium ions transportation on the surface. The best coating condition is found to have a high cycle life of $103mAh\;g^{-1}$ at the 100th cycle and a rate capability of $102.9mAh\;g^{-1}$ under 20 C. The detail electrochemical behaviors are investigated by AC impedance and galvanostatic charge and discharge test.

• 한국표면공학회지
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• 제56권1호
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• pp.104-114
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• 2023

Three dimensional (3D) porous structures consisting of Cu@CoO core-shell-type nano-dendrites were synthesized and tested as the anode materials in lithium secondary batteries. For this purpose, first, the 3D porous films comprising Cu@Co core-shell-type nano-dendrites with various thicknesses were fabricated through the electrochemical co-deposition of Cu and Co. Then the Co shells were selectively anodized to form Co hydroxides, which was finally dehydrated to get Cu@CoO nanodendrites. The resulting electrodes exhibited very high reversible specific capacity almost 1.4~2.4 times the theoretical capacity of commercial graphite, and excellent capacity retention (~90%@50^th cycle) as compared with those of the existing transition metal oxides. From the analysis of the cumulative irreversible capacity and morphology change during charge/discharge cycling, it proved that the excellent capacity retention was attributed to the unique structural feature of our core-shell structure where only the thin CoO shell participates in the lithium storage. In addition, our electrodes showed a superb rate performance (70.5%@10.8 C-rate), most likely due to the open porous structure of 3D films, large surface area thanks to the dendritic structure, and fast electron transport through Cu core network.

• 전기화학회지
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• 제4권2호
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• pp.53-57
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• 2001

전기자동차 운용시 빈번히 발생되는 차량의 주정차기간에 축전지는 자기방전을 일으켜 용량의 손실이 발생하게 된다. 따라서 전기자동차의 잔존용량을 정확히 측정하기 위해서는 자기방전에 의한 용량손실을 고려하여야 한다. 이 논문에서는 전기자동차 운용시 빈번히 발생할 것으로 예상되는 주정차기간에 대해 포괄적으로 적용할 수 있는 Ni/MH Battery의 자기방전율을 나타내는 일반식을 전산모사 방법 중 하나인 실험계획법을 이용하여 구하였으며 이를 시험데이터와 비교하였다. 실험계획법을 위한 온도영역으로는 전기자동차가 운용되는 $-20\~30^{\circ}C$의 온도구간을 선정하였으며, 축전지의 방치시간으로는 자기방전이 상대적으로 크게 일어나며 빈번히 발생할 것으로 예상되는 영역인 1일$\~$15일 범위를 선택하였다. 이와 같은 방법으로 실험계획법에 의해 구해진 축전지 자기방전율에 대한 일반식의 타당성을 검증하기 위해 축전지에 대한 자기방전시험을 수행하여 비교하였으며, 그 결과 실험계획법으로 예측한 축전지의 자기방전율은 시험데이터와 우수한 일치를 나타내었다.