• 한국전기전자재료학회:학술대회논문집
• /
• 한국전기전자재료학회 2005년도 추계학술대회 논문집 Vol.18
• /
• pp.256-257
• /
• 2005

We fabricated self-assembled monolayers(SAMs) onto quartz crystal microbalance(QCM) using viologen, which has been widely used as electron acceptor and electron transfer mediator. The viologen derivative exist in three redox states, namely. These redox reactions are highly reversible and can be cycled many times without significant side reactions, respectively. We studied the characteristics of charge transfer using different electrolyte solutions by electrochemical quartz crystal microbalance (EQCM). From the data, the redox peak currents were nearly equal charges during redox reaction and existed to an excellent linear interrelation between the scan rates and first redox peak currents. The redox reactions of viologen were highly reversible and the EQCM has been employed to monitor the electrochemically induced adsorption of SAMs during the redox reactions.

• 전기화학회지
• /
• 제17권2호
• /
• pp.79-85
• /
• 2014

리튬2차전지용 음극활물질로 연구되고 있는 실리콘은 흑연에 비하여 높은 이론용량 (4200mAh/g for $Li_{4.4}Si$)을 가지기 때문에 고용량 음극소재로 각광받고 있다. 이러한 실리콘 음극은 반복적인 충방전에 의해 활물질 입자의 심각한 부피변화와 균열에 의한 새로운 표면이 전해액에 계속적으로 노출되는 문제로 인하여 두껍고 불안정한 피막생성을 유도한다. 불안정한 구조의 피막은 실리콘 음극의 전기화학적 성능뿐만 아니라 고온 열안정성을 저해할 수 있기 때문에 본 연구에서는 실리콘의 열안정성 향상을 위해 전해액 첨가제를 도입하여 피막구조를 변경하고자 한다. 전해액 첨가제인 lithium bis(oxalato)borate (LiBOB)가 실리콘 음극표면에 피막을 효과적으로 형성하였으며, 만충전 상태의 실리콘 음극의 $60^{\circ}C$ 저장시 용량유지 특성을 개선하였으며 고온에서의 열안정성 크게 향상시켰다.

• Journal of Electrochemical Science and Technology
• /
• 제6권4호
• /
• pp.121-130
• /
• 2015

The micro emulsion method has been successfully used for preparing perovskite LaCoO₃ with uniform, fine-shaped nanoparticles showing high activity as electro catalysts in oxygen reduction reactions (ORRs). They are, therefore, promising candidates for the air-cathode in metal-air rechargeable batteries. Since the activity of a catalyst is highly dependent on its specific surface area, nanoparticles of the perovskite catalyst are desirable for catalyzing both oxygen reduction and evolution reactions. Herein, LaCoO₃ powder was also prepared by sol-gel method for comparison, with a broad particle distribution and high agglomeration. The electro catalytic properties of LaCoO₃ and LaCoO₃-carbon Super P mixture layers toward the ORR were studied comparatively using the rotating disk electrode technique in 0.1 M KOH electrolyte to elucidate the effect of carbon Super P. Koutecky-Levich theory was applied to acquire the overall electron transfer number (n) during the ORR, calculated to be ~3.74 for the LaCoO₃-Super P mixture, quite close to the theoretical value (4.0), and ~2.7 for carbon-free LaCoO₃. A synergistic effect toward the ORR is observed when carbon is present in the LaCoO₃ layer. Carbon is assumed to be more than an additive, enhancing the electronic conductivity of the oxide catalyst. It is suggested that ORRs, catalyzed by the LaCoO₃-Super P mixture, are dominated by a 2+2-electron transfer pathway to form the final, hydroxyl ion product.

• 한국분말재료학회지
• /
• 제25권1호
• /
• pp.7-11
• /
• 2018

In this study, we synthesize tungsten oxide thin films by electrodeposition and characterize their electrochromic properties. Depending on the deposition modes, compact and porous tungsten oxide films are fabricated on a transparent indium tin oxide (ITO) substrate. The morphology and crystal structure of the electrodeposited tungsten oxide thin films are investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). X-ray photoelectron spectroscopy is employed to verify the chemical composition and the oxidation state of the films. Compared to the compact tungsten oxides, the porous films show superior electrochemical activities with higher reversibility during electrochemical reactions. Furthermore, they exhibit very high color contrast (97.0%) and switching speed (3.1 and 3.2 s). The outstanding electrochromic performances of the porous tungsten oxide thin films are mainly attributed to the porous structure, which facilitates ion intercalation/deintercalation during electrochemical reactions.

• Journal of Electrochemical Science and Technology
• /
• 제12권4호
• /
• pp.377-386
• /
• 2021

The Li-rich oxides are promising cathode materials due to their high energy density. However, characteristics such as low rate capability, unstable cyclic performance, and rapid capacity fading during cycling prevent their commercialization. These characteristics are mainly attributed to the phase instability of the host structure and undesirable side reactions at the cathode/electrolyte interface. To suppress the phase transition during cycling and interfacial side reactions with the reactive electrolyte, K (potassium) doping and Nb oxide coating were simultaneously introduced to a Li-rich oxide (Li_1.2Ni_0.13Co_0.13Mn_0.54O₂). The capacity and rate capability of the Li-rich oxide were significantly enhanced by K doping. Considering the X-ray diffraction (XRD) analysis, the interslab thickness of LiO₂ increased and cation mixing decreased due to K doping, which facilitated Li migration during cycling and resulted in enhanced capacity and rate capability. The K-doped Li-rich oxide also exhibited considerably improved cyclic performance, probably because the large K⁺ ions disturb the migration of the transition metals causing the phase transition and act as a pillar stabilizing the host structure during cycling. The Nb oxide coating also considerably enhanced the capacity and rate capability of the samples, indicating that the undesirable interfacial layer formed from the side reaction was a major resistance factor that reduced the capacity of the cathode. This result confirms that the introduction of K doping and Nb oxide coating is an effective approach to enhance the electrochemical performance of Li-rich oxides.

• Journal of Electrochemical Science and Technology
• /
• 제14권4호
• /
• pp.361-368
• /
• 2023

In lithium-sulfur (Li-S) batteries, encapsulation of sulfur in activated carbon (AC) materials is a promising strategy for preventing the dissolution of lithium polysulfide into electrolytes and enhancing cycle life, because instead of solid-liquid-solid reactions, quasi-solid-state (QSS) reactions occur in the AC micropores. While a high weight fraction of sulfur in S/AC composites is essential for achieving a high energy density of Li-S cells, the deterioration mechanisms under such conditions are still unclear. In this study, we report the deterioration mechanisms during charge-discharge cycling when the discharge products overflow from the AC. Analysis using scanning electron microscopy and energy-dispersive X-ray spectrometry confirms that the sulfur in the S/AC composites migrates outside the AC as cycling progresses, and it is barely present in the AC after 20 cycles, which corresponds to the capacity decay of the cell. Impedance analysis clearly shows that the electrical resistance of the S/AC composite and the charge-transfer resistance of QSS reactions significantly increase as a result of sulfur migration. On the other hand, the charge-discharge cycling performance under limited-capacity conditions, where the discharge products are encapsulated inside the AC, is extremely stable. These results reveal the degradation mechanism of a Li-S cell with micro-porous carbon and provide crucial insights into the design of a S/AC composite cathode and its operating conditions needed to achieve stable cycling performance.

• Korean Chemical Engineering Research
• /
• 제61권4호
• /
• pp.598-603
• /
• 2023

촉매를 사용한 전기화학적 암모니아 생산은 주변 온도 및 압력 조건, 환경 친화적인 작동 및 고순도 암모니아 생산을 가능하게 함으로써 전통적인 하버-보쉬 방법을 대체할 대안으로서 가능성이 있다. 본 연구에서는 제1원리 계산을 사용하여 루테늄 촉매의 표면에서 발생하는 질소 환원 반응에 초점을 맞춘다. 루테늄의 (0001) 및 (1000) 표면에서 질소 환원에 대한 반응 경로를 모델링하여 반응 구조를 최적화하고 각 단계에 대한 유리한 경로를 예측했다. 각 표면에서의 N₂의 흡착 구성은 후속 반응 활동에 상당한 영향을 미쳤으며, 깁스자유에너지 분석은 가장 유리한 질소 환원 구성을 도출하였다. 루테늄의 (0001) 표면에서는 질소 분자가 표면에 수직으로 흡착하는 end-on 형태가 가장 유리한 N₂ 흡착에너지가 나타났으며 유사하게, (1000) 표면에서도 end-on 형태가 안정적인 흡착 에너지 값을 보였다. 이어서, distal 및 alternating 구성 모두에서 최적화된 수소 흡착을 통해 NH₃의 최종 탈착까지 이론적으로 완전한 반응 경로를 설명했다.

• Journal of Electrochemical Science and Technology
• /
• 제13권4호
• /
• pp.462-471
• /
• 2022

In this study, the electrochemical impedance characteristics of CO₂/H₂O co-reduction to produce CO/H₂ syngas were investigated in a low-temperature single cell. The effect of the operating conditions on the single-cell performance was evaluated at different feed concentrations and cell voltages, and the corresponding electrochemical impedance spectroscopy (EIS) data were collected and analyzed. The Nyquist plots exhibited two semicircles with separated characteristic frequencies of approximately 1 kHz and tens of Hz. The high-frequency semicircles, which depend only on the catholyte concentration, could be correlated to the charge transfer processes in competitive CO₂ reduction and hydrogen evolution reactions at the cathodes. The EIS characteristics of the CO₂/H₂O co-reduction single cell could be explained by the equivalent circuit suggested in this study. In this circuit, the cathodic mass transfer and anodic charge transfer processes are collectively represented by a parallel combination of resistance and a constant phase element to show low-frequency semicircles. Through nonlinear fitting using the equivalent circuit, the parameters for each electrochemical element, such as polarization resistances for high- and low-frequency processes, could be quantified as functions of feed concentration and cell voltage.

• Journal of Electrochemical Science and Technology
• /
• 제12권1호
• /
• pp.112-125
• /
• 2021

The new emerging "High entropy materials" attract the attention of the scientific society because of their simpler structure and spectacular applications in many fields. A novel nanocrystalline high entropy (Be,Mg,Ca,Sr,Zn,Ni)3O4 oxide has been successfully synthesized through mechanochemical treatment followed by sintering and air quenching. The present research work focuses on the possibility of single-phase formation in the aforementioned high entropy oxide despite the great difference in the atomic sizes of reactant alkaline earth and 3d transition metal oxides. Structural properties of (Be,Mg,Ca,Sr,Zn,Ni)3O4 high entropy oxide were explored by confirmation of its single-phase Fd-3m spinel structure by x-ray diffraction (XRD). Further, nanocrystalline nature and morphology were analyzed by scanning electron microscopy (SEM). Among thermal properties, thermogravimetric analysis (TGA) revealed that the (Be,Mg,Ca,Sr,Zn,Ni)3O4 high entropy oxide is thermally stable up to a temperature of 1200℃. Whereas phase evolution in (Be,Mg,Ca,Sr,Zn,Ni)3O4 high entropy oxide before and after sintering was analyzed through differential scanning calorimetry (DSC). Electrochemical studies of (Be,Mg,Ca,Sr,Zn,Ni)3O4 high entropy oxide consists of a comparison of thermodynamic and kinetic parameters of water and hydrazine hydrate oxidation. Values of activation energy for water oxidation (9.31 kJ mol-1) and hydrazine hydrate oxidation (13.93 kJ mol-1) reveal that (Be,Mg,Ca,Sr,Zn,Ni)3O4 high entropy oxide is catalytically more active towards water oxidation as compared to that of hydrazine hydrate oxidation. Electrochemical impedance spectroscopy is also performed to get insight into the kinetics of both types of reactions.

• Biotechnology and Bioprocess Engineering:BBE
• /
• 제9권2호
• /
• pp.107-111
• /
• 2004

A comparative study was performed to evaluate the signal amplification strategies in electrochemical affinity sensing, which included the direct electron transfer and diffusible-group mediated electron transfer between label enzymes that were specifically bound to target proteins and chemically modified electrode surfaces. As a platform surface for affinity recognition reactions, a double functionalized poly(amidoamine) dendrimer monolayer that was modified with ferrocene and biotin groups was constructed on a gold surface. With the chemically modified electrode, a model affinity sensing with avidin was investigated. The advantages of adopting the diffusible-group mediated signaling strategy were demonstrated in terms of signal sensitivity and stability.