Silicon alloys are considered promising anode active materials to replace Li-ion batteries by graphite powder, because they have a relatively high capacity of up to 4200 mAh/g, and are environmentally friendly and inexpensive ECO-materials. However, its poor charge/discharge properties, induced by cracking during cycles, constitute their most serious problem as anode electrode. In order to solve these problems, Si-Ge-Al alloys with porous structure are designed as anode alloy powders, to improve cycling stability. The alloys are melt-spun to obtain the rapidly solidified ribbons, and then ball-milled to make fine powders. The powders are etched using 1 M HCl solution, which gives the powders a porous structure by removing the element Al. Subsequently, in this study, the microstructures and the characteristics of the etched powders are evaluated for application as anode materials. As a result, the etched porous powder shows better electrochemical properties than as-milled Si-Ge-Al powder.

Physical and electrochemical qualities were analyzed after KOH activation of a direct methanol fuel cell using needle coke as anode supporter. The results of research on support loaded with platinum-ruthenium suggest that an activated KOH needle coke container has the lowest onset potential and the highest degree of catalyst activity among all commercial catalysts. Through an analysis of the CO stripping voltammetry, we found that KOH activated catalysis showed a 21% higher electrochemical active surface area (ECSA), with a value of 31.37 m2/g, than the ECSA of deactivated catalyst (25.82 m2/g). The latter figure was 15% higher than the value of one specific commercial catalyst (TEC86E86).

We performed this study to understand the effect of a single-crystalline anode on the mechanical properties of asdeposited films during electrochemical deposition. We used a (111) single- crystalline Cu plate as an anode, and Si substrates with Cr/Au conductive seed layers were prepared for the cathode. Electrodeposition was performed with a standard 3-electrode system in copper sulfate electrolyte. Interestingly, the grain boundaries of the as-deposited Cu thin films using single-crystalline Cu anode were not distinct; this is in contrast to the easily recognizable grain boundaries of the Cu thin films that were formed using a poly-crystalline Cu anode. Tensile testing was performed to obtain the mechanical properties of the Cu thin films. Ultimate tensile strength and elongation to failure of the Cu thin films fabricated using the (111) single-crystalline Cu anode were found to have increased by approximately 52 % and 37%, respectively, compared with those values of the Cu thin films fabricated using apoly-crystalline Cu anode. We applied ultrasonic irradiation during electrodeposition to disturb the uniform stream; we then observed no single-crystalline anode effect. Consequently, it is presumed that the single-crystalline Cu anode can induce a directional/uniform stream of ions in the electrolyte that can create films with smeared grain boundaries, which boundaries strongly affect the mechanical properties of the electrodeposited Cu films.

The work presented in this report was a detailed comparative study of the electrochemical response exhibited by graphite anodes in Li-ion batteries having different physical features. A comprehensive morphological and physical characterization was carried out for these graphite samples via X-ray diffraction and scanning electron microscopy. Later, the electrochemical performance was analyzed using galvanostatic charge/discharge testing and the galvanostatic intermittent titration technique for these graphite samples as negative electrode materials in battery operation. The results demonstrated that a material having a higher crystalline order exhibits enhanced electrochemical properties when evaluated in terms of rate-capability performance. All these materials were investigated at high C-rates ranging from 0.1C up to 10C. Such improved response was attributed to the crystalline morphology providing short layers, which facilitate rapid Li+ ions diffusivity and electron transport during the course of battery operation. The values obtained for the electrical conductivity of these graphite anodes support this possible explanation.

파이로프로세싱 전해환원 공정에서 현재 사용 중인 Pt 양극을 대체하기 위한 소재 개발은 매우 중요하다. 이 연구에서는 전 기화학 반응시 산소를 발생시키는 전도성 세라믹 양극으로서 TiN의 전기화학적 거동을 알아보았다. UO2의 전해환원이 일어 나는 동안 TiN 양극의 적합성과 안정성에 대한 평가를 진행하였다. LiCl-Li2O 용융염에서 TiN 양극을 이용하여 UO2를 전기 화학적으로 금속 U로 변환시킬 수 있었다. 반응 도중 TiN의 산화 반응은 관찰되지 않았다. 하지만 TiN 내부에서 공공이 생 기는 것을 확인하였으며, 이에 따라 소재 수명에 제한이 있을 것으로 판단된다.

In this study, several kinds of active carbons with high specific surface area and micro pore structure were prepared from the coconut shell charcoal using chemical activation method. The physical property of prepared active carbon was investigated by experimental variables such as activating chemical agents to char coal ratio, flow rate of inert gas and temperature. It was shown that chemical activation with KOH and NaOH was successfully able to make active carbons with high surface area of 1900~2500 m2/g and mean pore size of 1.85~2.32 nm. The coin cell using water-based binder in the electrolyte of LiPF6 dissolved in mixed organic solvents (EC:DMC:EMC=1:1:1 vol%) showed better capacity than that of oil-based binder. Also, it was found that the coin cell of water-based binder shows an improved cycling performance and coulombic efficiency.

Carbon-supported Pt catalyst systems containing defect adsorption sites on the anode of direct methanol fuel cells were investigated, to elucidate the mechanisms of H2 dissociation and carbon monoxide (CO) poisoning. Density functional theory calculations were carried out to determine the effect of defect sites located neighboring to or distant from the Pt catalyst on H2 and CO adsorption properties, based on electronic properties such as adsorption energy and electronic band gap. Interestingly, the presence of neighboring defect sites led to a reduction of H2 dissociation and CO poisoning due to atomic Pt filling the defect sites. At distant sites, H2 dissociation was active on Pt, but CO filled the defect sites to form carbon π-π bonds, thus enhancing the oxidation of the carbon surface. It should be noted that defect sites can cause CO poisoning, thereby deactivating the anode gradually.

In order to prepare anode materials for high power lithium ion secondary batteries, carbon composites were fabricated with a mixture of petroleum pitch and coke (PC) and a mixture of petroleum pitch, coke, and natural graphite (PCNG). Although natural graphite has a good reversible capacity, it has disadvantages of a sharp decrease in capacity during high rate charging and potential plateaus. This may cause difficulties in perceiving the capacity variations as a function of electrical potential. The coke anodes have advantages without potential plateaus and a high rate capability, but they have a low reversible capacity. With PC anode composites, the petroleum pitch/cokes mixture at 1:4 with heat treatment at 1000 oC (PC14-1000C) showed relatively high electrochemical properties. With PC-NG anode composites, the proper graphite contents were determined at 10~30 wt.%. The composites with a given content of natural graphite and remaining content of various petroleum pitch/cokes mixtures at 1:4~4:1 mass ratios were heated at 800~1200 oC. By increasing the content of petroleum pitch, reversible capacity increased, but a high rate capability decreased. For a given composition of carbonaceous composite, the discharge rate capability improved but the reversible capacity decreased with an increase in heat treatment temperature. The carbonaceous composites fabricated with a mixture of 30 wt.% natural graphite and 70 wt.% petroleum pitch/cokes mixture at 1:4 mass ratio and heat treated at 1000 oC showed relatively high electrochemical properties, of which the reversible capacity, initial efficiency, discharge rate capability (retention of discharge capacity in 10 C/0.2 C), and charge capacity at 5 C were 330 mAh/g, 79 %, 80 %, and 60 mAh/g, respectively.

The composite of porous silicon (Si) and amorphous carbon (C) is prepared by pyrolysis of a nano-porous Si + pitch mixture. The nano-porous Si is prepared by mechanical milling of magnesium powder with silicon monoxide (SiO) followed by removal of MgO with hydrochloric acid (etching process). The Brunauer-Emmett-Teller (BET) surface area of porous Si (64.52 m2g−1) is much higher than that before etching Si/MgO (4.28 m2g−1) which indicates pores are formed in Si after the etching process. Cycling stability is examined for the nano-porous Si + C composite and the result is compared with the composite of nonporous Si + C. The capacity retention of the former composite is 59.6% after 50 charge/discharge cycles while the latter shows only 28.0%. The pores of Si formed after the etching process is believed to accommodate large volumetric change of Si during charging and discharging process.

The effects of particle size of Li-Si alloy and LiCl-KCl addition as a binder phase for raw material of anode were investigated on the formability of the thermal battery anode. The formability was evaluated with respect to filling density, tap density, compaction density, spring-back and compressive strength. With increasing particle size of Li-Si alloy powder, densities increased while spring-back and compressive strength decreased. Since the small spring-back is beneficial to avoiding breakage of pressed compacts, larger particles might be more suitable for anode forming. The increasing amount of LiCl-KCl binder phase contributed to reducing spring-back, improving the formability of anode powder too. The control of particle size also seems to be helpful to get double pressed pellets, which consisted of two layer of anode and electrolyte.

Amorphous agglomerates of carbon nanospheres (CNS) with a diameter range of 10-50 nm were synthesized using the solution combustion method. High-resolution transmission elec-tron microscopy (HRTEM) revealed a densely packed high surface area of SP2-hybridized carbon; however, there were no crystalline structural components, as can be seen from the scanning electron microscopy, HRTEM, X-ray diffraction, Raman spectroscopy, and ther-mal gravimetric analyses. Electrochemical and thermo catalytic decomposition study results show that the material can be used as a potential electrode candidate for the fabrication of energy storage devices and also for the production of free hydrogen if such devices are used in a fluidized bed reactor loaded with the as-prepared CNS as the catalyst bed.

Silicon-carbon composite was prepared by the magnesiothermic reduction of mesoporous silica and subsequent impregnation with a carbon precursor. This was applied for use as an anode material for high-performance lithium-ion batteries. Well-ordered mesoporous silica(SBA-15) was employed as a starting material for the mesoporous silicon, and sucrose was used as a carbon source. It was found that complete removal of by-products (Mg2Si and Mg2SiO4) formed by side reactions of silica and magnesium during the magnesiothermic reduction, was a crucial factor for successful formation of mesoporous silicon. Successful formation of the silicon-carbon composite was well confirmed by appropriate characterization tools (e.g., N2 adsorption-desorption, small-angle X-ray scattering, X-ray diffraction, and thermogravimetric analyses). A lithium-ion battery was fabricated using the prepared silicon-carbon composite as the anode, and lithium foil as the counter-electrode. Electrochemical analysis revealed that the silicon-carbon composite showed better cycling stability than graphite, when used as the anode in the lithium-ion battery. This improvement could be due to the fact that carbon efficiently suppressed the change in volume of the silicon material caused by the charge-discharge cycle. This indicates that silicon-carbon composite, prepared via the magnesiothermic reduction and impregnation methods, could be an efficient anode material for lithium ion batteries.

Tungsten oxide films were prepared by an electrochemical deposition method for use as the anode in rechargeable lithium batteries. Continuous potentiostatic deposition of the film led to numerous cracks of the deposits while pulsed deposition significantly suppressed crack generation and film delamination. In particular, a crack-free dense tungsten oxide film with a thickness of ca. 210 nm was successfully created by pulsed deposition. The thickness of tungsten oxide was linearly proportional to deposition time. Compositional and structural analyses revealed that the as-prepared deposit was amorphous tungsten oxide and the heat treatment transformed it into crystalline triclinic tungsten oxide. Both the as-prepared and heat-treated samples reacted reversibly with lithium as the anode for rechargeable lithium batteries. Typical peaks for the conversion processes of tungsten oxides were observed in cyclic voltammograms, and the reversibility of the heat-treated sample exceeded that of the as-prepared one. Consistently, the cycling stability of the heat-treated sample proved to be much better than that of the as-prepared one in a galvanostatic charge/discharge experiment. These results demonstrate the feasibility of using electrolytic tungsten oxide films as the anode in rechargeable lithium batteries. However, further works are still needed to make a dense film with higher thickness and improved cycling stability for its practical use.

Microstructural and mechanical properties of Ni-YSZ fabricated using SPS processing have been investigated at various sintering temperatures. Our study shows samples to be applied as a SOFC anode have the proper porosity of 40% and high hardness when processed at 1100ºC. These results are comparable to the values obtained at 100- 200ºC higher sintering temperature reported by others. This result is important because when the fabrication processes are performed above 1100ºC, the mechanical property starts to decrease drastically. This is caused by the fast grain coarsening at the higher temperature, which initiates a mismatch between thermal expansion coefficients of Ni and YSZ and induces cracks as well.

The electrochemical performance for the corrosion of zinc anodes according to particle size and shape as anode in Zn/air batteries was study. We prepared five samples of Zn powder with different particle size and morphol- ogy. For analysis the particle size of theme, we measured particle size analysis (PSA). As the result, sample (e) had smaller particle size with 10.334 µm than others. For measuring the electrochemical performance of them, we measured the cyclic voltammetry and linear polarization in three electrode system (half-cell). For measuring the morphology change of them before and after cyclic voltammetry, we measured Field Emission Scanning Electron Microscope (FE- SEM). From the cyclic voltammetry, as the zinc powder had small size, we knew that it had large diffusion coefficient. From the linear polarization, as the zinc powder had small size, it was a good state with high polarization resistance as anode in Zn/air batteries. From the SEM images, the particle size had increased due to the dendrite formation after cyclic voltammetry. Therefore, the sample (e) with small size would have the best electrochemical performance between these samples.

고분자 전해질막 연료전지는 연료극의 연료와 공기극의 공기에 각각 H2S와 SO2이 포함되어 있을 때 그 성능이 심각하게 감소한다. 본 연구는 고분자전해질막 연료전지의 공기극과 연료극에 1 ppm에서 10 ppm의 불순물 가스를 공급하여 전기적 성능측정을 통해 복합적인 황불순물이 단위전지에 미치는 영향을 확인하였다. 최적의 운전조건에서 불순물가스를 피독하였을 때 SO2와 H2S의 농도가 증가할수록 성능이 급격히 감소하였다(단위전지 온도 65℃, 상대습도 100%). 그리고 황의 흡착은 MEA의 백금 촉매층 표면서 일어나며, 불순물 가스가 MEA에 누적되는 것을 확인하였다. 1, 3, 5, 및 10 ppm 4회의 연속적인 피독 후 연료전지의 성능이 0.71 V에서 0.54 V(76 %)로 감소하였다.

The properties of SOFC unit cells manufactured using the decalcomania method were investigated. SOFC unit cell manufacturing using the decalcomania method is a very simple process. In order to minimize the ohmic loss of flattened tube type anode supports of solid oxide fuel cells(SOFC), the cells were fabricated by producing an anode function layer, YSZ electrolyte, LSM electrode, etc., on the supports and laminating them. The influence of these materials on the power output characteristics was studied when laminating the components and laminating the anode function layer between the anode and the electrolyte to improve the output characteristics. Regarding the performance of the SOFC unit cell, the output was 246 mW/cm2 at a temperature of 800˚C in the case of not laminating the anode function layer; however, this value was improved by a factor of two to 574 mW/cm2 due to the decrease of the ohmic resistance and polarization resistance of the cell in the case of laminating the anode function layer. The outputs appeared to be as high as 574 and 246 mW/cm2 at a temperature of 800˚C in the case of using decalcomania paper when laminating the electrolyte layer using the in dip-coating method; however, the reason for this is that interfacial adhesion was improved due to the dense structure, which leads to a thin thickness of the electrolyte layer.

Silicon-based thin film was prepared at room temperature by an electrochemical deposition method and a feasibility study was conducted for its use as an anode material in a rechargeable lithium battery. The growth of the electrodeposits was mainly concentrated on the surface defects of the Cu substrate while that growth was trivial on the defect-free surface region. Intentional formation of random defects on the substrate by chemical etching led to uniform formation of deposits throughout the surface. The morphology of the electrodeposits reflected first the roughened surface of the substrate, but it became flattened as the deposition time increased, due primarily to the concentration of reduction current on the convex region of the deposits. The electrodeposits proved to be amorphous and to contain chlorine and carbon, together with silicon, indicating that the electrolyte is captured in the deposits during the fabrication process. The silicon in the deposits readily reacted with lithium, but thick deposits resulted in significant reaction overvoltage. The charge efficiency of oxidation (lithiation) to reduction (delithiation) was higher in the relatively thick deposit. This abnormal behavior needs to clarified in view of the thickness dependence of the internal residual stress and the relaxation tendency of the reaction-induced stress due to the porous structure of the deposits and the deposit components other than silicon.

Two different types of graphite, such as flake graphite (FG) and spherical graphite (SG), were used as anode materials for a lithium-ion secondary battery in order to investigate their electrochemical performance. The FG particles were prepared by pulverizing natural graphite with a planetary mill. The SG particles were treated by immersing them in acid solutions or mixing them with various carbon additives. With a longer milling time, the particle size of the FG decreased. Since smaller particles allow more exposure of the edge planes toward the electrolyte, it could be possible for the FG anodes with longer milling time to deliver high reversible capacity; however, their initial efficiency was found to have decreased. The initial efficiency of SG anodes with acid treatments was about 90%, showing an over 20% higher value than that of FG anodes. With acid treatment, the discharge rate capability and the initial efficiency improved slightly. The electrochemical properties of the SG anodes improved slightly with carbon additives such as acetylene black (AB), Super P, Ketjen black, and carbon nanotubes. Furthermore, the cyclability was much improved due to the effect of the conductive bridge made by carbon additives such as AB and Super P.