• Applied Chemistry for Engineering
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• v.25 no.1
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• pp.78-83
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• 2014

In this research, we evaluated the performance and characteristics of carbon supported PtM (M = Ni and Y) alloy catalysts (PtM/Cs) synthesized by a modified polyol method. With the PtM/Cs employed as a catalyst for the oxygen reduction reaction (ORR) of cathodes in proton exchange membrane fuel cells (PEMFCs), their catalytic and ORR activities and electrical performance were investigated and compared with those of commercial Pt/C. Their particle sizes, particle distributions and electrochemically active surface areas (EAS) were measured by TEM and cyclic voltammetry (CV), while their ORR activity and electrical performance were explored using linear sweeping voltammetries with rotating disk electrodes and rotating ring-disk electrodes as well as PEMFC single cell tests. TEM and CV measurements show that PtM/Cs have the compatible particle size and EAS with Pt/C. When it comes to ORR activity, PtM/C showed the equivalent or better half-wave potential, kinetic current density, transferred electron number per oxygen molecule and $H_2O_2$ production(%) to or than commerical Pt/C. Based on results gained by the three electrode tests, when the PEMFC single cell tests were carried out, the current density measured at 0.6 V and maximum power density of PEMFC single cell adopting PtM/C catalysts were better than those adopting Pt/C catalyst. It is therefore concluded that PtM/C catalysts synthesized by modified polyol can result in the equivalent or better ORR catalytic capability and PEMFC performance to or than commercial Pt/C catalyst.

• Journal of the Korean Electrochemical Society
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• v.14 no.2
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• pp.110-116
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• 2011

Ru black was used for cathode catalyst in polymer electrolyte membrane fuel cell which showed low performance at the initial test. However, it was observed that the performance of Ru black cathode was dramatically enhanced after certain kind of experiment compared with initial one. It might be due to an electrochemical treatment in which a voltage was applied to the Ru cathode for constant period time. When a constant potential of 0.1 V was applied to Ru cathode for 30 min, the fuel cell performance of Ru cathode showed the best results. In order to investigate the effect of electrochemical treatment on the performance enhancement, the characteristics of electrochemically treated Ru black was compared with that of Ru black which was reduced under $H_2$ atmosphere. From XRD results, it was turned out that Ru black was not completely converted to metallic Ru by electrochemical treatment, but it is sufficient to be one of reasons for the performance enhancement. According to the results of CO stripping voltammetry, it was observed that some Ru was removed from Ru electrode by electrochemical treatment which might have a bad effect on the fuel cell performance. The removal of some Ru from as-received Ru black by electrochemical treatment is also another reason for the enhancement of fuel cell performance.

• Journal of the Korean Electrochemical Society
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• v.11 no.1
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• pp.42-46
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• 2008

Even though fuel cell have high efficiency when pure hydrogen from gas tank is used as a fuel source, it is more beneficial to generate hydrogen from city gas (mainly methane) in residential application such as domestic or office environments. Thus hydrogen is generated by reforming process using hydrocarbon. Unfortunately, the reforming process for hydrogen production is accompanied with unavoidable impurities. Impurities such as CO, $CO_2$, $H_2S$, $NH_3$, $CH_4$, and $CH_4$ in hydrogen could cause negative effects on fuel cell performance. Those effects are kinetic losses due to poisoning of the electrode catalysts, ohmic losses due to proton conductivity reduction including membrane and catalyst ionomer layers, and mass transport losses due to degrading catalyst layer structure and hydrophobic property. Hydrogen produced from reformer eventually contains around 73% of $H_2$, 20% or less of $CO_2$, 5.8% of less of $N_2$, or 2% less of $CH_4$, and 10ppm or less of CO. This study is aimed at investigating the effect of carbon dioxide on fuel cell performance. The performance of PEM fuel cell was investigated using current vs. potential experiment, long run(10 hr) test, and electrochemical impedance measurement when the concentrations of carbon dioxide were 10%, 20% and 30%. Also, the concentration of impurity supplied to the fuel cell was verified by gas chromatography(GC).

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2018.06a
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• pp.62-62
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• 2018

Pt is still considered as one of the most active electrocatalysts for ORR in alkaline fuel cells. However, the high cost and scarcity of Pt hamper the widespread commercialization of fuel cells. As a strong candidate for the replacement of Pt catalyst, silver (Ag) has been extensively studied due to its high activity, abundance, and low cost. Ag is more stable than Pt in the pH range of 8~14 as the equilibrium potential of Ag/Ag+ being ${\approx}200mV$ higher than that of Pt/PtO. However, Ag is the overall catalytic activity of Ag for oxygen reduction reaction(ORR) is still not comparable to Pt catalyst since the surface Ag atoms are approximately 10 times less active than Pt atoms. Therefore, further enhancement in the ORR activity of Ag catalysts is necessary to be competitive with current cutting-edge Pt-based catalysts. We demonstrate the architectural design of Ag catalysts, synthesized using plasma discharge in liquid phase, for enhanced ORR kinetics in alkaline media. An attractive feature of this work is that the plasma status controlled via electric-field could form the Ag nanowires or dendrites without any chemical agents. The plasma reactor was made of a Teflon vessel with an inner diameter of 80 mm and a height of 80 mm, where a pair of tungsten(W) electrodes with a diameter of 2 mm was placed horizontally. The stock solutions were made by dissolving the 5-mM AgNO3 in DI water. For the synthesis of Agnanowires, the electricfield of 3.6kVcm-1 in a 200-ml AgNO3 aqueous solution was applied across the electrodes using a bipolar pulsed power supply(Kurita, Seisakusyo Co. Ltd). The repetition rate and pulse width were fixed at 30kHz and 2.0 us, respectively. The plasma discharge was carried out for a fixed reaction time of 60 min. In case of Ag nanodendrites, the electric field of 32kVcm-1 in a 200-ml AgNO3 aqueous solution was applied and other conditions were identical to the plasma discharge in water in terms of electrode configuration, repetition rate and discharge time. Using SEM and STEM, morphology of Ag nanowires and dendrites were investigated. With 3.6 kV/cm, Ag nanowire was obtained, while Ag dendrite was constructed with 32 kV/cm. The average diameter and legth of Ag nanowireses were 50 nm and 3.5 um, and thoes values of Ag dendrites were 40 nm and 3.0 um. As a results of XPS analysis, the surface defects in the Ag nanowires facilitated O2 incorporation into the surface region via the interaction between the oxygen and the electron cloud of the adjacent Ag atoms. The catalytic activity of Ag for oxygen reduction reaction(ORR) showed that the catalytic ORR activity of Ag nanowires are much better than Ag nanodendrites, and electron transfer number of Ag nanowires is similar to that of Pt (${\approx}4$).

• Applied Chemistry for Engineering
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• v.7 no.3
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• pp.543-553
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• 1996

Oxygen reduction in an alkaline fuel cell was studied by using perovskite type oxides as an oxygen electrode catalyst. The high surface area catalysts were prepared by malic acid method and had a formula of $La_{0.6}Sr_{0.4}Co_{1-x}Fe_xO_3$(x=0.00, 0.01, 0.10, 0.20, 0.35 and 0.50). From the result of XRD pattern and specific surface area due to the amount of Fe substitution and the consumption of ammonia-water, the complex formation of Fe ion with $NH_3$ was the main factor for both the phase stability of perovskite and the increase of specific surface area. Multi-step calcination was necessary to give a single phase of perovskite in catalyst precursor. The crystal structure of the catalysts was simple cubic perovskite, which was verified from the XRD patterns of the catalysts. The activity of oxygen reduction was monitored by the techniques of cyclic voltammetry, static voltage-current method, and current interruption method. The activity(current density) of oxygen reduction showed its minimum at x=0.01 and its maximum between 0.20 and 0.35 of x-value in $La_{0.6}Sr_{0.4}Co_{1-x}Fe_xO_3$. This tendency was independent of the change of surface area.

• Korean Chemical Engineering Research
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• v.61 no.3
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• pp.362-367
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• 2023

Recently, research and development of proton exchange membrane fuel cells (PEMFC) membranes are progressing in the direction of thinning to reduce prices and improve performance. Demand for hydrogen-powered vehicles for commercial vehicles is also increasing, and their durability should be five times greater than those for passenger vehicles. Despite the thinning of the membranes, the durability of the membranes must be increased five times, so the improvement of the durability of the membranes has become more important. Since the acceleration durability evaluation time also needs to be shortened, the protocol using oxygen instead of air in the existing protocol was applied to a 10 ㎛ thin membrane to evaluate durability. The accelerated durability test (Open circuit voltage holding) was terminated at 720 hours. If the air-based department of energy (DOE) protocol was used, a lifespan of 450,000 km of driving hours would be expected, with a durability of about 1,500 hours. During the chemical durability evaluation, the active area of the electrode decreased by 51%, suggesting that catalyst degradation had an effect on membrane durability. Reducing the catalyst degradation rate is expected to increase membrane durability.

• Resources Recycling
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• v.21 no.3
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• pp.15-20
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• 2012

In this paper, we carried out separation of membrane and leaching of Pt and Ru using hydrochloric acid from MEA(membrane-electrode assembly) of fuel cell. In this method, these were separated from MEA of fuel cell using the distilled water, 10 vol.% butanol solution and 15 vol.% cationic surfactant(Koremul-LN-7) by dipping method without the dispersion of catalyst particles. And the leaching of Pt and Ru containing in the separated carbon paper catalysts has been studied by hydrochloric acid using $HNO_3$ or $H_2O_2$ as a oxidant. The leaching ratio of Pt and Ru were higher when $H_2O_2$ was used as a oxidant and the optimum conditions were obtained in 8M HCl, the amount of $H_2O_2$ 5M and 6 hours of leaching time at $90^{\circ}C$. In this condition, extraction of Pt and Ru were 98% and 71.5%, respectively.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.16 no.8
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• pp.5728-5735
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• 2015

This study attempts to verify the applicability of ceramic membrane as a separator by comparing the power generation characteristics in single-chamber MFCs using ceramic membranes to those in the MFCs using nafion membrane. The generated power in MFCs by using acetate as a substrate was more stable than that by using formate, propionate and butyrate, respectively. It was shown that the generated power by using formate substrate in MFCs was unstable and a little higher than that by using acetate, and the power generated by using propionate and butyrate were lower than that by using acetate. In order to find out the Pt catalyst effect, it was compared the power generated in MFCs using Pt-coated carbon cloth as electrode to that power using normal carbon cloth. The power generated in MFCs using Pt-coated carbon cloth as electrode was 1.2 times higher than that using normal carbon cloth. The Pt-coated carbon cloth was about 5 times more expensive than normal carbon cloth. It is suggested that both power generation efficiency and cost together should be considered in selecting electrodes of MFCs. It was found that the ceramic membrane was superior to nafion membrane by comparing to the power generation characteristics obtained. It was shown that average voltage values were $523.67mV{\pm}49.41mV$ by using synthetic wastewater, in MFCs of ceramic membrane as a separator. While average voltage values were $424.09mV{\pm}79.95mV$ by using synthetic wastewater, in MFCs of nafion membrane as a separator. The organic removal efficiency, 41.7% by using ceramic membrane was a little bit higher than 40.8% by using nafion membrane. This research implies ceramic membrane can be a valid alternative to nafion membrane as a separator when considering the power generation and the efficiency of organics removal.

• Korean Chemical Engineering Research
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• v.43 no.1
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• pp.118-124
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• 2005

In this study, a novel deposition method of Pt catalysts onto Nafion membranes modified with polypyrrole (PPy) has been proposed for PEMFC application. The PPy/Nafion composite membranes were fabricated by chemical polymerization of pyrrole using $FeCl_3$ and $Na_2S_2O_8$ as initiator. The proton conductivity and water uptake of the chemically prepared PPy/Nafion composites were investigated. The ionic conductivity and water uptake of PPy/Nafion composite membrane prepared with $Na_2S_2O_8$ were decreased with polymerization time of pyrrole. In the case of $FeCl_3$, the ionic conductivity was almost retained and the water uptake was decreased with polymerization time of pyrrole. When the Pt particle was deposited on PPy/Nafion composites membrane by chemical reduction of $H_2PtCl_6$, the Pt loading on Nafion membrane was enhanced by polypyrrole due to electronic conduction property. The performance evaluation with membrane electrode assembly composed of Pt/PPy/Nafion composite and diffusion electrode was carried out using a single cell. As a result of fuel cell test, current density of $569mA/cm^2$ at 0.3 V has been obtained for MEA contained with Pt/PPy/Nafion composite. This study shows that direct deposition of Pt catalysts on Nafion impregnated polypyrrole is a promising method to prepare thin catalyst layer for the PEMFC.

• Transactions of the Korean hydrogen and new energy society
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• v.16 no.1
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• pp.31-39
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• 2005

Direct methanol fuel cell (DMFC) is considered as a candidate for portable power sources, that could overcome the disadvantages of lithium battery. But in order to attain commercial viability the long term stability of the DMFC should be achieved. Understanding the long-term behavior of membrane-electrode assembly (MEA) is a prerequisite to this purpose and the optimization of the MEA is also needed. In this study we have investigated the changes in performance and electrochemical properties of the MEA during extended operation and the effects of heat treatment of MEA on the long-term performance. The MEAs have been treated in an autoclave with saturated water vapor at 120$^{\circ}C$, vacuum oven at 140$^{\circ}C$ and boiling in organic solvents. The autoclaved MEA was found to be have the best long term performance. The on-off operation mode also increased the performance probably due to effective removal of products from the electrodes. Physical and electrochemical analyses using a scanning electron microscope, impedance analyser and half-cell technique have been done to characterize the MEAs.