The development of separation method of radioactive tritium is imperative for treating tritiumcontaminated water originating from nuclear facilities. Polymer electrolyte membrane electrolysis technology represents a promising alternative to conventional alkaline electrolysis for tritium enrichment. Nevertheless, there has been limited research conducted thus far on the composition of membrane electrode assemblies (MEAs) specifically optimized for tritium separation, as well as the methods used for their fabrication. In this study, we conducted an investigation aimed at optimizing MEAs specifically tailored for tritium separation. Our approach involved the systematic variation of MEA components, including the anode, cathode, porous transport layer, and electrode formation method. The water electrolysis efficiency and the H/D separation factor in deuterated water (1%) were evaluated with respect to both the preparation method and the composition of the MEA. To assess the long-term stability of the MEAs, changes in cell voltage, resistance, and the active electrode area were analyzed using impedance analysis and cyclic voltammetry. Furthermore, we examined H/D separation factor both before and after degradation. The results showed that MEAs with different anode/cathode configurations and electrode formation methods improved the electrolysis efficiency compared to commercial MEAs. In addition, the degree of change in the resistance value was also different depending on the electrode formation method, indicating that the electrode formation method has a significant impact on the stability of the electrolysis system. Therefore, the study showed that the efficiency and long-term stability of the water electrolzer can be improved by optimizing the MEA fabrication method.
For decontamination and quantification of trace amount of tritium in water, an efficient separation technology capable of enriching tritium in water is required. Electrolysis is a key technology for tritium enichment as it has a high H/T and D/T separation factors. To separate tritium, it is important to develop a proton exchange membrane (PEM) electrolyzer having high hydrogen isotope separation factor as well as high electrolyzer cell efficiency. However, there has not been sufficient research on the separation factor and cell efficiency according to the composition and manufacturing method of the membrane electrode assembly (MEA) Therefore, it is necessary to study the optimal composition and manufacturing method of the MEA in PEM electrolyzer. In this study, the H/D separation factor and water electrolysis cell efficiency of PEM electrolyzer were analyzed by changing the anode and cathode materials and electrode deposition method of the MEA. After the water electrolysis experiment using deionized water, the D/H ratio in water and hydrogen gas was measured using a cavity ring down spectrometer and a mass spectrometer, respectively, and the separation factor was calculated. To calculate the cell efficiency of water electrolysis, a polarization curves were obtained by measuring the voltage changes while increasing the current density. As a result of the study, the water electrolyzer cell efficiency of the MEA fabricated with different anode/cathode configurations and electrode formation methods was higher than that of commercial MEA. On the other hand, the difference in H/D separation factor was not significant depending on the MEA fabrication methods. Therefore, using a cell with high cell efficiency when the separation factor is the same will help construct a more efficient water electrolysis system by lowering the voltage required for water electrolysis.
Platinum (Pt) catalysts dispersed on carbon-based support materials are generally used in the polymer electrolyte membrane (PEM) fuel cells. In this study, commercial graphene nanoplatelets (GNPs), with different surface areas (320, 530, 800 m2 g− 1), were used as catalyst supports in PEM fuel cells. These GNPs were also pyrolyzed under the inert atmosphere, with and without melamine, as the nitrogen (N) source. Various characterizations (Elemental analysis, FTIR, Raman spectroscopy, BET, TEM, HRTEM, SAED, XRD, TGA, ICP-MS, contact angle measurement, CV, ORR, chronoamperometry, EIS, PEM fuel cell performance test) were performed for the detailed analysis of Pt/GNPs. Based on the three-electrode cell system, the lowest electrochemical surface area (ECSA) loss (29.9%), Pt mass activity loss (20.3%) and overall (charge and mass) resistance (42.2 Ω) were obtained with the Pt/M-530 catalyst. According to the in-situ PEM fuel cell performance results, the specific peak power density was recorded as (450 mW mg Pt− 1) for the Pt/R-530 catalyst, which has also the second most hydrophobic catalyst layer surface with the 146.5° ± 1.28° contact angle value. On the heels of Pt/R-530, the two best performances also belong to the Pt/M-530 (391 mW mg Pt− 1) and Pt/P-530 (378 mW mg Pt− 1) catalysts of the same group.
이산화탄소 전환 기술은 이산화탄소를 원료로 유용한 화합물을 생산하는 기술로서 지속적인 탄소원의 활용 및 고부가 가치의 화합물 생산을 통한 이익 창출이 가능하다. 다양한 이산화탄소 전환 기술 중에서도 전기 에너지를 이용한 이산화탄소 전환 기술은 유용 화합물 생산 외에도 신재생에너지 저장 기술로 활용할 수 있어서 최근 그 중요성이 부각되고 있다. 그러나 열역학적으로 안정한 이산화탄소의 환원 반응은 많은 에너지를 필요로 하므로 기술의 경제성 확보 및 실질적인 탄소 중립을 구현하기 위해서는 생성물에 대한 높은 선택성을 가지는 촉매 개발 및 효율적인 반응 시스템 개발이 필수적이다. 본 연구에서는 고분자 전해질 막을 이용하여 전기화학적 이산화탄소 전환을 통해 개미산염을 제조하였다.
Dimensional stability of polymer electrolyte membrane stands out always important issue as well as proton conductivity. The reinforced membrane can be a good solution to enhance the dimensional stability for not only perfluorosulfonic acid polymer but also hydrocarbon based polymer. In this study, we have prepared nanofiber reinforced polymer electrolyte membranes for proton exchange membrane fuel cells. The nanofiber reinforced PEMs was impregnated by introducing hydrocarbon polymer electrolytes into web-like substrate. Due to high porosity and the intrinsic structure of reinforced PEMs, dimensional stability are improved without sacrificing membrane performance. Consequently, reinforced PEMs exhibited higher physical properties than unreinforced PEMs.
In this study, graphite composites were fabricated by warm press molding method to realize commercialization of PEM fuel cells. Graphite composites have been considered as alternative economic materials for bipolar plate of PEM fuel cells. Graphite powder that enables to provide electrical conductivity was selected as the main substance. The graphite powder was mixed with phenolic resin and the mixture was pressed using a warm press method. First of all, the graphite powder was pulverized with a ball mill for the dense packing of composite. As the ball milling time increases, the average size of particles decreases and the size distribution becomes narrow. This allows for improvement of the uniformity of graphite composite. However, the surface electrical resistivity of graphite composite increases as the ball milling time increases. It is due to that graphite particles with amorphous phase are generated on the surface due to the friction and collision of particles during pulverizing. We found that the contact electrical resistivity of graphite particles increases as the particle size decreases. The contact electrical resistivity of graphite powders was reduced due to high molding pressure by warm press molding. This leads to improvement of the mechanical properties of graphite composite. Hydrogen gas impermeability was measured with the graphite composite, showing a possibility of the application for bipolar plate in fuel cell. And, I-V curves of the graphite composite bipolar plate exhibit a similar performance to the graphite bipolar plate.
In this study, we prepared porous cation exchange membrane using polystyrene such as, EPS (expanded polystyrene), SAN (styrene acrylonitrile copolymer) and HIPS (high impactive polystyrene). These polystyrenes were sulfonated by acetyl sulfate to make porous cation exchange membrane such as, SEPS, SSAN, SHIPS. SEM was employed to confirm porous structure of membrane, and IR spectroscopy was used to confirm sulfonation rate of ion exchange membrane. Water and methanol content were also increased with amount of sulfuric acid in reactants. SSAN-20 showed the highest value in water and methanol content. Fixed ion concentration and conductivity was also increased with an amount of sulfuric acid in reactants. Methanol permeability for SEPS-20, SSAN-20, SHIPS-20 was found to be 1.326 × 10-5 cm2/s, 1.527 × 10-5 cm2/s and 1.096 × 10-5 cm2/s respectively. From the result of electrodialysis experiment in 0.03 M Pb(NO3)2 aqueous solution, anion exclusion and cation selection effects were confirmed.
화석에너지 자원 고갈 및 경제발전에 따른 산업화가 가속화되면서 폐기물의 발생량이 지속적으로 증가하여 폐기물 에너지화 기술에 대한 관심이 급증하고 있다. 공정상에 발생하는 폐기물 중에서 특히, 메탄올의 경우에는 분리가 쉬우며 저장성이 용이하고 연료전지 사용 및 수소에너지로의 변환이 용이하므로 많은 전원장치에서 응용이 가능하다. 공정상에서 비상전원의 경우에는 배터리 또는 연료전지를 이용하게 된다. 이때 PEM 연료전지를 이용할 경우 배터리에 비해 에너지 밀도가 현저히 높기 때문에 장시간 비상전원 공급이 가능하다. 메탄올의 경우에는 다른 폐기물에 비해서 높은 수소 : 탄소 비를 가지며 낮은 끓는점을 가지면서 공정 폐기물에서 쉽게 추출할 수 있으며 저장하는데 별도의 장치가 필요 없고 또한 낮은 온도에서 간단한 조건에서 쉽게 개질이 가능하므로 연료전지 시스템에 적용이 용이하다. 본 연구에서는 공정상 추출한 메탄올을 비상전원장치의 연료로 사용한 PEM 연료전지에 적용이 가능한 메탄올 개질 반응에 대한 연구를 수행하였다. 수소를 생산하는 개질반응에는 열분해 반응, 수증기 개질 반응, 부분 산화 반응 및 수증기 개질 반응 및 부분 산화 반응의 조합으로 이루어진 자열 개질 반응이 존재한다. 4가지의 개질반응에 대한 각각의 실험을 수행하여 비상전원시스템으로의 적합성에 대한 연구를 수행하였다. 비상전원시스템의 경우에는 구조가 간단하고 부가 장치가 적을수록 가공, 제작 및 장치 구동 면에서 유리하고 또한 성공적인 비상 PEM 연료전지 구동을 위한 수소 생산을 위해서는 연료 개질 시스템은 복잡하게 구성되며 연료전지의 구동 온도가 낮을수록 더 많은 과정을 거치게 된다. 비상전원시스템에서 동적 부하 변동에 빠른 응답성을 가지며 동시에 메탄올에 대해서 비교적 안정적인 운전이 가능하며 외부 열원의 사용을 최소화 할 수 있는 개질 반응 연구를 수행하였다. 다양한 개질 반응에 대한 수소 발생률 및 BOP(Balance of Plant)의 비교 검증을 통하여 비상전원시스템에 가장 적합한 개질 반응에 대한 선택을 하였으며 선택된 개질 반응을 이용하여 비상 PEM 연료전지 전원장치 시스템에 적용시켰다. 이는 비상 PEM 연료전지 전원장치 뿐만 아니라 다양한 연료 처리 장치에 적용 가능할 것으로 판단된다.
Development and performance evaluation of the hydrogen generator by autothermal reforming process for emergency PEM fuel cell using methanol from process waste were carried out. Supply of gaseous hydrogen has been a technical barrier for its wide application. As a result, conventional reformer has either a separate heat source such as a catalytic combustor or a parallel process in the same reactor to generate heat. The later device is called ATR (Autothermal reforming). Typical product gas of ATR still contains a large amount of carbon monoxide that poisons electro-catalyst of the MEA. In the present study, we used the decomposition of hydrogen peroxide as a parallel exothermic reaction in the same reactor as the reformer. The decomposition of hydrogen peroxide releases water vapor and gaseous oxygen with enormous heat. The heat sustains the reforming reaction and the oxygen is used to recombine the carbon monoxide by oxidation. By parametric study, at the condition of 200oC and the rate of methanol to 40% of hydrogen peroxide is 4 to 1, the Carbon monoxide contents are reduced by less than 800 ppm. Using the present concept we could reduce the concentration of carbon monoxide in the product gas of the reformer by more than 80%. At that carbon monoxide contents, we can be possible to load the methanol-hydrogen peroxide ATR system without any devices.