• Membrane Journal
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• v.27 no.5
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• pp.389-398
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• 2017

The most important characteristic of the polymer electrolyte membranes (PEMs) for fuel cells, the proton conducting ability is mainly influenced by the distribution and morphology of the water channels inside the PEMs. Non-perfluorinated hydrocarbon PEMs are known to have weaker water channels than perfluorinated PEM, Nafion, and thus relatively low proton conducting ability. In this study, we used a mesoscale simulation technique to observe the water channel formation and phase separation behavior of hydrocarbon PEM, sulfonated polyimides, under the humidification condition. It was observed that the water molecules were distributed evenly through the entire hydrophilic region, and clear water clusters were formed only in the sulfonated polyimide having high sulfonation degree. In addition, it was observed that sulfonated polyimides have a difficulty in forming water channel under the low hydrated condition. These results clearly support the theories of the formation of water channels in non-perfluorinated hydrocarbon PEMs, and also well explain the tendency of proton conducting abilities of sulfonated polyimides. Thus, it is confirmed that mesoscale simulation techniques can be very effective in analyzing phase separation behavior and water channel formation in PEMs for fuel cells and elucidating the ion conducting abilities.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.415-417
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• 2009

A low temperature decal (LTD) transfer method is tried to fabricated hydrocarbon (HC) membrane based MEA. Sandwiched structures of outer ionomer/catalyst/carbon coating/substrate, which had been developed for Nafion membrane, are used for transfer of catalyst to the HC membrane. Performances of the HC MEA before and after 500hr continuous operation are compared and it is found that a severe delamination occurs at the interface between the HC membrane and the catalyst layer, which is the main reason of the low performance and its degradation. The delamination is due probably to the different nature of HC membrane to the Nafion ionomer. A substitutional method, therefore, is suggested to overcome this. In such a way, the outer ionomer process is removed and the low transfer rate of catalyst by skipping the ionomer process is compensated with optimization of other process variables such as transfer time or temperature. The resulting performance is superior to the original LTD method, which can be explained in terms of low resistive components both in ohmic and kinetic.

• Transactions of the Korean hydrogen and new energy society
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• v.28 no.3
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• pp.246-251
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• 2017

To fabricate a hydrocarbon polymer electrolyte composite membrane incorporated with Pt nanoparticle, the polymer electrolyte membrane made of a sulfonated-fluorinated hydrophilic-hydrophobic block copolymer (SFBC) and sulfonated poly (ether ether ketone) (SPEEK) blend in the wight ratio of 1 : 1 was synthesized, and a simple drying process was used in order to incorporate Pt nanoparticle into the SFBC/SPEEK film by reducing platinum (II) bis (acetylacetonate), Pt $(acac)_2$. The distribution of the Pt nanoparticles was observed by transmission electron microscopy (TEM), and mechanical and thermal properties were tested by universal testing machine (UTM) and thermogravimetry analyzer (TGA). Cation conductivity, ion exchange capacity (IEC) and I-V characteristics were estimated.

• Membrane Journal
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• v.26 no.1
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• pp.1-13
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• 2016

Fuel cells are regarded as a representative energy source expected to replace fossil fuels particularly used in internal combustion engines. One of the most important components is polymer electrolyte membranes (PEMs) acting as a proton conducting barrier to prevent fuel gas crossover. Since water channels act as proton pathways through PEMs, many researchers have been focused on the 'good phase-separation of hydrophilic moiety' which ensures high water retention under low humidity enough to keep the water channel for good proton conduction. Here, we summarized the strategies which have been adopted to synthesize sulfonated PEMs having high proton conductivities even under low humidified conditions, and hope this review will be helpful to design high performance hydrocarbon PEMs.

• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.97.1-97.1
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• 2011

저온에서 양이온 고분자막을 사용하는 고분자 연료전지의 경우 뛰어난 성능과 다양한 응용분야로 인해 많은 연구와 실증이 이루어지고 있지만 공기극에서의 느린 산소 환원반응으로 인해 백금과 같은 귀금속의 사용이 불가피하고 백금의 제한된 매장량과 높은 가격으로 인해 상용화가 늦어지고 있다. 그래서 많은 연구자들이 합금 촉매 또는 비귀금속 촉매를 이용한 전극 개발에 집중하고 있다. 알칼리 분위기에서 저가의 전이 금속들이 백금과 비슷한 활성을 보이고 고체 음이온 교환막이 개발됨에 따라 최근 알칼리 연료전지가 다시금 큰 주목을 받고 있다. 그러나 고분자 연료전지와는 달리 아직 촉매나 전해질막, 이오노머의 특성 및 메커니즘에 관해 별로 알려진 것이 없다. 본 연구에서는 직접 개발한 세공충진막 형태의 탄화수소계의 음이온 교환막과 비귀금속 공기극 촉매를 이용하여 막전극접합체(MEA)를 개발하였고 촉매 및 이오노머 함량과 같은 전극 조성, 막전극접합체의 제조 및 체결, 가습이나 가스조성 등의 단위전지 운전조건과 같은 다양한 변수에 대해에 최적 조건을 도출하고자 하였다. 공기극 촉매는 Cu-Fe/C를 이용한 상용 촉매를 이용하였고 이오노머의 경우는 탄화수소계의 상용 제품을 사용하였으며 음이온 교환막에 전극층을 형성하기 위해서는 스프레이 공정을 이용하였다. 단위전지를 통해 성능을 확인하였고 임피던스 및 CV를 통해 전기화학적인 특성을 규명하였다. 조건의 최적화를 통해 상당한 성능 향상을 이루었으나 추가적인 성능 향상 및 내구성 확보 등에 대해 계속적인 실험을 진행할 예정이다.

• Membrane Journal
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• v.33 no.3
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• pp.127-136
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• 2023

In this study, the electrochemical performance of a 5-layer fuel cell stack using silica composite membranes as polymer electrolyte membranes was evaluated. It was observed that the flow rate of the fuel gases plays a crucial role in stack performance, particularly being mainly dependent on the flow rate of hydrogen. Increasing the flow rate of oxygen resulted in negligible changes in performance, whereas an increase in the flow rate of hydrogen demonstrated performance improvements. However, this led to an imbalance in the ratio of hydrogen to oxygen flow rates, causing significant degradation in stack performance and durability. A decline in stack performance was also observed over time due to the degradation of stack components. This phenomenon was consistently observed in individual unit cells. Based on these findings, it was emphasized that, in addition to optimizing the performance of each component during stack operation, it is important to optimize design and operating conditions for uniform flow rate control. Lastly, the developed silica composite membrane was assessed to have sufficient performance for application in actual fuel cell systems, exhibiting a performance of over 25 W based on maximum power.

• Journal of Energy Engineering
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• v.19 no.2
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• pp.121-127
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• 2010

In present work, sulfonated poly(arylene biphenyklsulfone ether) copolymers containing hydroquinone moiety were successfully synthesized using 4,4'-bis[(4-chlorophenyl)sulfonyl]-1,1'-biphenyl(BCPSBP), hydroquinone sulfonic acid potassium salt(sHQ), 4,4'-sulfonyldiphenol and evaluated their characteristics. Three kinds of polymer electrolyte membranes, PBPSEH-HQ00, PBPSEH-HQ10 and PBPSEH-HQ30 were prepared by using mole fraction of sulfonated hydroquinone(sHQ). The structure of the fabricated polymers was analyzed using NMR, IR and GPC. The Mw(weight-average molecular weights) of the polymers were in the range of 62,000-213,000 g $mol^{-1}$, and the molecular weight distribution (Mw/Mn) varied from 1.66-4.04. The thermal analysis of the copolymers was carried out by TGA and DSC. The temperature of Td5% and Td10% was decreased with the mole fraction of sHQ but Tg was increased with the mole fraction. The water uptake, IEC and ion conductivity were increased with increasing the ionic cluster of the polymers. The proton conductivity equal to 9.4 mS $cm^{-1}$ was measured for the PBPSEH-HQ30 membrane at $90^{\circ}C$ and 100% relative humidity. From the observed results it is clear that the prepared hydrocarbon membrane can be considered as suitable polymer electrolyte membrane for the application of PEMFC.

• Korean Chemical Engineering Research
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• v.53 no.6
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• pp.690-694
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• 2015

Recently, direct formic acid fuel cells (DFAFC) among direct liquid fuel cells is studied actively. Economical hydrocarbon membranes alternative to fluorinated membranes for DFAFC's membrane are receiving attention. In this study, characteristics of sulfonated poly(ether ether ketone, sPEEK) and sulfonated poly(arylene ether sulfone, PAES) membranes were compared with Nafion membrane at DFAFC operation condition. Formic acid crossover current density of hydrocarbon membranes were lower than that of Nafion 211 fluorinated membrane. I-V performance of sPEEK MEA(Membrane and Electrode Assembly) was similar to that of Nafion 211 MEA due to similar membrane resistance each other. sPEEK MEA with low formic acid crossover showed higher stability compared with Nafion 211 MEA.

• Membrane Journal
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• v.27 no.2
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• pp.182-188
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• 2017

Sulfonated poly(arylene ether sulfone) (SPAES)-3-mercaptopropyl silica gel (3MPTSG) composite membranes with improved oxidative stability were prepared for polymer electrolyte fuel cell application. It has been reported that ether part of main chain of aromatic hydrocarbon based membranes were weak to radical attack to decrease membrane durability. In this study, the hydrophilic inorganic particles were introduced by minimizing a decrease in ion conductivity and increasing an oxidative stability. The composite membranes were investigated in terms of ionic conductivity, ion exchange capacity (IEC), FT-IR, TGA and contact angle, etc. As a result, increasing amount of the 3MPTSG resulted in decrease in proton conductivities and water uptakes at 100% R.H. but enhanced thermal and oxidative stabilities.

• Membrane Journal
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• v.25 no.5
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• pp.456-463
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• 2015

In this study, we synthesize novel silane based inorganics for preparation of the polymer electrolyte membrane with high proton conductivity under high temperature condition and developed membranes are characterized. SPAES, hydrocarbon based polymer are synthesized and used as main polymeric material. We used sol-gel method to prepare inorganic material with high performance using silica, phosphate and zirconium. Three types of inorganics were prepared by control of the mole ration of each component. As a result of EDX analysis, the inorganic materials are well dispersed in the polymer membrane. The water uptake of the composite membrane is increased by introduction of the hydrophilic inorganic material in the membrane. When the content of the zirconium in the membrane is increased, the proton conductivity of the composite membrane shows the higher value than pure SPAES membrane at the high temperature. And the silica based inorganics effect to increase the proton conductivity under low temperature condition.