• Polymer(Korea)
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• v.34 no.2
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• pp.137-143
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• 2010

A series of partially fluorinated, sulfonated poly(biphenylene-co-sulfone)ether containing perfluorocyclobutane(PFCB) groups were prepared for fuel cell applications through three synthetic steps: synthesis of trifluorovinylether-terminated monomers, thermal cycloaddition and post-sulfonation. Two kinds of trifluorovinylether-terminated monomers were synthesized and statistically copolymerized via thermal cycloaddition to obtain a series of polymers containing 20-60 mol% of biphenyl units(PBS-X). The post-sulfonation of PBS-X was carried out using chlorosulfonic acid(CSA) to obtain copolymers with various sulfonation levels(SPBS-X). All the synthesized compounds, monomers and polymers were characterized by $^1H$-NMR, $^{19}F$-NMR and FT-IR. It was confirmed that the ion exchange capacity(IEC), water uptake and ion conductivity of SPBS-X increased with the increment of sulfonated biphenyl units. Particularly, SPBS-60 showed higher ion conductivity compared to Nafion$^{(R)}$-115 at 25~80 $^{\circ}C$.

• Journal of Energy Engineering
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• v.25 no.4
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• pp.176-183
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• 2016

This study relates to a polymer electrolyte membrane for improved performance fuel cell, were researched with respect to properties required for driving a fuel cell. The bis(4-fluorophenyl)phenyl phosphine oxide was sulfonated using fuming sulfuric acid. Synthetic hydrophilic oligomer and the hydrophobic oligomer and the block copolymers were prepared via aromatic nucleophilic substitution polycondensation. A block copolymer structure and degree of sulfonation was analyzed by $^1H$-NMR and gel permeation chromatography(GPC) analysis. Thermal stability was confirmed by thermogravimetric analysis(TGA), block copolymer was stable at high temperature(>$200^{\circ}C$), The ion conductivity was measured in order to demonstrate the performance of fuel cell. Synthesis membrane was the increase of temperature was improved conductivity up to 58 mS/cm due to the influence of the developed ion clusters. The phase separation of the polymer was observed to make AFM analysis.

• Korean Membrane Journal
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• v.5 no.1
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• pp.18-24
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• 2003

In order to improve the mechanical properties of the sulfonated polysulfone (SPSf) membranes previously synthesized in our laboratory, poly(vinyl alcohol) (PVA) was blended which is well known as the excellent physical and chemical properties. The resulting membranes blended with several molecular weight of PVA varying from 13,000 to 124,000 have been characterized to investigate the effect of PVA molecular weight in terms of ion conductivities, methanol permeabilities, water contents and ion exchange capacities for both heat treated and untreated membranes at 150$^{\circ}C$. The proton conductivity is decreased as the molecular weight of PVA increases. The plain SPSf-6.0 showed the proton conductivity of 0.078 S/cm whereas the blended membrane with M.W. 31,000 PVA indicated 0.04 S/cm. For methanol permeabilities, when PVA is added to SPAf-6.0, methanol crossover is increased because of the gain of the hydrophilicity from 3.4 to 6.5${\times}$10$\^$-6/ $\textrm{cm}^2$/s. For the annealed blended membranes (with M.W. 31,000 PVA), both the methanol corssover and proton conductivity showed very consistent values, about 2.3${\times}$10$\^$-6/ $\textrm{cm}^2$/s and 0.036 S/cm, respectively.

• Journal of the Korean Chemical Society
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• v.59 no.5
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• pp.413-422
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• 2015

Proton exchange membrane (PEM), which transfers proton from the anode to the cathode, is the key component of the proton exchange membrane fuel cell (PEMFC). Nafion is widely used as PEM due to its high proton conductivity as well as excellent chemical and physical stabilities. However, its high cost and the environmental hazards limit the commercial application in PEMFCs. To overcome these disadvantages, various alternative polymer electrolytes have been investigated for fuel cell applications. We used densely sulfonated polymers to maximize the ion conductivity of the corresponding membrane. To overcome high swelling, dipole-dipole interaction was used by introducing nitrile groups into the polymer backbone. As a result, physically-crosslinked membranes showed improved swelling ratio despite of high water uptake. All the membranes with different hydrophilic-hydrophobic compositions showed higher conductivity, despite their lower IEC, than that of Nafion-117.

• 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.

• Journal of Energy Engineering
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• v.25 no.3
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• pp.66-72
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• 2016

In this study, a sulfonated poly(arylene ether ketone) block copolymer was prepared from hydrophilic oligomer and hydrophobic oligomer. The structure of the prepared membrane was characterized by $^1H$-NMR, FT-IR and GPC. The $M_w$(weight-average molecular weights) of the polymer was $209,700g\;mol^{-1}$ and the molecular weight distribution($M_w/M_n$) of 1.25 was obtained. The prepared membrane showed excellent thermal stability with gradual weight loss up to $200^{\circ}C$. The proton conductivity of SPAEK block copolymer reached the maximum of $9.0mS\;cm^{-1}$ at $90^{\circ}C$ under 100% relative humidity (RH). From the observed results, it is necessary to do more aggressive attempt to study the possibility of application as an ion-conductive composite electrolyte.

• Transactions of the Korean hydrogen and new energy society
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• v.30 no.3
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• pp.227-236
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• 2019

In this work, preparation and characterizations of hybrid membranes containing sulfonated poly(arylene ether sulfone) (SPES) and sulfonated poly(vinylidene fluoride-co-hexafluoropropylene) (SPVdF-co-HFP) (20, 30 or 40 wt%) were carried out. The structure of hybrid membranes was confirmed using X-ray diffraction (XRD) analysis and the Fourier transform infrared (FT-IR) spectroscopy. The prepared SPAES/SPVdF-30 membrane exhibits higher ionic conductivity of 68.9 mS/cm at $90^{\circ}C$ and 100% RH. Besides, the other studies showed that the hybrid membrane has good oxidation stability, thermal stability, and mechanical stability. Thus, we believe that the prepared hybrid membrane is suitable for the development of membranes for fuel cell applications.

• New & Renewable Energy
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• v.2 no.4 s.8
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• pp.46-55
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• 2006

본 연구는 불소그룹을 함유한 술폰화된 아릴렌에테르계 블록 공중합체 고분자 전해질막의 제조 및 연료전지 특성에 관한 것이다. 이러한 불소그룹을 함유한 술폰화된 아랄렌에테르계 블록 공중합체를 제조하기 위하여 양말단에 불소계 비닐기를 가지면서, 고분자 전환시 상온에서 술폰화 가능한 biphenyl계 단량체와 술폰화가 불가능한 sulfonyl계 단량체를 각각 합성하였다. Biphenyl계 단량체로 부터 올리고머를 합성한 후 sulfonyl계 단량체와 열적 고리화 부가중합을 하여 다양한 몰조성을 갖는 일련의 perfluorocyclobutane(PFCB)기를 포함하는 블록 공중합체를 제조하였다. 제조된 블록 공중합체를 상온에서 술폰화제인 chlorosulfonic acid(CSA)를 이용하여 후술폰화시켜 강산 이온기인 sulfonic acid를 biphenyl계 올리고머 부분에 선택적으로 도입하였다. 이렇게 제조된 술폰화된 고분자를 제막한 후 연료전지 특성을 Nafion-115와 비교하였다. 술폰화가 되는 올리고머 블록의 비율 증가에 따라 이온교환능력 (IEC)이 증가하였고 , 그에 따른 팽윤도 역시 증가하는 것을 보였다. 술폰화된 고분자들은 건조 및 습윤 상태에서도 기계적 강도가 우수하였다. 최적화된 술폰화 블록 고분자(S-2) 를 대상으로 membrane electrolyte assembly(MEA) 를 제조하여 연료전지 초기성능을 측정한 결과 Nafion-112와 유사한 전기화학적 성능을 나타내었다.

• 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.

• Journal of the Korean Electrochemical Society
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• v.19 no.2
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• pp.45-49
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• 2016

In order to mitigate oxidative degradation of polymer membrane during fuel cell operation, an organic radical quencher was introduced. Rutin was selected as a radical quencher and mixed with sulfonated poly(arylene ether sulfone) to prepare composite membrane. Physicochemical properties of the composite membranes such as water uptake and proton conductivity were characterized. Hydrogen peroxide exposure experiment, which can mimic accelerated oxidative stability test during fuel cell operation, was adopted to evaluate the oxidative stability of the membranes. The composite membranes containing Rutin showed similar proton conductivity and enhanced oxidative stability compared to pristine ones.