• Journal of the Korean Electrochemical Society
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• v.19 no.2
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• pp.39-44
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• 2016

Oxygen reduction reaction in the fuel cell (ORR) plays a dominant role in the overall reaction. In addition, the low compatibility between the membrane and the binder consisted of different materials, greatly reduces the efficiency of the fuel cell performance. In view of these two problems, geometrically modified copolymers with 9.9_Bis (4-hydroxyphenyl) were synthesized via condensation reaction instead of conventional biphenol and were adopted as hydrocarbon ionomer binders. By utilizing these binders, two kinds of MEAs using fluorinated Nafion membrane and hydrocarbon based membrane were manufactured in order to electrochemical performance evaluation. With current-voltage curves, there was no significant difference in the 0.6 V when two types of membrane were applied. Also, tafel slope became considerably lower as compared to the Nafion membrane. Thus, it is determined that the new hydrocarbon binder is expected to contribute the improvement in performance of fuel cells.

• Membrane Journal
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• v.21 no.4
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• pp.389-397
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• 2011

In this study, polymer composite membranes based on sulfonated poly(arylene ether sulfone) (SPAES) were prepared using a solution casting method with different amount of vermiculite (VMT) content. The dispersion of VMT particles in the SPAES matrix was confirmed by means of a scanning electron microscopy observation. The composite membrane containing less than 1 wt% of VMT has a smooth skin on the top and bottom, which means there is a good dispersion of VMT in the matrix. The water uptake of the composite membranes gradually increases as the temperature increases, and the results confirm that all the adsorbed water is bound water because VMT has a strong water affinity on account of its high cation exchange value. A composite membrane with a VMT content of less than 1 wt% increases the proton conductivity and reduces the methanol permeability. Of all the composite membranes, the membrane SPAES/VMT 1.0 has the best fuel cell performance in terms of membrane selectivity. The performance value of SPAES/VMT 1.0 is double that of Nafion 112, which suggests that SPAES/VMT1.0 could be an excellent candidate for direct methanol fuel cells.

• 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.

• Journal of the Korean Electrochemical Society
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• v.17 no.1
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• pp.44-48
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• 2014

Sulfonated poly(arylene ether sulfone)-cerium composite membranes with improved oxidative stability were prepared for proton exchange membrane fuel cell application. Oxidative stability of the composite membranes changed depending on the amount of incorporated metal. Their water uptake, IEC and proton conductivity were also affected. ICP analysis confirmed trace of cerium ion in the composite membranes and $^1H$-NMR indicated successful coordination of sulfonic acid groups with the metal ions. Increasing amount of the cerium ion resulted in decrease in proton conductivities and water uptake, but enhanced oxidative stabilities. A hydrogen peroxide exposure equipment was used for the test of oxidative stability of the composite membranes, which enabled to mimic fuel cell operating condition compared with conventional Fenton's test.

• Membrane Journal
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• v.21 no.3
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• pp.247-255
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• 2011

In this study, to obtain good dispersity of graphene which has excellent conductivity and mechanical strength, the graphene was modified by two different methods. Then the SPAES/graphene hybrid membranes were fabricated from different graphene contents. We compared performance of composite membrane with different preparing method of graphene and content of modified graphene. The morphology of the composite membranes has been investigated using SEM. Chemical structure of modified graphene was analyzed using by FT-IR and EDX. The proton conductivity and methanol permeability of the hybrid membranes were studied with changing graphene content from 0.5 to 3.0 wt.%. The SPAES/modified graphene composite membranes showed high proton conductivity (0.21 S/cm) compared with the SPAES membrane (0.09 S/cm) at $80^{\circ}C$ and 100% relative humidity condition. And the methanol permeability was decreased linearly as the content of modified graphene increased from 0 to 1.5 wt%.

• Korean Chemical Engineering Research
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• v.54 no.4
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• pp.453-458
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• 2016

Microbial fuel cells (MFC) were operated with pig wastes and PEMFC (Proton Exchange Membrane Fuel Cells) MEA (Membrane and Electrode Assembly). Performance of hydrocarbon membrane was compared with that of perfluoro membrane at MFC condition. Sulfonated-Poly(Arylene Ether Sulfone) was used as hydrocarbon membrane and Gore membrane was used as perfluoro membrane. OCV of sPAES MEA was 50mV higher than that of Gore MEA and power density of sPAES MEA was similar that of Gore MEA. Reinforcement of sPAES membrane stabilized the performance of MEA in MFC. The highest performance was obtained at temperature of $45^{\circ}C$ and with culture solution circulation rate of 50 ml/min. The highest power density was $1,100mW/m^2$ at optimum condition in MFC using pig waste.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.1
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• pp.42-50
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• 2011

The Montmorillonite (MMT) in the polymer matrix is expected to reduce methanol permeability due to the tortous path formed by dispersed silicate layers. However, the polymer composite membranes containing non-proton conducting inorganic particle tend to show low proton conductivity. To solve this problem, we used an ion exchange method to prepare functionalized MMT with various silane coupling agents. The modified MMT was randomly dispersed in sulfonated poly (arylene ether sulfone) (SPAES) matrix to prepare SPAES/modified MMT composite membranes. The performances of hybrid membranes for DMFCs application were investigated. The SPAES/modified composite membrane showed increased proton conductivity compared with the non-modified MMT composite membrane. However, the methanol permeability of the SPAES/modified membrane was higher than that of the non-modified MMT.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.135.1-135.1
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• 2010

최근 고온에서 사용 가능한 PEMFC용 고분자전해질 막 개발에 대한 연구가 활발히 진행되고 있다. PEMFC가 고온에서 작동하게 되면 높은 성능과 많은 장점을 갖게 된다. PEMFC를 $100^{\circ}C$ 이상에서 운전하게 될 경우 백금 전극 반응을 향상시켜 고가의 백금 촉매 양을 줄일 수 있게 되고, 수소연료 속에 미량 포함된 CO에 의한 촉매표면 피독현상에 대한 내구성을 높일 수 있어 저 순도 수소연료 사용이 가능해 진다. 또한 가습장치와 수소 연료 개질장치의 부피를 줄일 수 있게 되어 전체적인 PEMFC 시스템이 단순화 된다. 현재 연료전지용 고분자 전해질막으로 DuPont사의 과-불소계 고분자 전해질막인 Nafion$^{(R)}$이 가장 널리 사용되고 있다. Nafion$^{(R)}$은 유연한 분자구조 안에 소수성이 강한 주사슬과 친수성을 나타내는 술폰산이 결합된 곁사슬이 존재하여 술폰화 곁사슬의 클러스터 둘레에는 친수성 영역이 형성이 되기때문에 소수/친수 상 분리가 잘되어 이온 클러스터 형성이 용이하지만 제조비용이 높은 단점을 갖고 있다. 특히, 전해질 막내에서 Bronsted base 역할을 하는 물에 의해 이온전도가 이루어지기 때문에 고온에서는 수분증발로 인해 성능이 급격히 감소된다. 따라서, 본 연구에서는 고온 저가습 조건에서 운전이 가능하고 Nafion이 갖는 문제점을 해결하고자, 내열특성이 뛰어나며 높은 수소이온 전도도 학보가 용이한 Sulfonated Poly(aryl ether)sulfone(SPAES) 고분자 전해질에, 고온에서도 수화성이 유지될 수 있도록 지르코니아를 황산화한 sulfated zirconia(s-$ZrO_2$)를 함침하여 복합 고분자전해질막을 제조하여 고온 저가습 조건에서의 수소이온 전도 특성에 관한 연구를 수행하였다. 개발된 막의 물리/화학적 특성은 water content(Wup%), 이온교환 용량(IEC, meq $g^{-1}$), 수소이온전도도(s $cm^{-1}$) 열 중량 분석(TGA), X선 회절분석(XRD) 등을 통하여 분석 및 관찰하였다. 내화학 및 열적 특성분석 결과, 황산화 반응공정으로 $ZrO_2$에 술폰산기가 안정적으로 결합하고 있음이 관찰되었으며, 본 연구에서 개발된 유 무기 복합막이 $250^{\circ}C$이상 열적안정성을 확보하고 있는 것으로 판단되었다. $100^{\circ}C$ 이하의 저온 영역에서, 일정 비율의 s-$ZrO_2$/SPAES막에서 이온교환용량(IEC)이 순수 SPAES 막보다 낮음에도 불구하고, water uptake가 증가함과 동시에 수소이온 전도도가 향상된 것을 관찰하였다. 또한, 고온에서는 수소이온이 자유롭게 이동할 수 있는 water channel을 형성하는 free water는 증발 하지만 s-$ZrO_2$와 SPAES의 술폰산기 사이에 강력하게 결합하고 있는 bound Water는 $100^{\circ}C$ 이상의 고온 영역에서도 존재하여, 비록 무가습 조건에서도 일정 비율의 s-$ZrO_2$/SPAES50 전해질 막의 경우, 높은 전도도를 나타냄을 관찰할 수 있었다. 따라서 본 연구를 통해 저가습 고온 적용을 목적으로 개발된 s-$ZrO_2$/SPAES50막은 우수한 내열 특성을 나타냄과 동시에 저가습 고온 영역($120^{\circ}C$, $50RH{\downarrow}$)에서 높은 수소이온 전도도를 유지하여, 고온 저가습 연료전지 운전에 적합할 것으로 사료된다.

• Membrane Journal
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• v.24 no.4
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• pp.301-310
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• 2014

In this study, the silica nanoparticles were considerably chosen to improve a dimensional stability, proton transport and electrochemical performance of the resulting inorganic-organic nanocomposite membranes. For this purpose, hydrophobic silica (Aerosil$^{(R)}$ 812, Degussa) and hydrophilic silica (Aerosil$^{(R)}$ 380, Degussa) nanoparticles were, respectively, introduced into a Sulfonated poly(arylene ether sulfone) (SPAES) polymer matrix. The $SiO_2$ particles are evenly dispersed in a SPAES matrix by the aid of a non-ionic surfactant (Pluronics$^{(R)}$ L64). A $SiO_2$ content plays an important role in membrane microstructures and membrane properties such as proton conductivity and water uptake. Therefore, to study nanocomposite membranes with excessive amount of silica, the content of silica nanoparticles were increased up to 5 wt%. Interestingly, a hydrophobic $SiO_2$ containing nanocomposite membrane showed better electrochemical performance (29% higher than pristine SPAES) despite of low proton conductivity due to its adhesive properties with a catalyst layer in a single cell test. All the silica-SPAES membranes exhibited better performance than a pristine SPAES membrane.