• 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.20 no.4
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• pp.278-289
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• 2010

A series of composite membranes based on sulfonated poly(arylene ether sulfone) (SPAES) were prepared via addition of tetraethyl orthosilicate (TEOS) and solution casting method. The morphological structure, water uptake, proton conductivity of the resulting composite membranes were extensively investigated as function of the content of TEOS. By the sol-gel reaction, TEOS molecules were not completely converted to $SiO_2$ particles, but formed only oligomer-type. Also, EDS confirms that the resulting silicon dioxide was homogeneously distributed in the composite membranes. As the content of TEOS increased, the prepared membranes increased water uptake and proton conductivity at high temperature and low relative humidity condition. In particular, considerably high proton conductivity (0.015 S/cm) at $120^{\circ}C$ and 48%RH was demonstrated in the composite membrane containing 200% TEOS, which is 10 times greater than that of unmodified SPAES membrane. Also, the composite membranes were found to have enhanced thermal stability compared to the unmodified membrane.

• 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.21 no.1
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• pp.30-38
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• 2011

Composite membranes based on sulfonated poly(aryl ether) sulfone (SPAES) with different sulfated zirconia nanoparticles ($s-ZrO_2$) ratio are synthesized and investigated for the improvement of the hydration and the proton conductivity at high temperature and no humidification for fuel cell applications. X-ray diffraction technique is employed to characterize the structure and the size of $s-ZrO_2$ nanoparticles. The sulfation effect of $s-ZrO_2$ nanoparticles is verified by FT-IR analysis. The properties of the SPAES composite membranes with the various $s-ZrO_2$ ratio are evaluated by ion exchange capacity and water content. The proton conductivities of the composite membranes are estimated at room temperature with full hydration and at the various high temperature without external humidification. The composite membrane with 5 wt% $s-ZrO_2$ shows the highest proton conductivity. The proton conductivities are $0.9292\;S\;cm^{-1}$ at room temperature with full hydration and $0.0018\;S\;cm^{-1}$ at $120^{\circ}C$ without external humidification, respectively.

• Membrane Journal
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• v.26 no.4
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• pp.310-317
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• 2016

Lithium ion secondary battery (LISB) is an energy conversion system operated via charging-discharging cycle based on Lithium ion migration. LISB has a lot of advantages such as high energy density, low self-discharge rate, and a relatively high lifetime. Recently, increasing demands of electric vehicles have been encouraging the development of LISB with high capacity. Unfortunately, it causes some critical safety issues. It includes dendrite formation on negative electrode, resulting in electric shortage problems and battery explosion. Also, the elevated temperatures occurred during the LISB operation induces thermal shrinkage of polyolefin (e.g., polyethylene and polypropylene) separators. Consequently, the low thermal stability leads to decay of LISB performances and the reduction of lifetime. In this study, sulfonated poly (arylene ether sulfone) (SPAES) random copolymers were used as key materials to prepare polyolefin pore-filling separator. The resulting separators were evaluated in the term of metal ion chelation capability associated with dendrite formation, $Li^+$ ion conductivity and thermal durability.

• 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.

• Membrane Journal
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• v.18 no.4
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• pp.274-281
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• 2008

Covalent-crosslinked sulfonated poly(arylene ether sulfone) (SPAES) copolymers were synthesized copolymerization technique and additionally crosslinked with divinylbenzene (DVB). To optimize the reaction condition, a concentration of crosslinking agent and a reaction time were varied in the ranges of $30{\sim}90\;v/v%$ and $30{\sim}720\;min$. The properties of the crosslinked membranes were investigated by SEM, TGA and the measurement of proton conductivity. It was found that the proton conductivity of crosslinked membranes decreased depending on a degree of crosslinking while water uptake and methanol permeability reduced.