• Journal of Hydrogen and New Energy
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• v.33 no.1
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• pp.19-27
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• 2022

A series of QPAE/TiO₂-x (x = 1, 4, 7 and 10 wt%) organic/inorganic composite membranes were prepared as electrolyte membranes for alkaline anion exchange membrane fuel cells by controlling the content of inorganic filler with quaternized poly(arylene ether) (QPAE) random copolymer. Among the prepared QPAE/TiO₂-x organic/inorganic composite membranes, the highest ionic conductivity was 26.6 mS cm^-1 at 30℃ in QPAE/TiO₂-7 composite membrane, which was improvement over the ionic conductivity value of 6.4 mS cm^-1 (at 30℃) of the pristine QPAE membrane. Furthermore, the water uptake, swelling ratio, ionic exchange capacity, and thermal property of QPAE/TiO₂-x composite membranes were improved compared to the pristine QPAE membrane. The results of these studies suggest that the fabricated QPAE/TiO₂-x composite membranes have good prospects for alkaline anion exchange membrane fuel cell applications.

• Journal of the Korean Ceramic Society
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• v.39 no.7
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• pp.635-641
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• 2002

Electrical conduction of $SrZrO_3$ doped with $Y_2O_3$ was measured as a function of gas atmosphere and temperature by impedance spectroscopy. Hydrogen dissolution, due to an enhanced driving force in the presence of oxygen, results in protonation by water incorporation. Proton conductivity increased with water vapor pressure, ${P_w}^{1/2}$. In the pure hydrogen atmosphere, the dissolution of hydrogen,$H_2(g)=2H_{i}$ +2e', is supposed to be driven by a reduced activity of electrons, ascribable to their trapping in oxygen vacancies. The activation energy of electrical conductivity was 50 kJ/mol, in wet argon atmosphere in the temperature range of $600~900^{\circ}C$, similar to those reported for proton conduction in the literature. Grain boundary effect in proton conduction was substantial in the 10% doped case at temperatures lower than $700^{\circ}C$.

• Membrane Journal
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• v.33 no.6
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• pp.325-343
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• 2023

Direct methanol fuel cells (DMFCs) have been attracting attention as energy conversion devices that can directly supply methanol liquid fuel without a fuel reforming process. The commercial polymer electrolyte membranes (PEMs) currently applied to DMFC are perfluorosulfonic acid ionomer-based PEMs, which exhibit high proton conductivity and physicochemical stability during the operation. However, problems such as high methanol permeability and environmental pollutants generated during decomposition require the development of PEMs for DMFCs using novel ionomers. Recently, studies have been reported to develop PEMs using hydrocarbon-based ionomers that exhibit low fuel permeability and high physicochemical stability. This review introduces the following studies on hydrocarbon-based PEMs for DMFC applications: 1) synthesis of grafting copolymers that exhibit distinct hydrophilic/hydrophobic phase-separated structure to improve both proton conductivity and methanol selectivity, 2) introduction of cross-linked structure during PEM fabrication to reduce the methanol permeability and improve dimensional stability, and 3) incorporation of organic/inorganic composites or reinforcing substrates to develop reinforced composite membranes showing improved PEM performances and durability.

• Proceedings of the Korean Vacuum Society Conference
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• 1999.07a
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• pp.201-201
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• 1999

소수성의 특성을 가지는^g , pp (polypropylene)의 표면을 이온 보조 반응법(IAR)으로 처리하여 친수성으로 개질하였다. 이온빔 보조 반응법은 고에너지 이온빔을 이용한 기존의 표면처리 방식과는 달리 1keV 영역의 에너지를 가진 이온빔을 조사하면서 시료 주위에 반응성 가스를 불어넣어 줌으로써 표면의 성질을 변화시키는 방법이다. 여기서 조사된 수소이온의 에너지는 0.6에서 1.0keV까지 변화시키고 시료의 주변에 불어주는 산소의 양은 0에서 8ml/min으로 변화시켰으며 이온 조사량은 5x1014에서 1x1017ions/$\textrm{cm}^2$까지 변화시켰다. 그 결과 처리하지 않은 시료의 접촉각은 93$^{\circ}$이었으며 이온조사량이 1x1017ions/$\textrm{cm}^2$이고 가속에너지가 1.0keV인 조건에서 수소 이온빔만으로 처리한 시편의 경우 접촉각은 60$^{\circ}$정도 였으나 수소이온보조 반응법으로 처리한 시편의 경우는 $10^{\circ}$이하까지 접촉각이 감소하였음을 알 수 있었다. 이는 표면처리에 따른 표면의 친수성 작용기의 형성을 예상할 수 있으며 그 존잴르 확인하기 위하여 대기중과 물속에서 각각 보관한 시료의 접촉각과 표면에너지를 계산하여보았다. 그 결과 대기중에서 방치한 시편의 경우40$^{\circ}$ 정도로 감소하였으나 증류수에 보관한 시료의 경우는 15$^{\circ}$정도의 변화를 보였다. 물과 Formamide의 접촉각의 측정으로 표면에너지를 계산한 결과 산소분위기에서 수소이온빔으로 처리된 시료는 23dyne/cm에서 64dyne/cm이상까지 변화함을 관찰하였다. 위의 결과들이 표면거칠기에 미치는 영향을 고찰하기 위해 처리되지 않은^g , pp 의 근(root mean square)값은 8.30nm이었고 1kevdpsj지에서 불어준 산소4ml/min이고 이온 조사량이 1x1017ions/$\textrm{cm}^2$인 경우 접촉각은 $10^{\circ}$를 나타냈으며 rms값은 20.8nm를 나타내었다. XPS (X-ray photoelectron spectroscopy) 분석을 통하여 1x1017ions/$\textrm{cm}^2$에서 산소기체를 4ml/min 불어넣어준 후 C-O, C=O, (C=O)-O등의 친수성 작용기가 형성되었음을 확인하였다.^g , pp 의 접착력을 알아보기 위해 유성 페인트를 전도성 고분자위에 후막 처리하였다. 스카치 테이프를 테스트를 통하여 이온 보조 반응법으로 처리된^g , pp 표면이 처리하지 않은 시편에 비하여 접착력 향상되었음을 확인하였다.

• Membrane Journal
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• v.29 no.1
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• pp.30-36
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• 2019

In this study, we reported a solid-state supercapacitor consisting of titanium nitride (TiN) nanofiber and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT-PSS) conducting polymer electrode and poly(vinyl alcohol) (PVA)-based polymer electrolyte membrane. The TiN nanofiber was selected as electrode materials due to high electron conductivity and 2-dimensional structure which is beneficial for scaffold effect. PEDOT-PSS is suitable for organic/inorganic composites due to good redox reaction with hydrogen ions in electrolyte and good dispersion in solution. By synergetic effect of TiN nanofiber and PEDOT-PSS, the PEDOT-PSS/TiN electrode showed higher surface area than the flat Ti foil substrate. The PVA-based polymer electrolyte membrane could prevent leakage and explosion problem of conventional liquid electrolyte and possess high specific capacitance due to the fast ion diffusion of small $H^+$ ions. The specific capacitance of PEDOT-PSS/TiN supercapacitor reached 75 F/g, which was much higher than that of conventional carbon-based supercapacitors.

• Membrane Journal
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• v.16 no.4
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• pp.241-251
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• 2006

In this study, crosslinked copolyimides with random (r-) and block (b-) structure were fabricated using N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid and pentanediol as crosslinkers. Linear r- and b-sulfonated copolyimides were also fabricated for comparison. Ion exchange capacities of r- and b-copolyimides were very similar to each other owing to their strong dependence of sulfonic acid content. The physical crosslinking via dimerization of carboxylic acid groups induced a reduced average interchain distance in b-copolyimide without crosslinkers. Consequently, its water uptake and methanol permeability were lower than those of r-sulfonated copolyimides. Simultaneously, the reduced interchain distance increased the content of fixed-charged ions per unit volume. The high fixed-charged ion density contributed to an enhancement of proton conductivity In the b-sulfonated copolyimide. Crosslinking caused the reduction of average interchain distance between polymer chains irrespective of types of crosslinker and polymer structure, leading to low methanol permeability. On the contrary, their proton conductivity was improved owing to formation of effective hydrophilic channels responsible for proton conduction. In particular, this trend was observed in r-copolyimide containing a fixed charged ion.

• 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.

• 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.

• 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.

• Korean Chemical Engineering Research
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• v.56 no.1
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• pp.1-5
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• 2018

In this work, we study the ion conductivity by analyzing the impedance to the high current density range that the PEMFC (Proton Exchange Membrane Fuel Cell) is actually operated. The effect of GDL (Gas Diffusion Layer)presence on impedance was investigated indirectly by measuring hydrogen permeability. When the RH (Relative Humidity)was higher than 60% in the low current range (< $80mA/cm^2$), the moisture content of the polymer membrane was sufficient and the ion conductivity of the membrane was not influenced by the current change. However, when RH was low, ion conductivity increased due to water production as current density increased. The ion conductivity of the membrane obtained by HFR (High Frequency Resistance) in the high current region ($100{\sim}800mA/cm^2$)was compared with the measured value and simulated value. At RH 100%, both experimental and simulated values showed constant ion conductivity without being influenced by current change. At 30~70% of RH, the ionic conductivity increased with increasing current density and tended to be constant.