• Bulletin of the Korean Chemical Society
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• 제26권2호
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• pp.241-247
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• 2005

A series of proton conductive inorganic-organic hybrid membranes doped with phosphoric acid ($H_3PO_4$) and/or triethylphosphate (PO(OEt)$_3$) have been prepared by sol-gel process with 3-glycidoxypropyltrimethoxysilane (GPTMS), 3-aminopropyltriethoxysilane (APTES) and tetraethoxysilane (TEOS) as precursors. High proton conductivity of 3.0 ${\times}$ $10^{-3}$ S/cm with composition of 50TEOS-30GPTMS-20APTES-50$H_3PO_4$ was obtained at 120 ${^{\circ}C}$ under 50% relative humidity. Thermal stability of membrane was significantly enhanced by the presence of SiO$_2$ framework up to 250 ${^{\circ}C}$. XRD revealed that the gels are amorphous. IR spectra showed a good complexation of $H_3PO_4$ in the matrix. The conductivity under 75% relative humidity was significantly improved by addition of APTES due to the increase in concentration of defected site in hybrid matrix. The effect of PO(OEt)$_3$, humidifying time, and heat-treatment were also investigated. PO(OEt)$_3$ had no improvement on conductivity and conductivity increased with humidifying time, however, decreased with heating temperature.

• 한국재료학회지
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• 제28권5호
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• pp.308-314
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• 2018

Among the fuel cell electrolyte candidates in the intermediate temperature range, glass materials show stable physical properties and are also expected to have higher ion conductivity than crystalline materials. In particular, phosphate glass has a high mobility of protons since such a structure maintains a hydrogen bond network that leads to high proton conductivity. Recently, defects like volatilization of phosphorus and destruction of the bonding structure have remarkably improved with introduction of cations, such as Zr4+ and Nb5+, into phosphate. In particular, niobium has proton conductivity on the surface because of higher surface acidity. It can also retain phosphorus content during heat treatment and improve chemical stability by bonding with phosphorus. In this study, we fabricate niobium phosphate glass thin films through sol-gel processing, and we report the chemical stability and electrical properties. The existence of the hydroxyl group in the phosphate is confirmed and found to be preserved at the intermediate temperature region of $150-450^{\circ}C$.

• 멤브레인
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• 제14권1호
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• pp.44-52
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• 2004

본 연구는 직접메탄을 연료전지(Direct Methanol Fuel Cell)에 적용가능한 양이온교환막 개발에 관한 것으로 poly(vinyl alcohol) (PVA)에 가교제로 poly(acrylic acid-co-maleic acid) (PAM)와 hydroquinonesulfonic acid (HQSA)를 이용하여 가교제의 함량을 변화시키면서 막을 제조하였다. 제조한 막은 가교제의 함량 변화에 따라 메탄을 투과도, 이온전도도를 측정하였으며 기본적인 이온교환막의 특성인 함수율, 이온교환용량 그리고 고정이온농도 등을 측정하였다. PAM 함량이 증가함에 따라 메탄을 투과도와 이온전도도 및 함수율이 조금 증가하는 추세를 보이다 9 wt%부터 감소하는 경향을 보였는데 이는 PAM의 친수성기보다는 가교효과의 영향이라 사료되며 HQSA 함량을 변화시켰을 때는 이온전도도, 함수율 그리고 이온교환용량이 전반적으로 증가하였는데 그 증가폭은 미비하였다.

• The Korean Journal of Ceramics
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• 제5권3호
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• pp.288-295
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• 1999

Partial conductivities contributed by electron holes, oxygen ions, and protons were caluclated in $SrZr_{0.95}Y_{0.05}O_{2.975}$, using the reported formulae derived from the defect chemistry of HTPCs. Required parameters were obtained from the graphical analysis of total conductivity variation against partial pressure of water vapor and oxygen. Predicted overall conductivities showed a reasonable agreement with experimental measurements. The conductivity of the material showed a linear increase with square root of the water vapor pressure. This increase was due to proton conduction in an almost pure ionic conductivity. The calculation of partial conductivities at $800^{\circ}C$ resulted in an almost pure ionic conductivity at $P_{02}=10^{-10}$ atm and a predominant hole conductivity at $P_{02}=10^{-10}$ atm. Pure proton conduction was not expected at this temperature, contrary to the earlier reports. Discussions were made in relation with reported thermodynamic data and defect structure of the material. It was shown that from the total conductivity dependence on water vapor pressure, the pure ionic conductivity at low oxygen partial pressures could be separated into protonic and oxygen ionic conductivity in $ZrO_2$-based HTPCs.

• 전기화학회지
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• 제6권2호
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• pp.141-144
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• 2003

Proton conducting polymeric gels as the electrolytes of electrochemical capacitors have been prepared by two different methods: 1) swelling a polymethacrylate-based polymer matrix in aqueous solutions of inorganic and organic acids, and 2) polymerizing complexes of anhydrous acids and prepolymers with organic plasticizer. The FT-IR spectra strongly suggest that the carbonyl groups in the polymer matrix interact with protons from the doped acids. High ionic (proton) conductivity in the range of $6\times10^{-4}-4\times10^{-2}\;S\;cm^{-1}$ was obtained at room temperature for the aqueous gels. The non-aqueous polymer complexes showed rather low ionic conductivity, but it was about $10^{-3}\;S\;cm^{-1}\;at\;70^{\circ}C$ for the $H_3PO_4$ doped polymer electrolyte. The mechanisms of ion (proton) conduction in the polymeric systems are discussed.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.272-272
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• 2006

In recent years, water-free polymer electrolyte membranes are attracting serious attention due to the possibility of the fuel cell operation at intermediate temperatures ($100{\sim}200^{\circ}C$). It was reported that phosphonic acids have proton conductivity under anhydrous conditions and in particular, relatively high proton conductivity could be obtained from the composite materials with heterocycles such as imidazole, pyrazole, etc. In this work, styrene based polymers, poly((4-vinylbenzyloxy)alkylphosphonic acid), which have phophonic acid group at the end of alkyl chain was synthesized. These polymers were analyzed in terms of thermal stability and proton conductivity. Additionally, cyclic oligosiloxanes tethered with triazole were prepared and analyzed.

• 한국복합재료학회:학술대회논문집
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• 한국복합재료학회 2005년도 추계학술발표대회 논문집
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• pp.87-90
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• 2005

This paper presents an evaluation of the effect of titanium dioxide nanoparticles in sulfonated poly(ether ether ketone) (SPEEK) with sulfonation degree of 57%. A series of inorganic-organic hybrid membranes were prepared with a systematic variation of titanium dioxide nanoparticles content. Their water uptake, methanol permeability and proton conductivity as a function of temperature were investigated. The results obtained show that the inorganic oxide network decreases the proton conductivity and water swelling. It is also found that increase in inorganic oxide content leads to decrease of methanol permeability. In terms of morphology, membranes are homogeneous and exhibit a good adhesion between inorganic domains and the polymer matrix. The properties of the composite membranes are compared with standard nafion membrane.

• The Korean Journal of Ceramics
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• 제7권2호
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• pp.93-96
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• 2001

The Y- or Yb-doped SrZrO$_3$ proton conductors were fabricated using the powders prepared by the self-propagating high-temperature synthesis (SHS). The electrical conductivity was evaluated from an a.c. impedance measurements. The conductivity of SrZr$_{0.92}$Yb$_{0.08}$O$_{3-\delta}$ was 1.8$\times$10$^{-3}$ Scm$^{-1}$ at $900^{\circ}C$ in dry air atmosphere and its activation energy was 0.50 eV. The conductivity in wet air was larger, compared with the dry air, and the activaton energy of SrZr$_{0.92}$Yb$_{0.08}$O$_{3-\delta}$ in wet air was 0.40 eV.

• 한국산학기술학회:학술대회논문집
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• 한국산학기술학회 2004년도 춘계학술대회
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• pp.96-99
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• 2004

A new proton conductive inorganic-organic hybrid membrane doped with $H_3PO_4$ was fabricated via sol-gel process wit 3- glycidoxypropyltrimethoxysilane(GPTMS), 3-aminopropyltriethoxysilane(APTES) and tetraethoxysilane(TEOS) asprecursors. Theproto conductivity of about 3.0$\times10^{-3}S/cm$ was obtained at $120^{\circ}C$ under $50\%$ relative humidity (R.H). DTA curves showed that the thermal stability of the membrane is significantly enhanced by the presence of $SiO_2$ framework up to $250^{\circ}C$. SEM and XRD revealed that the gel is microporou and amorphous. The addition of APTES improved the conductivity of the membranes and the effect of the APTES on the conductivity was also discussed in this paper.

• 한국초전도학회:학술대회논문집
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• 한국초전도학회 2006년도 High Temperature Superconductivity Vol.XVI
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• pp.49-49
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• 2006