• Membrane Journal
• /
• v.23 no.4
• /
• pp.290-296
• /
• 2013

Poly(vinylidenefluoride-co-chlorotrifluoroethylene) P(VDF-co-CTFE) polymer was attached to methacrylic acid (MAA) in the presence of 1,8-diazabicyclo[5,4,0]undec-7-ene(DBU) catalyst to prepare P(VDF-co-CTFE)-MAA copolymer. The modified P(VDF-co-CTFE)-MAA was polymerized with 2-sulfoethyl methacrylate (SEMA) monomer in the presence of 4',4'-azobis(4-cyanovaleric acid(ACVA) initiator by free radical polymerization to form the proton conducting membrane. The ratio of the SEMA was increased in the membrane to increase the presence of the acidic group. The maximum IEC value that was observed at 50% SEMA was around 0.82 meq/g, which is consistent with the water uptake value. The highest proton conductivity achieved by P(VDF-co-CTFE)-MAA/SEMA membrane with 50% SEMA was approximately 0.041 S/cm. This indicates that the available ionic group for the proton conduction increases with the increase in the SEMA in the membrane.

• Bulletin of the Korean Chemical Society
• /
• v.34 no.6
• /
• pp.1763-1770
• /
• 2013

A series of the block copolymers were successfully synthesized from post-sulfonated hydrophilic and hydrophobic macromers via three-step copolymerization. The degrees of sulfonation (DS) of the copolymers (10%, 30%, or 50%) were controlled by changing the molar ratio of the hydrophilic and hydrophobic parts. The resulting block copolymers were characterized by $^1H$ NMR and other technologies. The membranes were successfully cast using dimethyl sulfoxide (DMSO) solution at $100^{\circ}C$. The copolymers were characterized to confirm chemical structure by $^1H$ NMR and FT-IR. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) demonstrated that all sulfonated block copolymers exhibited good thermal stability with an initial weight loss at temperatures above $240^{\circ}C$. The membranes showed acceptable ion exchange capacity (IEC) and water uptake values in accordance with DS. The maximum proton conductivity was 184 mS $cm^{-1}$ in block copolymer-50 at $60^{\circ}C$ and 100% relative humidity, while the conductivity of Nifion-115 was 160 mS $cm^{-1}$ under the same measurement conditions. AFM images of the block copolymer membranes showed well separated the hydrophilic and hydrophobic domains. From the observed results it is that the prepared block membranes can be considered as suitable polymer electrolyte membranes for the application of polymer electrolyte membrane fuel cells (PEMFC).

• Proceedings of the Membrane Society of Korea Conference
• /
• 2008.05a
• /
• pp.147-150
• /
• 2008

• Membrane Journal
• /
• v.27 no.5
• /
• pp.389-398
• /
• 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.

• Transactions of the Korean hydrogen and new energy society
• /
• v.28 no.2
• /
• pp.144-149
• /
• 2017

A proton-conducting bisphenylpropaned sulfonated fluorinated blockcopolymer (BPSFBC) was synthesized. Five kinds of polymer electrolyted composite membranes were preparated by incorporating silica ($SiO_2$) with various weight ratio. And their characteristics were investigated by FT-IR (fourier transform infrared), $^1H-NMR$ ($^1H$ nuclear magnetic resonance), TGA (thermogravimetric analysis), water uptake, FE-SEM (field emission scanning electron microscopes), and ion conductivity properties. The water uptake and ion conductivity were increased until 9 wt% $SiO_2$, and then decreased. The maximum proton conductivity equal to $52mScm^{-1}$ was measured for the BPSFBC/$SiO_2$-9 composite membrane at $90^{\circ}C$ and 100% relative humidity. From the measured results, it is distinct that the manufactured composite membrane BPSFBC/$SiO_2$-9 can be considered as a polymer membrane suitable for a fuel cell electrolyte.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 2007.11a
• /
• pp.218-218
• /
• 2007

고체 전해질로서 $CsH_2PO_4$결정은 $230^{\circ}C$ 이상에서 전기전도도가 $10^{-2}\;{\Omega}^{-1}cm^{-1}$의 값에 도달하는 초양성자(Superprotonic) 상태로 상전이를 한다. 이러한 이유로 $CsH_2PO_4$ 결정은 $230^{\circ}C$ 부근에서 사용할 수 있는 연료전지로 개발되어왔다. 실용적인 면에서 단결정의 경우보다 다결정의 물성 및 응용 연구가 많았는데, 입자 크기에 따른 체계적인 연구는 잘 이루어지지 않았다. 본 발표에서는 $CsH_2PO_4$ 다결정을 합성하여 SEM 및 micro Raman spectra를 조사하였다. SEM의 결과 입자들의 평균 크기는 100 nm 이었으며, micro Raman spectra는 Bulk $CsH_2PO_4$의 spectra 와 큰 차이를 보이지 않았다. $PO_4$의 내부진동은 거의 같은 주파수대를 보여주나, $300\;cm^{-1}$이하의 저주파 수 영역에서는 광학적 포논의 픽이 잘 보이지 않았다. 그 원인이 micro Raman 장치의 측정 특성인지, 물리적 변화인지는 확실치 않다.

• Membrane Journal
• /
• v.18 no.3
• /
• pp.234-240
• /
• 2008

This work demonstrates the preparation of proton conducting crosslinked polymer electrolyte membranes by blending polystrene-b-poly(hydroxyethyl acrylate) (PS-b-PHEA) and poly(vinyl alcohol) (PVA) at 1 : 1 wt ratio. The PHEA block of the diblock copolymer was crosslinked with PVA using sulfosuccinic acid (SA) via the esterification reaction between -OH of membrane and -COOH of SA, as confirmed by FT-IR spectroscopy. Ion exchange capacity (IEC) continuously increased from 0.14 to 0.91 meq/g with increasing concentrations of SA, due to the increasing portion of charged groups in the membrane. In contrast, the water uptake increased up to 20.0 wt% of SA concentration above which it decreased monotonically. The membrane also exhibited a maximum proton conductivity of 0.024 S/cm at 20.0 wt% of SA concentration. The maximum behavior of water uptake and proton conductivity is considered to be due to competitive effect between the increase of ionic sites and the crosslinking reaction according to the SA concentration.

• Macromolecular Research
• /
• v.16 no.6
• /
• pp.549-554
• /
• 2008

Proton conducting crosslinked membranes were prepared using polymer blends of polystyrene-b-poly(hydroxyethyl acrylate)-b-poly(styrene sulfonic acid) (PS-b-PHEA-b-PSSA) and poly(vinyl alcohol) (PVA). PS-b-PHEA-b-PSSA triblock copolymer at 28:21:51 wt% was synthesized sequentially using atom transfer radical polymerization (ATRP). FT-IR spectroscopy showed that after thermal ($120^{\circ}C$, 2 h) and chemical (sulfosuccinic acid, SA) treatments of the membranes, the middle PHEA block of the triblock copolymer was crosslinked with PVA through an esterification reaction between the -OH group of the membrane and the -COOH group of SA. The ion exchange capacity (IEC) decreased from 1.56 to 0.61 meq/g with increasing amount of PVA. Therefore, the proton conductivity at room temperature decreased from 0.044 to 0.018 S/cm. However, the introduction of PVA resulted in a decrease in water uptake from 87.0 to 44.3%, providing good mechanical properties applicable to the membrane electrode assembly (MEA) of fuel cells. Transmission electron microscopy (TEM) showed that the membrane was microphase-separated with a nanometer range with good connectivity of the $SO_3H$ ionic aggregates. The power density of a single $H_2/O_2$ fuel cell system using the membrane with 50 wt% PVA was $230\;mW/cm^2$ at $70^{\circ}C$ with a relative humidity of 100%. Thermogravimetric analysis (TGA) also showed a decrease in the thermal stability of the membranes with increasing PVA concentration.

• Journal of Sensor Science and Technology
• /
• v.24 no.1
• /
• pp.6-9
• /
• 2015

Conventional leak detectors are widely based on helium gas sensors. However, the usage of hydrogen sensors in leak detectors has increased because of the high prices of helium leak detectors and the dearth in the supply of helium gas. In this study, a hydrogen leak detector was developed using solid-state hydrogen sensors. The hydrogen sensors are based on Park-Rapp probes with heterojunctions made by oxygen-ion conducting Yttria-stabilized zirconia and proton-conducting In-doped $CaZrO_3$. The hydrogen sensors were used for determining the potential difference between air and air balanced 5 ppm of $H_2$. Even though the Park-Rapp probe shows an excellent selectivity for hydrogen, the sensitivity of the sensor was low because of the low concentration of hydrogen, and the oxygen on the surface of the sensor. In order to increase the sensitivity of the sensor, the sensors were connected in series by Pt wires to increase the potential difference. The sensors were tested at temperatures ranging from $500-600^{\circ}C$.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 2003.11a
• /
• pp.42-45
• /
• 2003

Inorganic polymer based hybrid membranes consisting of zirconium oxide and polydimethylsiloxane (PDMS) have been synthesized by sol-gel processes. The hybrid membranes showed thermal stability and flexibility up to $300^{\circ}C$. The membrane becomes proton conducting polymer electrolyte when added with 12-phosphotungstic acid (PWA). The conductivity of the membranes was measured in the temperature range from room temperature to $150^{\circ}C$ under saturated humidity and a maximum conductivity of $5{\times}10^{-5}\;Sm^{-1}$ was obtained at $150^{\circ}C$.