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Synthesis of proton conducting mesoporous materials and composite membranes for high temperature proton exchange membrane (PEM) fuel cells

Posted on:2005-07-07Degree:Ph.DType:Thesis
University:The University of Texas at DallasCandidate:Feng, FangxiaFull Text:PDF
GTID:2452390008499979Subject:Chemistry
Abstract/Summary:
Tungstosilicate mesoporous materials (WMM) were synthesized using the ionic surfactant cetyltrimethylammonium bromide (C16H33N +(CH3)3Br- CTMABr) and non-ionic surfactants, including C12H25(OCH2CH 2)10OH (Brij 22, C12EO10OH), C 16H33(OCH2CH2)10OH (Brij 56, C16EO10OH), and C18H37(OCH 2CH2)10OH (Brij 76, C18EO10OH). The proton conductivities were measured by AC impedance spectroscopy. Using CTMABr, the highest W/Si ratio achieved for the molecular sieve product was 0.03. The conductivity ranged from 0.5 to 2.2 x 10-2 S/cm, where the highest conductivity was observed with the H3PO 4 based preparation. Non-ionic surfactants produced materials with a W/Si ratio as high as 0.05 without any dense WO3 impurities. These samples showed thicker pore walls (39A), higher thermal stability, and higher proton conductivity (4.0 x 10-2 S/cm). The WMMs were also employed to make a composite membrane with linear polyethyleneimine (PEI), 3-glycidoxypropyltrimethoxysilane (GLYMO), bis(trifluoromethanesulfonyl)imide (HTFSI). At 100°C and 100% relative humidity, the composite membrane with 30 wt.% calcined (at 500°C) WMM showed the highest conductivity of 6.1 x 10-2 S/cm. At 130°C and 20% relative humidity, the highest conductivity of 6.4 x 10-3 S/cm was obtained for the composite membrane with 30 wt.% as-synthesized WMM. Transparent free-standing mesoporous silica (MS) films were synthesized from a system of TMOS-Brij-Acid-H2O. The non-ionic surfactants used included Brij 22 (Cl2EO10OH), Brij 56 (C16EO 10OH), and Brij 76 (C18EO10OH). The acids used include HCl, H3PO4, and CF3SO3H. The effect of synthesis parameters on the synthesis and the proton conductivity of mesoporous silica were investigated. The Brij 56/CF3SO 3H based product showed the highest conductivity of 6.5 x 10 -2 S/cm at room temperature. Composite was prepared by combing TMOS, Brij surfactant, acid (HCl, H3PO4, or CF 3SO3H), N-[3-(trimethoxysilyl)propyl]-ethylenediamine (EDATMS), 3-glycidoxypropylmethoxysilane (GLYMO), and bis(trifluoromethanesulfonyl)imide (HTFSI). The effect of TMOS/template content and the acid on the conductivity as well as H2/O2 performance were investigated. The results indicated that the incorporation of TMOs/surfactant/acid could increase the proton conductivity and the fuel cell performance. Sulfonated silica/heteropolyacid (HPA) composite membranes were investigated for high temperature proton exchange membrane (PEM) fuel cells. HPAs included tungstosilicic acid (WSA) and tungstophosphoric acid (WPA). The influence of the HPA type, and HPA content on the proton conductivity and fuel cell performance was investigated. (Abstract shortened by UMI.)...
Keywords/Search Tags:Proton, Mesoporous, Fuel, Composite membrane, Conductivity, Materials, Non-ionic surfactants, HPA
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