An NMR and SAXS investigation of DMFC composite recast Nafion membranes containing ceramic fillers

Small angle X-ray scattering (SAXS) and nuclear magnetic resonance (NMR) investigations of recast composite and bare Nafion membranes have been carried out. The self-diffusion coefficients of water and methanol have been determined over a wide temperature range by PFGSE 1H NMR method. The transport mechanism appears to be influenced by surface properties of inorganic fillers. Acidic silica filler appears to promote proton transport in the membrane with respect to basic alumina. An interaction of the silica surface with methanol molecules is also envisaged from the analysis of proton self diffusion coefficients of methanol. The SAXS analysis revealed a modification of the polymer structure immersed in pure methanol or methanol solution with respect to water. A significant increase of the average ion clusters dimension is observed for the composite SiO2 membrane.

[1]  Edward L Cussler,et al.  Composite membranes for direct methanol fuel cells , 2001 .

[2]  J. Kerres Development of ionomer membranes for fuel cells , 2001 .

[3]  V. Antonucci,et al.  FTIR spectroscopic investigation of inorganic fillers for composite DMFC membranes , 2003 .

[4]  R. Savinell,et al.  Evaluation of a Sol-Gel Derived Nafion/Silica Hybrid Membrane for Polymer Electrolyte Membrane Fuel Cell Applications: II. Methanol Uptake and Methanol Permeability , 2001 .

[5]  C. Kontoyannis,et al.  Development and Characterization of Acid-Doped Polybenzimidazole/Sulfonated Polysulfone Blend Polymer Electrolytes for Fuel Cells , 2001 .

[6]  K. Kreuer On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells , 2001 .

[7]  K. Friedrich,et al.  Transport properties of ionomer composite membranes for direct methanol fuel cells , 2002 .

[8]  V. Antonucci,et al.  The influence of functional groups on the surface acid-base characteristics of carbon blacks , 1989 .

[9]  Antonino S. Aricò,et al.  Comparison of Ethanol and Methanol Oxidation in a Liquid‐Feed Solid Polymer Electrolyte Fuel Cell at High Temperature , 1999 .

[10]  G. Ranieri,et al.  Analysis of water self-diffusion in polycrystalline lamellar systems by pulsed field gradient nuclear magnetic resonance experiments , 1993 .

[11]  B. Schulte,et al.  Organic/inorganic composite membranes for application in DMFC , 2003 .

[12]  Antonino S. Aricò,et al.  DMFCs: From Fundamental Aspects to Technology Development , 2001 .

[13]  Andrew B. Bocarsly,et al.  Silicon Oxide Nafion Composite Membranes for Proton-Exchange Membrane Fuel Cell Operation at 80-140°C , 2002 .

[14]  J. Putaux,et al.  Anisotropy of structure and transport properties in sulfonated polyimide membranes , 2003 .

[15]  Yoon,et al.  Effects of Short-Chain Alcohols and Pyridine on the Hydration Forces between Silica Surfaces. , 1998, Journal of colloid and interface science.

[16]  Robert F. Savinell,et al.  Evaluation of Ethanol, 1‐Propanol, and 2‐Propanol in a Direct Oxidation Polymer‐Electrolyte Fuel Cell A Real‐Time Mass Spectrometry Study , 1995 .

[17]  S. Greenbaum,et al.  Studies of Water in Nafion Membranes Using Deuteron and Oxygen‐17 Nuclear Magnetic Resonance, and Dielectric Relaxation Techniques , 1993 .