Nanocomposite membranes based on polybenzimidazole and ZrO2 for high-temperature proton exchange membrane fuel cells.

Owing to the numerous benefits obtained when operating proton exchange membrane fuel cells at elevated temperature (>100 °C), the development of thermally stable proton exchange membranes that demonstrate conductivity under anhydrous conditions remains a significant goal for fuel cell technology. This paper presents composite membranes consisting of poly[2,2'-(m-phenylene)-5,5'-bibenzimidazole] (PBI4N) impregnated with a ZrO2 nanofiller of varying content (ranging from 0 to 22 wt %). The structure-property relationships of the acid-doped and undoped composite membranes have been studied using thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, wide-angle X-ray scattering, infrared spectroscopy, and broadband electrical spectroscopy. Results indicate that the level of nanofiller has a significant effect on the membrane properties. From 0 to 8 wt %, the acid uptake as well as the thermal and mechanical properties of the membrane increase. As the nanofiller level is increased from 8 to 22 wt % the opposite effect is observed. At 185 °C, the ionic conductivity of [PBI4N(ZrO2 )0.231 ](H3 PO4 )13 is found to be 1.04×10(-1)  S cm(-1) . This renders membranes of this type promising candidates for use in high-temperature proton exchange membrane fuel cells.

Interplay between water uptake, ion interactions, and conductivity in an e-beam grafted poly(ethylene-co-tetrafluoroethylene) anion exchange membrane.

We demonstrate that the true hydroxide conductivity in an e-beam grafted poly(ethylene-co-tetrafluoroethylene) [ETFE] anion exchange membrane (AEM) is as high as 132 mS cm(-1) at 80 °C and 95% RH, comparable to a proton exchange membrane, but with very much less water present in the film. To understand this behaviour we studied ion transport of hydroxide, carbonate, bicarbonate and chloride, as well as water uptake and distribution. Water uptake of the AEM in water vapor is an order of magnitude lower than when submerged in liquid water. In addition (19)F pulse field gradient spin echo NMR indicates that there is little tortuosity in the ionic pathways through the film. A complete analysis of the IR spectrum of the AEM and the analyses of water absorption using FT-IR led to conclusion that the fluorinated backbone chains do not interact with water and that two types of water domains exist within the membrane. The reduction in conductivity was measured during exposure of the OH(-) form of the AEM to air at 95% RH and was seen to be much slower than the reaction of CO2 with OH(-) as the amount of water in the film determines its ionic conductivity and at relative wet RHs its re-organization is slow.

Broadband electric spectroscopy at high CO2 pressure: dipole moment of CO2 and relaxation phenomena of the CO2-poly(vinyl chloride) system.

Broadband electric spectroscopy (BES) is a technique that shows promise in studying the interactions of dense or supercritical gases with polymers, particularly with respect to chain mobility. Polymers that are treated with dense gases show a reduction in the viscosity, glass transition, and melting temperature. A high pressure cell for BES has been constructed that can be used from ambient temperature and pressure to 353 K and 15 MPa and over a frequency range from 20 Hz to 1 MHz. In the past, the dielectric constant of CO(2) was determined by measurements at only one or two frequency values. New instrumentation and technology allow this experiment to be expanded to cover a wider frequency range. BES measurements of CO(2) do not show any relaxation peaks in the permittivity from 20 Hz to 1 MHz and 1 to 6 MPa. By these measurements, the CO(2) dielectric constant was evaluated between 0.1 and 6 MPa. Cell testing with poly(vinyl chloride) (PVC) at 323 K and CO(2) pressures from 0.1 to 13 MPa indicate an increase in the chain segmental motion at high pressures resulting from a reduction in the glass transition temperature of the PVC-CO(2) system due to plasticization by CO(2).

A formalism relating the conductivity of functionalized nanoparticles to constituent ligand molecules and application to water-containing silica.

A formalism is presented that relates adsorption-desorption phenomena to the charge transfer events that take place on the surface of functionalized nanoparticles. The equations are applied to experimental results for the scaled electrical conductivity of a hydrophilic fumed silica with a nanoparticle diameter of 7 nm. Insight into the distribution of water on the surface of the nanoparticles is obtained.

Vibrational studies and properties of hybrid inorganic-organic proton conducting membranes based on Nafion and hafnium oxide nanoparticles.

In this report, we will describe the effect of different concentrations of HfO2 nanopowders on the structure and properties of [Nafion/(HfO2)n] membranes with n = 0, 3, 5, 9, 11, 13, and 15 wt %, respectively. Films were prepared by a solvent casting procedure using HfO2 oxoclusters and Nafion. Seven new homogeneous membranes were obtained with thicknesses ranging from 200 to 350 microm. Each membrane is characterized by a rough HfO2-rich surface and a smooth Nafion-rich surface, with different physical-chemical properties. Membrane characterization was accomplished by means of thermogravimetric analysis (TGA), morphological measurements (environmental scanning electron microscopy) and vibrational spectroscopy (Fourier transform infrared attenuated total reflectance spectroscopy and Fourier transform Raman spectroscopy). These systems can be described in terms of five types of water domains, Nafion-HfO2 species with well-defined stoichiometry surrounded by Nafion and hydrated hafnia. The highest conductivity at 125 degrees C (3.2 x 10-2 S x cm(-1)) was measured on the [Nafion/(HfO2)5] film by electrical spectroscopy, with a stability range of conductivity between 5 and 115 degrees C.