Influence of Anions on Proton-Conducting Membranes Based on Neutralized Nafion 117, Triethylammonium Methanesulfonate, and Triethylammonium Perfluorobutanesulfonate. 2. Electrical Properties

The electrical properties of a Nafion proton exchange membrane change dramatically when neutralized and then doped with a proton-conducting ionic liquid (PCIL). Broadband electric spectroscopy elucidates the molecular relaxation and polarization phenomena of neutralized Nafion (nN117) doped with triethylammonium methanesulfonate (TMS) and triethylammonium perfluorobutanesulfonate (TPFBu) ionic liquids. These data, coupled with those of part 1 suggest proton conduction mechanisms for both the pure PCILs and in PCIL-doped nN117. At 130 °C, the PCILs have conductivities of σ_TMS = 1.4 × 10^–2S/cm and σ_TPFBu = 9 × 10^–3S/cm, while correspondingly doped nN117 have conductivities of σ_NTMS = 6.1 × 10^–3 S/cm and σ_NTPFBu = 1.8 × 10^–3S/cm. The pure PCILs show three interfacial polarizations associated with proton transfer mechanisms above the melting point. PCIL-doped nN117 also has three interfacial polarizations that depend on the nanostructure characteristics of the PCIL sorbed within the nN117 polar domains. Below the PCIL melting point, doped nN117 has two dielectric relaxations, α and β, associated with dipolar relaxations involving both the sorbed PCILs and the ionomer matrix. The data indicate a long-range charge transfer process that occurs through proton exchange between cationic clusters. Segmental motion of the polymer chains and the molecular dimensions of the ionic liquid nanoaggregates mediate this charge transfer

High-Temperature Ionic-Conducting Material: Advanced Structure and Improved Performance

A new composite proton-conducting material based on the association of an ionic liquid and a porous polymer support was prepared with the aim of applying it as an electrolyte in a proton exchange membrane fuel cell (PEMFC) at elevated temperature (130 °C). The porous support was made from a high glass-transition temperature polymer (<i>T</i>g) by using the vapor-induced phase separation (VIPS) method in conditions leading to highly interconnected porous films. The ionic liquid tested was obtained by the reaction of a sulfonic acid with a tertiary amine and presents enough high-temperature stability to be used at elevated temperatures. Composite samples were prepared by immersing pieces of porous film in the ionic liquids under test. The porous support was characterized by scanning electron microscopy (SEM), gas permeation, and thermogravimetric analysis (TGA) tests, and the composite samples were characterized by mechanical and proton-conduction measurements. At 130 °C, this new material exhibits proton conductivity (20 mS cm^–1) below, but very close to, that of the pure ionic liquid (31 mS cm^–1) and presents, up to at least 150 °C, a storage modulus exceeding 200 MPa. This is very promising considering the PEMFC applications