Tuning transport properties by manipulating the phase segregation of tetramethyldisiloxane segments in modified polyimide electrolytes

A series of copolymer electrolytes containing 4,4′-oxydianiline (ODA)-based sulfonated polyimide and siloxane segments, in various ratios, are prepared and characterized for direct methanol fuel cell applications. The chemical Structure of the sulfonated copolymers is confirmed by FT-IR and NMR. The prepared composite membranes are found to be flexible and show good thermal stability as well as good proton conductivity. A maximum proton conductivity of 5.78 × 10−2 S cm−1 (cf. Nafion117 = 8.31 × 10−2 S cm−1) is obtained for the sulfonated polyimide blended with sulfonated polyimide with a grafted tetramethyldisiloxane segment (cf. SPI_DSX75 membrane) at 90 °C. The membranes showed low methanol crossover below 10−7 cm2 s−1 (cf. Nafion117 = 10−6 cm2 s−1). The transport properties of the membranes are found to be strongly influenced by water uptake and by the number and nature of the ionic clusters in the hydrophilic domains. When the number of siloxane segments is increased, the relationship between the methanol self-diffusion coefficient (DM) and water molecules per sulfonic acid group (λ) indicate that the water molecules are interacting with channels inside the membrane. In addition, the segregated nanophase also affects the ion transport and sometimes enhances the corresponding ionic conductivity. TEM and SAXS analyses shows evidence for phase segregation in the membranes and reveal the influence of flexible siloxane segments in ionic clustering.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideResearch highlights▶ We synthesized sulfonated polyimides containing siloxane segments as DMFC electrolytes. ▶ Nanoscale segregation of electrolytes were tuned by incorporating siloxane units for lower fuel permeation. ▶ Transport properties of the membranes are correlated very well with their morphologies and microstructure.