Three-dimensionally ordered macroporous polyimide composite membrane with controlled pore size for direct methanol fuel cells

Three-dimensionally ordered macroporous (3DOM) polyimide matrix with different pore size (1.3 μm–200 nm) was fabricated, and its structural effect on some properties of composite membrane was investigated. The composite membrane prepared by impregnation of 2-acrylamido-2-methylpropanesulfonic acid polymer (PAMPS) exhibited swelling ratios as low as 2–3% in water or methanol solutions, compared with about 400% of PAMPS itself. The swelling ratio of composite membrane was constant regardless of the 3DOM pore size. However, methanol permeability strongly depended on the pore size. In particular, it was drastically reduced when connecting windows among macropores became less than 100 nm. On the other hand, proton conductivity changed with 3DOM matrix porosity according to Archie's law. The porosity of 3DOM matrix is basically constant even if the pore size changes. Therefore, we suppressed the methanol crossover without lowering of proton conductivity due to reducing the matrix pore size, and the selectivity (proton conductivity/methanol permeability) of 1.2 × 10⁵ S cm⁻³ s, which was one order of magnitude greater than that of Nafion^®, was achieved.