Sulfonated Polyimide Membranes Constructed by Main‐Chain and Molecular‐Network Engineering Strategy for Direct Methanol Fuel Cell

Excessive swelling is one important factor that leads to high fuel permeability and limited operating concentration of methanol for proton exchange membranes. Herein, a collaborative strategy of main‐chain and molecular‐network engineering is applied to lower swelling ratio and improve methanol resistance for highly sulfonated polyimide. Two m‐phenylenediamine monomers (4‐(2,3,5,6‐tetrafluoro‐4‐vinylphenoxy)benzene‐1,3‐diamine and 4,6‐bis(2,3,5,6‐tetrafluoro‐4‐vinylphenoxy)benzene‐1,3‐diamine) with tetrafluorostyrol groups are designed and synthesized. Two series of cross‐linked sulfonated polyimides (CSPI‐Ts, CSPI‐Bs) are prepared from the two diamines, 4,4′‐diaminostilbene‐2,2′‐disulfonic acid and 1,4,5,8‐naphthalenetetracarboxylicdianhydride. The rigid main‐chain structure is cornerstone for wet CSPI‐Ts and CSPI‐Bs remaining stable at elevated temperatures. The introduction of hydrophobic cross‐linked network further improves their dimensional stability and methanol resistance. CSPI‐Ts and CSPI‐Bs show obviously improved performances containing high proton conductivity (121 ± 0.27–158 ± 0.35 S cm−1), low swelling ratio (9.6 ± 0.40%–16.1 ± 0.01%) and methanol permeability (4.14–7.69 × 10−7 cm2 s−1) at 80 °C. The direct methanol fuel cell (DMFC) is assembled from CSPI‐T‐10 with balanced properties, and it exhibits high maximum power density (PDmax) of 82.3 and 72.6 mW cm−2 in 2 and 10 m methanol solution, respectively. The ratio of PDmax in 10 m methanol solution to the value in 2 m methanol solution is as high as 88%. The CSPI‐T‐10 is promising proton exchange membrane candidate for DMFC application. Cross‐linked sulfonated polyimide membranes (CSPI) with excellent methanol resistance and dimensional stability are successfully developed through a collaborative strategy of main‐chain and molecular‐network engineering. The direct methanol fuel cell assembled with CSPI has high power density of 82.3 and 72.6 mW cm−2 in 2 and 10 m methanol solution.