Construction of a new continuous proton transport channel through a covalent crosslinking reaction between carboxyl and amino groups

• A continuous proton transport channel was constructed by covalent cross-linked.
• The membranes showed low methanol permeability and high proton conductivity.
• The membranes exhibited desirable mechanical performance at both 25 °C and 80 °C.

Sulfonated poly(arylene ether ketone sulfone) bearing pendant carboxylic acid groups (C-SPAEKS) and sulfonated poly(arylene ether ketone sulfone) containing amino groups (Am-SPAEKS) were used to prepare C-SPAEKS/Am-SPAEKS crosslinked membranes. 1H NMR and Fourier transform infrared spectra proved that C-SPAEKS and Am-SPAEKS copolymers, as well as C-SPAEKS/Am-SPAEKS crosslinked membrane, were successfully synthesized. TEM images showed that a continuous proton transport channel formed after crosslinking. Thermogravimetric analysis curves demonstrated that the thermal property of the crosslinked membranes improved. The crosslinked membranes exhibited suitable mechanical properties at 25 and 80 °C. The methanol permeability of C-SPAEKS/Am-SPAEKS-40 was 2.35 × 10−7 cm2 s−1 at 60 °C, which was lower than that of C-SPAEKS (24.12 × 10−7 cm2 s−1) and Am-SPAEKS (17.91 × 10−7 cm2 s−1). The proton conductivity of C-SPAEKS/Am-SPAEKS-40 was 0.089 S cm−1, which was higher than that of C-SPAEKS and Am-SPAEKS at 80 °C. The results proved that C-SPAEKS/Am-SPAEKS crosslinked membranes were potential proton exchange membranes for direct methanol fuel cell applications.