In Situ Growth of COF on PAN Nanofibers to Improve Proton Conductivity and Dimensional Stability in Proton Exchange Membranes

Abstract

Perfluorosulfonic acid (PFSA) polymer is considered as a proton exchange membrane material with great potential. Nevertheless, excessive water absorption caused by abundant sulfonic acid groups makes PFSA have low dimensional stabilities. In order to improve the dimensional stability of PFSA membranes, nanofibers are introduced into PFSA membranes. However, because nanofibers lack proton conducting groups, it usually reduces the proton conductivities of PFSA membranes. It is a challenge to improve dimensional stabilities while maintaining high proton conductivities. Due to the structural designability, covalent organic frameworks (COFs) with proton conductive groups are chosen to improve the overall performance of PFSA membranes. Herein, COFs synthesized in situ on three-dimensional PAN nanofibers were introduced into PFSA to prepare PFSA@PAN/TpPa-SO3H sandwiched membranes. The PFSA@PAN/TpPa-SO3H-5 composite membrane exhibited outstanding proton conductivity, which reached 260.81 mS·cm−1 at 80 °C and 100% RH, and only decreased by 4.7% in 264 h. The power density of a single fuel cell with PFSA@PAN/TpPa-SO3H-5 was as high as 392.7 mW·cm−2. Compared with the pristine PFSA membrane, the conductivity of PFSA@PAN/TpPa-SO3H-5 increased by 70.0 mS·cm−1, and the area swelling ratio decreased by 8.1%. Our work provides a novel strategy to prepare continuous proton transport channels to simultaneously improve conductivities and dimensional stabilities of proton exchange membranes.