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.

The rich −SO₃H groups enable sulfonated poly (ether ether ketone) (SPEEK) to possess excellent proton conductivities in proton exchange membrane (PEM), but cause excessive water absorption, resulting in the decline of dimensional stability. It is a challenge to resolve the conflict between conductivity and stability. Owing to its unique structural designability, covalent organic frameworks (COFs) have been used to regulate the performances of PEMs. The authors propose the use of COFs with acidic and basic groups for meeting the requirements of proton conductivity and dimensional stability. Herein, COFs containing different groups (sulfoacid, pyridine, and both) were uniformly dispersed into the SPEEK matrix by in situ synthesis, and the effects on the properties of SPEEK matrix PEMs were revealed. The sulfoacid group significantly improves proton conductivities. At 60 °C, under 95% RH, the conductivity of the SPEEK/TpPa−SO₃H-20 composite membrane was 443.6 mS·cm⁻¹, which was 3.3 times that of the pristine SPEEK membrane. The pyridine group reduced the swelling ratio at 50 °C from 220.7% to 2.4%, indicating an enhancement in dimensional stability. Combining the benefits of sulfoacid and pyridine groups, SPEEK/TpPa−(SO₃H-Py) composite membrane has a conductivity of 360.3 mS·cm⁻¹ at 60 °C and 95% RH, which is 1.86 times that of SPEEK, and its swelling ratio is 11.8%, about 1/20 of that of SPEEK membrane. The method of in situ combination and regulation of groups open up a way for the development of SPEEK/COFs composite PEMs.

Research on the rheological performance and mechanism of polymer nanocomposites (PNCs), mainly focuses on non-polar polymer matrices, but rarely on strongly polar ones. To fill this gap, this paper explores the influence of nanofillers on the rheological properties of poly (vinylidene difluoride) (PVDF). The effects of particle diameter and content on the microstructure, rheology, crystallization, and mechanical properties of PVDF/SiO₂ were analyzed, by TEM, DLS, DMA, and DSC. The results show that nanoparticles can greatly reduce the entanglement degree and viscosity of PVDF (up to 76%), without affecting the hydrogen bonds of the matrix, which can be explained by selective adsorption theory. Moreover, uniformly dispersed nanoparticles can promote the crystallization and mechanical properties of PVDF. In summary, the viscosity regulation mechanism of nanoparticles for non-polar polymers, is also applicable to PVDF, with strong polarity, which is of great value for exploring the rheological behavior of PNCs and guiding the process of polymers.