3D Network Structural Poly (Aryl Ether Ketone)-Polybenzimidazole Polymer for High-Temperature Proton Exchange Membrane Fuel Cells

Poor mechanical property is a critical problem for phosphoric acid-doped high-temperature proton exchange membranes (HT-PEMs). In order to address this concern, in this work, a 3D network structural poly (aryl ether ketone)-polybenzimidazole (PAEK-cr-PBI) polymer electrolyte membrane was successfully synthesized through crosslinking reaction between poly (aryl ether ketone) with the pendant carboxyl group (PAEK-COOH) and amino-terminated polybenzimidazole (PBI-4NH2). PAEK-COOH with a poly (aryl ether ketone) backbone endows superior thermal, mechanical, and chemical stability, while PBI-4NH2 serves as both a proton conductor and a crosslinker with basic imidazole groups to absorb phosphoric acid. Moreover, the composite membrane of PAEK-cr-PBI blended with linear PBI (PAEK-cr-PBI@PBI) was also prepared. Both membranes with a proper phosphoric acid (PA) uptake exhibit an excellent proton conductivity of around 50 mS cm-1 at 170°C, which is comparable to that of the well-documented PA-doped PBI membrane. Furthermore, the PA-doped PAEK-cr-PBI membrane shows superior mechanical properties of 17 MPa compared with common PA-doped PBI. Based upon these encouraging results, the as-synthesized PAEK-cr-PBI gives a highly practical promise for its application in high-temperature proton exchange membrane fuel cells (HT-PEMFCs)

A Novel High Temperature Fuel Cell Proton Exchange Membrane with Nanoscale Phase Separation Structure Based on Crosslinked Polybenzimidazole with Poly(vinylbenzyl chloride)

A semi-aromatic polybenzimidazole (DPBI) is synthesized via polycondensation of decanedioic acid (DCDA) and 3,3-diaminobenzidine (DAB) in a mixed phosphorus pentoxide/methanesulfonic acid (PPMA) solvent. Ascribing to in-situ macromolecular crosslinker of ploly((vinylbenzyl chloride) (PVBC), a robust crosslinked DPBI membrane (DPBI-xPVBC, x refers to the weight percentage of PVBC in the membrane) can be obtained. Comprehensive properties of the DPBI and DPBI-xPVBC membranes are investigated, including chemical structure, antioxidant stability, mechanical strength, PA uptake and electrochemical performances. Compared with pristine DPBI membrane, the PA doped DPBI-xPVBC membranes exhibit excellent antioxidative stability, high proton conductivity and enhanced mechanical strength. The PA doped DPBI-10PVBC membrane shows a proton conductivity of 49 mS cm−1 at 160 °C without humidification. Particularly, it reveals an enhanced H2/O2 single cell performance with the maximum peak power density of 405 mW cm−2, which is 29% higher than that of pristine DPBI membrane (314 mW cm−2). In addition, the cell is very stable in 50 h, indicating the in-situ crosslinked DPBI with a macromolecular crosslinker of PVBC is an efficient way to improve the overall performance of HT-PEMs for high performance HT-PEMFCs

Polybenzimidazole Confined in Semi-Interpenetrating Networks of Crosslinked Poly (Arylene Ether Ketone) for High Temperature Proton Exchange Membrane

As a traditional high-temperature proton exchange membrane (HT-PEM), phosphoric acid (PA)-doped polybenzimidazole (PBI) is often subject to severe mechanical strength deterioration owing to the “plasticizing effect” of a large amount of PA. In order to address this issue, we fabricated the HT-PEMs with a crosslinked network of poly (arylene ether ketone) to confine polybenzimidazole in semi-interpenetration network using self-synthesized amino-terminated PBI (PBI-4NH2) as a crosslinker. Compared with the pristine linear poly [2,2′-(p-oxdiphenylene)-5,5′-benzimidazole] (OPBI) membrane, the designed HT-PEMs (semi-IPN/xPBI), in the semi-IPN means that the membranes with a semi-interpenetration structure and x represent the combined weight percentage of PBI-4NH2 and OPBI. In addition, they also demonstrate an enhanced anti-oxidative stability and superior mechanical properties without the sacrifice of conductivity. The semi-IPN/70PBI exhibits a higher proton conductivity than OPBI at temperatures ranging from 80 to 180 °C. The HT-PEMFC with semi-IPN/70PBI exhibits excellent H2/O2 single cell performance with a power density of 660 mW cm−2 at 160 °C with flow rates of 250 and 500 mL min−1 for dry H2 and O2 at a backpressure of 0.03 MPa, which is 18% higher than that of OPBI (561 mW cm−2) under the same test conditions. The results indicate that the introduction of PBI containing crosslinked networks is a promising approach to improve the comprehensive performance of HT-PEMs