To broaden the operating temperature range of phosphoric acid (PA) doped polybenzimidazole membrane-based proton exchange membrane fuel cells (PEMFCs) toward low temperatures, a novel series of poly(2,5-benzimidazole) (ABPBI)/sulfonated sepiolite (S-Sep) composite membranes (ABPBI/S-Sep) with low PA doping levels (DLs) were prepared via in-situ synthesis. The desirably enhanced mechanical, thermal, and oxidative stabilities of ABPBI/S-Sep composite membranes were achieved by constructing ABPBI chains arranged along the sepiolite (Sep) fibers and acid-base crosslinks formed between S-Sep fibrous particles and ABPBI chains. Benefiting from the richness of high temperature stable bound water and the excellent water absorbability of Sep particles that enable the formation of additive proton conducting paths, the composite membranes retained bounded PA and achieved much higher proton conductivities under both anhydrous and hydrous conditions compared to PA-doped ABPBI membranes. Proton conductivity values above 0.01 S/cm at 40–90 °C/20–98% RH conditions and 90–180 °C/anhydrous conditions as well as peak power density of 0.13 and 0.23 W/cm 2 at 80 and 180 °C with 0% RH, respectively from the ABPBI/2S-Sep composite membrane are more holistic compared to Nafion at low temperatures and polybenzimidazole-based membranes at high temperatures, respectively. The excellent properties of ABPBI/S-Sep composite membranes suggest them as prospective candidates for PEMFCs applications in a wide temperature range.
Due to its uncomplicated manufacturing procedure for large-scale industrialization and adaptable conductivity, the competitive proton exchange membrane (PEM) matrix employed is sulfonated poly (ether ether ketone). However, the conflict between the strong proton conductivity and high stability of SPEEK-based PEM constantly upsets the equilibrium; the primary chain of SPEEK will conduct more protons if additional sulfonic acid is introduced, but it also causes a high swelling ratio and lowers stability. To tackle this challenging issue, we coupled the high intrinsic proton conductivity of phosphotungstic acid (HPW) and the excellent stability of polyimide (PI) nanofibers in a single PEM. In particular, sandwich-structure hybrid membranes (PI/SPEEK + HPW) were created to reduce HPW loss under operational conditions, further improving stability. Consequently, the swelling ratio and conductivity of the premium sandwich-structure PI/SPEEK + HPW-20 were 29% and 223.4 mS cm −1 under 60 °C and 100% RH, their respective values were 8% larger than those of SPEEK. Its proton conductivity reached 170.9 mS cm −1 during 13 days of exposure under 60 °C and 100% RH, which would be 30% better than that of SPEEK over the same treatment. Protons in these membranes were transported through Grotthus and vehicle mechanism, and the establishment of an acid-rich layer at the surface among PI nanofiber with HPW/SPEEK, which was confirmed by FTIR, XPS , and TEM , is responsible for these superior performances. From our point of view, our findings might encourage more studies into the creation of high-performance PEM.
Jia Wang,De Wang,Zelin Zhao,Ganggang Chang,Wei Guo,Jun Xu,Yinyu Xiang,Junrui Li,Junsheng Li
Developing cost-effective ruthenium (Ru)-based HER electrocatalysts as alternatives to commercial Pt/C is crucial for the advancement of proton exchange membrane water electrolysis (PEMWE). However, the strong hydrogen adsorption of Ru-based catalysts restricts its activity. Herein, a strategy is reported to tune the electronic structure and improve mass transfer by implanting Ru atoms onto the (002) facet of two-dimensional zeolitic imidazolate framework-67 (Ru@ L ZIF (002) ) to optimize the d -band center ( ε d ) of Ru and the hydrogen spillover behavior. Benefiting from the ultrathin nanosheet structure and optimized ε d of Ru, the over-strong H adsorption energy is weakened and the electron/mass transfer is facilitated. Ru@ L ZIF (002) exhibits an overpotential of 9.2 mV at 10 mA cm −2 and a long-lasting stability of 35 days at 100 mA cm −2 . The mass activity and price activity of Ru@ L ZIF (002) is 2.9 and 14.7 times higher than Pt/C, respectively. More impressively, Ru@ L ZIF (002) delivers a cell voltage of 2.01 V at a high current density of 4 A cm −2 in PEMWE. The excellent long-term durability of 1200 hours operating at 4 A cm −2 with an ultralow decay rate of 7.5 × 10 −3 mV h −1 has been achieved, making it promising as a cost-effective alternative to Pt/C catalyst for PEMWE applications.
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