Quaternized polymers as electrode ionomeric binders enable fuel cell operation under high-pH or anhydrous conditions. Herein we report quaternized poly(fluorene) ionomers with controlled hydrophobicity (contact angle of electrodes with the ionomers 109–164°) by changing the length of tethered fluoroalkyl chains. The anion-exchange membrane fuel cell employing the hydrophobic ionomer exhibits improved durability (voltage loss 0.41 mV h–1) through better water management. The high-temperature proton-exchange-membrane fuel cell using the ionomer shows superior H2/air performance (1.7 A cm–2 at 0.4 V). The finding in this study highlights the benefits of hydrophobic ionomers for emerging fuel cell applications.
Understanding the H3PO4 effect on the catalyst’s activity under a relevant condition is important for high-temperature polymer electrolyte membrane fuel cell (HT-PEMFC) catalyst research. Here, we report a high-temperature rotating disk electrode (HT-RDE) study of oxygen reduction reaction (ORR) in H3PO4. With the regular electrochemical protocol, we found that H3PO4 reduction could occur during cyclic voltammetry study and form a reductive speciesphosphorus acid (H3PO3). To obtain reliable ORR measurement, we optimized the protocol to avoid the H3PO3 generation. The ORR activity of carbon-supported PtM (M = Fe, Co, Ni, Ru, Pd, and Ir) bimetallic alloy catalysts measured with this HT-RDE method showed higher ORR activity than Pt. To understand the alloying effect, we combine experiments in diluted solutions to distinguish the alloying effect on Pt–O binding and Pt–H3PO4 binding. The results indicate that H3PO4 mainly reduces available sites for ORR, with little effect on neighboring site’s Pt–O binding via Pt–H3PO4 interaction, which is also supported by the density functional theory calculation of the Pt–O binding energy with/without H2PO4. Further study in a phosphoric acid-doped quaternary ammonium-biphosphate ion pair coordinated polyphenylene (PA-QAPOH) membrane electrode assembly (MEA) shows that the active alloy catalyst has better performance in both the HT-RDE and MEA. Also, the MEA gives higher ORR activity than the HT-RDE because of the higher pressure and less phosphoric acid content of the MEA. Yet, the gap between the HT-RDE and MEA is significantly smaller than that between the room temperature (RT)-RDE and MEA, suggesting the importance of temperature and H3PO4 concentration in understanding ORR in HT-PEMFCs.
High temperature proton exchange membrane fuel cells (HT-PEMFCs) have several merits over low temperature PEMFCs, including simplified fuel cell systems and high CO tolerance. Recently developed ion-pair HT-PEMFCs1 has a significantly lower concentration of phosphoric acids in the membrane-electrode assembly (MEA) that allows ion-conducting binders (ionomers) in the electrodes. Here, we first explain the difference in MEA configurations and fuel cell performance between conventional polybenzimidazole-based and ion-pair HT-PEMFCs2. Next, we discuss catalyst challenges for ion-pair HT-PEMFCs by comparing half-cell and single-cell results. We focus on three critical areas in that electrocatalysts face challenges: i) phosphate anion poisoning on oxygen reduction reaction catalysts, ii) phenyl adsorption on hydrogen oxidation reaction catalysts and iii) phosphoric acid flooding. Research progress mitigating those adverse effects is demonstrated using various commercial Pt-based catalysts and homemade ionomers. Lastly, we provide general directions for designing high-performing catalysts of ion-pair HT-PEMFCs. References Lee, K. S.; Spendelow, J. S.; Choe, Y. K. Fujimoto, C.; Kim, Y. S. An Operationally Flexible Fuel Cell Based on Quaternary Ammonium-Biphosphate Ion Pairs, Nature Energy, 1, 16120 (2016). Lim, K. H.; Lee, A. S.; Atanasov, V.; Kerres, J.; Park, E. J.; Adhikari, S.; Maurya, S.; Manriquez, L. D.; Jung, J.; Fujimoto, C.; Matanovic, I.; Jankovic, J.; Hu, Z.; Jia, H.; Kim, Y. S. Protonated phosphonic acid electrodes for high power heavy-duty vehicle fuel cells, Nature Energy, 7, 248 (2022).
Quaternized polymers as ionomeric binders in the electrode enable the operation of alternative fuel cells under high pH conditions or anhydrous conditions to overcome the challenges of the proton exchange membrane fuel cells. Hydrophobicity of the ionomers derived from high fluorine content is beneficial to electrode performance, but due to the synthetic difficulties, not many fluorinated quaternized ionomers have been reported with their influence on electrode behavior in these emerging fuel cells. In this presentation, we report a series of quaternized poly(fluorene)s with controlled hydrophobicity by changing the length of flexible fluoroalkyl chains. The contact angle of the electrodes containing the ionomers ranged from 108.7 to 163.8°, comparable to that of the perfluorosulfonic acid-bonded electrodes. The anion exchange membrane fuel cells employing the ionomer exhibits improved durability (voltage loss 0.41 mV h−1) through better water management. The high-temperature proton-exchange membrane fuel cell using the ionomer showed superior H2/air performance (1.4 A cm-2 at 0.4 V). The study of the fluorinated poly(fluorene) highlights the benefits of hydrophobic ionomers for highly efficient and cost-effective fuel cell systems.
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