Dias Frederico G de A, Veiga Amanda G, Andreopoulou Aikaterini K, Kallitsis Joannis K, Rocco Maria Luiza M
Institute of Chemistry, Federal University of Rio de Janeiro, 21949-900 Rio de Janeiro, RJ, Brazil.
Department of Chemistry, University of Patras, GR26504 Patras, Greece.
ACS Omega. 2020 Jun 25;5(26):15901-15910. doi: 10.1021/acsomega.0c01039. eCollection 2020 Jul 7.
Acid-doped reinforced polymer electrolyte membranes for high-temperature polymer electrolyte membrane fuel cell applications (HT PEMFCs) are presented and spectroscopically studied. Fully aromatic polyethers are employed bearing main chain pyridine units as the proton accepting sites, which have two different substitution patterns of the pyridine units, namely, 2,5- or 2,6-pyridine. This fact enables control of the solubility and of the acid doping ability of the polymeric membranes. Reinforcement is accomplished via incorporation of a PTFE woven fabric during the casting procedure for fabrication of the membranes. High acid uptake of the reinforced membranes was maintained for the 2,6-pyridine-based copolymers with high pyridine unit content. Studies of the swelling behavior of these reinforced membranes revealed that they expand mainly along the -axis, which helps to avoid extensive damage in case of humidity or temperature changes during the fuel cell operation. Additionally, spectroscopic techniques are employed, namely, X-ray photoelectron spectroscopy, X-ray photoelectron spectroscopy with depth profile, near-edge X-ray absorption fine structure, and reflection electron energy loss spectroscopy, for the in-depth study of the two copolymer membranes doped with phosphoric acid. Through these spectroscopic evaluations, modifications in the membranes' chemical structure, orientation, composition, and electronic structure after the reinforcement and doping processes were elaborated and unveiled.
本文介绍了用于高温聚合物电解质膜燃料电池(HT PEMFCs)的酸掺杂增强聚合物电解质膜,并对其进行了光谱研究。采用全芳香聚醚,其主链带有吡啶单元作为质子接受位点,吡啶单元有两种不同的取代模式,即2,5 - 或2,6 - 吡啶。这一事实使得能够控制聚合物膜的溶解性和酸掺杂能力。在制备膜的浇铸过程中,通过加入聚四氟乙烯织物来实现增强。对于具有高吡啶单元含量的基于2,6 - 吡啶的共聚物,增强膜保持了高酸吸收量。对这些增强膜的溶胀行为研究表明,它们主要沿 - 轴膨胀,这有助于避免在燃料电池运行期间湿度或温度变化时受到广泛损坏。此外,采用光谱技术,即X射线光电子能谱、具有深度剖析的X射线光电子能谱、近边X射线吸收精细结构和反射电子能量损失谱,对两种掺杂磷酸的共聚物膜进行深入研究。通过这些光谱评估,阐述并揭示了增强和掺杂过程后膜的化学结构、取向、组成和电子结构的变化。