Hameed Arif Sahul, Munusamy Saravanabhavan, Gokulapriyan Ramasamy, Yoo Dong Jin
Department of Chemistry, KPR Institute of Engineering and Technology, Uthupalayam, Tamil Nadu 641 407, India.
Department of Energy Storage/Conversion Engineering of Graduate School (BK21 FOUR), Hydrogen and Fuel Cell Research Center, Jeonbuk National University, 567 Baekje-daero, Deokjingu, Jeonju-si, Jeollabuk-do 54896, Republic of Korea.
ACS Appl Mater Interfaces. 2025 Jul 2;17(26):37951-37964. doi: 10.1021/acsami.5c06145. Epub 2025 Jun 18.
The development of high-performance anion exchange membranes (AEMs) remains a major challenge in commercializing alkaline fuel cells. Significant efforts have been directed toward enhancing the ionic conductivity, mechanical strength, and alkaline stability of AEMs. Among various strategies, modifying commercially available polymers has emerged as an effective and straightforward approach. In this work, we focused on fabricating an eco-friendly polymer membrane using poly(vinyl alcohol) (PVA). Specifically, two polymer membranes, poly[vinyl alcohol--4-(1-methylpiperidinium iodide) benzylidene acetal] (PVA-PB-MI) and poly[vinyl alcohol--4,4'-(1,6-hexanediylbis(1-piperidinium) benzylidene acetal) dibromide] (PVA-PB-DBH), were synthesized through the acetylation of PVA with 4-(1-piperidinyl)benzaldehyde, followed by quaternization using methyl iodide and 1,6-dibromohexane. Structural confirmation of the synthesized membranes was carried out using H NMR and FTIR spectroscopy. The resulting cross-linked PVA-PB-DBH membrane exhibited superior hydroxide ion conductivity that reached 72.5 mS cm at 90 °C and maintained lower water uptake and swelling ratio in comparison to those of non-cross-linked PVA-PB-MI, which displayed a conductivity of 49.7 mS cm. The reduced water uptake and improved ion conductivity of the cross-linked membrane were due to the hydrophobic nature and microphase separation within the polymer matrix, which was confirmed by contact angle and atomic force microscopy (AFM) analysis. A theoretical study of the alkaline stability of polymer membranes was carried out by using density functional theory (DFT).
高性能阴离子交换膜(AEMs)的开发仍然是碱性燃料电池商业化面临的一项重大挑战。人们已投入大量精力来提高AEMs的离子电导率、机械强度和碱性稳定性。在各种策略中,对市售聚合物进行改性已成为一种有效且直接的方法。在这项工作中,我们专注于使用聚乙烯醇(PVA)制备一种环保型聚合物膜。具体而言,通过PVA与4-(1-哌啶基)苯甲醛的乙酰化反应,随后分别用甲基碘和1,6-二溴己烷进行季铵化反应,合成了两种聚合物膜,即聚[乙烯醇-4-(1-甲基哌啶碘化苄叉缩醛)](PVA-PB-MI)和聚[乙烯醇-4,4'-(1,6-己二基双(1-哌啶基)苄叉缩醛)二溴化物](PVA-PB-DBH)。使用核磁共振氢谱(H NMR)和傅里叶变换红外光谱(FTIR)对合成的膜进行结构确认。所得的交联PVA-PB-DBH膜表现出优异的氢氧根离子电导率,在90℃时达到72.5 mS/cm,与非交联的PVA-PB-MI相比,其吸水率和溶胀率更低,后者的电导率为49.7 mS/cm。交联膜吸水率降低和离子电导率提高是由于聚合物基质内的疏水性和微相分离,这通过接触角和原子力显微镜(AFM)分析得到证实。利用密度泛函理论(DFT)对聚合物膜的碱性稳定性进行了理论研究。