On the Development of Naphthalene-Based Sulfonated Polyimide Membranes for Fuel Cell Applications
On the Development of Naphthalene-Based Sulfonated Polyimide Membranes for Fuel Cell Applications
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DOI：
10.1295/polymj.38.197
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发表时间：
2006-03
期刊：
影响因子：
2.8
通讯作者：
Yan Yin;Otoo Yamada;Kazuhiro Tanaka;K. Okamoto
中科院分区：
文献类型：
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作者：
Yan Yin;Otoo Yamada;Kazuhiro Tanaka;K. Okamoto
本文从质子导电性、膜溶胀行为、膜对水的稳定性以及聚合物电解质燃料电池(PEFCs)和直接甲醇燃料电池(DMFCs)的燃料电池性能等方面综述了近年来基于萘系磺化聚酰亚胺(SPIS)的燃料电池的研究进展。从粘度、机械强度和质子导电性的角度，从磺化二胺的化学结构和SPI膜的形态等方面详细讨论了SPI膜的结构与性能的关系。离子交换容量(IEC)、磺化二胺的碱性、构型(对位、间位或邻位取向)和高分子链的化学结构(线型或网状结构)对SPI膜的水稳定性和机械强度有很大影响。由高碱性磺化二胺衍生而成的具有支化/交联结构的SPI在130°C的水中表现出超过200-300小时的相当高的水稳定性，表明作为质子交换膜的潜力高达100°C。SPI膜在较高的相对湿度和较低的甲醇渗透率下具有相当高的质子传导性。在燃料电池操作条件下，水和甲醇通过膜的过程不是由质子迁移引起的电渗透控制的，而是由活度差异引起的扩散控制的。这与全氟磺化膜如Nafion的情况有很大不同，并导致了对燃料电池性能的有利影响。SPI膜表现出与Nafion 112相当的高PEFC性能。此外，SPI膜在甲醇浓度较高(20-50wt%)的DMFC体系中表现出更高的性能，优于Nafion，在中温(40-80℃)下具有很高的应用潜力。
This article reviews the recent progress made over the past years based on naphthalene-based sulfonated polyimides (SPIs) in terms of proton conductivity, membrane swelling behavior, membrane stability toward water, and fuel cell performance in polymer electrolyte fuel cells (PEFCs) or direct methanol fuel cells (DMFCs). The structure-property relationship of SPI membranes is discussed in details with respect to the chemical structure of various sulfonated diamines and morphology of SPI membranes from the viewpoints of viscosity, mechanical strength and proton conductivity. Ion exchange capacity (IEC), basicity of sulfonated diamine, configuration (para-, meta-, or ortho-orientation) and chemical structure of polymer chain (linear or net-work) show great influence on the water stability and mechanical strength of SPI membrane. The SPIs with a branched/crosslinked structure and derived from highly basic sulfonated diamines display reasonably high water stability of more than 200–300 h in water at 130 °C, suggesting high potential as PEMs operating at temperatures up to 100 °C. The SPI membranes have fairly high proton conductivity at higher relative humidities and low methanol permeability. The water and methanol crossover through membrane under the fuel cell operation conditions is not controlled by electro-osmosis due to proton transport but by diffusion due to activity difference. This is quite different from the case of perfluorosulfonated membranes such as Nafion and results in the advantageous effects on fuel cell performance. SPI membranes displayed high PEFC performances comparable to those of Nafion 112. In addition, SPI membranes displayed higher performances in DMFC systems with higher methanol concentration (20–50 wt %), which is superior to Nafion and have high potential for DMFC applications at mediate temperatures (40–80 °C).