無機/有機高分子混成膜應用於燃料電池質子交換膜

Inorganic/organic polymer hybrid membranes for proton exchange membranes in fuel cell

余青育(Chin-Yu Yi)

指導教授 ： 謝國煌

國立臺灣大學/工學院/化學工程學研究所/碩士(2005年)

https://doi.org/10.6342/NTU.2005.02864

摘要

由於使用Nafion為質子交換膜有高成本、高甲醇穿透率、且限制操作溫度(<100 ℃)。故在本研究，我們合成一系列新式無機有機高分子膜應用在直接甲醇燃料電池。首先，把有機官能基引入矽氧烷產生交聯的有機無機混成物質，使這質子交換膜具有高溫穩定性且好的機械性質。用3-(trimethoxysilyl)propyl methacrylate(MSMA)跟不同比例的官能基單體先經由自由基聚合成共聚合物，之後再由於溶膠-凝膠法產生交聯的有機無機混成薄膜。使用FTIR、GPC來鑑定膜材結構與分子量，以TGA、DSC、SEM分別鑑定其熱性質與微觀型態，並探討不同結構膜材的質子導電率與甲醇穿透率。
在本研究中，交連無機有機高分子混成膜帶有羧酸基(COOH)的質子導電度約10-6~10-4 S/cm，而帶有磺酸根的質子導電度約10-4~10-2 S/cm。交連無機有機高分子混成膜比Nafion 117膜(約10-6 cm3/s)的甲醇穿透率(10-8~10-7 cm2/s)低。交連無機有機高分子混成膜有效減低甲醇穿越，並可利用有機無機不同比例來調整導電度與甲醇滲透率。

關鍵字

DMFC ； 質子交換膜 ； MSMA ； 質子導電率 ； 甲醇穿透率

並列摘要

Because of Nafion used as proton exchange membrane is confronted with high cost, high methanol permeability, and limited operating temperature (<100℃). Our study is to synthesize a series of novel inorganic/organic polymer membranes used as proton exchange membranes in direct methanol fuel cells (DMFC). At first, the introduction of the organo functional groups into polysiloxanes yields the crosslinked inorganic/organic polymer hybrid membranes. The hybrids containing crosslinked networks have the potential for high temperature stabilities and good mechanical property. Copolymer of 3-(trimethoxysilyl)propyl methacrylate (MSMA) with various ratios of functional group monomer were prepared by free radical polymerization, and then the inorganic/organic polymer hybrids were produced by sol-gel process. The structure and molecular weight of membrane is characterized by FTIR and GPC. Furthermore, TGA, DSC, SEM are used to analyze thermal properties and morphology of these membranes.
In our study, these results showed that crosslinked inorganic/organic polymer hybrid membranes with carboxylic acid group had the conductivity in the range of 10-6 to 10-4 S/cm, and those with sulfonic acid group is in the range of 10-4 to 10-2 S/cm. and showed a reduced methanol permeability (10-8 ~ 10-7 cm2/s) for Nafion 117(10-6 cm2/s). The crosslinked inorganic/organic polymer hybrid membrane was effective in reducing methanol crossover. The proton conductivity and methanol permeability can be controlled by various ratios of the two reactant monomers.

並列關鍵字

DMFC ； proton exchange membrane ； MSMA ； proton conductivity ； permeability

參考文獻

36.沈坤昇，”PTFE-Nafion 的製作與性能研究”，碩士論文，元智大學(2003).

25.I. Honma, O. Nishikawa, T. Sugimoto, S. Nomura, H. Nakajima, Fuel cells, 2, 52(2002).

28.B. Jirgensons, M. E. Stranmains, Colloid Chemistry, McMillan, New York (1962).

3.Y. Sone, P. Ekdunge, and D. Simonsson, J. Electrochem. Soc., 143, 1254 (1996).

6.Y. Wei, D. Yang, and L. Tang, Makromol. Chem., Rapid Commun, 14, 273 (1993).