燃料電池用之二氧化矽離子膠交換膜之製備與性質之研究

The Preparation and Properties of Silica Ionogel for Proton Exchange Membrane on Fuel cell

常維強(Wei-Chiang Chang)

指導教授 ： 陳玉惠

中原大學/理學院/化學研究所/碩士(2013年)

https://doi.org/10.6840/cycu201301077

摘要

本研究首先合成Trimethylammonium methanesulfonate [TMA-MS]、Triethylammonium methanesulfonate [TEA-MS]、triethylammonium tetrafluoroborate [TEA-BF4]、及trimethylammonium tetrafluoroborate, [TMA-BF4] 四種質子離子熔液，並以NMR、FTIR鑑定其結構，以TGA分析質子離子熔液之熱性質；黏度計測定質子離子熔液之黏度；NMR測其擴散係數；並利用電化學阻抗儀分析質子離子熔液之離子導電度及解離度。再利用溶膠-凝膠法(Sol-gel method)以矽酸乙酯Tetraethylorthosilicate (TEOS)為前驅物與該四種質子離子熔液分別製備Ionogel-MS、Ionogel-ES、
Ionogel-MB、Ionogel-EB各種離子凝膠(Ionogel)，並探討離子凝膠(Ionogel)的結構、熱穩定性、離子導電度及作為燃料電池之電解質之電池效能。熱分析結果顯示，所有離子凝膠(Ionogel)的熱穩定性良好，均可達225°C以上，主要歸因於無機相SiO2 骨架及質子離子熔液的高熱穩定性，所有製備之離子凝膠(Ionogel)中在120℃且無加濕的條件下，以Ionogel-ES具有最高之導電度為3.85×10-2 S/cm。
此外，本研究亦探討選用不同質子離子熔液製備離子凝膠(Ionogel)與添加氯磺酸對離子凝膠(Ionogel)應用於燃料電池之電解質對電池效能之影響；結果顯示：30℃下Ionogel-ES在92 mA/cm2 可得到最大能量密度為43.33 mW/cm2。再將Ionogel-ES添加氯磺酸後之Ionogel-S之離子導電度及電池效能皆有上升。在120°C且無加濕的條件下Ionogel-S-3具有最高之導電度為1.52×10-1 S/cm，應用於燃料電池上，120°C且無加濕的條件下Ionogel-S3最大的電流密度為76mA/cm2，在56mA/cm2 可得到最大能量密度為22.81 mW/cm2。

關鍵字

燃料電池 ； 質子離子熔液 ； 離子凝膠 ； 非加濕環境

並列摘要

Four protic ionic liquids (PILs), Trimethylammonium Methanesulfonate [TMA-MS]、Triethylammonium Methanesulfonate [TEA-MS]、Triethylammonium Tetrafluoroborate [TEA-BF4]、Trimethylammonium Tetrafluoroborate, [TMA-BF4],were synthesized. The structures, the thermal properties, viscoity, diffusion coefficient, ionic conductivities and degree of dissociation of the protic ionic liquids were examined by FTIR and NMR spectroscopies, TGA, viscometer, NMR and AC impedance measurement, respectively.
Four kinds of ionogels, namely,Ionogel-ES, Ionogel-MS, Ionogel-EB and Ionogel-MB, were prepared by sol-gel process with tetraethylorthosilicate (TEOS) as silica precursor and the four as-prepared protic ionic liquids, TMA-MS、TEA-MS、TEA-BF4、TMA-BF4, as additive, respectively.
The structural, thermal stability and ion conductivities of four inogels were investigated. Thermal analysis confirmed that the Ionogels were thermally stable up to 225 °C due to the presence of the high stable inorganic SiO2 framework and of PILs.
The effect of the PILs on the properties of the ionogels has also been studied. The results showed that the highest ion conductivity (3.85×10-2 S/cm) of the ionogels measured at 120 °C under dry condition was obtained from Ionogel-ES. Besides, a maximum power density value of 40.81 mW/cm2 at 0.4 Voltage was obtained from the single cell of PEMFC fabricated with Ionogel-ES as PEM at 30 °C under dry condition.
In addition, the chlorosulfuric acid doped ionogel (Ionogel-ES-S) was also prepared by adding chlorosulfuric acid into Ionogel-ES. The ion conductivity and cell performance of the Ionogel-ES-S are enhanced. It was found that at 120 ℃ under anhydrous conditions the ion conductivity of Ionogel-S-3 was increased to 1.52×10-1 S/cm. Besides, a maximum power density value of 22.81 mW/cm2 at 56 mA/cm2 was obtained from the single cell of PEMFC fabricated with Ionogel-S-3 as PEM at 120 °C.

並列關鍵字

protic ionic liquids ； ionogel ； without humidifation ； fuel cell

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