磺酸化二氮雜萘聯苯聚醚酮與磺酸化聚芳香烴醚醚酮酮膜材之鑑定

Characterization of Sulfonated Poly(phthalazinone ether ketone) and Sulfonated Poly(arylene ether ether ketone ketone) Membrane

林稚閔(Chih-Min Lin)

指導教授 ： 孫ㄧ明

元智大學/工程學院/化學工程與材料科學學系/碩士(2006年)

摘要

本研究比較不同磺酸化SPPEK DS0.86 和1.10及SPAEEKK不同含量0.7和0.8的磺酸化4,4’-biphenol，並利用乾式成膜法在玻璃板上。
SPPEK-086、SPPEK-110、SPAEEKK-070及SPAEEKK-080膜材的最初熱裂解溫度均高於230 oC。在熱壓製作MEA，可以耐受相當高的熱壓溫度，膜材的結構不會遭到破壞。膜材質子傳導度，隨著磺酸化程度及溫度的上升而提升。因為質子傳導活化能接近14-40 KJ/mol，所以質子傳導方式均屬Grotthus與vehicle mechanism兩種方式同時進行來傳導。當溫度在80 oC，SPAEEKK-080為3.9×10-2 S/cm接近Nafion-117的質子傳導度。
SPPEK-086及SPAEEKK-070的甲醇水溶液吸收量變化與Nafion-117 相近。高磺酸化程度的膜材SPPEK-110在3 M甲醇水溶液溫度為60 oC時，膜材會產生過度膨潤的現象。滲透蒸發實驗觀察，所有膜材其甲醇阻擋效果均優於Nafion-117。Side-by-side滲透係數實驗，所有膜材的滲透係數也低於Nafion-117。四種膜材中，SPAEEKK-070有最佳的阻擋甲醇的能力。SPAEEKK系列的膜材隨著溫度上升，甲醇滲透係數變化小。所以SPAEEKK系列膜材阻擋甲醇滲透是最佳的膜材。
SPPEK-086、SPPEK-110、SPAEEKK-070及SPAEEKK-080膜材質子傳導度均低於Nafion-117；但阻擋甲醇滲透能力均優於Nafion-117，所以在甲醇燃料電池系中可能可以得到一較好的電池效能，且有較長的電池壽命。

關鍵字

磺酸化聚電解質 ； 質子傳導度 ； 滲透係數 ； 甲醇燃料電池

並列摘要

In this study, sulfonated poly(phthalazinone ether ketone) with degree of sulfonation (DS) of 0.86 and 1.10 and sulfonated poly(arylene ether ether ketone ketone) with sulfonated 4,4’-biphenol content (B) of 0.7 and 0.8 were fabricated into membranes on glass plates by solvent casting method.
SPPEKs and SPAEEKKs had excellent thermal stability for use in the preparation of MEA for DMFC because the degradation temperature of them was higher than 230 oC. The proton conductivity of SPPEK and SPAEEKK membranes increased as temperature and the degree of sulfonation. The proton conductivity of SPAEEKK-080 was 3.9×10-2 S/cm which was closed to Nafion-117 at 80 oC. According to the activation energy of proton conductivity was closed to 14-40 KJ/mol, proton transport might follow Grotthus and vehicle mechanisms simultaneously.
SPPEK-086 and SPAEEKK-070 had similar solution uptake to Nafion-117. SPPEK-110 might dissolve in 3 M methanol solution at 60 oC. In pervaporation and side-by-side studies, all the SPPEK and SPAEEKK membranes had lower flux and methanol permeability than Nafion-117.Methanol permeabilities were relatively constant for SPAEEKK membranes when temperature is varied. SPAEEKK-070 membrane had the lowest methanol permeability among all the test membranes. Therefore, SPAEEKKs might be a better choice to prevent methanol crossover at high temperature.
Although the proton conductivity of SPPEK and SPAEEKK membranes were lower than Nafion-117, the methanol permeability of them were much lower than Nafion-117.SPPEK and SPAEEKK membranes still could be considered as a candidate for MEA preparation in direct methanol fuel cell.

並列關鍵字

SPPEK ； SPAEEKK ； direct methanol fuel cell ； proton conductivity ； permeabilities

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