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Student Number 982203030
Author Hou Guan-ting(侯官廷)
Author's Email Address a1103171107@yahoo.com.tw
Statistics This thesis had been viewed 516 times. Download 21 times.
Department Chemistry
Year 2010
Semester 2
Degree Master
Type of Document Master's Thesis
Language zh-TW.Big5 Chinese
Title Sulfonated TiO2 Nanotube / Nafion composite membrane for High Temperature Proton Exchange Membrane Fuel Cell (PEMFC)
Date of Defense 2011-06-20
Page Count 90
Keyword
  • Nafion
  • PEMFC
  • sulfonated TiO2 nanotube
  • Abstract Nafion has more excellent stability and conductivity in comparison to other materials. However, Nafion shows severe loss of water and reduced proton conductivity under high temperature operating conditions. Proton exchange membrane prepared by inorganic nanomaterials composite can increase water retention at high temperatures. These composite membranes can maintain high conductivity at high temperatures and even enhances cell performance at low humidity condition. In this study, a novel organic/inorganic composite proton conducting membrane were prepared by blending Nafion with sulfonate functionalized Titania nanotube,and applied to PEMFC operating at high temperatures. Sulfonat functionalized titania nanotubes (sTNT) resolves the draw-backs of of phase separation commonly occured in organic/inorganic composite meterials. In addition, composite membran exhibit good water retention behavior at high temperatures because the high surface interaction with of sTNT. Furthermore, composite with sTNT created a highly efficient proton conducting channels, forming a continuous and long-range proton transfer behavior existed between the organic and inorganic interface which yield favorable proton conductivity at high temperature and low humidity.
      From TEM measurement, we observed these sTNT which cross through many ionic clusters in these composite membranes. And we also found that presence of sTNT changed the crystallinity of the membranes by XRD. This phenomenon has a direct effect in water uptake and permeability, in addition to facilitate long-range proton conductivity, The sTNT showed a much better water retention and conductivity than titania nanoparticle by DSC. The study shows 5wt% of sTNT yielded the most balanced performance of ion conductivity and water uptake property. At 100℃ and 40% relative humidity, the proton conductivity of the 5wt% sTNT composite membrane is 8 mS/cm, a great improvement over 2 mS/cm for a recast Nafion membrane. DMFC performance for this composite membrane is 50 mW/cm2 better than 40 mW/cm2 with pure Nafion at 70℃. The study shows the composite membrane formed from the addition of sTNT, created different types of membrane morphology and nano-structures which affected water ad-/desorption and proton conducting behavior. A strategy to improve fuel cell performance can be established by improving these membrane morphology and nano-structures.
    Table of Content 目錄              頁次
    中文摘要…………………………………………………………………………i
    英文摘要…………………………………………………………………………ii
    謝誌…………………………………………………………………………………iv
    目錄……………………………………………………………………………………v
    表目錄…………………………………………………………………………viii
    圖目錄………………………………………………………………………………ix
    第一章 緒論………………………………………………………………………1
      1-1 前言…………………………………………………………………1
      1-2 燃料電池原理及其組成………………………………2
      1-3 研究動機…………………………………………………………4
    第二章 文獻回顧………………………………………………………………6
      2-1 燃料電池質子交換膜介紹……………………………6
      2-2 Nafion薄膜改良…………………………………………11
       2-2-1 Nafion/小分子化合物複合薄膜…12
       2-2-2 Nafion/無機物複合薄膜………………13
      2-3 非PFSA系列薄膜…………………………………………21
       2-3-1 碳氫(芳香環)高分子薄膜………………21
       2-3-2 酸鹼複合高分子薄膜…………………………27
      
    第三章 實驗方法與原理…………………………………………………30
      3-1 實驗儀器及技術原理……………………………………30
       3-1-1傅立葉式紅外線吸收光譜儀磁共振光譜儀
          ……………………………………………………………………30
       3-1-2 熱重分析儀(Thermal Gravimetric Analysis, TGA)
          ……………………………………………………………………30
     3-1-3 示差掃描熱卡計(Differential Scanning Calorimeter, DSC)
          ……………………………………………………………………31
     3-1-4 X光繞射分析(X-ray Diffraction,XRD)
          ……………………………………………………………………31
     3-1-5 穿透式電子顯微鏡(Transmission Electron Microscopy,TEM)
          ……………………………………………………………………32
     3-1-6 NMR變溫擴散實驗(VT-diffsion)
          ……………………………………………………………………32
     3-1-7 薄膜吸水量(Water uptake)與膨潤(Swelling)
          ……………………………………………………………………32
     3-1-8 離子交換容積(Ion exchange Capacity,IEC)
          ……………………………………………………………………33
     3-1-9 甲醇滲透率(Methanol Permeability)
          ……………………………………………………………………34
     3-1-10 質子導電度(Proton conductivity)
          ……………………………………………………………………35
     3-1-11 DMFC單電池效能測試…………………………………37
    3-2 物質合成及薄膜製備…………………………………………………38
       3-2-1 合成Titanate Nanotube………………38
       3-2-2 奈米管表面磺酸化修飾…………………………38
       3-2-3 Nafion solution製備……………………39
       3-2-4 sTNT/Nafion複合薄膜製備………………39
       3-2-5 Nafion 117前處理………………………………39
       3-2-6 薄膜TEM觀察前處理………………………………39
      3-3 實驗藥品………………………………………………………………40
      3-4 樣品命名規則………………………………………………………42
      
    第四章 結果與討論………………………………………………………………43
      4-1 磺酸化二氧化鈦奈米管………………………………………44
       4-1-1 FT-IR表面官能基鑑定……………………………44
       4-1-2 X光繞射分析………………………………………………45
       4-1-3 TEM&SEM微結構鑑定 ……………………………46
       4-1-4 DSC保水性質分析……………………………………48
      4-2 sTNT/Nafion複合膜性質與效能分析…………49
       4-2-1 不同溶劑影響………………………………………………49
          含水量、尺寸膨潤、質子導電度及甲醇滲透綜合比較
           ………………………………………………………………………50
          XRD薄膜結晶程度比較…………………………………55
          SAXS小角度散射微結構分析………………………57
          薄膜變濕導電度測試………………………………………58
          甲醇滲透……………………………………………………………59
       4-2-2 不同sTNT含量之影響…………………………………60
          穿透式電子顯微鏡TEM……………………………………61
          TGA&DSC熱穩定性比較…………………………………63
          XRD薄膜結晶程度比較……………………………………66
          SAXS小角度散射微結構分析…………………………68
          保水能力分析………………………………………………………69
          NMR水分子擴散速率比較…………………………………73
          質子導電度比較…………………………………………………74
          甲醇滲透………………………………………………………………78
          DMFC單電池效能測試………………………………………79
    第五章 結論與未來展望………………………………………………………………82
    第六章 參考文獻……………………………………………………………………………85
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    Date of Submission 2011-07-26

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