透過您的圖書館登入
IP:44.223.5.218
  • 學位論文

全氟磺酸高分子之原子轉移自由基聚合反應及於燃料電池材料之合成研究

Atom Transfer Radical Polymerization of Perfluorosulfonic Acid Polymer for Preparation of Proton Exchange Membranes for Fuel Cells

指導教授 : 劉英麟
若您是本文的作者,可授權文章由華藝線上圖書館中協助推廣。

摘要


本研究以Nafion為例,闡明全氟磺酸高分子的化學反應性,證實全氟磺酸高分子鏈上的某些C-F官能基具有原子轉移自由基加成/聚合反應活性,並利用此反應合成Nafion的接枝共聚合物以及Nafion/氧化石墨烯(graphene oxide,GO)的有機-無機混成物,作為開發高性能燃料電池用的質子交換膜之應用。 於合成方面,首先將Nafion與溴化亞銅(copper (I) bromide,CuBr)和2,2’-聯吡啶(2,2’-bipyridyl,BPY)進行鹵素交換實驗,並以傅立葉轉換紅外線光譜分析儀(Fourier transform infrared spectrometer,FTIR)和X光光電子光譜(X-ray photoelectron spectroscopy,XPS)驗證,證明Nafion上具有溴原子,亦即Nafion的氟原子與溴化亞銅的溴原子成功進行交換,初步證明Nafion可進行原子轉移自由基加成/聚合反應。接著將Nafion分別與多壁碳奈米管(multiwall carbon nanotubes,MWCNT)、n-異丙基丙烯醯胺(n-isopropylacrylamide,NIPAAm)、進行原子轉移自由基加成/聚合反應,得到的產物分別以傅立葉轉換紅外線光譜分析儀、X光光電子光譜、拉曼光譜儀、熱重分析儀以及19氟核磁共振光譜儀等進行分析。實驗結果顯示Nafion分別與上述的化合物進行ATRA/ATRP反應。此外,更以商業用膜Nafion 212與styrene進行表面起始原子轉移自由基聚合反應,並以全反射-傅立葉轉換紅外線光譜儀(atenuated total reflectance-fourier transform infrared spectrometer,ATR-FTIR)、X光光電子光譜、表面接觸角分析儀(contact angle)及場發射掃描式電子顯微鏡配備元素微分析系統(field Emission scanning electron microscope with EDS,SEM)證明,成功的以表面起始原子轉移自由基聚合反應於Nafion 212的膜面上長出聚苯乙烯(polystyrene)高分子刷。 之後,將Nafion分別與氧化石墨烯和苯乙烯磺酸钠(sodium 4-vinylbenzene sulfonate,NaSS)進行原子轉移自由基加成反應以及原子轉移自由基聚合反應,得到有機-無機混成物,GO-Nafion以及接枝共聚合物,Nafion- PSSNa,並以傅立葉轉換紅外線光譜分析儀、X光光電子光譜和熱重分析儀進行分析鑑定;最後,將產物與Nafion進行鑄膜程序,分別製成具有不同含量的GO-Nafion和Nafion-PSS的GO-Nafion/Nafion及Nafion-PSS/ Nafion系列複合膜材,並進行質子交換膜燃料電池(proton exchange membrane fuel cell,PEMFC)的相關應用。GO-Nafion/Nafion及Nafion-PSS/Nafion複合膜材除了進行膜性質的相關測試外,亦量測其質子導電度。其結果顯示,隨磺酸根的增加,複合膜的含水量和質子導電度亦隨之上升,但膜的尺寸安定性也跟著下降;此外,Nafion-PSS添加量為15%時,質子傳導度不僅優於Nafion 212,更為重鑄Nafion膜的2倍。而GO-Nafion的添加量分別0.1%時,質子傳導度約為重鑄Nafion膜的1.5倍,且於質子交換膜燃料電池的測試結果與Nafion 212膜的相當。

並列摘要


In this research, we demonstrate the C-F group of the chemical inert perfluorosulfonic acid polymers, such as Nafion, is reactive with atom transfer radical addition / atom transfer radical polymerization (ATRA/ATRP). As a macroinitiator, Nafion is reacted with sodium 4-vinylbenzenesulfonate (NaSS) and graphene oxide (GO) respectively to form the graft copolymer and organic-inorganic hybrid material by ATRP and ATRA. This two products can be acted as proton exchange membranes in the proton exchange membrane fuel cell (PEMFC) application. In the experimental section, for proving that Nafion is able to react through ATRA or ATRP method, Nafion is reactive with copper (I) bromide (CuBr) and 2,2’-bipyridyl (BPY) by halogen exchange reaction. The analysis results of Fourier Transform Infrared Spectrometer (FTIR) show that Nafion and transition metal complex can be successfully reacted by using halogen exchange reaction, which means that Nafion is reactive by ATRA/ATRP methods. To further confirm this experiment result, Nafion, as macroinitior, is reactive with MWCNT, n-isopropyl acrylamide (NIPAAm) and styrene by ATRA, ATRP and Surface- initiated ATRP methods respectively. All the products are characterized by FTIR、XPS、Raman、TGA or 19F NMR. The results show that MWCNT-Nafion, Nafion-PNIPAAm and Nafion 212-PS are able to be composed successfully by ATRA or ATRP methods, and these results can also re-confirm that Nafion is reactive through ATRA or ATRP methods. Then Nafion is reacted with Graphene oxide (GO) and Sodium 4-vinylbenzene sulfonate (NaSS) respectively by ATRA and ATRP methods to produce Nafion-PNaSS (graft copolymer) and GO-Nafion (organic-inorganic hybrid material). Besides some basic characterization examinations like FTIR, XPS, Raman and TGA, two kinds of proton exchange membranes (PEM) are made to test proton conductivity. The PEMs are produced by dispersing GO-Nafion and dissolving the Nafion-PNaSS respectively into the Nafion solution with different sample loadings, which are named as GO-Nafion/Nafion and Nafion-PSS/ Nafion composite membranes. In the membrane properties and proton conductivity test, as the amount of Nafion-PNaSS or GO-Nafion goes up, the composite membranes increase water uptakes capability and rise proton conductivity; however, the dimensional changes are also increasing with the rising amount of Nafion-PNaSS or GO-Nafion. Furthermore, the proton conductivities reach their highest points as the loading of the GO-Nafion and Nafion-PNaSS are 0.1% and 15% respectively. The proton conductivities of GO-Nafion_0.1% is 1.5-fold higher than Nafion_ Recast, and the PEMFC performance of GO-Nafion_0.1% is beter than Nafion 212’s. In the Nafion-PSS/Nafion complex membranes section, the proton conductivities of Nafion-PSS_15% is not only beter than Nafion 212, but twiceas much as Nafion_ Recast.

並列關鍵字

Nafion ATRP PEMFC

參考文獻


53. 薛康琳. 燃料電池內的電化學反應-觸媒與反應動力. Journal of the Chinese Chemical Society. 2004, 62, 149-56.
Grove, W.R. On the Gas Voltaic Battery.-Experinzents Made with a View of Ascertaining the Rationale of its Action and its Application to Eudiometry. Philosophical Transactions of the Royal Society of London. 1843, 133, 91-112.
2. Sharaf, O.Z., Orhan, M.F. An Overview of Fuel Cell Technology: Fundamentals and Applications. Renewable and Sustainable Energy Reviews. 2014, 32, 810-53.
3. Deabate, S., Gebel, G.e., Huguet, P., Morin, A., Pourcelly, G. 3 In Situ and Operando Determination of the Water Content Distribution in Proton Conducting Membranes for Fuel Cells: a Critical Review. Energy & Environmental Science. 2012, 5, 8824-47.
4. Lamy, C., Jones, D.J., Coutanceau, C., Brault, P., Martemianov, S. Do Not Forget the Electrochemical Characteristics of the Membrane Electrode Assembly When Designing a Proton Exchange Membrane Fuel Cell Stack. Electrochimica Acta. 2011, 56, 10406-23.

延伸閱讀