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研究生：	沈政勳 Shen, Cheng-Hsun
論文名稱：	用於中高溫型燃料電池的質子交換膜合成與性質之研究 Synthesis and properties of medium to high temperature proton exchange membranes for fuel cell applications
指導教授：	許聯崇 Hsu, Lien-Chung
學位類別：	博士 Doctor
系所名稱：	工學院 - 材料科學及工程學系 Department of Materials Science and Engineering
論文出版年：	2013
畢業學年度：	102
語文別：	英文
論文頁數：	133
中文關鍵詞：	燃料電池、膜材、導電度、交聯、聚苯咪唑、聚亞芳基醚碸、聚亞芳基醚咪唑
外文關鍵詞：	fuel cells, membranes, conductivity, cross-linking, polybenzimidazole, poly(arylene ether sulfone), poly(arylene ether benzimidazole)
相關次數：	點閱：93 下載：1
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首先，在此論文所研究的是，交聯的多孔性聚苯咪唑（PBI）膜的製備，使用混合低分子量的化合物（致孔劑），並且聚合物與交聯劑形成交聯性高分子膜，以提高機械強度和質子傳導性。由SEM圖示可顯示多孔高分子膜的橫截面得到孔的大小和形態。應用交聯劑，對二氯亞甲基苯，可以有效地提高含浸磷酸後的多孔PBI膜的機械性能。 CpPBI-60膜，其含浸磷酸量有9 莫耳，其拉伸模數為0.45 GPa。交聯的多孔性PBI膜具有良好的機械強度，使得它們能夠含浸更多的磷酸，因此，具有較高的質子傳導性。由Fenton’s test可得知，在自由基環境下多孔隙高分子膜的共價鍵交聯結構，使其有氧化穩定性的作用。從交聯性多孔質PBI膜含浸磷酸量顯示，電導率的增加是隨著孔隙率與的含浸磷酸量增加而增加。阻抗分析顯示交聯多孔PBI膜的導電性，在160 ℃無水條件下可以達到2.1 x 10-2 S/cm。
在本論文研究的第二部分，一個新的磺酸化的有機化合物，1H-imidazole-4-sulfonic acid (ImSA)，成功地被合成。一系列的含氟PBI與1H-imidazole-4-sulfonic acid進行混摻，用以改善PBI膜的電導率。加入ImSA可使PBI膜可塑化；斷裂伸長率增加。含浸磷酸的PBI/ImSA膜的導電性隨溫度和ImSA混摻量增加而增加。在160 ℃時含浸磷酸的PBI/ImSA的電導率可以達到7 x 10-2 S/cm。加入ImSA顯著提高了導電性，但它稍微降低PBI膜的機械性質。
第三部分，一個全新且具有苯咪唑側鏈基團的單體成功地合成，並將其應用於親核取代聚合反應合成聚亞芳基醚碸（PAES）和聚亞芳基醚咪唑（PAEB）。 PAES和PAEB在N，N-二甲基乙醯胺（DMAc）濃度為0.5 g/L下進行測量，得到的固有粘度分別為0.56和0.93 dL/g。由FTIR，1H-NMR和元素分析進行此含苯咪唑單體，PAES和PAEB的結構分析。這些聚合物在室溫下，在常用有機溶劑中具有優異的溶解性，諸如DMAc，二甲基亞碸（DMSO），和N-甲基吡咯烷酮（NMP）等。由於PAES和PAEB側鏈的醯胺和咪唑基具有強的分子間氫鍵，故其顯示高Tg，分別可達374和381 ℃。在空氣環境下量測，PAES和PAEB的5％熱失重溫度，分別約為472和522 ℃。PAES和PAEB膜材的含浸磷酸量分別可達5.6和15.3 莫耳。含浸磷酸的膜材質子導電度隨溫度的增加而增加，在160 ℃時可以達到10-3到10-2 S/cm之間。
第四部分，在此研究中合成的PBI共聚物含有羥基官能團。在此研究中，製備一系列交聯性聚苯咪唑薄膜，經由主鏈上的羥基作為交聯連接點。得到的膜材進行氧化穩定性，熱性能，機械性能，和質子導電性的分析。交聯膜材與非交聯膜材相比，有較佳的機械增強和熱性質。此外，膜的熱裂解溫度隨交聯程度的增加而增加。Fenton’s test可作為膜材氧化穩定性的參考，交聯膜材的氧化穩定性有顯著改善。在160 ℃下，含浸磷酸的交聯膜材質子導電性，可以保持在約8 x 10-3 S/cm。

First, cross-linked porous polybenzimidazole (PBI) membranes were prepared by mixing a low-molecular-weight compound (porogen) and a crosslinker with the polymer to form cross-linked polymer membranes in order to increase the mechanical strength and proton conductivity. SEM images of the cross-section of the porous polymer membranes show the pore size and morphology. The cross-linking by p-xylylene dichloride can effectively improve the mechanical properties of the porous PBI membranes after phosphoric acid doping. The CpPBI-60 membrane, which is doped with 9 moles of phosphoric acid has a tensile modulus of 0.45 GPa. The good mechanical strength of the cross-linked porous PBI membranes makes them possible to hold more phosphoric acid, and consequently, higher proton conductivity. Fenton’s test indicated that the covalently cross-linked structure played an important role in the radical oxidative stability of the porous membranes. The doping level of phosphoric acid in the cross-linked porous PBI membranes showed that the enhanced conductivity was due to the increase of porosity, which results in the increase of acid uptake. Impedance analysis showed that the conductivity of the cross-linked porous PBI membranes could reach 2.1 x 10 -2 S/cm at 160 oC under anhydrous condition.
Second, a new sulfonated organic compound, 1H-imidazole-4-sulfonic acid (ImSA), was successfully synthesized. A series of the polybenzimidazole (PBI) /1H-imidazole-4-sulfonic acid hybrid membranes were prepared from an organosoluble, fluorine-containing PBI with ImSA to improve the conductivity of PBI membranes. The introduction of ImSA rendered the plasticizing effect of the PBI membranes with the increase of elongation at break. The conductivity of the phosphoric acid doped PBI/ImSA hybrid membranes increased with both the temperature and the ImSA content. The conductivity of acid doped PBI/ImSA could reach 7 × 10-2 (S/cm) at 160 oC. The addition of ImSA could significantly improve the conductivity, but it slightly reduces the mechanical properties of the pristine PBI membranes.
Third, a new benzimidazole containing monomer has been synthesized for the preparation of poly(arylene ether sulfone) (PAES) and poly(arylene ether benzimidazole) (PAEB) with benzimidazole side groups by nucleophilic substitution polymerization. PAES and PAEB had inherent viscosities of 0.56 and 0.93 dL/g, respectively, measured in N,N-dimethylacetamide (DMAc) at a concentration of 0.5 g/dL. The structures of the benzimidazole containing monomer, PEAS and PAEB were characterized by FTIR, 1H-NMR, and elemental analysis. These polymers showed excellent solubility in common organic solvents, such as DMAc, dimethyl sulfoxide (DMSO), and N-methyl-pyrrolidinone (NMP) at room temperature. Due to the strong intermolecular hydrogen bonding from the amide and imidazole groups in the side chains, the PAES and PAEB had unusually high Tg’s at 374 and 381 oC, correspondingly. The 5% weight loss temperatures of PAES and PAEB were around 472 and 522 oC in air, respectively. The phosphoric acid doping levels of PAES and PAEB membranes were 5.6 and 15.3. The proton conductivity of phosphoric acid doped membranes increased with increasing temperatures, and reached to a range of 10-3 to 10-2 Scm-1 at 160 oC.
Fourth, a polybenzimidazole (PBI) copolymer containing hydroxyl functional groups was synthesized in this study. A series of cross-linked polybenzimidazole membranes have been prepared that is connected by the hydroxyl groups on the main chain. The obtained membranes are investigated in terms of oxidative stability, thermal properties, mechanical properties, and proton conductivity. The mechanical and thermal properties are enhanced in the cross-linked membranes compared to the non-cross-linked membrane. In addition, the thermal degradation temperature of membranes increased with the degree of cross-linking. The Fenton’s test was used as the reference of oxidative stability of the membranes, while the cross-linking led to significant improvement in oxidative stability of the membranes. The proton conductivity of phosphoric acid doped cross-linked membranes could be maintained in about 8 x 10-3 Scm-1 at 160 oC.

Contents
摘要	I
Abstract	III
誌謝	VI
Contents	VII
Table of contents	XI
Figure of contents	XII
CHAPTER 1 INTRODUCTION	1
1-1 Background	1
1-2 Type of fuel cells	3
1-3 Research motivation	6
CHAPTER 2 LITERATURE REVIEW	10
2-1 Proton exchange membrane fuel cells	10
2-2 PEMFC electrocatalysts and catalyst layers	12
2-3 The CO poisoning effect	13
2-4  Introduction of polybenzimidazole	14
2-4-1 Polybenzimidazole	14
2-4-2 Synthesis of PBI	15
2-4-3 Chemical structures of various PBIs	19
2-4-4 PBI applications	20
2-4-5 Mechanisms of proton transport in the fuel cell material	21
2-5 Porous PBI	25
2-6 Cross-linked PBI	28
2-7 Fenton’s test	31
CHAPTER 3 EXPERIMENTAL METHODS	33
3-1 Materials	33
3-2 Experimental instruments	34
3-3 Experimental	36
3-3-1 Synthesis and preparation of polybenzimidazole membranes	36
3-3-1-1 Synthesis of polybenzimidazole	36
3-3-1-2 Preparation of porous polybenzimidazole membranes	37
3-3-1-3 Preparation of cross-linked porous polybenzimidazole membranes	37
3-3-2 Synthesis of ImSA and preparation of hybrid membranes	39
3-3-2-1 Synthesis of 1H-imidazole-4-sulfonic acid (ImSA)	39
3-3-2-2 Preparation of ImSA-PBI hybrid membranes	40
3-3-3 Preparation of monomer and synthesis of poly(arylene ether)s	40
3-3-3-1 Preparation of benzimidazole containing monomer	40
3-3-3-2 Synthesis of 2,2'-bis(4-fluoro-phenyl)-6,6'-bibenzimidazole (BFPB)	42
3-3-3-3 Synthesis of poly(arylene ether sulfone) (PAES)	44
3-3-3-4 Synthesis of poly(arylene ether benzimidazole) (PAEB)	44
3-3-3-5 Preparation of poly(arylene ether)s membranes	45
3-3-4 Polymer synthesis	46
3-3-4-1 Synthesis of PBI30OH copolymer	46
3-3-4-2 Preparation of Cross-linked Polybenzimidazole Membranes	47
3-3-5 Phosphoric acid doping of polymer membranes	49
3-4 Characterization methods	50
3-4-1 Inherent Viscosity	50
3-4-2 Fourier Transfer-Infrared Spectrometry (FTIR)	51
3-4-3 Nuclear Magnetic Resonance (NMR)	51
3-4-4 Thermogravimetric Analysis (TGA)	52
3-4-5 Transmission Electron Microscopy (TEM)	53
3-4-6 Scanning Electron Microscope (SEM)	53
3-4-7 Thermal Mechanical Analysis (TMA)	54
3-4-8 Tensile Properties Analysis	55
3-4-9 Methanol Permeability	56
3-4-10 AC impedance	57
3-4-11 Proton conductivity	59
CHAPTER 4 RESULTS AND DISCUSSION	61
4-1 Cross-linked porous polybenzimidazole membranes	61
4-1-1 Preparation of porous PBI and cross-linked porous membranes	61
4-1-2 Morphology of porous PBI membranes	62
4-1-3 Characterization of cross-linked PBI membranes	64
4-1-4 Mechanical properties of porous and cross-linked porous PBI membranes	65
4-1-5 Chemical stability	68
4-1-6 Proton conductivity	70
4-2 Polybenzimidazole/1H-imidazole-4-sulfonic acid hybrid membranes	74
4-2-1 Synthesis of 1H-imidazole-4-sulfonic acid (ImSA)	74
4-2-2 Characterization of ImSA-PBI hybrid membranes	74
4-2-3 Thermal properties of ImSA-PBI hybrid membranes	77
4-2-4 Mechanical properties of ImSA-PBI hybrid membranes	79
4-2-5 Methanol permeability of ImSA-PBI hybrid membranes	79
4-2-6 Proton conductivity of ImSA-PBI hybrid membranes	81
4-3 Membranes base on poly(arylene ether)s with benzimidazole side groups……………………………………………………………………..84
4-3-1 Polymer Synthesis and Membrane Fabrication	84
4-3-2 Thermal and Mechanical Properties of PAES and PAEB	90
4-3-3 Proton Conductivity of PAES and PAEB Membranes	92
4-4 Novel cross-linked polybenzimidazole membranes	94
4-4-1 Synthesis and characterization of PBI30OH-X-di and PBI30OH-X-si	94
4-4-2 Thermal properties	97
4-4-3 Mechanical properties	101
4-4-4 Chemical stability	104
4-4-5 Proton Conductivity	105
CHAPTER 5 CONCLUSIONS	108
REFERENCES	111
                                    

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