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研究生：	席妮瑪 Ni’mah, Hikmatun
論文名稱：	燃料電池用之磺酸化磷酸鋯/全氟磺酸高分子複合膜之合成與鑑定 Synthesis and Characterization of Sulfonated Zirconium-Phosphate/Perfluorosulfonated Composite Membrane for Fuel Cell Applications
指導教授：	郭炳林 Kuo, Ping-Lin
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2009
畢業學年度：	97
語文別：	英文
論文頁數：	77
外文關鍵詞：	zirconium-phosphate nanoplates, Nafion, polysiloxanes, fuel cells, composite membrane, sol-gel process
相關次數：	點閱：73 下載：0
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A new class of nanocomposite membrane has been developed by incorporating cross-linked polysiloxane-bearing zirconium-phosphate nanoplates into Nafion matrix via sol-gel process followed by solution casting and sulfonating. The chemical structures of the composite membranes were confirmed by FT-IR, 31P-MAS NMR, and XPS spectra. SEM characterization was used to observe the morphology of the composite membranes. All the composite membranes were characterized in terms of IEC, water uptake, methanol permeability, proton conductivity, state of water, and oxidative stability. Best results were obtained on the C composite membrane recast from polysiloxane-zirconium phosphate/Nafion (20wt % solid content) with a polysiloxane: zirconium phosphate molar ratio of 1:1. The methanol permeability of the C composite membranes is 5.5x10-7 cm2s-1 at 30oC. Its proton conductivity is 0.050 S/cm at 30oC, 0.164 S/cm at 95oC, in 95%RH, and 1.1×10-2 S/cm at 80oC in 30%RH which outperformed the pure Nafion 117 membrane, whose conductivity is 0.026 S/cm at 30oC, 0.071 S/cm at 95oC, in 95%RH, and 5.1×10-3 S/cm at 80oC in 30%RH, under the same condition. The C composite membrane also shows acceptable oxidative stability in Fenton’s reagent at 80oC for 1 h which retains 98.81% of its original weight after testing and only declines of 11% after testing for 125 hours. The PEM fuel cells assembled with C composite membrane shows good performance at 100oC of 499.9mW/cm2. This work demonstrates the promising potential of the modified polysiloxane-zirconium phosphate/Nafion composite membranes for the development of high-performance and high-stability PEM fuel cells at high temperatures.

CONTENTS

ABSTRACT………………………………………………………………………………...i
ACKNOWLEDGEMENT………………………………………………………………...ii
LIST OF TABLES………………………………………………………………………...iv
LIST OF FIGURES………………………………………………………………………..v

CHAPTER I  INTRODUCTION…………………………………………………………1
1 Background of Fuel Cell Development…………………………………………1
2 Polymer Electrolyte Membrane Fuel Cell………………………………………2
3 Proton Exchange Membranes…………………………………………………...4
4 Composite Proton Exchange Membranes………………………………………8
5 Research Motivation…………………………………………………………….9
CHAPTER II  THEOREMS…………………………………………………………….11
1 Basic Principle of Fuel Cell……………………………………………………11
2 Proton Exchange Membrane Fuel Cell (PEMFC)……………………………..15
3 Direct Methanol Fuel Cell……………………………………………………..17
4 Parameters of Proton Exchange Membranes…………………………………..18
5 Water Management in the Membrane…………………………………………21
6 Morphology and transport properties of PEM…………………………………23
7 Development of polymer electrolyte membrane………………………………26
7.1 Modification of PFSA membrane with hygroscopic oxide……………...29
7.2 Modification of PFSA membrane with solid conductor inorganic……...30
8 Sol-Gel Reaction Mechanism………………………………………………….32
9 Alternating Current Measurement……………………………………………..34
CHAPTER III  EXPERIMENTAL SECTION………………………………………...36
1 Materials……………………………………………………………………….36
2 Sample Preparation…………………………………………………………….36
2.1 Preparation of α–Zirconium Phosphate (α-ZrP)…………………………36
2.2 Preparation of Sulfonated α-ZrP nanoplates/Nafion membranes………..36
3 Characterizations………………………………………………………………37
3.1 X-Ray Diffraction………………………………………………………..37
3.2 Scanning Electron Microscopy (SEM)…………………………………..38 
3.3 Transmission Electron Microscopy (TEM)……………………………...38
3.4 ATR-FTIR spectroscopy………………………………………………...38
3.5 State of Water……………………………………………………………38
3.6 Proton Conductivity Measurements……………………………………..39
3.7 Solid-state NMR…………………………………………………………39
3.8 Water Uptake Calculation……………………………………………….40
3.9 Ion Exchange Capacity…………………………………………………..40
3.10 X-ray Photoelectron Spectroscopy……………………………………..40
3.11 Methanol Permeability…………………………………………………40
3.12 Oxidative stability……………………………………………………...41
3.13 Preparation of Membrane Electrode Assembly (MEA)………………..41
CHAPTER IV  RESULT AND DISCUSSION…………………………………………43
1 Synthesis of α-Zirconium Phosphate (α-ZrP) Nanoplates……………………..43
1.1 XRD Characterization…………………………………………………...44
1.2 Morphology of α-ZrP……………………………………………………44
2 Preparation of sulfonated α-ZrP nanoplates/ Nafion composite membrane…...47
3 Ion Exchange Capacity………………………………………………………...50
4 Microscopic Characterization………………………………………………….51
5 FT-IR Analysis of Interaction between Polysiloxane, α-ZrP and Nafion..........53
6 31P-MAS NMR………………………………………………………………...56
7 XPS Analysis…………………………………………………………………..58
8 Water Uptake Measurement…………………………………………………...60
9 DSC (State of Water)…………………………………………………………..61
10 Methanol Permeability……………………………………………………….63
11 Proton Conductivity Measurement…………………………………………...64
12 Oxidative Stability……………………………………………………………67
13 PEMFC Test………………………………………………………………….69
CHAPTER V  CONCLUSION…………………………………………………………..72
REFERENCES…………………………………………………………………………...73
CURRICULUM VITAE…………………………………………………………………78
                                    

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