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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 鄭淑芬(Soofin Cheng) | |
dc.contributor.author | Ciao-Wei Yang | en |
dc.contributor.author | 楊巧薇 | zh_TW |
dc.date.accessioned | 2021-06-08T03:16:16Z | - |
dc.date.copyright | 2017-02-16 | |
dc.date.issued | 2017 | |
dc.date.submitted | 2017-01-25 | |
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dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/21025 | - |
dc.description.abstract | 本研究合成介孔二氧化矽奈米顆粒分別為SBA-15和MSN,且利用溶劑揮發法將這些奈米顆粒材料混入Nafion®中形成複合膜。我們用粉末X光繞射、氮氣吸脫附、熱重分析、元素分析和掃描式電子顯微鏡鑑定這些材料的物理化學性質,且為了比較奈米顆粒含量、有無孔洞引導試劑和有無磺酸官能基對複合膜的影響,並測量其複合膜的甲醇穿透、質子傳導和電池性能。本研究發現孔洞引導試劑存在於孔洞中會阻擋甲醇穿透到陰極,但是不同的孔洞引導試劑 (P123和CTMABr)對於質子傳導會有不同的效果。至於帶有磺酸官能基的介孔奈米顆粒材料混入Nafion®中,則可以有效的幫助質子傳導。
為了觀察孔洞引導試劑對複合膜的影響,分別合成含有界面活性劑 SBA-15奈米顆粒 (S-SBA-15n) 和萃取過不含界面活性劑的SBA-15奈米顆粒 (Ex-SBA-15n) 兩種,所合成的複合膜命名為x%-S-SBA-15n和x%-Ex-SBA-15n (x%:材料對Nafion®的重量百分比;S:界面活性劑在孔洞中;Ex:界面活性劑被萃取)。此研究觀察到P123的醚官能基可以幫助質子傳導,因此含介面活性劑的S-SBA-15n系列的複合膜擁有較高的質子傳導和較低的甲醇穿透,尤其將其組裝成單電池時,發現5% S-SBA-15n複合膜擁有最高的功率密度大約為117 mW cm-2,比recasting膜高出80%並且比商業用的膜Nafion® 117高出23%。 我們也合成介孔二氧化矽奈米粒子 (MSNs),且將此材料混入Nafion®中形成複合膜,一樣是為了觀察孔洞引導試劑對複合膜的影響,所合成的複合膜命名為x%-S-MSN和x%-Ex-MSN。結果顯示S-MSN複合膜的甲醇穿透會低於Ex-MSN複合膜是由於CTMA+存在於S-MSN的孔洞中,但是CTMA+為四級銨鹽會降低質子傳導率,所以S-MSN系列複合膜比Ex-MSN系列複合膜擁有較低的質子傳導,其中5%-Ex-MSN複合膜擁有較高的功率密度約131 mW cm-2,比recasting膜高出2倍並且比商用Nafion® 117高出36%。 我們將SBA-15n 和MSN所形成的複合膜做比較,我們發現含有介面活性劑存在於孔洞中皆可有效地降低甲醇穿透,其中更發現Ex-MSN擁有最高的質子傳導和功率密度,因Ex-MSN含有較多的矽醇基(silanol group)於材料表面。 將Ex-SBA-15n的樣品官能基化,分別帶有5%和10%的丙基磺酸官能基,並將其混入Nafion®中後,觀察磺酸官能基對複合膜的影響。複合膜含有低負載量的磺酸Ex-SBA-15n可以幫助質子傳導但也增加甲醇穿透,其中5%-Ex-SBA-15n-10% -SO3H擁有最高的功率密度約為133 mW cm-2,比recasting膜約高出2倍並且比商用Nafion® 117高出39%。 也將Ex-MSN的樣品官能基化,分別帶有4%和10%的丙基磺酸官能基,並將其混入Nafion®中後,希望能更有效的提升質子傳導並提升功率密度。但卻無法有效地提質子傳導和功率密度,仍然是5%-Ex-MSN複合膜擁有較高的功率密度約131 mW cm-2。 同時也將S-SBA-15n的樣品官能基化,分別帶有4%和12%的丙基磺酸官能基,並將其混入Nafion®中後,希望能提高質子傳導也同時能降低甲醇穿透。複合膜含有低負載量的磺酸S-SBA-15n可以幫助質子傳導但也降低甲醇穿透,其中1%-Ex-SBA-15n-4%-SO3H擁有最高的功率密度約為120 mW cm-2,比recasting膜約高出1.8倍並且比商用Nafion® 117高出25%。 | zh_TW |
dc.description.abstract | Nanoparticles of mesoporous silica including SBA-15 and MSN were prepared and loaded into Nafion® to form composite membranes by solvent casting method. The physico-chemical properties of these nanoparticles were examined with powder-XRD, N2 sorption, TGA, EA and SEM. The methanol permeability, proton conductivity, and cell performance of the resultant composite membranes were compared in terms of the amount of nanoparticles, whether the pore-directing agents were removed and the influence of extra sulfonic acid groups. The pore-directing agents in the pores of mesoporous silica were found to resist methanol crossover to cathode. However, mesoporous silicas with different kinds of pore-directing agents (P123 and CTMABr) had different influences on proton conductivity.
The SBA-15 nanoparticles containing P123 surfactants (S-SBA-15n) and that extracted with ethanol (Ex-SBA-15n) are used in order to see the effect of pore-directing agent on the performance of resultant composite membranes. The as-prepared membranes were denoted as x%-S-SBA-15n, and x%-Ex-SBA-15n (x%: weight percentage of material relative to NafionⓇ; S: surfactant within mesopores; Ex: surfactant extracted). The ether groups on P123 were found to assist proton transfer. Consequently, higher proton conductivity and lower methanol penetration were obtained on the composite membranes with S-SBA-15n than Ex-SBA-15n. The single cell assembled with 5%-S-SBA-15n composite membrane gave higher power density of 117 mW cm-2 at 60˚C than 5 wt%-Ex-SBA-15n, which was about 80% higher than the cell with recasting membrane and 23% higher than that with Nafion® 117. Mesoporous silica nanoparticles (MSNs) were also prepared and mixed in Nafion® to form composite membranes. The MSNs containing CTMA+ surfactants (S-MSN) and that extracted with ethanol (Ex-MSN) are used in order to also see the effect of pore-directing agent on the performance of resultant composite membranes. The result showed that methanol permeability of S-MSN composite membranes was lower than Ex-MSN, attributing to that the mesopores of S-MSN was filled with CTMA+. However, CTMA+ was a quaternary ammonium salt, which would resist proton transfer. Consequently, lower proton conductivity was obtained for the S-MSN composite membranes than Ex-MSN. The single cell assembled with 5 wt%-Ex-MSN/Nafion composite membrane gave highest power density of 131 mW cm-2 at 60˚C, which was about 2 times higher than the cell with recasting membrane and 36% higher than that with Nafion® 117. The composite membranes of SBA-15n and MSN were compared. Our lab found that both of pore-directing agents in the mesopores (P123 and CTMA+) can effectively improve the methanol permeability and Ex-MSN composite membranes have the highest proton conductivity and power density due to a large amount of silanol group on the surface of Ex-MSN. The S-SBA-15n samples were also functionalized with 4% and 12% propylsulfonic acid groups to form composite membranes in order to examine the influence of sulfonic acid groups. The sulfonic acid groups can assist proton transferring and P123 decrease the methanol permeability at low loading of inorganic fillers. The composite membrane of 1%-S-SBA-15n-4%SO3H had the highest power density of 120 mW cm-2 at 60˚C, which was about 1.8 times higher than the cell with recasting membrane and 25% higher than that with Nafion® 117. The Ex-SBA-15n samples were functionalized with 5% and 10% propylsulfonic acid groups to form composite membranes in order to examine the influence of sulfonic acid groups. The sulfonic acid groups can assist proton transferring but increase the methanol permeability at low loading of inorganic fillers. The composite membrane of 5%-Ex-SBA-15n-10%-MPTMS-SO3H had the highest power density of 133 mW cm-2 at 60˚C, which was about 2 times higher than the cell with recasting membrane and 39% higher than that with Nafion® 117. The Ex-MSN samples were also functionalized with 4% and 10% propylsulfonic acid groups to form composite membranes in order to examine the influence of sulfonic acid groups, expecting that the sulfonic acid groups could assist proton transferring. However, the highest proton conductivities and power density was obtained by 5%-Ex-MSN composite membrane. | en |
dc.description.provenance | Made available in DSpace on 2021-06-08T03:16:16Z (GMT). No. of bitstreams: 1 ntu-106-D00223105-1.pdf: 8104292 bytes, checksum: 982201c93e25b140727ac3b4ad8836e1 (MD5) Previous issue date: 2017 | en |
dc.description.tableofcontents | 謝誌 I
摘要 II Abstract IV Content VII Figure captions XII Scheme index XXIII Table index XXIV Chapter 1 Introduction 1 1.1 Fuel cells 1 1.1.1 The history of fuel cells 1 1.1.2 Fuel cells – basic principles 5 1.1.3 Performance of fuel cells 8 1.1.4 Types of fuel cells 11 1.2 Direct methanol fuel cell (DMFC) 17 1.2.1 Principle of DMFC operation 17 1.2.2 Characteristics of DMFCs 19 1.3 Proton exchange membrane (PEM) 20 1.3.1 Types of Proton Exchange Membranes 21 1.3.2 Composites membranes 28 1.4 Mesoporous materials 29 1.5 Motivation 37 Chapter 2 Experimental 40 2.1 Reagents 40 2.2 Synthesis of fillers and membranes 41 2.2.1 Synthesis of SBA-15 Nanoparticles with/without Surfactants 41 2.2.2 Synthesis of sulfonic acid functionalized SBA-15 Nanoparticles 41 2.2.3 Synthesis of MSN (mesoporous silica nanoparticle) with/without Surfactants 43 2.2.4 Synthesis of sulfonic acid functionalized MSN 43 2.2.5 Preparation of Composite Membranes 44 2.3 Characterization of fillers and membranes 46 2.3.1 Powder X-ray diffraction 46 2.3.2 N2 adsorption-desorption isotherm 47 2.3.3 Scanning electron microscopy (SEM) and elemental mapping 49 2.3.4 Thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA) and Small Angle X-ray Scattering (SAXA) 50 2.3.5 Water uptake 50 2.3.6 Methanol permeability 51 2.3.7 Proton conductivity 52 2.3.8 Single Cell Performance 53 Chapter 3 Effect of different pore-directing agents in SBA-15 nanoparticles or MSN and comparison with SBA-15n and MSN on the performance of NafionⓇ/SBA-15n and NafionⓇ/MSN composite membranes for DMFC 56 3.1 Characterization of SBA-15n and MSN powders 56 3.1.1 XRD of SBA-15n and MSN powders 56 3.1.2 N2 sorption isotherms of SBA-15n and MSN powers 57 3.1.3 SEM and TEM of SBA-15n and MSN powers 59 3.1.4 TGA and DTG of SBA-15n and MSN powers 61 3.1.5 29Si MAS NMR spectra 64 3.2 Characterization of SBA-15n and MSN composite membranes 65 3.2.1 Mapping of SBA-15n and MSN composite membranes 65 3.2.2 Mechanical properties of SBA-15n and MSN composite membranes 71 3.2.3 TGA of SBA-15n and MSN composite membranes 73 3.2.4 SAXS of SBA-15n and MSN composite membranes 75 3.2.5 Methanol permeability of SBA-15n and MSN composite membranes 77 3.2.6 Proton conductivity of SBA-15n and MSN composite membranes 82 3.2.7 Water uptake of SBA-15n and MSN composite membranes 86 3.2.8 Selectivity of SBA-15n and MSN composite membranes 90 3.2.9 Cell performances of SBA-15n and MSN composite membranes 93 3.2.10 Long-term test of SBA-15n and MSN composite membranes 105 3.3 Conclusions 107 Chapter 4 Effect of the amount of sulfonic acid group on the performance of NafionⓇ/Ex-SBA-15n-y%-SO3H and NafionⓇ/Ex-MSN-y%-SO3H composite membranes for DMFC 110 4.1 Characterization of Ex-SBA15n, Ex-SBA-15n-y%-SO3H, Ex-MSN and Ex-MSN-y%-SO3H powders 110 4.1.1 XRD of Ex-SBA-15n, Ex-SBA-15n-y%-SO3H, Ex-MSN and Ex-MSN-y%-SO3H powders 110 4.1.2 N2 sorption isotherms of Ex-SBA-15n, Ex-SBA-15n-5%-SO3H and Ex-SBA-15n-10%-SO3H powders 111 4.1.3 SEM of Ex-SBA-15n, Ex-SBA-15n-5%-SO3H and Ex-SBA-15n-10%-SO3H powders 114 4.1.4 TGA of Ex-SBA-15n, Ex-SBA-15n-5%-SO3H and Ex-SBA-15n-10%-SO3H powders 116 4.2 Characterization of Ex-SBA15n, Ex-SBA-15n-y%-SO3H, Ex-MSN and Ex-MSN-y%-SO3H composite membranes 119 4.2.1 Mapping of Ex-SBA-15n, Ex-SBA-15n-y%-SO3H, Ex-MSN and Ex-MSN-y%-SO3H composite membranes 119 4.2.2 Methanol permeability of Ex-SBA-15n, Ex-SBA-15n-5%-SO3H, Ex-MSN and Ex-SBA-15n-10%-SO3H composite membranes 122 4.2.3 Proton conductivity of Ex-SBA-15n, Ex-SBA-15n-y%-SO3H, Ex-MSN and Ex-MSN-y%-SO3H composite membranes 126 4.2.4 Water uptake of Ex-SBA-15n, Ex-SBA-15n-y%-SO3H, Ex-MSN and Ex-MSN-y%-SO3H composite membranes 130 4.2.5 Selectivity of Ex-SBA-15n, Ex-SBA-15n-y%-SO3H, Ex-MSN and Ex-MSN-y%-SO3H composite membranes 132 4.2.6 Cell performances of Ex-SBA-15n, Ex-SBA-15n-5%-SO3H and Ex-SBA-15n-10%-SO3H composite membranes 134 4.3 Conclusion 145 Chapter 5 Effect of sulfonic acid group amount in S-SBA-15 nanoparticles on the performance of NafionⓇ/S-SBA-15n-y%-SO3H composite membranes for DMFC 148 5.1 Characterization of S-SBA15n, S-SBA-15n-4%-SO3H and S-SBA-15n-12%-SO3H powders 148 5.1.1 XRD of S-SBA-15n, S-SBA-15n-5%-SO3H and S-SBA-15n-12%-SO3H powders 148 5.1.2 N2 sorption isotherms of S-SBA-15n, S-SBA-15n-4%-SO3H and S-SBA-15n-12%-SO3H powders 149 5.1.3 TGA of S-SBA-15n, S-SBA-15n-5%-SO3H and S-SBA-15n-12%-SO3H powders 151 5.2.3 Proton conductivity of S-SBA-15n, S-SBA-15n-4%-SO3H and S-SBA-15n-12%-SO3H composite membranes 157 5.2.4 Water uptake of S-SBA-15n, S-SBA-15n-4%-SO3H and S-SBA-15n-12%-SO3H composite membranes 159 5.2.5 Selectivity of S-SBA-15n, S-SBA-15n-4%-SO3H and S-SBA-15n-12%-SO3H composite membranes 160 5.2.6 Cell performances of S-SBA-15n, S-SBA-15n-4%-SO3H and S-SBA-15n-12%-SO3H composite membranes 162 5.3 Conclusion 168 Chapter 6 References 170 | |
dc.language.iso | en | |
dc.title | Nafion®/介孔二氧化矽複合材料之質子交換膜應用於直接甲醇燃料電池 | zh_TW |
dc.title | Nafion®/Mesoporous Silica Composite Membranes as Proton Exchange Membrane for DMFC | en |
dc.type | Thesis | |
dc.date.schoolyear | 105-1 | |
dc.description.degree | 博士 | |
dc.contributor.oralexamcommittee | 陳貴賢(Kuei-Hsien Chen),陳浩銘(Hao-Ming, Chen),王錫福(Sea-Fue Wang),王承浩(Chen-Hao Wang) | |
dc.subject.keyword | 直接甲醇燃料電池,SBA-15,MSN,Nafion,甲醇穿透,質子傳導,電池特性, | zh_TW |
dc.subject.keyword | DMFC,SBA-15,MSN,NafionR,methanol permeability,proton conductivity,cell performance, | en |
dc.relation.page | 178 | |
dc.identifier.doi | 10.6342/NTU201700272 | |
dc.rights.note | 未授權 | |
dc.date.accepted | 2017-01-26 | |
dc.contributor.author-college | 理學院 | zh_TW |
dc.contributor.author-dept | 化學研究所 | zh_TW |
顯示於系所單位: | 化學系 |
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