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研究生:鄭承瑋
研究生(外文):Cheng-WeiCheng
論文名稱:新支鏈型聚苯咪唑及其矽氧烷交聯複合薄膜於鹼性陰離子交換膜燃料電池之研究
論文名稱(外文):Novel Side-Chain-Type Polybenzimidazole and Siloxane Cross-linked Membranes for Anion Exchange Membrane Fuel Cells
指導教授:許聯崇
指導教授(外文):Lien-Chung Hsu
學位類別:碩士
校院名稱:國立成功大學
系所名稱:材料科學及工程學系
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2020
畢業學年度:108
語文別:中文
論文頁數:90
中文關鍵詞:支鏈型聚苯咪唑陰離子交換膜燃料電池有機無機複合薄膜高分子固態電解質塔弗測試
外文關鍵詞:side-chain type polybenzimidazoleanion exchange membrane fuel cellorganic-inorganic hybrid membranepolymer electrolyte membraneTafel test
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本研究利用3,3-Diaminobenzidine和2,2-Bis(4-carboxyphenyl)-hexafluoropropane為單體成功合成含氟聚苯咪唑(6F-PBI),並使用1,6-Dibromohexane和1,2-Dimethylimidazole成功合成離子液體3-(6-Bromohexyl)-1,2-dimethylimidazolium作為陽離子官能基支鏈,接於6F-PBI主鏈高分子上,製成6FPBI-BrIm1,2薄膜;另添加10 %的(3-Chloropropyl)triethoxysilane作為可交聯位置,並以(3-Chloropropyl)trimethoxysilane、1,2-Dimethylimidazole合成出的離子液體1-methyl-3-[3-(trimethoxy-λ4-silyl)propyl]imidazolium chloride (MTMSPI)作為交聯劑製成出6F-PBI-10S-BrIm1,2交聯薄膜。
6FPBI-BrIm1,2和6FPBI-10S-BrIm1,2薄膜在60 ℃ 時分別具有0.0318、0.0132 S/cm的離子傳導度,皆達到目前陰離子交換膜燃料電池所需的標準(〉10-2 S/cm),最高的離子傳導度出現在6FPBI-BrIm1,2於80 ℃ 下,可達0.0502 S/cm。單電池測試的部分,開路電壓皆穩定且在0.95 V以上,說明其可有效防止氣體穿越,6FPBI-BrIm1,2薄膜於50 ℃下,電流密度90 mA/cm2時有最高功率22 mW/cm2
In this study, fluorine-containing polybenzimidazole (6F-PBI) was successfully synthesized. A 6FPBI-BrIm1,2 polymer was synthesized by adding 3-(6-Bromohexyl)-1,2-dimethylimidazolium (Br-6-Im1,2) ionic liquid as a pendant side chain. 6FPBI-10S-BrIm1,2 copolymer was synthesized by adding 10% (3-Chloropropyl)triethoxysilane and 90% Br-6-Im1,2. A cross-linked membrane was prepared using a 6FPBI-10S-BrIm1,2 copolymer with ionic liquid 1-methyl-3-[3-(trimethoxy-λ4-silyl)propyl]imidazolium chloride as the cross-linker, which exhibited improved dimensional stability, mechanical properties, and oxidative stability. The 6FPBI-BrIm1,2 and 6FPBI-10S-BrIm1,2 membranes showed hydroxide conductivities of 0.0318 and 0.0132 S/cm at 60 ℃ respectively. Both reached the hydroxide conductivity criteria established in recent research (〉10-2 S/cm). The highest hydroxide conductivity was 0.0502 S/cm by 6FPBI-BrIm1,2 membrane at 80 ℃ . In the single cell test, we used a 4 cm2 commercial gas diffusion electrode (FuMA-Tech) with a Pt loading of 1 mg/cm2 and then compared the cell performance with the 6FPBI-BrIm1,2 and commercial (FAA-30-5) membranes. Both of them exhibited open circuit voltages of over 0.95V. In the case of the 6FPBI-BrIm1,2 MEA, the power density reached 22 mW/cm2 at 50 ℃ , which was higher than that of the commercial MEA under the same testing conditions.
摘要 I
Extended Abstract II
誌謝 IX
總目錄 XI
表目錄 XV
圖目錄 XVI
第一章 緒論 1
1.1 前言 1
1.2 研究背景 5
1.3 研究動機與目的 7
第二章 文獻回顧與原理 10
2.1 陰離子交換膜燃料電池簡介 10
2.2 陰離子交換膜燃料電池原理 14
2.3 氫氧根離子傳導原理 17
2.4 陰離子交換膜性質提升 20
2.5 有機/無機奈米複合材料 22
2.5.1 有機/無機奈米複合材料之簡介 22
2.5.2 溶膠-凝膠法簡介 (Sol-gel method) 22
2.6 單電池測試與膜電極組衰退機制 24
第三章 實驗方法與步驟 28
3.1 實驗材料 28
3.2 實驗儀器 29
3.3 實驗步驟 29
3.3.1 Polybenzimidazole (6F-PBI)合成 29
3.3.2 離子液體(Ionic liquids)之合成 30
3.3.3 支鏈型6FPBI-BrIm1,2/6FPBI-10S-BrIm1,2之合成 31
3.3.4 6FPBI-10S-BrIm1,2交聯膜製備 37
3.4 結構鑑定 37
3.4.1 傅立葉傳換紅外線光譜分析 (FT-IR) 37
3.4.2 核磁共振光譜分析 (1H-NMR) 38
3.5 薄膜性質分析 39
3.5.1 固有黏度量測 (Inherent viscosity) 39
3.5.2 離子交換容量 (Ionic exchange capacity) 39
3.5.3 吸水性(Water uptake)、尺寸安定性(Swelling ratio)和水合數(Hydrated number, λ) 40
3.5.4 熱重損失分析儀 (TGA) 41
3.5.5 薄膜鹼安定性分析 (Alkaline stability) 41
3.5.6 原子力顯微鏡(Atomic Force Microscope, AFM) 42
3.5.7 機械性質分析 (Mechanical properties) 42
3.5.8 抗氧化能力分析 (Oxidative stability test) 42
3.6 氫氧根離子導電度量測 (Hydroxide conductivity) 43
3.7 膜電極製備 (Membrane electrode assembly, MEA) 48
3.8 單電池測試 48
3.8.1 單電池組裝 48
3.8.2 單電池效能測試 50
第四章 結果與討論 51
4.1 合成結構鑑定分析 51
4.1.1 6F-PBI合成 51
4.1.2 6F-PBI固有黏度量測 52
4.1.3 6FPBI-BrIm1,2/6FPBI-10S-BrIm1,2薄膜製備 52
4.1.4 核磁共振光譜分析 (NMR) 56
4.1.5 傅立葉轉換紅外線光譜分析 (FT-IR) 61
4.2 6FPBI-BrIm1,2/6FPBI-10S-BrIm1,2薄膜性質分析 63
4.2.1 離子交換容量、吸水性與尺寸安定性分析 63
4.2.2 熱性質分析 (TGA) 65
4.2.3 氫氧根離子傳導度分析 (Hydroxide conductivity) 67
4.2.4 鹼安定性測試 (Alkaline stability) 69
4.2.5 薄膜表面型態量測 (Membrane morphology) 70
4.2.6 薄膜機械性質分析 (Mechanical properties) 71
4.2.7 抗氧化能力分析 (Oxidative stability test) 73
4.3 陰離子交換膜單電池測試 75
第五章 結論與未來展望 78
第六章 參考資料 80
[1]“BP Statistical Review of World Energy (2019)
[2]Bossel, Ulf, Christian Friedrich Schönbein, and William Robert Grove. The Birth of the Fuel Cell. European Fuel Cell Forum, Oberrohrdorf, (2000).
[3]Grove, William Robert. XXIV. On voltaic series and the combination of gases by platinum. The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science 14.86-87 (1839): 127-130.
[4]Wikipedia, The illustration was reproduced by author from Sir William R. Grove's original work.
[5]Renewable energy systems, Fuel Cell Today (2012).
[6]U. S. DOE, Fuel Cell Factsheet (2010).
[7]Fuel Cell Today, http://www.fuelcelltoday.com/about-fuel-cells/case-studies/renewable-energy-systems
[8]Kordesch, Karl, and Günter Simader. Fuel cells and their applications. Vol. 117. Weinheim: VCh, (1996).
[9]https://www.fuelcellstore.com/
[10]https://www.monex.com/
[11]Pollet, Bruno G., Iain Staffell, and Jin Lei Shang. Current status of hybrid, battery and fuel cell electric vehicles: From electrochemistry to market prospects. Electrochimica Acta 84 (2012): 235-249.
[12]http://www.fuelcelltoday.com/
[13]Gülzow, Erich. Alkaline fuel cells: a critical view. Journal of Power Sources 61.1-2 (1996): 99-104.
[14]Modestov, A. D., et al. MEA for alkaline direct ethanol fuel cell with alkali doped PBI membrane and non-platinum electrodes. Journal of Power Sources 188.2 (2009): 502-506.
[15]Asazawa, Koichiro, et al. A platinum‐free zero‐carbon‐emission easy fuelling direct hydrazine fuel cell for vehicles. Angewandte Chemie International Edition 46.42 (2007): 8024-8027.
[16]Schulze, Mathias, and Erich Gülzow. Degradation of nickel anodes in alkaline fuel cells. Journal of Power Sources 127.1-2 (2004): 252-263.
[17]McLean, G. F., et al. An assessment of alkaline fuel cell technology. International Journal of Hydrogen Energy 27.5 (2002): 507-526.
[18]Agel, E., J. Bouet, and J. F. Fauvarque. Characterization and use of anionic membranes for alkaline fuel cells. Journal of Power Sources 101.2 (2001): 267-274.
[19]Danks, Timothy N., Robert CT Slade, and John R. Varcoe. Comparison of PVDF-and FEP-based radiation-grafted alkaline anion-exchange membranes for use in low temperature portable DMFCs. Journal of Materials Chemistry 12.12 (2002): 3371-3373.
[20]Sakamoto, Tomokazu, et al. Study of Pt-free anode catalysts for anion exchange membrane fuel cells. Catalysis today 164.1 (2011): 181-185.
[21]Filpi, Antonio, Massimiliano Boccia, and H. A. Gasteiger. Pt-free cathode catalyst performance in H2/O2 anion-exchange membrane fuel cells (AMFCs). ECS Transactions 16.2 (2008): 1835.
[22]Shao, Zhi-Gang, et al. Hybrid Nafion–inorganic oxides membrane doped with heteropolyacids for high temperature operation of proton exchange membrane fuel cell. Solid state ionics 177.7-8 (2006): 779-785.
[23]Devrim, Yılser, Hüseyin Devrim, and Inci Eroglu. Polybenzimidazole/SiO2 hybrid membranes for high temperature proton exchange membrane fuel cells. international journal of hydrogen energy 41.23 (2016): 10044-10052.
[24]Qu, Chao, et al. A high-performance anion exchange membrane based on bi-guanidinium bridged polysilsesquioxane for alkaline fuel cell application. Journal of Materials Chemistry 22.17 (2012): 8203-8207.
[25]Li, Xiaoliang, et al. Improved conductivity and stability of anion exchange membrane modified with bi-phenylguanidinium bridged silsesquioxane. International Journal of Hydrogen Energy 42.33 (2017): 21016-21026.
[26]Varcoe, John R., et al. Anion-exchange membranes in electrochemical energy systems. Energy & environmental science 7.10 (2014): 3135-3191.
[27]Varcoe, John R. Investigations of the ex situ ionic conductivities at 30 C of metal-cation-free quaternary ammonium alkaline anion-exchange membranes in static atmospheres of different relative humidities. Physical Chemistry Chemical Physics 9.12 (2007): 1479-1486.
[28]Fuel Cell Technology Handbook, CRC Press LLC, 2003.
[29]蔡正修、黃秋萍、黃筱君,工業材料雜誌,377期,p.33, 2018/05
[30]Hickner, Michael A. Strategies for developing new anion exchange membranes and electrode ionomers. The Electrochemical Society Interface 26.1 (2017): 69-73.
[31]Subianto, Surya. Recent advances in polybenzimidazole/phosphoric acid membranes for high‐temperature fuel cells. Polymer International 63.7 (2014): 1134-1144.
[32]Mustain, William E. Understanding how high-performance anion exchange membrane fuel cells were achieved: Component, interfacial, and cell-level factors. Current Opinion in Electrochemistry 12 (2018): 233-239.
[33]Wainright, J. S., et al. Acid‐doped polybenzimidazoles: a new polymer electrolyte. Journal of the Electrochemical Society 142.7 (1995): L121-L123.
[34]Henkensmeier, Dirk, et al. Polybenzimidazolium‐Based Solid Electrolytes. Macromolecular Materials and Engineering 296.10 (2011): 899-908.
[35]Hou, Hongying, et al. Synthesis and characterization of a new anion exchange membrane by a green and facile route. International Journal of Hydrogen Energy 36.18 (2011): 11955-11960.
[36]Ataollahi, Narges. Anion Exchange Membranes (AEMs), based on Polyamine Obtained by Modifying Polyketone, for Electrochemical Applications. Diss. University of Trento, 2018.
[37]Merle, Géraldine, Matthias Wessling, and Kitty Nijmeijer. Anion exchange membranes for alkaline fuel cells: A review. Journal of Membrane Science 377.1-2 (2011): 1-35.
[38]Takaba, Hiromitsu, et al. Molecular modeling of OH− transport in poly (arylene ether sulfone ketone) s containing quaternized ammonio-substituted fluorenyl groups as anion exchange membranes. Journal of Membrane Science 522 (2017): 237-244.
[39]Zawodzinski, TA, Membranes Performance and Evaluation, NSF Workshop on Engineering Fundamentals of Low Temperature PEM Fuel Cells (Arlington, VA, November 2001)
[40]Chen, Chen, et al. Hydroxide solvation and transport in anion exchange membranes. Journal of the American Chemical Society 138.3 (2016): 991-1000.
[41]Vijayakumar, Vijayalekshmi, and Sang Yong Nam. Recent advancements in applications of alkaline anion exchange membranes for polymer electrolyte fuel cells. Journal of Industrial and Engineering Chemistry 70 (2019): 70-86.
[42]Lin, Chen Xiao, et al. Side-chain-type anion exchange membranes bearing pendant quaternary ammonium groups via flexible spacers for fuel cells. Journal of Materials Chemistry A 4.36 (2016): 13938-13948.
[43]Gong, Xue, et al. Design of pendent imidazolium side chain with flexible ether-containing spacer for alkaline anion exchange membrane. Journal of Membrane Science 523 (2017): 216-224.
[44]Kimura, Takeshi, and Yohtaro Yamazaki. Effects of CO2 concentration and electric current on the ionic conductivity of anion exchange membranes for fuel cells. Electrochemistry 79.2 (2011): 94-97.
[45]Varcoe, John R., et al. Anion-exchange membranes in electrochemical energy systems. Energy & environmental science 7.10 (2014): 3135-3191.
[46]Cheng, Jie, Gaohong He, and Fengxiang Zhang. A mini-review on anion exchange membranes for fuel cell applications: stability issue and addressing strategies. International Journal of Hydrogen Energy 40.23 (2015): 7348-7360.
[47]Shen, Cheng-Hsun, and Steve Lien-chung Hsu. Synthesis of novel cross-linked polybenzimidazole membranes for high temperature proton exchange membrane fuel cells. Journal of membrane science 443 (2013): 138-143.
[48]Lin, Chen Xiao, et al. Crosslinked side-chain-type anion exchange membranes with enhanced conductivity and dimensional stability. Journal of membrane science 539 (2017): 24-33.
[49]蔡中燕,化工資訊,1998,p.28.
[50]Messersmith, Phillip B., and Emmanuel P. Giannelis. Synthesis and barrier properties of poly (ε‐caprolactone)‐layered silicate nanocomposites. Journal of Polymer Science Part A: Polymer Chemistry 33.7 (1995): 1047-1057.
[51]Burnside, Shelly D., and Emmanuel P. Giannelis. Synthesis and properties of new poly (dimethylsiloxane) nanocomposites. Chemistry of materials 7.9 (1995): 1597-1600.
[52]Ishida, Hatsuo, Sandi Campbell, and John Blackwell. General approach to nanocomposite preparation. Chemistry of Materials 12.5 (2000): 1260-1267.
[53]B. Pivovar, Alkaline membrane fuel cell workshop final report, in: Proceedings from the Alkaline Membrane Fuel Cell Workshop, Arlington, Virginia, May 8-9, 2011.
[54]Zhou, Tianchi, et al. A review of radiation-grafted polymer electrolyte membranes for alkaline polymer electrolyte membrane fuel cells. Journal of Power Sources 293 (2015): 946-975.
[55]Inaba, Minoru. Durability of electrocatalysts in polymer electrolyte fuel cells. ECS Transactions 25.1 (2009): 573-581.
[56]Zhang, Xiaojuan, et al. Olefin metathesis-crosslinked, bulky imidazolium-based anion exchange membranes with excellent base stability and mechanical properties. Journal of Membrane Science (2019): 117793.
[57]Zhang, Xiaojuan, et al. Enhancement of the mechanical properties of anion exchange membranes with bulky imidazolium by “thiol-ene crosslinking. Journal of Membrane Science (2019): 117700.
[58]Gottesfeld, Shimshon, et al. Anion exchange membrane fuel cells: Current status and remaining challenges. Journal of Power Sources 375 (2018): 170-184.
[59]Kwon, Sohyun, Anil HN Rao, and Tae-Hyun Kim. Anion exchange membranes based on terminally crosslinked methyl morpholinium-functionalized poly (arylene ether sulfone) s. Journal of Power Sources 375 (2018): 421-432.
[60]Thomas, Owen D., et al. A stable hydroxide-conducting polymer. Journal of the American Chemical Society 134.26 (2012): 10753-10756.
[61]Liu, Fang Hua, et al. Anion exchange membranes with well-developed conductive channels: Effect of the functional groups. Journal of membrane science 564 (2018): 298-307.
[62]Chuang, Shih‐Wei, and Steve Lien‐Chung Hsu. Synthesis and properties of a new fluorine‐containing polybenzimidazole for high‐temperature fuel‐cell applications. Journal of Polymer Science Part A: Polymer Chemistry 44.15 (2006): 4508-4513.
[63]Qian, Guoqing, and Brian C. Benicewicz. Synthesis and characterization of high molecular weight hexafluoroisopropylidene‐containing polybenzimidazole for high‐temperature polymer electrolyte membrane fuel cells. Journal of Polymer Science Part A: Polymer Chemistry 47.16 (2009): 4064-4073.
[64]He, Ronghuan, et al. Physicochemical properties of phosphoric acid doped polybenzimidazole membranes for fuel cells. Journal of Membrane Science 277.1-2 (2006): 38-45.
[65]Jheng, Li-cheng, et al. Quaternized polybenzimidazoles with imidazolium cation moieties for anion exchange membrane fuel cells. Journal of membrane science 460 (2014): 160-170.
[66]Xiong, Ying, et al. Synthesis and characterization of cross-linked quaternized poly (vinyl alcohol)/chitosan composite anion exchange membranes for fuel cells. Journal of Power Sources 183.2 (2008): 447-453.
[67]Wu, Yonghui, et al. Novel silica/poly (2, 6-dimethyl-1, 4-phenylene oxide) hybrid anion-exchange membranes for alkaline fuel cells: effect of silica content and the single cell performance. Journal of Power Sources 195.10 (2010): 3069-3076.
[68]Chen, Jiqin, et al. Novel imidazole‐grafted hybrid anion exchange membranes based on poly (2, 6‐dimethyl‐1, 4‐phenylene oxide) for fuel cell applications. Journal of Applied Polymer Science 135.12 (2018): 46034.
[69]Li, Xiuhua, et al. Quaternized poly (arylene ether) ionomers containing triphenyl methane groups for alkaline anion exchange membranes. Journal of Materials Chemistry A 1.13 (2013): 4324-4335.
[70]Gong, Shoutao, et al. Blend anion exchange membranes containing polymer of intrinsic microporosity for fuel cell application. Journal of Membrane Science 595 (2020): 117541.
[71]Sheng, Weibing, et al. Quaternized poly (2, 6-dimethyl-1, 4-phenylene oxide) anion exchange membranes with pendant sterically-protected imidazoliums for alkaline fuel cells. Journal of Membrane Science 601 (2020): 117881.
[72]Wang, Yang, et al. Improving fuel cell performance of an anion exchange membrane by terminal pending bis-cations on a flexible side chain. Journal of Membrane Science 595 (2020): 117483.
[73]Wei, Haibing, et al. Side-chain-type imidazolium-functionalized anion exchange membranes: The effects of additional hydrophobic side chains and their hydrophobicity. Journal of membrane science 579 (2019): 219-229.
[74]Liu, Fuqiang, et al. Nafion/PTFE composite membranes for fuel cell applications. Journal of Membrane Science 212.1-2 (2003): 213-223.
[75]Gaudiana, Russell A., and Robert T. Conley. Weak‐link versus active carbon degradation routes in the oxidation of aromatic heterocyclic systems. Journal of Polymer Science Part B: Polymer Letters 7.11 (1969): 793-801.
[76]Hübner, Gerold, and Emil Roduner. EPR investigation of HO/radical initiated degradation reactions of sulfonated aromatics as model compounds for fuel cell proton conducting membranes. Journal of Materials Chemistry 9.2 (1999): 409-418.
[77]Inaba, Minoru, et al. Effect of agglomeration of Pt/C catalyst on hydrogen peroxide formation. Electrochemical and solid-state letters 7.12 (2004): A474-A476.
[78]Kinumoto, Taro, et al. Durability of perfluorinated ionomer membrane against hydrogen peroxide. Journal of power Sources 158.2 (2006): 1222-1228.
[79]Hu, Bo, et al. Azide-assisted crosslinked quaternized polysulfone with reduced graphene oxide for highly stable anion exchange membranes. Journal of Membrane Science 530 (2017): 84-94.
[80]Liu, Lei, et al. Quaternized poly (2, 6-dimethyl-1, 4-phenylene oxide) anion exchange membranes based on isomeric benzyltrimethylammonium cations for alkaline fuel cells. Journal of Membrane Science (2020): 118133.
[81]Yang, Kuan, et al. The effect of polymer backbones and cation functional groups on properties of anion exchange membranes for fuel cells. Journal of Membrane Science (2020): 118025.
[82]Omasta, T. J., et al. Importance of balancing membrane and electrode water in anion exchange membrane fuel cells. Journal of Power Sources 375 (2018): 205-213.
[83]Carmo, Marcelo, et al. Development and electrochemical studies of membrane electrode assemblies for polymer electrolyte alkaline fuel cells using FAA membrane and ionomer. Journal of power sources 230 (2013): 169-175.
[84]Woo, Seunghee, et al. Current understanding of catalyst/ionomer interfacial structure and phenomena affecting the oxygen reduction reaction in cathode catalyst layers of proton exchange membrane fuel cells. Current Opinion in Electrochemistry (2020).
[85]Carlson, Annika, et al. Electrode parameters and operating conditions influencing the performance of anion exchange membrane fuel cells. Electrochimica Acta 277 (2018): 151-160.
[86]Wright, Andrew G., et al. Hexamethyl-p-terphenyl poly (benzimidazolium): a universal hydroxide-conducting polymer for energy conversion devices. Energy & Environmental Science 9.6 (2016): 2130-2142.
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