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研究生： 謝宜
Hsieh, Yi-Yun
論文名稱： 以快速加熱法合成含氮拆層石墨及其應用在質子交換膜燃料電池之陰極觸媒特性
Rapid Thermal Synthesis of N-doped Exfoliated Graphite and the Properties for Its Application on the Cathodic Catalyst in Proton Exchange Membrane Fuel Cell
指導教授： 楊明長
Yang, Ming-Chang
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： 2014
畢業學年度： 102
語文別： 中文
論文頁數： 184
中文關鍵詞： 快速加熱法 、含氮拆層石墨 、陰極觸媒 、質子交換膜燃料電池
外文關鍵詞： Rapid thermal synthesis, Nitrogen-doped exfoliated graphite, Cathodic catalyst, Proton exchange membrane fuel cell
相關次數： 點閱：86  下載：1 
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    • 本研究以拆層石墨作為觸媒擔體，透過氮原子摻入法，增加拆層石墨表面活性座數量，減小白金粒徑，提升白金分散性，並增強白金顆粒的比活性，以獲得質子交換膜燃料電池高活性的氧氣還原觸媒。 本研究將PVP與氧化石墨烯混摻後，使用快速加熱法合成含氮拆層石墨，作為擔體擔載白金，探討裂解時間、裂解溫度，和PVP與氧化石墨烯混摻比等條件對觸媒特性之影響。將最佳條件之含氮拆層石墨，與毛球狀碳材混摻後擔載白金，探討混摻重量比對觸媒活性及質子交換膜燃料電池效能影響。
    實驗結果顯示，在PVP與氧化石墨烯混摻重量比為2：1，裂解溫度1000oC，裂解時間20分鐘的含氮拆層石墨有最小D/G值1.58；含氮拆層石墨擔體觸媒比未含氮的拆層石墨觸媒，具有較佳白金分散性、較小白金粒徑及較佳的觸媒活性；裂解溫度1000oC，裂解時間1分鐘合成含氮拆層石墨擔體，擔載白金觸媒後層間距相較於未摻雜的石墨烯(0.345 nm)可達0.368 nm。
    裂解溫度為900oC，裂解時間為5分鐘，合成含氮拆層石墨擔體之白金觸媒，有最大質量活性，其0.65、0.7及0.75 V (vs. Ag/AgCl)下的質量活性，分別為0.82、2.34及5.75 A/g Pt；而氮摻雜的鍵結型態pyridinic-N、pyrrolic-N、quaternary-N及pyridinic-N-O含量總和與質量活性呈現中度正相關。將此最佳合成條件含氮拆層石墨與毛球狀碳材混摻並擔載白金。半電池測試結果顯示，混摻重量比1：1所得的觸媒有最大電化學活性面積209.7 C/g Pt，最正的起始電位0.789 V (vs. Ag/AgCl)，及在0.65 V (vs. Ag/AgCl)下有最大質量活性9.66 A/g Pt，為商用觸媒Johnson Matthey 1.44倍。單電池測試結果，混摻重量比1：1的觸媒有最小電荷轉移電阻、最小陰極阻抗及最大之最大放電功率，最大放電功率為商用觸媒的1.19倍。

    Exfoliated graphite was used as the carbon support in this study. Nitrogen-doping was applied to increase active sites, decrease Pt particle size, facilitate Pt dispersion, and enhance the specific activity of the active site, thereby high catalytic activity of oxygen reduction was obtained for proton exchange membrane fuel cells (PEMFC).
    Nitrogen-doped exfoliated graphite was synthesized by rapid thermal method of polyvinylpyrrolidone (PVP)-graphite oxide (GO) blend and used as a catalyst support. The effects of pyrolysis time, pyrolysis temperature, and the weight ratio of PVP to GO on the catalyst properties and electrochemical activity were explored. Nitrogen-doped exfoliated graphite fabricated in the optimum condition was then blended with fluffy-like carbon. The effects of the fluffy-like carbon content on the catalyst activity and the performance of PEMFC were investigated.
    The experimental results show that the smallest D/G (1.58) was obtained for the nitrogen-doped exfoliated graphite which was synthesized with PVP/graphite oxide ratio of 2:1 at 1000 oC for 20 min. The nitrogen-doped exfoliated graphite give better dispersion, smaller particle size and better catalytic activity than exfoliated graphite without nitrogen-doping. The interlayer spacing was 0.368 nm for the nitrogen-doped exfoliated graphite synthesized at 1000 oC for 1 min, compared to 0.345 nm for the exfoliated graphite without nitrogen doping.
    From electrochemical analysis, after Pt loading on the nitrogen-doped exfoliated graphite which was synthesized with PVP/GO = 2 at 900oC for 5 minutes showed the highest mass activity 0.82, 2.34 and 5.75 A/g Pt at 0.75, 0.7 and 0.65 V(vs. Ag/AgCl), respectively. The total content of pyridinic-N, pyrrolic-N,quaternary-N and pyridinic-N-O of doping nitrogen showed moderately positive correlation with mass activities.
    A composite was prepared with the best N-doped exfoliated graphite and fluffy-like carbon at a weight ratio of 1:1. The loading of Pt on this composite showed the largest electrochemical surface area 209.7 C/g Pt and the most positive onset potential. At 0.65 V (vs.Ag/AgCl), this catalyst also gave the highest mass activity 9.66 A/g Pt, about 44% increase comparing to that from a commercial catalyst (Johnson Matthey). In single cell tests, this catalyst had the smallest charge transfer resistance, cathode resistance, and 19% increase in maximum power density comparing to the commercial catalyst.

    摘 要 I Abstract II 致 謝 IV 目 錄 V 圖目錄 IX 表目錄 XVI 符號說明 XVIII 第一章 緒論 1 1.1前言 1 1.2燃料電池簡介 2 1.2.1 燃料電池起源 2 1.2.2 燃料電池特色 2 1.2.3 燃料電池種類 3 1.3 質子交換膜燃料電池現況與挑戰 7 第二章 原理與文獻回顧 10 2.1質子交換膜燃料電池原理 10 2.1.1 質子交換膜 11 2.1.2 陽極觸媒材料 11 2.1.3 陰極觸媒材料 12 2.1.4 氧氣還原機制 12 2.1.5 電池放電極化現象 15 2.1.6 電池阻抗分析 18 2.1.6.1 極化曲線分析 18 2.1.6.2 交流阻抗分析 19 2.1.7 參考電極的應用 25 2.2 觸媒載體 28 2.2.1 碳黑 28 2.2.2 多孔性碳材 29 2.2.3 奈米碳管 29 2.2.4 毛球型碳材 30 2.2.5 石墨烯及拆層石墨 31 2.2.5.1 拆層石墨及石墨烯製備方法 31 2.2.5.2 修飾石墨烯及拆層石墨方法 32 2.3 研究動機 36 第三章 實驗方法 38 3.1 研究樣品之命名 38 3.2 藥品 38 3.3 實驗儀器 40 3.4 實驗步驟 42 3.4.1 氧化石墨烯製備 42 3.4.2 聚乙烯吡咯烷酮(PVP)修飾氧化石墨烯 42 3.4.3 快速加熱法 44 3.4.4 毛球狀碳材之製備 45 3.4.5 毛球狀碳材之酸洗 45 3.4.6 白金觸媒之製備 46 3.4.7 觸媒之電化學活性測試 47 3.4.7.1 半電池電極與觸媒漿料製備 47 3.4.7.2 循環伏安法 48 3.4.7.3 線性掃描法 48 3.4.8 單電池放電測試 49 3.4.8.1 質子交換膜前處理 49 3.4.8.2 單電池參考電極製備 50 3.4.8.3 單電池電極與觸媒漿料製備 51 3.4.8.4 膜電極組熱壓製備 52 3.4.8.5 單電池極化曲線分析 52 3.4.9 交流阻抗分析 54 3.4.10 觸媒材料之鑑定與分析 54 3.4.10.1 接觸角 54 3.4.10.2 穿透式電子顯微鏡 54 3.4.10.3 掃描式電子顯微鏡 54 3.4.10.4 全反射-傅立葉轉換紅外線光譜 55 3.4.10.5 拉曼光譜 56 3.4.10.6 X光電子能譜儀 56 3.4.10.7 X光繞射繞射儀 57 3.4.10.8 熱重分析儀 57 3.4.10.9 元素分析儀 57 3.4.10.10 碳材吸附面積測試 57 第四章 結果與討論 58 4.1 PVP與氧化石墨烯混摻 58 4.1.1 FTIR 58 4.1.2 接觸角分析 59 4.1.3 X光繞射儀 60 4.2 含氮拆層石墨 61 4.2.1 裂解時間對觸媒特性影響 62 4.2.1.1 FTIR 62 4.2.1.2 拉曼光譜 63 4.2.1.3 接觸角 65 4.2.1.4 XPS及元素分析 66 4.2.1.5 TEM 70 4.2.1.6 X光繞射儀 78 4.2.1.7 觸媒活性測試 80 4.2.2 裂解溫度對觸媒特性影響 91 4.2.2.1 FTIR 92 4.2.2.2 拉曼光譜 93 4.2.2.3 接觸角 93 4.2.2.4 XPS及元素分析 95 4.2.2.5 TEM 98 4.2.2.6 X光繞射儀 103 4.2.2.7 觸媒活性測試 104 4.2.3 PVP與氧化石墨烯重量比對觸媒特性影響 117 4.2.3.1 FTIR 117 4.2.3.2 拉曼光譜 117 4.2.3.3 接觸角分析 119 4.2.3.4 XPS及元素分析 119 4.2.3.5 TEM 121 4.2.3.6 X光繞射儀 123 4.2.3.7 觸媒活性測試 124 4.3 含氮拆層石墨與毛球狀碳材混摻比例對觸媒活性影響 133 4.3.1 接觸角 133 4.3.2 SEM 134 4.3.3 觸媒活性測試 134 4.3.4 單電池測試與交流阻抗分析 142 第五章 結論 154 參考文獻 156 附錄一 延伸摘要 170 附錄二 接觸角分析圖 180

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