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研究生： 詹靖儀
Jhan, Jing-Yi
論文名稱： 聚苯胺衍生氮摻雜中空球狀中孔洞碳材之製備鑑定與於直接甲醇燃料電池觸媒之應用
Syntheses and Characterization of N-doped Hollow Spheres like Mesoporous Carbons from Polyaniline for Electrocatalyst of DMFCs Application.
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： 2010
畢業學年度： 98
語文別： 中文
論文頁數： 107
中文關鍵詞： 氮摻雜 、中孔洞碳材 、電極觸媒 、直接甲醇燃料電池
外文關鍵詞： N-doped, mesoporous carbon, electrocatalyst, direct methanol fuel cells
相關次數： 點閱：166  下載：2 
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    • 本研究以中空球狀氧化矽當模板，利用體積拓印法，將苯胺聚合於中空球狀氧化矽模板上，經高溫碳化，形成碳及氧化矽複合物，再經強鹼移去氧化矽，即合成出高氮碳原子比(N/C = 7~17 %)的新穎之氮摻雜中空球狀中孔洞碳材。
    使用不同聚合劑對苯胺的比例及在不同溫度下碳化，會直接影響氮碳原子比及碳材外觀型態。實驗中以四點碳針測量、等溫物理吸脫附曲線、XRD及Raman 光譜分析測量碳材的物理特性，由結果可知氮摻雜中空球狀中孔洞碳材的導電度比無氮摻雜中空球狀中孔洞碳材高，且依然具有相當高的表面積(994 m2/g)，結晶也較無氮摻雜中空球狀中孔洞碳材佳，且碳材本身對氧氣具有催化活性。
    以乙二醇化學還原法製備鉑奈米粒子，並擔載鉑觸媒於碳材表面。由穿透式電子顯微鏡(TEM)觀察顯示鉑奈米顆粒皆均勻分布於碳載體表面。ESCA分析顯示氮原子確實以pyrrolic、pyridinic及Quaternary結構存在於碳結構內。其電化學活性表面積為87 m2/g Pt，為中空球狀中孔洞碳材做為擔體之觸媒的4~8倍。
    實際用於甲醇直接燃料電池測試後，氮摻雜中空球狀中孔洞碳材擔載鉑觸媒(P851)應用於陰極(氧氣進料)效能為25.2 mW/cm2，高出商用品觸媒E-TEK 19 %，更為無氮摻雜中空球狀中孔洞碳材擔載白金觸媒的2.7倍。而乙二醇於鹼性環境中還原鉑擔載於氮摻雜中空球狀中孔洞碳材經400℃氫氣環境下鍛燒後的樣品(P852(cal.))應用於陽極(甲醇進料) 效能為24 mW/cm2，高出E-TEK 13 %，更為中空球狀中孔洞碳材為載體擔載白金觸媒的效能高2倍。綜合各種實驗結果，可知氮摻雜中空球狀中孔洞碳材應用於燃料電池的陰極觸媒層，是一個極具潛力的觸媒擔體。

    A new type of catalyst support, hollow spheres of N-doped mesoporous carbon, was synthesized via pyrolysis of silica hollow spheres/polyaniline composite. The surface morphology and the size of N-doped mesoporous carbon particles was found to be influenced by altering the ratio of aniline/silica. The ratio of N/C was controlled by changing the composition of aniline and APS, and the temperature of carbonization. A possible structural evolution of the N-doped mesoporous carbon is proposed based on the results obtained from a variety of characterization techniques. The sample P850 appears the more appropriate property for application in fuel cells.
    N-doped carbon-supported platinum nanocatalyst was prepared by chemical reduction using ethylene glycol. The images of TEM showed that platinum nano-particles are well-distributed on the surface of the N-doped carbon support. ESCA showed that pyrrolic, pyridinic and Quaternary types of nitrogen atoms existed in the functionalized carbon. The electrochemical active surface area is 87 m2/g Pt which is 8 times higher than that (11 m2/g Pt) of the raw hollow mesoporous carbon spheres.
    In the direct methanol fuel cell operation, we obtained a power density of 25.2 mW/cm2 by using the platinum supported on hollow spheres of N-doped mesoporous carbon (P851) as the cathode, which is 19% higher than E-TEK 20%Pt/C (21.2 mW/cm2), and 2.7 times higher than the cell by using hollow mesoporous carbon spheres supported Pt catalyst (9.2 mW/cm2) as the cathode. In comparison, the power density of the cell by using the platinum reduced in base environment supported on hollow spheres of N-doped mesoporous carbon which was after calcination (P852(cal.)) as the anode is 24.0 mW/cm2. The successful advancement in this N-doped nanostructured carbon for fuel cell catalyst presents a significant achievement in both the scientific and engineering fields.

    目次 摘要 I 英文摘要 III 致謝 IV 目次 V 表目錄 VII 圖目錄 VIII 第一章 序論 1 1.1 簡介燃料電池 1 1.1.1 燃料電池起源及簡介 1 1.1.2 燃料電池種類 1 1.1.3 燃料電池優點及現今發展 6 1.2 直接甲醇燃料電池(DMFC) 8 1.2.1 直接甲醇燃料電池工作原理 8 1.2.2 觸媒層 10 1.2.3 固態高分子電解質：質子交換膜 11 第二章 理論 13 2.1　中孔洞材料 13 2.1.1 中孔洞碳材簡介與應用 14 2.2　電極觸媒 15 2.2.1 金屬觸媒簡介及種類 15 2.2.2 電極觸媒載體重要性 17 2.3　氮原子添加材料 21 2.4　電化學測試 24 2.4.1 循環伏安法(cyclic voltammetry, CV) 24 2.4.2 電化學活性表面積測試 30 2.5　膜電極組(Membrane Electrode Assembly, MEA) 36 2.5.1 極化現象 37 2.5.2 極化曲線 38 第三章 實驗 43 3.1　實驗藥品與材料 43 3.2　樣品合成 44 3.2.2 無氮摻雜中空球狀中孔洞碳材觸媒擔體合成 44 3.2.2 氮摻雜中空球狀中孔洞碳材觸媒擔體合成 45 3.2.3 奈米金屬電極觸媒合成 47 3.2.4 製備電化學測試工作電極 50 3.2.5 製備膜電極組 51 3.3　樣品分析與儀器 53 3.3.1 X光繞射儀(XRD) 53 3.3.2 掃描式電子顯微鏡(SEM) 54 3.3.3 穿透式電子顯微鏡(TEM) 54 3.3.4 顯微拉曼光譜儀(Raman Spectroscopy) 55 3.3.5 單電池設備(Single cell equipment) 56 第四章 研究結果與討論 57 4.1 氮摻雜中空球狀中孔洞碳材分析 57 4.1.1 不同型態中孔洞碳材分析 57 4.1.2 等溫物理吸脫附及元素分析 64 4.1.3 X光繞射分析及導電度分析 67 4.1.4 拉曼光譜(Raman)分析 70 4.1.5 碳材料熱重分析儀測試, TGA 72 4.1.6 碳材料氧氣還原反應測試, ORR 73 4.2　奈米金屬電極觸媒分析 74 4.2.1 奈米金屬電極觸媒型態分析 75 4.2.2 XRD繞射分析 81 4.2.3 化學分析電子光譜儀, ESCA 83 4.3　電極觸媒電化學分析 86 4.3.1 電化學活性表面積測試, EASA 86 4.3.2 氧氣還原反應測試, ORR 89 4.4.3 甲醇氧化反應測試, MOR 92 4.4　單電池組效能測試 95 第五章 結論 99 第六章 參考文獻 101   表目錄 表1. 1 各式燃料電池差異比較[3] 3 表2. 1 孔洞材料尺寸分類 13 表3. 1 不同APS / aniline及樣品名 46 表3. 2 不同碳化溫度及樣品名 46 表3. 3 單壁奈米碳管Raman光譜峰波位置表。 56 表4. 1 樣品與元素分析結果表 64 表4. 2 不同樣品氮氣吸脫附性質表 66 表4. 3 樣品導電度表 70 表4. 4 不同合成條件樣品對照表 75 表4. 5 樣品經XRD及TEM所得直徑表 81 表4. 6 不同樣品電化學活性表面積測試表 87 表4. 7 不同樣品氧氣還原反應測試數據表 89 表4. 8 不同樣品甲醇氧化反應測試數據表 93 表4. 9 電極觸媒單電池組測試數據整理表 96   圖目錄 圖1. 1 燃料電池種類、反應及操作溫度[2] 2 圖1. 2 DMFC的發電工作原理[10] 9 圖1. 3 Nafion® 結構式[13] 11 圖1. 4 Nafion膜之結構，其中A.疏水性主幹；B.氣體可穿透之具彈性氟碳鏈；C.含水的離子群 [14] 12 圖2. 1 MCM-41 合成示意圖[15] 14 圖2. 2 孔洞材料運用於電極反應示意圖[20] 15 圖2. 3 左圖闡述如果皆是鉑觸媒，會將OH-緊緊抓住，阻擋反應物O2的接近；若加入鎳(右圖)，則促進O2直接還原成O2-[32] 17 圖2. 4 Franklin碳結構示意圖[35] 19 圖2. 5 石墨烯為2D基本石墨化構造，可形成0D的巴克球、1D的單壁奈米碳管及3D的石墨[36] 19 圖2. 6 氮摻雜碳材料，氮在不同位置的名稱及化學分析電子儀(Electron Spectroscopy for Chemical Analysis, ESCA)的束縛能(Binding energy, BE)。[52] 23 圖2. 7 典型直流電循環伏安法實驗三角波圖。a. 正向線性電壓掃描；b. 切換電位(Es)；c. 逆向線性電壓掃描；d. 第一圈掃描終止電壓。[53] 25 圖2. 8 典型可逆式循環伏安圖，反應式：O + ne- ↔ R。A. 氧化峰；B. 還原峰。[54] 26 圖2. 9 氧化物及還原物在氧化反應過程中於電極表面附近濃度分布。(a) 一開始未反應時；(b,d) 正向及反向電壓掃描時；(c) 電極表面達到無氧化物時。[54] 27 圖2. 10 不同鉑結晶面在酸性電解質中的循環伏安圖。(A) 鉑結晶面為(111)；(B) 鉑結晶面為(110)；(C) 鉑結晶面(100)。1為在0.1 M HClO4；2為在0.1 M H2SO4；3為在H3PO4。掃描速率為50 mVS-1。[58] 32 圖2. 11 氫原子吸附在面心立方堆積的不同晶面是意圖。(a) 1,2吸附於(100)晶面；(b) 3,5吸附於(110)晶面；(c) 4吸附於(111)晶面。[59] 32 圖2. 12 鉑在硫酸電解質溶液循環伏安圖。[60] 34 圖2. 13 在0.05 M H2SO4電解液中平滑的鉑電極循環伏安圖，顯示氫原子吸脫附峰積分後電荷值。[62] 35 圖2. 14 MEA構造及製備程序。 36 圖2. 15 DMFC MEA上反應示意圖。 37 圖2. 16 直接甲醇燃料電池之極化曲線及其組成電極極化曲線。[68] 41 圖2. 17 典型燃料電池(AFC, PEMFC, PAFC)在低溫或中問操作下電池電壓-電流密度關係圖，顯示出活化控制區、質傳控制區、歐姆控制區。[69] 42 圖3. 1 PEO-PF resin-silica複合物經不同熱處理條件可得中空球狀中孔洞碳材及中空球狀中孔洞氧化矽模板。[圖由成大化學系林弘萍老師提供] 45 圖3. 2 實驗流程圖 49 圖3. 3 玻璃化碳電極頭 51 圖3. 4 三極式電化學測試電池 51 圖3. 5 單電池構造示意圖。 52 圖3. 6 單壁奈米碳管Raman光譜。 55 圖3. 7 單電池設備系統裝置圖 56 圖4. 1 在放大倍率10000下中空球狀氧化矽模板及不同條件製備中孔洞碳材SEM圖。(a) 中空球狀氧化矽模板，(b) 無氮摻雜中空球狀中孔洞碳材，(c)~(f)為不同aniline / silica比例製備之氮摻雜中空球狀中孔洞碳材：(c) Pani2.5，(d) Pani2，(e) Pani1.5，(f) Pani1.5’。(樣品的製備條件請參照表3. 1) 60 圖4. 2 在放大倍率50000下不同條件製備中孔洞碳材SEM圖。 (a) 無氮摻雜中空球狀中孔洞碳材，(b)~(e)為不同aniline / silica比例製備之氮摻雜中空球狀中孔洞碳材：(b) Pani2.5，(c) Pani2，(d) Pani1.5，(e) Pani1.5’。(樣品的製備條件請參照表3. 1) 61 圖4. 3 在200000及50000放大倍率下中空球狀氧化矽模板及氮摻雜中空球狀中孔洞碳材TEM圖。(a) 放大倍率為200000的中空球狀氧化矽模板，(b) 放大倍率為50000的中空球狀氧化矽模板，(c) 放大倍率為200000的Pani2，(d) 放大倍率為5000的Pani2。 62 圖4. 4 在10000及50000放大倍率下不同條件製備中孔洞碳材SEM圖。(a) 放大倍率為10000的P850，(b) 放大倍率為50000的P850，(c) 放大倍率為10000的P700，(d) 放大倍率為50000的P700，(e) 放大倍率為10000的P550，(f) 放大倍率為50000的P550。(樣品的製備條件請參照表3. 2) 63 圖4. 5 (a) APS / aniline與氮碳原子比關係圖；(b)碳化溫度與氮碳原子比關係圖。 64 圖4. 6 不同碳化溫度樣品的BET表面積及微孔面積比例關係圖 67 圖4. 7 不同silica / aniline比所合成之氮摻雜中空球狀中孔洞碳材樣品X光繞射圖。 69 圖4. 8 不同碳化溫度之氮摻雜中空球狀中孔洞碳材樣品X光繞射圖 70 圖4. 9 不同碳化溫度製備樣品之顯微拉曼光譜儀分析圖譜 71 圖4. 10 不同碳材料熱重分析圖 72 圖4. 11 不同碳材料載體氧氣還原反應循環伏安圖 74 圖4. 12 乙二醇氧化機制[72] 76 圖4. 13 放大倍率200000下電極觸媒之TEM圖：(a) Pt/XC72；(b) Pt/MPCt；(C) P851 77 圖4. 14 放大倍率200000下電極觸媒之TEM圖：(a) P851(cal.)；(b) P852；(C) P852(cal.) 78 圖4. 15 放大倍率400000下電極觸媒之TEM圖：(a) Pt/XC72；(b) Pt/MPC；(C) P851。右側為粒徑分布圖及平均粒徑。 79 圖4. 16 放大倍率400000下電極觸媒之TEM圖：(a) P851(cal.)；(b) P852；(C) P852(cal.)。右側為粒徑分布圖及平均粒徑。 80 圖4. 17 不同碳材料載體擔載鉑奈米金屬觸媒XRD圖 82 圖4. 18 不同鉑奈米金屬合成方式電極觸媒XRD圖 82 圖4. 23 不同碳載體電極觸媒電化學活性表面積測試循環伏安圖 88 圖4. 24 不同鉑奈米金屬合成方式電極觸媒電化學活性表面積測試循環伏安圖 88 圖4. 25 不同碳載體電極觸媒氧氣還原反應測試循環伏安圖 91 圖4. 26 不同鉑奈米金屬合成方式電極觸媒氧氣還原反應測試循環伏安圖 91 圖4. 27 不同碳載體電極觸媒甲醇氧化反應測試循環伏安圖 94 圖4. 28 不同鉑奈米金屬合成方式電極觸媒甲醇氧化反應測試循環伏安圖 94 圖4. 29 不同碳載體電極觸媒於直接甲醇燃料電池陰極(O2)，陽極觸媒(MeOH)為Etek(20 wt. % Pt)，70 ℃下單電池組效能測試極化曲線 97 圖4. 30 不同鉑奈米金屬合成方式電極觸媒於直接甲醇燃料電池陰極(O2)，陽極觸媒(MeOH)為Etek(20 wt. % Pt)，70 ℃下單電池組效能測試極化曲線 97 圖4. 31 不同碳載體電極觸媒於直接甲醇燃料陽極(MeOH)，陰極(O2)觸媒為Etek(20 wt. % Pt)，70 ℃下單電池組效能測試極化曲線 98 圖4. 32 不同鉑奈米金屬合成方式電極觸媒於直接甲醇燃料陽極(MeOH)，陰極(O2)觸媒為Etek(20 wt. % Pt)，70 ℃下單電池組效能測試極化曲線 98

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