本論文以實驗方法探討碳纖維束雙極板應用在直接甲醇燃料電池的特性。研究包含不同碳纖維束結構對電池性能的影響，此外利用高溫熱壓來改變交換膜內部結構，達到阻隔相鄰電池氫離子的側向移動現象，最後將此兩種技術應用到可攜式DMFC的電池組。
本研究的碳纖維束雙極板包含無鋸齒狀與鋸齒狀兩種，實驗發現兩者在陰極低進氣壓力下，性能皆比傳統石墨雙極板佳。當陽極與陰極側碳纖維束皆改成鋸齒狀時，對性能的改善更佳，尤其在高電流密度時，當陰陽兩極皆採用鋸齒結構比不採用鋸齒結構時，功率密度最高可提升27.6％ 。
另一組實驗為探討氫離子的側向橫移。當電池組採用多電池共用同一交換膜的banded-type MEA時，發現氫離子有橫移的現象，使得串接電池組的性能無法完全表現，為了阻隔氫離子橫移的現象，故於相鄰兩電極間的交換膜進行短暫高溫熱壓，熱壓後發現氫離子橫移現象可有效阻隔，電池串接後性能比熱壓前得到10％的提昇。
最後本實驗在雙層式共2*6-cell平板型DMFC中，每一個電池面積為0.5*5 cm2，共用的兩片交換膜使用Nafion117、陽極觸媒Pt/Ru含量為4 mg/cm2，陰極觸媒Pt含量為4 mg/cm2，甲醇濃度3M，陰極端採用自然進氣，實驗在室溫下操作，以目前手工製作下的電池阻最大輸出功率密度為8.0mW/cm2，總功率為240 mW。但預計若此電池組每一電池的品質均一，總功率應可提昇到480 mW ，此功率將可供應各種手機的操作需要。

In this thesis the experimental method is used to study the characteristics of a DMFC when a heterogeneous carbon fiber bipolar plate is applied to it. The first main study is about the effect of the different structures of the carbon fiber bunch on the fuel cell performance. Additionally, a high temperature hot-pressing process is performed to change the inner molecular structure so that the hydrogen ion can be blocked to avoid the lateral migration between two adjacent cells. Finally, the two techniques are applied to make our new portable DMFC stack.
The bipolar plates with the sawtooth or non-sawtooth carbon fiber bunches have been used in making our DMFC stack. The experimental results display that the performances of the two structures both are better than the traditional graphite bipolar plate. However, the performance of DMFC with the sawtooth bipolar plate is much better than that without sawtooth, especially in high current density. When carbon fiber bunches with sawtooth use at anode and cathode of bipolar plates, the performance can be enhanced and its power density 27.6% higher than that without sawtooth.
During our study we also found that part of hydrogen ions can laterally migrate to its adjacent cathode and do not directly cross to its opposite cathode, when the banded type MEA are used to multiple cell stack. Therefore, the performance cannot be performed well due to this type ion transfer. In order to block the lateral migration, the narrow area of the membrane between two adjacent electrodes is pressed with a high temperature hot-pressing device. After a short time hot-press between two adjacent electrodes, the hydrogenion migration phenomenon reduced, and the performance had been improved about 10% higher than that without hot-press.
Finally, a double layer 2x6-cell flat type DMFC is made. This 12-cell stack is composed of each electrode area 0.5x5cm2, two sheets of membrane for 6-cell using Nafion 117, the anode catalyst Pt-Ru loading 4mg/cm2, and cathode catalyst Pt loading 4mg/cm2, the methanol concentration 3M, air-breathing, and operating in room temperature. The output power of the cell can reach an average power density 8.0mW/cm2 and total power 240mW with our handmade stack. If the performance of each fuel cell is more uniform, we expect that total power can reach 480 mW. The power level should be satisfied for any kind mobile phone.

目錄………………………………………………………………………I
圖目錄…………………………………………………………………..IV
表目錄………………………………………………………………….VI
論文摘要（中文）……………………………………………………..VIII
論文摘要（英文）………………………………………………………IX

第一章 緒論…………………………….……………………………….1
1.1 前言……………………………………………………………...1
1.2 燃料電池的種類……………………………………………… ..2
1.3 文獻回顧………………………………………………………...6
1.4研究目的………………………………………………………...12
第二章 直接甲醇燃料電池（DMFC）……………………...10
2.1 背景簡介……………………………………………………….13
2.2 直接甲醇燃料電池之結構………………………………….....14
2.3 膜極組( Membrane Electrode Assembly , MEA )……………..14
2.3.1 質子交換膜……………………………………………..15
2.3.2 催化層…………………………………………………..17
2.3.3 擴散層…………………………………………………..19

第三章 DMF的原理與反應機制（DMFC）…………………...20
3.1直接甲醇燃料電池的工作原理……………………………..…19
3.2甲醇於DMFC中之理論消耗量………………………………….22
3.3燃料電池質傳現象…………………………………………..….23
3.4燃料電池極化現象……………………………………………...23
3.5燃料電池的極化曲線…………………………………..……….25

第四章 非均質碳纖維雙極板與MEA之製作
4.1研發碳纖維雙極板之目的……………………………………...26
4.1.1新型雙極板之製作材料……………………………..…...28
3.1.2碳纖維束排之製作流程……………………………...…..28
3.1.3黏結劑選用原則………………………….…..………….29
3.1.4碳纖維束排電阻量測系統…………………..…………. 30
4.2 MEA的製作……………..………………………………………....31
4.2.1質子交換膜的前處理…………………………………......31
4.2.2電極的預備……..………………………………………....31
4.2.3 MEA的壓製(Bended type) ……………………………....32
4.3電池組構件製作………..……………………………………….......32
4.4 結語…………..…………………..…………………………….......32
第五章 可攜式直接甲醇燃料電池組之設計製作……………35
5.1測試條件……………………….………………………………..35
5.1.1單一電池組測試………………….………………………35
5.1.2兩個cell電池組測試……………………………………..35
5.2可攜式直接甲醇燃料電池組………………………………..….36

第六 實驗結果與分析…………………………………………..….39
6.1碳纖維於不同結合壓力下對性能之影響…….…..………..….39
6.2不同碳纖維束結構對性能之影響…….…….…..………..…….41
6.2.1不同陽極端碳纖維束結構對性能之影響……………….41
6.2.2不同陰極端碳纖維束結構對性能之影響……………….42
6.3離子橫移對性能的影響………...…………….....………..…….43
6.4手機之電池組性能特性分析…………….....………..…...…….45
6.4.1氧化劑供應對輸出功率的影響….....………..….……….45
6.4.2燃料電池隨著使用時間之影響研究..………..………….45
6.5電池組於手機上之實際應用.....……………………...…..…….47

第七章 結論…………………………………………………….……49
7.1 結論…………………………………………………………….49
7.2 未來可進行之工作…………………………………………….49
參考文獻………………………………………………………………50

圖目錄
圖3.1 直接甲醇燃料電池工作原理示意圖.………………………..53
圖3.2 直接甲醇燃料電池極化曲線示意圖.………………………..54
圖4.1 傳統硬質表面極板與電極碳布之接觸示意圖………….…..55
圖4.2 新型碳纖維雙極板與電極碳布之接觸示意圖……………...56
圖4.3 碳纖維雙極板示意圖………………………………………...57
圖4.4 碳纖維束製作流程圖………………………………………...58
圖4.5 不同壓力下，雙極板與碳布總電阻量測裝置……..………...59
圖4.6 碳纖維束排與碳布組合後總電阻量測示意圖……………...59
圖4.7 熱壓完成6-cell banded type MEA…………….……………..60
圖4.8 熱壓MEA之設備說明………………………….…………...60
圖4.9 PMMA的單體為甲基丙烯酸甲酯(MMA)，其物理、化學性
能表.………………………………………………………….61
圖5.1 測試碳纖維於不同壓力的測試模組..……………………….62
圖5.2 鋸齒與無鋸齒的條狀碳纖維束照片……………………..….62
圖5.3 已壓製完成之MEA…...……………………………..………63
圖5.4 電池組的零件圖……..………………………………….……64
圖5.4 燃料電池側邊碳纖維双極板是意圖(a)鋸齒(b)無鋸齒……..65
圖5.6 兩片MEA所組成之燃料儲存槽…….…………….….……..65
圖5.7 平板式雙層12-cell電池組組件………...………………..…66
圖6.1 碳纖維極板於四種不同結合壓力下性能之比較……….…..67
圖6.2 碳纖維双極板於不同負载下，輸出電壓與結合壓力之關係.67
圖6.3 平板型2-cell DMFC，陽極碳纖維束呈鋸齒狀與無鋸齒狀雙
極板，輸出電壓與功率密度vs電流密度之比較……………68
圖6.4 平板型2-cell DMFC，陰極碳纖維束呈鋸齒狀與無鋸齒狀雙
極板，輸出電壓與功率密度vs電流密度之比較….…….......68
圖6.5 平板型2-cell DMFC，陽極與陰極碳纖維束呈鋸齒狀，輸出
電壓與功率密度vs電流密度之比較………………………..69
圖6.6 離子無阻隔與有阻隔橫向移動之比較………….….……….70
圖6.7 交換膜未熱壓前，個別cell與串接時性能之比較…………71
圖6.8 交換膜經熱壓後，個別cell與串接時性能之比較……..……71
圖6.9 交換膜經兩次熱壓後，個別cell與串接時性能之比較...….72
圖6.10 平板式12-cell電池組不同氧化劑供應方式，總電壓與功率
隨電流之變化之性能曲線……………………………….…..72
圖6.11 平板式12-cell電池組串聯，自然吸氣與純氧氣兩種供氣方式下，電壓與功率密度vs.電流密度之比較………………..73
圖6.12 平板式12-cell電池組第一組電池組（6個）的性能曲線….73
圖6.13 平板式12-cell電池組第二組電池組（6個）的性能曲線..…74
圖6.14 MEA長時間使用/放置後經再處理過後對電池性能電壓、電
流、能量之影響……………………..……………………….74
圖6.15 MEA長時間使用/放置後經再處理過後性能電壓、電流密度
與能量密度的之表現………………….………………….….75
圖6.16 燃料電池組與驅動手機示意圖………………………….…..75
圖6.17 燃料電池於手機之待機測試………….……………...….…..76
圖6.18 燃料電池於手機上待機之應用………………………..….…76

表目錄
表6.1數種DMFC之比較…………………………….……………….77
表6.1實驗室開發出不同DMFC電池組之比較..……………………..78

1. "Open circuit voltage and methanol crossover in DMFCs", Zhigang Qi, Arthur Kaufman, Journal of Power Sources, 110, 177-185, 2002.
2. "Performance of an air-breathing direct methanol fuel cell", C.Y. Chen, P. Wang, Journal of Power Sources, 113, 145-150, 2003.
3. "Direct methanol fuel-cell combined with a small back-up battery", Jaesung Han, Eun-Sung Park, Journal of Power Sources, 112, 477-483, 2002.
4. "The effect of methanol concentration on the performance of a passive DMFC", J.G. Liu, T.S. Zhao , R. Chen, C.W. Wong , Electrochemistry Communications, 7, 288-294 ,2005.
5. "Effect of CO in the anode fuel on the performance of PEM fuel cell cathode", Zhigang Qi, Chunzhi He, Arthur Kaufman, Journal of Power Sources, 111, 139-247, 2002.
6. "Influence of electrode structure on the performance of a direct methanol fuel cell", Zhaobin Wei, Suli Wang, Baolian Yi, Jianguo Lin, Journal of Power Sources, 106, 364-369, 2002.
7. "Development of high-power electrodes for a liquid-feed direct methanol fuel cell", C.Lim, C.Y.Wang, Journal of Power Sources, 113, 145-150, 2003.
8. "Design and fabrication of pumpless small direct methanol fuel cells for portable applications", Takahiro Shimizu, Toshiyuki Mommaa, Mohamed Mohamedia,Tetsuya Osaka a, Srinivasan Sarangapani
, Journal of power sources ,137,277-283,2004.
9. "高性能新型碳纖維雙極板在DMFC之應用研究"，蘇烽堅，碩士論文，國立中山大學機械工程研究所，中華民國九十三年六月。
10. "Characterization of electrode structures and the related performance of direct methanol fuel cell," C.Y. Chen , C.S. Tsao , Institute of Energy Research(INER) .
11. "Experimental studies of a direct methanol fuel cell", Jiabin Ge , Hongtan Liu , Department of Mechanical Engineering , University of Miami , Coral Gables, FL33146, USA, Journal of power sources , 142,56-69,2005.
12. "In situ visualization study of CO2 gas bubble behavior in DMFC anode flow fields ",H. Yang , T.S. Zhao, Q. Ye, Department on Mechanical Engineering, China , Journal of power sources , 139,79-90, 2005.