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研究生: 傅品齊
Fu, Pin-Chi
論文名稱: 多重技術整合之微機電式μDMFC開發與性能評估
Development and performance evaluation of MEMS-based μDMFCs with integrating multiple technologies
指導教授: 楊啓榮
Yang, Chii-Rong
學位類別: 碩士
Master
系所名稱: 機電工程學系
Department of Mechatronic Engineering
論文出版年: 2018
畢業學年度: 106
語文別: 中文
論文頁數: 113
中文關鍵詞: 直接甲醇燃料電池多孔矽穿孔矽二元金屬界面活性劑
英文關鍵詞: direct methanol fuel cell, porous silicon, through silicon via, binary metal, surfactant
DOI URL: http://doi.org/10.6345/THE.NTNU.DME.010.2018.E08
論文種類: 學術論文
相關次數: 點閱:195下載:0
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直接甲醇燃料電池(Direct methanol fuel cell, DMFC)具備能於低溫下工作、能量密度高、啟動速度快、燃料易取得、易攜帶、安全與穩定與低污染等優點,因此在未來有希望能取代鋰電池成為新一代的行動能源裝置。本研究以微機電系統(Micro-electromechanical system, MEMS)技術製作微型直接甲醇燃料電池(DMFC) ,並簡化元件結構與降低生產成本,以因應未來將其應用於行動電子產品之微小化需求。本研究主要以矽晶片作為燃料電池之基材,並整合「TMAH濕蝕刻技術」、「光輔助電化學蝕刻技術」、「PtRu二元金屬化鍍技術」以及「甲醇改質技術」,製作微流道搭配多孔矽(Porous silicon, PS),以及微流道搭配穿孔矽(Through silicon via, TSV) 擴散層結構之燃料電池電極板,並將其應用於微型直接甲醇燃料電池的製作。
本研究成功將PtRu二元金屬均勻複合於石墨烯與奈米碳管表面(PtRu/G-CNT),其Pt與Ru含量比分別為34.1 Wt.%與2.6 Wt.%,而在半電池表現,PtRu/G-CNT之氧化電流峰值為5 mA/cm2,是Pt/G-CNT以及PtRu/G的2.02倍與2.4倍。在電極組合部分,陽極與陰極分別使用多孔矽擴散層電極和穿孔矽擴散層電極的組合(PS+TSV),能得到最佳的電池性能表現,其最大開路電壓為0.4 V,與PS+PS相比增加約1.5倍,而與TSV+TSV相比增加約6.7倍。在添加界面活性劑改質甲醇燃料的評估試驗中得知,界面活性劑MA適於作為甲醇之濕潤劑,並能從添加濃度控制對甲醇氧化能力與濕潤性之影響,同時也能增加二氧化碳氣泡脫離,避免覆蓋觸媒層造成毒化,進而提升燃料電池之性能表現。在添加界面活性劑MA量為0.1 %時,其最大功率密度為0.336 mW/cm2與最大開路電壓為0.48 V,相較於未添加界面活性劑MA分別提升了1.4倍與1.2倍,說明加入少量界面活性劑能促進甲醇藉由多孔矽擴散至觸媒層進行反應,但若加入過多界面活性劑將會影響甲醇氧化效率,因而造成電池性能的下降。

Direct methanol fuel cell (DMFC) has the advantages of being able to work at low temperature, high energy density, fast starting speed, easy fuel availability, easy portability, safety, stability, and low pollution. Therefore, DMFCs were thought as the next generation of power suppliers to replace lithium battery in the future. In this study, micro-electromechanical system (MEMS) technology was used to fabricate micro direct methanol fuel cells (DMFCs), simplifying component structure and reducing production costs in order to meet the needs of miniaturization of mobile electronic products in the future. In order to meet the miniaturization demand of portable electronic devices, this research tried to fabricate a μDMFC, simplify component, and lower cost by using MEMS technique. This research used TMAH etching, PEACE, PtRu chemical reduction, and methanol modification to fabricate the porous silicon diffusion layer (PS) electrode with channel structure and through silicon via (TSV) electrode with channel structure.
This study successfully synthesis PtRu binary metal uniformly to the surface of graphene and carbon nanotubes. The PtRu content ratio is 34.1 wt.% and 2.6 wt.%, respectively. In the half-cell performance, the peak current of oxidation of PtRu/G-CNT is 5 mA/cm2, which is 2.02 times and 2.4 times that of Pt/G-CNT and PtRu/G. Experiments show that using the PS electrode in anode and the TSV electrode in cathode would get the maximum open circuit voltage (0.4 V), which is 1.5 times and 6.7 times that of PS+PS and TSV+TSV. In the evaluation test of adding surfactant-modified methanol fuel, it is known that surfactant MA is suitable as a wetting agent for methanol, and it can influence the oxidation ability and wettability of methanol by concentration controlling. and also increase carbon dioxide bubbles. At the same time, it can improve the performance of the fuel cell by increasing the detachment of carbon dioxide bubbles to avoiding the poison caused by covering catalyst layer. When the amount of MA added is 0.1%, the maximum power density is 0.336 mW/cm2 and ,the maximum open circuit voltage is 0.48 V, which is 1.4 times and 1.2 times than un-added respectively. It is indicated that the addition of a small amount of surfactant can promote the reaction of methanol to the catalyst layer by diffusion of porous. However, if too much surfactant is added, the oxidation efficiency of methanol will be affected, resulting in a decrease in battery performance.

摘要 i 總目錄 iv 圖目錄 vii 表目錄 xiii 第一章 緒論 1 1.1 前言 1 1.2 微機電系統簡介 3 1.3 燃料電池構造簡介及其優點 5 1.3.1 燃料電池的分類 6 1.3.2 質子交換膜燃料電池 9 1.4 微型直接甲醇燃料電池之工作原理與未來挑戰 10 1.5 研究動機 16 第二章 文獻回顧 17 2.1 微/奈米機電系統製程應用於燃料電池之製作 17 2.2 多孔矽應用於燃料電池擴散層 22 2.2.1 多孔矽簡介 22 2.2.2 電化學蝕刻概論 23 2.2.3 光輔助電化學蝕刻之多孔矽製備法 26 2.2.4 多孔矽於燃料電池之應用 28 2.3 結合奈米碳材之燃料電池製作 34 2.3.1 碳元素材料簡介 34 2.3.2 石墨烯與奈米碳管簡介 35 2.3.3 奈米碳材於燃料電池之應用 38 2.4 界面活性劑 43 2.4.1 界面活性劑的結構與種類 43 2.4.2 界面活性劑對氣泡移除之應用 45 2.4.3 界面活性劑在燃料電池之應用 45 第三章 實驗設計與規劃 49 3.1 實驗設計 49 3.2 實驗規劃 52 3.2.1 二元金屬化鍍於奈米碳材 52 3.2.2 流場與擴散層之圖案定義 55 3.2.3 濕式蝕刻製程 62 3.2.4 直接甲醇燃料電池組裝流程 68 3.3 實驗設備 72 第四章 實驗結果與討論 74 4.1 化鍍PtRu/G-CNT複合材料之製作 74 4.1.1 PtRu/G-CNT形貌分析 74 4.1.2 PtRu/G-CNT含量分析 77 4.1.3 半電池電性測量 81 4.2 電池元件之製作 84 4.2.1 微流道深蝕刻製程 84 4.2.2 光化學輔助蝕刻製程 86 4.2.3 微流道搭配穿孔矽蝕刻製程 95 4.2.4 直接甲醇燃料電池組裝 96 4.3 全電池性能測試 97 4.3.1 電極組合之性能測試與評估 98 4.3.2 甲醇改質之性能測試與評估 99 第五章 結論與未來展望 104 5.1 結論 104 5-2 未來展望 105 參考文獻 107

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