鈦磷酸鹽離子導體應用於聚苯並咪唑質子交換膜燃料電池

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研究生：	曾令威 Ling-wei Tseng
論文名稱：	鈦磷酸鹽離子導體應用於聚苯並咪唑質子交換膜燃料電池 Application of titanium phosphates ion conductor to proton exchange membrane fuel cell with polybenzimidazole electrolyte
指導教授：	蔡大翔 Dah-shyang Tsai
口試委員:	林秀麗 Hsiu-li Lin 陳燿騰 Yaw-terng Chern
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2012
畢業學年度：	100
語文別：	中文
論文頁數：	95
中文關鍵詞：	鈦磷酸鹽、核殼結構、質子交換膜燃料電池
外文關鍵詞：	Titanium phosphate, Core-Shell structure, Proton Exchange Membrane Fuel Cell(PEMFC)
相關次數：	點閱：367 下載：3
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本論文包含兩部份：先合成出於160-260℃溫度範圍內具有高質子導電率之鈦磷酸鹽，再將鈦磷酸鹽與質子交換膜整合並於相同溫度範圍內量測效能表現。
在鈦磷酸鹽的結果中：我們合成出具有核殼結構特色之低價數金屬摻雜鈦磷酸鹽。以Ti0.9Mg0.1P3.0Oy晶體為核材，外面包覆非晶質之Ti0.9Mg0.1P5.0Oy殼層。富磷殼層提供質子傳導的主要途徑。實驗結果顯示核殼結構鈦磷酸鹽於溫度100-260℃之質子導電率皆在4.0×10-2 S cm-1以上。高的磷與鈦莫耳比之樣品，其質子導電率在100-260℃超過6.0×10-2 S cm-1，更明確地，質子導電率在260℃達到0.13 S cm-1。
在鈦磷酸鹽應用於PEMFC中，我們聚焦在離子導體於膜電極中的應用。電極的配方包含85wt % Pt/C(觸媒)、10 wt% Ti0.9Mg0.1P3.5Oy(離子導體)、5 wt% PTFE (黏著劑)時，具有最佳的電功率表現。當陽極白金觸媒承載量為0.6mg/cm2且陰極白金觸媒承載量為1.0 mg/cm2時，單電池於180℃達到最大電功率密度為146 mW/cm2。

This thesis involves two parts; synthesis of titanium phosphates with high proton conductivity ranging in 160-260℃, performance measurement of a proton exchange membrane fuel cell (PEMFC) integrating the titanium phosphate in the same temperature range.
On the results of titanium phosphate- we synthesize a number of titanium phosphates doped with low valence metal which are featured with a core-shell structure. The core material is crystalline Ti0.9Mg0.1P3.0Oy, which is coated with the shell of noncrystalline Ti0.9Mg0.1P5.0Oy. The phosphorus-rich shell serves as the main passage of proton conduction. Experimental results show that the proton conductivity of core-shell titanium phosphates can be more than 4.0×10-2 S cm-1 at 100-260℃. The specimens of high molar ratio of phosphorus over titanium, its proton conductivity exceeds 6.0×10-2 S cm-1 at 100-260℃, more specifically, the 260℃ proton conductivity reaches 0.13 Scm-1.
On the application of titanium phosphates to PEMFC- We focus on its electrode application as the ionomer. The electrode formulation, including 85 wt% Pt/C (catalyst), 10 wt% Ti0.9Mg0.1P3.5Oy (ionomer), 5 wt% PTFE (binder), gives the best cell performance. With a 0.6mg/cm2 Pt loading for anode and 1.0 mg/cm2 Pt loading for cathode, the peak power of the single cell reaches 146 mW/cm2 at 180℃.

誌謝	I
摘要	II
ABSTRACT	III
目錄	IV
圖目錄	IX
表目錄	XIII
第一章 緒論	1
1前言	1
2 研究動機	2
第二章 文獻回顧與理論基礎	7
1 質子交換膜燃料電池之工作原理及發展趨勢	7
2 質子傳導機制(Proton conduction mechanism)	12
2.1 載具機制(vehicle mechanism)	13
2.2 Grotthus機制(Grotthus mechanism)	14
3 有機質子傳導膜及無機固態電解質材料	15
3.1 有機高溫型質子傳導膜	15
3.1.1 H3PO4/PBI在燃料電池上的應用	16
3.1.2 PBI於高溫型質子交換膜燃料電池之應用	18
3.2 高溫型無機質子導體	18
3.2.1 含氫的固態無機酸(Solid acids)	19
3.2.2 多磷酸鹽複合材料	20
3.2.3 不含氫固態無機磷酸鹽	22
3.3 有機/無機混成薄膜	25
4 電極	27
5 膜電極組極化現象	32
6 膜電極組之活化過程	34
第三章 實驗方法與分析儀器	37
1 實驗藥品	37
2 儀器設備	39
3 實驗方法	40
3.1 固態燒結法合成過渡金屬磷酸鹽質子導體材料	40
3.1.1實驗流程	40
3.1.2核殼結構鎂摻雜鈦磷酸鹽質子導體材料的製備	41
3.1.3異價金屬陽離子摻雜鈦磷酸鹽質子導體材料	42
3.2 質子交換膜燃料電池之膜電極組製備	44
3.2.1 觸媒漿料製備及電極製作	44
3.2.2 膜電極組壓合及組裝步驟	46
4 材料與電化學特性分析	49
4.1 X光繞射晶相分析(XRD)	49
4.2 交流阻抗分析(AC Impedance)-質子導電率量測	50
4.2.1交流阻抗分析基本原理	50
4.2.2 質子導電率量測	53
4.3 燃料電池之測試	56
4.3.1測試系統簡介	56
4.3.2 電池電流-電壓測試	58
第四章 結果與討論	59
1 異價金屬陽離子摻雜之鈦磷酸鹽	61
1.1 交流阻抗分析	61
1.2 質子導電率	65
2 鎂摻雜鈦磷酸鹽之XRD相鑑定	68
3 核殼結構之鎂摻雜鈦磷酸鹽	70
3.1 交流阻抗分析	70
3.2 質子導電率	74
4 無機磷酸鹽應用於膜電極中之單電池效能分析	77
4.1 陰陽極觸媒層中離子導體含量對電功率密度表現的影響	79
4.2 陰陽極觸媒承載量對電功率密度表現的影響	81
4.3 陰極端不同進料氣體對單電池表現的影響	83
4.3.1 電功率密度表現	83
4.3.2 交流阻抗分析	84
4.4 離子導體(磷與金屬比例)對電功率密度表現的影響	85
第五章 結論	87
參考文獻	89
附錄A	94
附錄B	95

                                

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