石墨烯與氮化物於金屬多孔材之抗蝕特性與高溫質子交換膜燃料電池應用之研究

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吳冠穎(Guan-Ying Wu) 查詢紙本館藏

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能源工程研究所

論文名稱

石墨烯與氮化物於金屬多孔材之抗蝕特性與高溫質子交換膜燃料電池應用之研究
(Research on the Corrosion Resistance Characteristics of Graphene and Nitride Coatings on the Surface of Metal Porous Materials and Their Applications in High-Temperature Proton Exchange Membrane Fuel Cells)

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至系統瀏覽論文 (2028-9-1以後開放)

摘要(中)

中文摘要
本研究使用金屬多孔材為質子交換膜燃料電池之流場，金屬多孔材具有高孔隙率、質量輕及導電性佳之特性，作為燃料電池流道與傳統流道相比不具遮蔽效應。由於高溫燃料電池運作時內部為酸性之環境，會侵蝕流道進而影響燃料電池壽命，為了防止磷酸水溶液腐蝕金屬多孔材而釋出金屬離子毒化膜電極組中的觸媒，需透過表面鍍層處理提升金屬多孔材之抗腐蝕性、導電性與疏水性等。本研究使用石墨烯、氮化鈦、氮化鋯及氮化鉻作為抗腐蝕鍍層，透過表面微觀結構、接觸角與腐蝕測試分析材料性質，並組成單電池分析性能表現。
腐蝕極化結果顯示石墨烯鍍層於模擬高溫燃料電池環境之抗蝕能力優於其它鍍層，石墨烯鍍層之多孔材比無鍍層之多孔材腐蝕電流大幅降低約58%，比常見氮化鈦鍍層降低約21%。且腐蝕量測前後之表面微結構型態分析表明，石墨烯鍍層顯示出更好的抗腐蝕穩定性。以石墨烯鍍層鎳多孔材組裝的PEMFC單電池，於180 oC下定電流在400 mA/cm2量測長時間之耐久性，石墨烯鍍層較無鍍層發泡材之燃料電池之電壓衰退率減少48.8%。藉由石墨烯之高電導率、機械強度等優勢，應用於高溫質子交換膜燃料電池，可提高電池之耐久性及穩定性。

摘要(英)

Abstract
This study uses metal porous materials as the flow field for high-temperature proton exchange membrane fuel cells (HT-PEMFCs). Metal porous materials exhibit characteristics such as high porosity, light weight, and excellent conductivity, which make them advantageous compared to traditional flow channels, as they can eliminate shielding effect. During the operation of HT-PEMFCs, the internal environment is acidic, which can corrode the metal flow channels and thereby affect the durability of the fuel cells. To prevent corrosion of metal porous materials by leakage phosphoric acid solutions from proton exchange membrane, it is necessary to enhance the corrosion resistance, conductivity, and hydrophobicity of the porous metal materials through surface coating treatments.
In this study, we used graphene, titanium nitride, zirconium nitride, and chromium nitride as anti-corrosion coatings. We analyzed the properties of these materials through surface morphology observation, contact angle measurements, and corrosion tests, and incorporated them into single cells to analyze their performance.
The corrosion polarization results show that the corrosion resistance of the graphene coating in a simulated HT-PEMFC environment is superior to other coatings. The corrosion current of the graphene-coated porous material is significantly reduced by approximately 58% compared to the pristine porous material and reduced by approximately 21% compared to the commonly used titanium nitride coating. Analysis of the microstructure before and after corrosion testing reveals that the graphene coating exhibits better corrosion resistance stability. In a HT-PEMFC single cell assembled with a graphene-coated nickel porous material, the fuel cell demonstrated long-term durability at a constant current of 400 mA/cm2 at 180 °C. The voltage decay rate of the fuel cell with the graphene coating was 48.8% less than that of the pristine metal porous material.

關鍵字(中)

★ 高溫質子交換膜燃料電池
★ 磷酸
★ 腐蝕
★ 石墨烯
★ 金屬多孔材

關鍵字(英)

論文目次

目錄
中文摘要 vi
Abstract vii
誌謝 ix
目錄 x
圖目錄 xiv
表目錄 xx
符號說明 xxii
第一章緒論 1
1-1　　前言 1
1-2　　質子交換膜燃料電池 5
1-2-1 燃料電池種類 5
1-2-2 質子交換膜燃料電池工作原理 8
1-2-3 質子交換膜燃料電池之組成結構 12
1-2-4 燃料電池極化現象 20
1-3　　鍍層製備原理及方式 27
1-3-1物理氣相沉積（Physical Vapor Deposition, PVD） 27
1-3-2化學氣象沉積(Chemical Vapor Deposition, CVD) 28
1-4　　電化學交流阻抗基本原理 30
1-5　　研究動機與方向 32
第二章文獻回顧 35
2-1　　金屬極板與多孔材流道分析 35
2-2　　TiN鍍層分析 35
2-3　　ZrN鍍層分析 36
2-4　　CrN鍍層分析 37
2-5　　Graphene鍍層分析 38
2-6　　燃料電池之電化學交流阻抗分析 39
第三章實驗方法與設備 42
3-1　　實驗架構流程 42
3-2　　鍍層之製備 43
3-3　　表面結構分析 47
3-3-1 場發射掃描式電子顯微鏡 47
3-3-2 能量色散X射線譜(Energy-Dispersive X-Ray Spectroscopy, EDS) 48
3-3-3 拉曼光譜儀 49
3-4　　接觸角量測 52
3-5　　腐蝕極化量測 53
3-6　　燃料電池之各元件介紹 55
3-6-1　膜電極組(Membrane and Electrode Assembly, MEA) 56
3-6-3　鎳多孔材 58
3-6-4　金屬流道與雙極板 60
3-6-5　端板 60
3-7　　燃料電池測試系統 61
3-8　　燃料電池極化現象 65
3-9　　電化學交流阻抗分析儀 68
第四章結果與討論 74
4-1　　模擬於高溫型質子交換膜燃料電池腐蝕極化測試 74
4-2　　接觸角量測 85
4-3　　單電池性能測試 88
4-3-1　單電池性能量測 88
4-3-2　背壓之單電池性能測試 92
4-4　　電化學交流阻抗頻譜測試 96
4-5　　高溫型質子交換膜燃料電池耐久性測試 99
4-5-1　長時間耐久性測試 100
4-5-2　長時間耐久性電化學交流阻抗頻譜測試 103
4-6　　多孔材表面鍍層分析 107
4-6-1　石墨烯鍍層品質檢測 107
4-6-2　石墨烯鍍層表面形貌 113
4-6-3　石墨烯鍍層元素分析 124
第五章結論與未來規劃 130
5-1　　結論 130
5-2　　未來規劃 131
參考文獻 133

參考文獻

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指導教授

曾重仁

審核日期

2023-7-19

推文