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研究生: 蔡淳名
Tsai, Chun-Ming
論文名稱: 應用於鈉/鋰二氧化碳電池之釕複合奈米碳管陰極觸媒
Cathode Catalysts of Ruthenium Composite Carbon Nanotubes for Sodium / Lithium Carbon Dioxide Battery
指導教授: 胡淑芬
Hu, Shu-Fen
學位類別: 碩士
Master
系所名稱: 物理學系
Department of Physics
論文出版年: 2020
畢業學年度: 108
語文別: 中文
論文頁數: 97
中文關鍵詞: 鈉二氧化碳電池鋰二氧化碳電池陰極催化觸媒釕奈米粒子新能源材料多壁奈米碳管
英文關鍵詞: Sodium carbon dioxide battery, Lithium carbon dioxide battery, Cathode catalyst materials, Ruthenium nanoparticle, Multi-walled carbon nanotubes, Energy materials
DOI URL: http://doi.org/10.6345/NTNU202001038
論文種類: 學術論文
相關次數: 點閱:151下載:0
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  • 自18世紀工業革命,人類生活型態巨大改變。人們對於能源需求與日俱增,然以傳統石化燃料作為能源來源,於產生能源過程中製造大量之二氧化碳等溫室氣體,致使全球暖化問題。又因石化燃料枯竭危機,促使綠色替代能源之相關研究蓬勃發展。電池為目前廣泛應用之儲能系統,鈉/鋰二氧化碳電池(sodium/lithium carbon dioxide battery)因具備重量輕、高能量密度與高比電容量之優勢,可解決溫室氣體排放之問題,且鈉金屬具低成本與地球含量高等優點,已成為極具潛力之儲能裝置。
    本研究乃合成釕奈米粒子複合多壁碳奈米管(Multi-walled carbon nanotubes)作為鈉/鋰二氧化碳電池觸媒陰極。藉高活性之釕奈米粒子修飾多壁奈米碳管,奈米碳管具良好之熱穩定性與導電性質,且高體表面積之特性助於儲存放電產物。釕奈米粒子於充電時有效催化放電產物之分解,改善其循環壽命與過電位。本研究以鈉金屬與鋰金屬作為電池陽極材料並比較電池效能,因鈉成本低廉且產量高,故本研究期望鈉金屬取代成本高之鋰金屬。本研究合成之多壁碳奈米管修飾釕奈米粒子(Ru/MWCNTs)作為鈉/鋰二氧化碳電池之陰極觸媒,除有效分解沉積於陰極上之放電產物進而提高循環壽命,亦於鈉/鋰二氧化碳電池比較中證實鈉二氧化碳電池之可行性與其效能不亞於鋰二氧化碳電池,可知鈉二氧化碳電池極具發展與研究之潛力,其為低成本與高理論能量密度之新一代綠能儲能系統。

    Since the industrial revolution in the 18th century, people's demand for energy is increasing day by day, but traditionally using fossil fuel as an energy source to produce a large number of greenhouse gases such as carbon emissions in the process of generating energy has caused the global warming problem to be imminent and the crisis of depletion of petrochemical fuel. Promote the vigorous development of research related to green alternative energy. The battery is currently the widely used energy storage system. Sodium/lithium carbon dioxide battery has the advantages of a lightweight, high energy density and high specific capacity. To solve the problem of greenhouse gas emissions, sodium metal has become a potential energy storage device in recent years because of its low cost and high earth content.
    The synthesis of ruthenium nanoparticles composites multi-wall carbon nanotubes as a sodium/lithium carbon dioxide battery catalyst. Multi-walled carbon nanotubes are modified with highly active ruthenium nanoparticles. The carbon nanotubes have good thermal stability and electrical conductivity, and the high specific surface area facilitates the deposition of stored discharge products. Ruthenium nanoparticles effectively catalyze the decomposition of discharge products during charging, improving their cycle life, and overpotential phenomena. This project also used lithium metal and sodium metal as battery anode materials and compared battery performance. Due to the low cost and high yield of sodium, we expect that sodium metal will gradually replace the high-cost lithium metal. The multi-walled carbon nanotubes modified ruthenium nanoparticles (Ru/MWCNTs) synthesized in this project are used as cathode catalysts for sodium/lithium carbon dioxide batteries. In addition to effectively decomposing the discharge products deposited on the cathode to improve cycle life, also used in sodium/the comparison of lithium carbon dioxide batteries proves that the feasibility and performance of sodium carbon dioxide batteries are no less than that of lithium carbon dioxide batteries. It can be seen that sodium carbon dioxide batteries have great potential for development and research, and provide low-cost and new-generation green energy storage systems with high theoretical density.

    致謝I 摘要II 目錄V 圖目錄IX 表目錄XIII 第一章 緒論 1 1.1鋰離子電池 2 1.2鈉/鋰空氣電池 4 1.2.1鋰二氧化碳電池 5 1.2.1.1鋰二氧化碳電池之工作原理 5 1.3 鋰二氧化碳電池充放電機制探討 7 1.3.1放電機制之探討 7 1.3.2充電機制之探討 10 1.4 鋰空氣電池之問題 13 1.5鈉二氧化碳電池 16 1.5.1鈉二氧化碳電池之工作原理 16 1.6鈉二氧化碳電池之充放電機制探討 17 1.6.1放電機制之探討 17 1.6.2充電機制之探討 19 1.7鈉/鋰二氧化碳電池種類 21 1.7.1 有機體系鈉/鋰二氧化碳電池 21 1.7.1.1 有機體系鈉/鋰二氧化碳電池溶劑種類 22 1.7.2混合體系鈉/鋰二氧化碳電池 24 1.7.3準固態體系鈉/鋰二氧化碳電池 24 1.7.4全固態體系鈉/鋰二氧化碳電池 24 1.8常用之鈉/鋰二氧化碳電池陰極觸媒材料 25 1.8.1碳材料 25 1.8.1.1科琴黑 25 1.8.1.2 Super P 25 1.8.1.3石墨烯 25 1.8.1.4奈米碳管 26 1.8.1.5碳奈米纖維 27 1.8.2貴金屬材料 27 1.8.2.1鉑 28 1.8.2.2銥 28 1.8.2.3釕 29 1.8.3 本研究相關之文獻地圖 30 1.8.3.1 鋰二氧化碳電池之釕奈米粒子觸媒材料總結整理 30 1.8.3.2 鈉二氧化碳電池之釕奈米粒子觸媒材料總結整理 32 1.9研究動機與目的 32 第二章 實驗步驟與儀器分析原理 35 2.1 釕奈米粒子修飾多壁奈米碳管複合材料之合成 36 2.1.1配製釕奈米粒子複合奈米碳管之複合材料 37 2.1.2陰極觸媒漿料與電極配製 38 2.1.3 鈕扣型電池組裝 39 2.1.4 鈉/鋰二氧化碳電池測試系統 41 2.2 材料結構鑑定 42 2.2.1 X光繞射儀(X-ray diffraction; XRD) 42 2.2.2掃描式電子顯微鏡(scanning electron microscope; SEM) 44 2.2.3穿透式電子顯微鏡(transmission electron microscope; TEM) 45 2.2.4 X射線光電子能譜儀(X-ray photoelectron spectroscopy; XPS) 47 2.2.5 X光吸收光譜(X-ray absorption spectroscopy; XAS) 49 2.2.6 X光吸收光譜之近邊緣結構(X-ray absorption near-edge structure; XANES) 50 2.2.7 X光吸收光譜之延伸區精細結構(extended X-ray absorption fine structure;EXAFS) 51 2.2.8 拉曼光譜儀(Raman spectroscopy) 52 2.2.9 電化學交流阻抗法(electrochemical impedance spectrum; EIS) 55 2.2.10 循環伏安法(cyclic voltammetry; CV) 57 2.2.11 充放電測試儀 58 第三章 結果與討論 59 3.1釕奈米粒子/奈米碳管複合材料與其相關鑑定 59 3.1.1 XRD鑑定分析 59 3.1.2 SEM表面形貌分析 60 3.1.3 TEM結構分析 62 3.1.4 XPS分析 63 3.1.5 XANES鑑定 64 3.1.6 EXAFS鑑定 65 3.2釕奈米粒子複合奈米碳管之電性分析 67 3.2.1循環伏安法(CV) 67 3.2.2電化學阻抗譜圖 (EIS) 69 3.2.3 充放電分析 73 3.2.3.1最大充放電測試 73 3.2.3.2循環穩定性測試 75 3.3 釕奈米粒子複合奈米碳管材料之充放電機制探討 77 3.3.1 ex-situ XRD放電產物鑑定 78 3.3.2 SEM產物形貌分析 81 3.3.3 Raman放電產物鑑定 83 3.3.4 XPS表面產物鑑定 84 3.3.5 XANES催化觸媒鑑定 87 3.3.6 EXAFS催化觸媒鑑定 88 第四章 結論 90 未來展望 91 參考文獻 92

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