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研究生: 廖重皓
Liao, Chung-Hao
論文名稱: 鋰氧氣電池之釕貴金屬催化反應機制
Mechanism of Noble Metal Ruthenium Catalyzed Reaction in Lithium Oxygen Batteries
指導教授: 胡淑芬
Hu, Shu-Fen
口試委員: 劉佳兒
Liu, Chia-Erh
江佩勳
Jiang, Pei-Hsun
胡淑芬
Hu, Shu-Fen
口試日期: 2023/07/25
學位類別: 碩士
Master
系所名稱: 物理學系
Department of Physics
論文出版年: 2023
畢業學年度: 111
語文別: 中文
論文頁數: 87
中文關鍵詞: 鋰氧氣電池Ru/CNT陰極貴金屬催化機制奈米X光繞射
英文關鍵詞: Li–O2 battery, Ru/CNT cathode, noble metal catalytic mechanism, X-ray Nanodiffraction
研究方法: 實驗設計法紮根理論法比較研究
DOI URL: http://doi.org/10.6345/NTNU202301001
論文種類: 學術論文
相關次數: 點閱:107下載:2
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近年來鋰氧氣電池之研究受到高度重視,因其具極高之能量密度,被視為新世代電動車能源。然而目前於實際應用上仍然存在許多挑戰,例如:過電位高、循環穩定性差、低充電速率,此些問題均與鋰氧氣電池放電產物Li2O2之差勁導電性、導離子性相關。目前研究中,普遍使用貴金屬釕Ru進行催化,並與多壁奈米碳管形成陰極複合材料(Ru/CNT),使用Ru/CNT陰極具大表面積、高放電容量與較低過電位之特點。然而我們對於釕金屬之催化機制了解甚少,且相較於傳統鋰離子電池仍然存在過高之過電位與低循環性能。
本研究藉由濺鍍技術控制局部性分布之釕金屬催化劑,探討貴金屬Ru之充電反應催化機制,並使用奈米X光繞射儀觀測Li2O2之分解與Ru之局部性分布關係。本研究顯示液態電池系統中Li2O2為均相分解,固態電池系統中Li2O2為異相分解,與Ru接觸之Li2O2先行被分解,表示電解液(TEGDME)參與Ru之催化作用,Ru催化效果與電解液之分解相關,其分解之可溶性副產物充當電子受體Acceptor或Redox Mediator (RM),幫助絕緣之Li2O2傳導電子,藉此有效降低充電過電位,但同時也縮短電池之循環壽命。

In recent years, research on lithium-oxygen battery has been highly valued, because of their extremely high energy density, it is regarded as the energy source of the new generation of electric vehicles. However, practical applications still face many challenges, such as high overpotential, poor cycle stability, and low charging rate. These problems are all related to the poor conductivity and ion conductivity of Li2O2, the discharge product of lithium-oxygen batteries. In the current research, the noble metal ruthenium Ru is commonly used for catalysis, and the cathode composite material (Ru/CNT) is formed with multi-walled carbon nanotubes. The Ru/CNT cathode has the characteristics of a large surface area, high discharge capacity, and low overpotential. However, we know little about the catalytic mechanism of ruthenium metal, and compared with traditional lithium-ion batteries, there are still too high overpotential and low cycle performance.
In this study, the locally distributed ruthenium metal catalyst was controlled by sputtering technology. The catalytic mechanism of the charging reaction of noble metal Ru was investigated. The relationship between the decomposition of Li2O2 and the local distribution of Ru was observed using a nanometer X-ray diffractometer. This study shows that Li2O2 decomposes in a homogeneous process in a liquid battery system, and Li2O2 decomposes in a heterogeneous process in a solid-state battery system. The Li2O2 in contact with Ru is decomposed first, which means that the electrolyte (TEGDME) participates in the catalysis of Ru. The catalytic effect of Ru is related to the decomposition of the electrolyte. The soluble by-products of its decomposition act as electron acceptors or Redox Mediators (RM), helping the insulating Li2O2 conduct electrons, thereby effectively reducing the charging overpotential and shortening the battery's cycle life.

謝誌 I 摘要 II ABSTRACT III 第一章 緒論 1 1.1電池之發展 1 1.1.1一次電池 2 1.1.2二次電池 3 1.2二次電池之概述 4 1.2.1鋰離子電池 5 1.2.2鋰氧氣電池 7 1.2.2.1鋰氧氣電池之放電機制 8 1.2.2.2鋰氧氣電池之充電機制 10 1.2.2.3鋰氧氣電池之充電機制問題 12 1.3 陰極材料 13 1.3.1 碳材改製 14 1.3.2 奈米碳管 14 1.3.3 碳纖維 16 1.3.4 石墨烯 17 1.4 催化劑 18 1.4.1 貴金屬 18 1.4.2 氧化還原介質 22 1.5 黏結劑 22 1.5.1黏結劑功能 22 1.5.2 鋰空氣電池常見黏結劑 23 1.5.2.1 聚偏二氟乙烯 23 1.5.2.2 聚四氟乙烯 24 1.5.2.3 羧甲基纖維素 25 1.6 電解質 25 1.6.1 有機電解液 26 1.6.1.1 有機電解質溶劑 29 1.6.1.2 常見電解質溶質 33 1.6.2 水系電解液 34 1.6.3 混合電解液 35 1.6.4 固態電解質 36 1.6.4.1陶瓷固態電解質 36 1.6.4.2聚合物電解質 38 1.7研究動機與目的 40 第二章 實驗步驟與儀器分析原理 41 2.1 實驗步驟 41 2.1.1 陰極合成與配製 41 2.1.2 陰極塗佈 42 2.1.3 貴金屬濺鍍 43 2.1.4 電池組裝 44 2.1.5 鋰氧電池測試系統 46 2.2儀器分析原理 47 2.2.1 X光繞射儀(X-ray diffractometer ; XRD) 48 2.2.2掃描式電子顯微鏡(scanning electron microscopy; SEM) 50 2.2.2.1 二次電子(secondary electron image; SEI) 51 2.2.2.2 能量色散 X 射線光譜(energy-dispersive X-ray spectroscopy; EDS) 51 2.2.3 奈米X光繞射儀(X-ray nanodiffraction; XND) 52 2.2.4 X光吸收光譜儀(X-ray absorption spectroscopy; XAS) 54 2.2.5氣相層析質譜儀(gas chromatography-mass spectrometry; GC-MS) 56 2.2.6傅立葉轉換紅外光譜 (fourier-transform infrared spectroscopy; FTIR) 58 2.2.7充放電測試儀(Cycling machine) 59 第三章 結果與討論 60 3.1 電池陰極材料鑑定 60 3.1.1 陰極形貌之SEM分析 60 3.1.2 濺鍍釕金屬之XAS分析 61 3.1.3 釕金屬局部性分布之EDS分析 62 3.2 釕金屬催化性能鑑定 63 3.2.1循環充放電分析 64 3.2.2放電產物之XRD鑑定分析 65 3.2.3放電產物之SEM形貌分析 66 3.3 釕金屬催化機制之探討 68 3.3.1 XRD鑑定分析 68 3.3.2 XND鑑定分析 70 3.3.3 FTIR鑑定分析 74 3.3.4 GC-MS鑑定分析 75 第四章 結論 76 參考文獻 78

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