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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 劉如熹 | zh_TW |
| dc.contributor.advisor | Ru-Shi Liu | en |
| dc.contributor.author | 吳約安 | zh_TW |
| dc.contributor.author | Yueh-An Wu | en |
| dc.date.accessioned | 2026-07-08T16:43:55Z | - |
| dc.date.available | 2026-07-09 | - |
| dc.date.copyright | 2026-07-08 | - |
| dc.date.issued | 2026 | - |
| dc.date.submitted | 2026-06-18 | - |
| dc.identifier.citation | [1] Galvani, L. De Viribus Electricitatis in Motu Musculari. Commentarius. De Bonoiensi Scientiarum et Artium Intituo atque Academie Commentarii 1791, 7, 363–418.
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/102566 | - |
| dc.description.abstract | 近年隨電動車、人工智慧及資料中心之蓬勃發展，儲能需求日益提升。然而鋰離子電池已趨近於理論極限，金屬空氣電池具高能量密度、成本優勢及潛在應用價值，逐漸受產業與學術界關注。相較於鋰氧電池易因鋰枝晶生成導致電池短路、鋅氧電池受析氫腐蝕且放電可逆性差及鈉空氣電池因於空氣中反應性高易導致安全性風險，鎂氧電池(magnesium–oxygen battery)兼具高能量密度、永續性及安全性，故被視為極具潛力之金屬空氣電池。然其實際應用仍受限於放電產物堆積、界面極化、過電位過高等問題，關鍵瓶頸主要來自於放電產物氧化鎂之絕緣特性。
本研究藉四甲基哌啶氧化物(2,2,6,6-tetramethylpiperidine-1-oxyl; TEMPO)作為氧化還原介質(redox mediator; RM)應用於半固態電解質聚偏氟乙烯-六氟丙烯共聚物(polyvinylidene fluoride hexafluoropropylene; PVDF-HFP)，以促進放電產物分解並提升鎂氧電池之電化學效能。實驗結果證實，添加0.75 M TEMPO之鎂氧電池相較於未添加TEMPO之鎂氧電池，其循環壽命由20圈提升至45圈，增幅達125%，同時過電位由1.51 V降低至0.77 V，降幅達49%，證實TEMPO有助於提升鎂氧電池之循環壽命與降低過電位。 本研究新穎性乃藉同步輻射中心之X光吸收光譜、Tauc plot及理論計算，揭示放電產物內部存在鎂氧缺陷並進行能隙分析討論。經實驗計算，放電生成之氧化鎂因內部鎂氧缺陷之形成，使其能隙(band gap)由7.8 eV顯著降低至4.3 eV。進一步藉密度泛函理論計算(density functional theory; DFT)證實，當氧化鎂引入氧空缺後，禁帶(forbidden band)內將形成額外缺陷態(defect states)與中間能階(mid-gap state)，進而調控其電子結構與電荷傳輸行為，使原本絕緣之放電產物轉化為具電子傳導能力之缺陷型結構，有利於後續充電反應中之可逆分解，提升鎂氧電池之效能。 | zh_TW |
| dc.description.abstract | With the rapid development of electric vehicles, artificial intelligence, and data centers, the demand for energy storage has increased significantly. Due to the theoretical limitations for lithium-ion batteries, metal–air batteries have attracted further attention owing to their high energy density and low cost. Compared with other metal–oxygen batteries, magnesium–oxygen (Mg–O2) batteries have emerged as highly promising candidates for metal–air batteries owing to their high energy density, sustainability, and intrinsic safety. However, their practical application is still hindered by discharge product accumulation and high overpotential. Among these issues, the key bottleneck mainly arises from the insulating nature of the discharge product.
To enhance the performance of magnesium–oxygen batteries, the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was introduced as a redox mediator into a PVDF-HFP semi-solid-state electrolyte to promote the decomposition of discharge products and improve the electrochemical performance. The addition of 0.75 M TEMPO extended the cycle life by 125% and reduced the overpotential by 49%. This study validates that TEMPO markedly enhances the cycling stability and reaction kinetics. This work elucidates the internal magnesium–oxygen defect states in the discharge product and provides a detailed band gap analysis through experimental techniques and density functional theory (DFT) calculations. Experimental results reveal that the formation of these defects significantly reduces the band gap of the discharged MgO from 7.8 eV to 4.3 eV, effectively lowering the barrier to charge transport. This transition promotes reversible decomposition during charging, providing a critical pathway for optimizing the electrochemical efficiency of magnesium–oxygen batteries. | en |
| dc.description.provenance | Submitted by admin ntu (admin@lib.ntu.edu.tw) on 2026-07-08T16:43:55Z No. of bitstreams: 0 | en |
| dc.description.provenance | Made available in DSpace on 2026-07-08T16:43:55Z (GMT). No. of bitstreams: 0 | en |
| dc.description.tableofcontents | 口試委員會審定書 i
誌謝 ii 摘要 iii Abstract iv 目次 v 圖次 ix 表次 xv 1 第一章 緒論 1 1.1 電化學概論 1 1.1.1 電化學歷史 1 1.1.2 電化學之熱力學 3 1.1.3 電化學之動力學 4 1.2 儲能系統發展 6 1.2.1 鋰離子電池(Li-Ion Battery) 6 1.2.2 燃料電池(Fuel Cell) 7 1.3 金屬空氣電池(Metal–Air Battery) 11 1.3.1 鋰氧電池(Li–O2 Battery) 14 1.3.2 鋅氧電池(Zn–O2 Battery) 20 1.3.3 鎂氧電池(Mg–O2 Battery) 24 1.4 鎂氧電池之電解質 29 1.4.1 水系電解質(Aqueous Electrolyte) 30 1.4.2 非水系電解質(Aprotic Electrolyte) 32 1.4.3 聚合物電解質(Polymer Electrolyte) 35 1.5 氧化還原介質(Redox Mediator; RM) 36 1.5.1 氧化還原介質之發展歷史 36 1.5.2 氧化還原介質於金屬空氣電池之反應機制 37 1.5.3 氧化還原介質於金屬空氣電池之應用 38 1.6 鎂氧電池之陰極觸媒與催化劑 41 1.6.1 貴金屬催化劑 41 1.6.2 過渡金屬與雙金屬催化劑 43 1.7 以專利與論文地圖探討鎂氧電池之挑戰 45 1.7.1 專利地圖 45 1.7.2 論文地圖 49 1.8 研究動機與目的 54 2 第二章 實驗步驟與儀器原理介紹 55 2.1 實驗藥品 55 2.2 實驗步驟 57 2.2.1 含釕之奈米碳管合成 57 2.2.2 陰極漿料配製 57 2.2.3 半固態電解質之合成 58 2.2.4 氧化還原介質配製 59 2.2.5 鈕扣型鎂氧電池之組裝 60 2.2.6 軟包型鎂氧電池之組裝 62 2.3 儀器分析原理 63 2.3.1 X光繞射儀(X-Ray Diffractometer; XRD) 64 2.3.2 X光吸收光譜(X-Ray Absorption Spectroscopy; XAS) 65 2.3.3 場發射掃描式電子顯微鏡(Field Emission Scanning Electron Microscope; FESEM) 68 2.3.4 場發射穿透式電子顯微鏡(Field Emission Transmission Electron Microscope; FETEM) 70 2.3.5 拉曼光譜(Raman Spectroscopy) 71 2.3.6 X光光電子能譜儀(X-Ray Photoelectron Spectroscopy; XPS) 74 2.3.7 充放電機(Cycling Machine) 76 2.3.8 循環伏安法(Cyclic Voltammetry; CV) 77 2.3.9 電化學阻抗頻譜(Electrochemical Impedance Spectroscopy; EIS) 79 2.3.10 流變儀(Rheometer) 81 2.3.11 光致發光光譜(Photoluminescence Spectroscopy; PL) 82 2.3.12 密度泛函理論(Density functional Theory; DFT) 84 3 第三章 結果與討論 85 3.1 含釕之奈米碳管(RuCNT)之結構鑑定 85 3.1.1 含釕之奈米碳管(RuCNT)之定性鑑定 85 3.1.2 含釕之奈米碳管(RuCNT)之形貌分析 86 3.2 半固態電解質之性能分析 88 3.2.1 半固態電解質之離子傳輸 88 3.2.2 電化學穩定性測試 90 3.3 TEMPO氧化還原介質之性質分析 92 3.3.1 奈米碳管之拉曼光譜與界面交互作用探討 92 3.3.2 氧化還原介質之循環伏安測試 93 3.4 TEMPO氧化還原介質應用於鈕扣型鎂氧電池之電化學測試 95 3.4.1 恆電流循環測試 95 3.4.2 以實驗設計方法探討TEMPO於鎂氧電池之過電位分析 98 3.4.3 氬氣環境之恆電流循環測試 100 3.4.4 恆電流最大放電測試 101 3.4.5 恆電流充放電測試 102 3.4.6 TEMPO 氧化還原介質之電化學動力學分析 103 3.4.7 軟包型鎂氧電池 105 3.5 TEMPO氧化還原介質應用於鎂氧電池之放電產物鑑定 107 3.5.1 X光光電子能譜儀 107 3.5.2 軟X光吸收光譜 113 3.5.3 陰極放電產物之形貌鑑定 116 3.6 TEMPO應用於鎂氧電池之反應機制 126 3.6.1 TEMPO濃度調控之黏度行為對質傳動力學分析 126 3.6.2 放電產物之能隙分析與氧缺陷鑑定 129 3.6.3 基於密度泛函理論之能帶結構與態密度(DOS)理論計算 132 4 第四章 結論 133 5 參考文獻 134 | - |
| dc.language.iso | zh_TW | - |
| dc.subject | 鎂氧電池 | - |
| dc.subject | 四甲基哌啶氧化物 | - |
| dc.subject | 氧化還原介質 | - |
| dc.subject | 半固態電解質 | - |
| dc.subject | magnesium–oxygen battery | - |
| dc.subject | 2,2,6,6-tetramethylpiperidine-1-oxyl | - |
| dc.subject | redox mediator | - |
| dc.subject | semi-solid-state electrolyte | - |
| dc.title | 以四甲基哌啶氧化物之氧化還原介質應用於半固態鎂氧氣電池 | zh_TW |
| dc.title | Application of 2,2,6,6-Tetramethylpiperidine-1-oxyl as a Redox Mediator in Semi-Solid-State Magnesium–Oxygen Batteries | en |
| dc.type | Thesis | - |
| dc.date.schoolyear | 114-2 | - |
| dc.description.degree | 碩士 | - |
| dc.contributor.oralexamcommittee | 陳致融;王丞浩;高夢瑤;劉佳兒 | zh_TW |
| dc.contributor.oralexamcommittee | Chih-Jung Chen;Chen-Hao Wang;Meng-yao Gao ;Chia-Erh Liu | en |
| dc.subject.keyword | 鎂氧電池; 四甲基哌啶氧化物; 氧化還原介質; 半固態電解質 | zh_TW |
| dc.subject.keyword | magnesium–oxygen battery; 2,2,6,6-tetramethylpiperidine-1-oxyl; redox mediator; semi-solid-state electrolyte | en |
| dc.relation.page | 159 | - |
| dc.identifier.doi | 10.6342/NTU202601270 | - |
| dc.rights.note | 同意授權(限校園內公開) | - |
| dc.date.accepted | 2026-06-18 | - |
| dc.contributor.author-college | 重點科技研究學院 | - |
| dc.contributor.author-dept | 奈米工程與科學學位學程 | - |
| dc.date.embargo-lift | 2026-12-18 | - |
| 顯示於系所單位： | 奈米工程與科學學位學程 | |
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