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研究生： 林冠宏
Lin, Guan-Hong
論文名稱： 以固態反應法製備鈦基複合氧化物作為負極材料之臨場分析與應用
Solid-State Synthesis of TiO2–SnO2 Composite Oxide Anodes with Spinodal Decomposition for Lithium-Ion Batteries: Electrochemical Performance and In-Situ XRD Analysis
指導教授： 向性一
Hsiang, Hsing-I
學位類別： 碩士
Master
系所名稱： 智慧半導體及永續製造學院 - 智慧與永續製造學位學程
Program on Smart and Sustainable Manufacturing
論文出版年： 2026
畢業學年度： 114
語文別： 中文
論文頁數： 110
中文關鍵詞： 二氧化鈦 、二氧化錫 、組成調變 、相分離 、固溶體 、固態反應法 、碳包覆 、鋰電池 、負極材料
外文關鍵詞： titanium dioxide, tin dioxide, composition modulation, phase separation, solid solution, solid-state reaction, carbon coating, lithium-ion battery, anode material
相關次數： 點閱：5  下載：0 
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    • 本研究以 TiO2-SnO2 rutile 固溶體之退火誘發相分離與 Ti-rich/Sn-rich組成分配作為鋰離子電池負極材料設計概念，並搭配碳包覆改善電子傳輸。材料分析採用XRD、operando XRD、STEM-EDS、SAED、充放電循環、倍率性能、循環伏安法與交流阻抗分析。結果顯示，在An1h@C、An4h@C與 An10h@C 三組已進行電化學測試的樣品中，初始去鋰化容量由 570.5 mAh/g 提升至1049.7 mAh/g，100圈後容量維持率由18.8 %提升至35.2 %。XRD 峰分離、SAED 晶面間距變化與EDS line-scan 結果顯示退火後產生Ti-rich/Sn-rich 組成分配，此現象與 TiO2-SnO2系統文獻所報導之 spinodal decomposition 行為相符，但仍需調幅波長、相區連續性與多區域統計進一步確認。由於An0h@C未進行電化學測試，本研究僅能指出退火時間與低倍率容量提升之相關性，而不能直接證明退火誘發組成調變相較未退火固溶體具有本質優勢。整體容量衰退仍明顯，EIS/DRT結果亦顯示循環後界面阻抗與質傳相關阻抗增加，說明Sn相關體積變化與SEI不穩定仍是主要限制。

    This study uses annealing-induced phase separation and Ti-rich/Sn-rich composition partitioning in a TiO₂-SnO₂ rutile solid solution as a design strategy for lithium-ion battery anode materials, together with carbon coating to improve electron transport. XRD, operando XRD, STEM-EDS, SAED, galvanostatic cycling, rate-capability testing, cyclic voltammetry, and electrochemical impedance/DRT analyses were conducted.
    Among the electrochemically tested An1h@C, An4h@C, and An10h@C samples, the initial delithiation capacity increased from 570.5 to 1049.7 mAh g⁻¹, and the capacity retention after 100 cycles increased from 18.8% to 35.2%. XRD peak splitting, SAED d-spacing changes, and EDS line-scan results indicate Ti-rich/Sn-rich composition partitioning after annealing. This behavior is consistent with spinodal decomposition reported for TiO₂-SnO₂ systems, but further confirmation of modulation wavelength, phase-domain continuity, and multi-area statistics is still required.
    Because An0h@C was not electrochemically tested, this study can only establish a correlation between annealing time and improved low-rate capacity, rather than directly proving an intrinsic advantage over the unannealed solid solution. Overall capacity fading remains evident, and EIS/DRT results show increased interfacial and transport-related resistance after cycling, indicating that Sn-related volume change and SEI instability remain the primary limitations.

    摘要 I 誌謝 XXX 目錄 XXXI 圖目錄 XXXIII 表目錄 XXXVI 第一章 緒論 1 1.1 前言 1 1.2 研究動機 3 1.3 研究目的 4 第二章 文獻回顧 6 2.1 鋰離子電池負極之儲鋰機制 6 2.2 SnO₂負極之反應機制與失效行為 8 2.3 TiO₂及TiO₂–SnO₂複合材料 10 2.4 TiO2–SnO₂固溶體、相分離與組成調變 16 2.5 碳包覆與界面穩定化策略 17 2.6 電化學分析與operando XRD 17 2.7 本研究之研究定位 18 第三章 實驗方法與設計 19 3.1 實驗設計 19 3.2 實驗材料 20 3.3 活性材料製備 21 3.4 材料鑑定分析 22 3.4.1 X光繞射儀(X-Ray Diffractometer, XRD) 22 3.4.2 穿透式電子顯微鏡與STEM-EDS/SAED分析 22 3.5 半電池組裝測試 24 3.5.1 半電池組裝 24 3.5.2 充放電測試 24 3.5.3 循環伏安法 25 3.5.4 定電位交流阻抗測試 27 3.6 臨場XRD分析 29 第四章 數據結果與討論 31 4.1 鈦錫複合氧化物之結構與組成分析 31 4.1.1 X光繞射分析 31 4.1.2 SAED與EDS分析 35 4.1.3 充放電循環性能 40 4.1.4 倍率性能 44 4.1.5 循環伏安分析 46 4.1.6 EIS與DRT分析 49 4.2 同步輻射operando XRD分析 53 4.3 結構—電化學性能關係 59 第五章 結論 60 第六章 未來展望 63 6.1 建立完整對照組 63 6.2 定量退火誘發組成調變 63 6.3 定量碳包覆與顆粒特性 63 6.4 直接觀察循環造成的結構與界面失效 64 6.5 改善EIS、DRT與傳輸分析 64 6.6 完善operando結構分析 64 第七章 參考文獻 66

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