臺灣博碩士論文加值系統

鈦酸鈉作為負極材料，具有二氧化鈦層與鈉離子層堆疊之層狀結構，之間有供應鈉離子進行嵌入嵌出的鈉離子通道，與現今最常使用來做為負極的硬碳層狀結構相似，且工作電壓低，可以做為理想的鈉電池負極材料。在本研究中的鈦酸鈉（Na₂Ti₃O₇）是以固態反應法合成，並比較摻雜不同莫耳比例的鋰之後，其結構、形貌以及充放電特性上之表現差異。鈦酸鈉以850度下持溫時間5、8、11於大氣氣氛下進行燒結，燒結後顆粒粒徑在2~10微米，呈短棒狀形貌，而摻雜鋰之後可發現整體顆粒較為緻密，提高摻雜鋰比例之後則有熔融狀顆粒出現。以具有層狀結構的單斜晶系鈦酸鈉（Na₂Ti₃O₇）作為鈉離子電池的負極材料，並摻雜鋰以研究鈦酸鈉在電性上之表現差異。實驗中組成之半電池在電壓區間0.01~3V之間進行充放電測試，各樣本首圈放電容量平均約在70 mAh/g (4mA/g, 0.1C)，不可逆率40%，3圈及10圈後電容量損失率約為60%。

The sodium titanate (Na₂Ti₃O₇) as the anode material with the layered structure constructing by titanium dioxide layer and sodium ion layer. And also a pathway between these layer structures providing the sodium ion intercalation, yet its low working voltage. These supposing the sodium titanate as an alternative choice for the anode material of sodium-ion batteries in the future. The sodium titanate (Na₂Ti₃O₇) anode material in this research synthesis by conventional solid state reaction under 850 degree Celsius with different condition. The crystal structure and surface morphology of sodium titanate (Na₂Ti₃O₇) were monoclinic with a rod like shape, particle size between 2 ~10 micron. The overall particle density of sodium titanate increase with the molar ratio of lithium increase in the sodium titanate. Finally the sodium half-cell CR 2032 present a first discharge capacity70 mAh/g (4mA/g, 0.1C) with about 40% capacity lost. After third and 10th cycle, capacity drop to about 40% compare to the first cycle. The charge-discharge curve has been test under 0.01~3V.

摘要 i
ABSTRACT ii
誌謝 iii
目錄 iv
表目錄 vi
圖目錄 vii
第一章 緒論 1
1-1前言 1
1-2 研究背景及文獻回顧 2
1-3 研究動機與目的 4
第二章 基礎理論與文獻回顧 5
2-1 儲能技術之發展 5
2-2鹼金屬離子電池 5
2-3 鈉電池負極材料發展 7
2-3-1鈦基化合物電極材料 8
2-3-2鈦酸鈉負極材料 13
2-4鈦酸鈉負極材料製備 21
2-4-1 固態反應法 21
2-4-2 沉澱法 22
2-4-3 水熱法 22
2-4-4 溶膠凝膠法 22
2-4-5 噴霧法 22
第三章 實驗製程及量測 23
3-1 實驗架構 23
3-1-1鈦酸鈉層狀負極材料製備 23
3-1-2半電池組成 23
3-2 實驗藥品 24
3-2-1 鈦酸鈉負極材料製備 24
3-2-2 極片製備暨半電池組裝 24
3-3 實驗設備 25
3-3-1 滾軸式球磨機 (MUBM-340-RTD) 25
3-3-2 高溫燒結爐 (DENG YNG, DF40) 25
3-3-3 行星式球磨機 (Gold Max, G-Mixer 400S) 26
3-3-4 極片塗佈機 (浩聚實業有限公司，LE-CT75) 26
3-3-5 極片滾壓機 (T·VERTER, N2-2P5-H) 27
3-3-6 厭氧操作箱 (MBRAUN, Unilab-B) 27
3-3-7電化學測試平台(佳優科技股份有限公司，BAT-750B) 28
3-4 實驗流程 29
3-5 鈦酸鈉粉末製備暨結構測定 30
3-5-1 鈦酸鈉負極材料製備 30
3-5-2 X射線繞射分析儀 (X-Ray diffraction, XRD) 31
3-5-3 掃描式電子顯微鏡 ( Scanning electron microscopy, SEM ) 32
3-5-4 拉曼光譜分析儀(Raman scattering spectrometer) 33
3-6 半電池組裝暨電化學測試 34
3-6-1 鈦酸鈉負極材料極片製備暨電池組裝 34
第四章 結果與討論 36
4-1 X光繞射圖譜分析 36
4-1-2 摻雜鋰之鈦酸鈉繞射圖譜分析 37
4-2 掃描式電子顯微鏡形貌分析 39
4-3 拉曼光譜分析 42
4-4 充放電測試－CR 2032 鈕扣型半電池 43
第五章 結論 48

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