LiMn2O4尖晶石因為內部的空缺結構可以容納鋰離子的進出而可以成為鋰二次電池陰極材料，且因其與現有鋰鈷、鋰鎳系統較低價位與高安全性的優勢使其極具未來的發展性，但要發展鋰錳尖晶石成為電池陰極材料，亦有較低電容量及低生命週期的缺點需克服，了解尖晶石材料在充放電過程中的結構與相變化為改善材料性質的重點。
利用熱擴散的原理可以使鋰離子進入尖晶石的內部空缺，與充放電情形相似，所以用690℃的溫度，使Li2CO3分解出鋰離子，並擴散進入LiMn2O4內，以X-ray對熱處理後的LiMn2O4尖晶石進行檢測，發現當鋰離子進佔鋰錳尖晶石內部的空缺位置時，尖晶石的晶格大小會產生膨脹，而膨脹極限為原晶格常數的12%。
在450℃ ~ 600℃的溫度範圍內使Li2CO3與LiMn2O4一起進行熱處理，以X-ray檢測發現Li2CO3與LiMn2O4在溫度到達500℃時先發生 Li2CO3 + LiMn2O4 + O2 → 2Li2MnO3 + CO2 ↑的化學反應，到570℃以後則再發生Li+ + LiMn2O4 → Li1+xMn2O4的塞入反應。
以穿透式電子顯微鏡觀察LiMn2O4尖晶石的晶粒，發現晶粒的形狀以{111}的面最容易出現，使得晶粒呈八面體及四面體形。

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1. 簡介(Introduction)----------------------------------------------------------------------- 1
2. 文獻回顧(Literature Review)---------------------------------------------------------- 2
2.1. 鋰離子二次電池的陰極材料----------------------------------------------------2
2.2. LiMn2O4的相變化及其對充放電過程的影響------------------------------ 10
2.3. LiMn2O4在280K溫度下的Jahn-Teller結構相變化---------------------- 12
2.4. 尖晶石晶粒形狀及γ- plot ----------------------------------------------------17

3. 實驗步驟(Experimental Procedure)------------------------------------------------- 22
3.1. 實驗藥品(Experimental chemicals)------------------------------------------- 22
3.2. 實驗樣本製作(Preparation of samples)-------------------------------------- 22
3.2.1. LiMn2O4 粉晶製作---------------------------------------------------------- 22
3.2.2. LiMn2O4 燒結塊製備------------------------------------------------------- 22
3.2.3. Li2CO3 燒結塊製備--------------------------------------------------------- 23
3.2.4. 熱處理試片製備------------------------------------------------------------- 23
3.2.5. 電解試片製備---------------------------------------------------------------- 23
3.2.6. 充放電試片製備------------------------------------------------------------- 24
3.2.7. LiMn2O4粉末TEM及800℃/12h退火後的LiMn2O4粉末
TEM試片製作--------------------------------------------------------------- 24
3.3. X-ray 繞射(X-ray diffractometry)--------------------------------------------- 25
3.4. TEM 分析------------------------------------------------------------------------ 25

4. 實驗結果(Results)--------------------------------------------------------------------- 26
4.1. X-ray 繞射分析結果(XRD)--------------------------------------------------- 26
4.1.1. LiMn2O4粉體製備----------------------------------------------------------- 26
4.1.2. LiMn2O4 燒結塊試片之X-ray 分析(Ⅰ)-------------------------------- 26
4.1.3. LiMn2O4 燒結塊試片之X-ray 分析(Ⅱ)-------------------------------- 28
4.1.4. LiMn2O4 燒結塊試片之X-ray 分析(Ⅲ)-------------------------------- 30
4.1.5. LiMn2O4 燒結塊試片之X-ray 分析(Ⅳ)-------------------------------- 32
4.1.6. LiMn2O4 燒結塊/Li2CO3 燒結塊電解反應分析----------------------- 34
4.1.7. LiMn2O4 燒結塊/ LiMn2O4 燒結塊電解反應分析-------------------- 35
4.1.8. Li/LiMn2O4 燒結塊充電反應分析---------------------------------------- 36
4.1.9. Li/LiMn2O4 燒結塊逆充電反應分析------------------------------------- 38
4.2. 透射式電子顯微鏡分析(TEM) ---------------------------------------------- 40
4.2.1. LiMn2O4 尖晶石粉晶TEM分析------------------------------------------ 40

4.2.2. 800℃/退火12h的LiMn2O4 尖晶石粉晶TEM分析------------------- 44

5. 結果討論(Discussion of results)----------------------------------------------------- 49
5.1. LiMn2O4 粉體及燒結塊---------------------------------------------------------- 49
5.2. 過量鋰離子對LiMn2O4 燒結塊的影響-------------------------------------- 50
5.3. 常溫電解對LiMn2O4 燒結塊的影響----------------------------------------- 53
5.4. 充電及逆充電反應對LiMn2O4 燒結塊的影響----------------------------- 54
5.5. 尖晶石γ- plot 及晶粉外型---------------------------------------------------- 56

6. 結論(Conclusions)-------------------------------------------------------------------- 63

未來進行方向------------------------------------------------------------------------------ 64

參考資料(References)--------------------------------------------------------------------- 65

附錄 (Appendix)-------------------------------------------------------------------------- 68

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