臺灣博碩士論文加值系統

近年來，隨著科技興盛且面臨能源耗竭的時代，鋰離子電池應用於許多3C電子產品及交通工具的主要動力來源如：數位相機、行動電話、筆記型電腦、電動車、油電混合車等。並成為現代不可以或缺的能源之一。早於1990年代由日本SONY公司點燃了鋰離子電池生命之火，並經許多專家學者及廠商不斷努力開發及創新下，至今已普遍應用在生活中，但由於不當使用或運輸製造的過程當中容易造成事故的發生，因此嚴重的威脅及影響使用者安全，有專家學者曾提出鋰離子電池在充放電過程或環境溫度高於200℃時，正極材料與有機電解質會產生反應並釋出氧氣，導致電池過熱、洩漏、起火及爆炸等事故的發生，因此安全疑慮也成為眾人關注的議題之一。
本研究為了釐清正極材料與有機電解質間之熱危害特性，在不含鋰鹽、黏著劑等其他電池組件干擾的情況下模擬鋰離子電池放電後之熱不穩定現象。研究利用微差掃描熱卡計(Differential Scanning Calorimeter, DSC)，探討市售鋰離子電池常用之鋰正極材料LiCoO2、LiMn2O4、LiFePO4、LiNi0.8Co0.2O2、LiCoO2(Al2O3)、LiNi1/3Mn1/3Co1/3O2、LiNi0.5Mn0.3Co0.2O2、LiNi0.8Co0.15Al0.05O2等，搭配商業鋰離子電池常用有機電解質分別以單一DMC、DEC、EC及混合(DMC/EC)、(DEC/EC)等之反應特性。最後藉由測定結果數據（如Onset Temperature,Tonset起始放熱溫度、熱焓值及熱圖譜Thermogram等資料）進行分析評估各別正極材料與電解質間之熱不穩定現象。研究結果可作為未來開發及提升鋰離子電池安全設計之基礎考量。
研究發現鋰化正極材料LiFePO4熱穩定性較佳且無明顯的放熱現象，而鋰化正極材料LiMn2O4約至225℃-258℃開始有放熱現象並有兩個明顯放熱峰值，熱穩定性較差，其他鋰化正極材料約至300℃之後才有所反應。並可從鋰化正極材料搭配單一及混合有機電解質結果得知，當混合電解質(DMC/EC、DEC/EC)後熱穩定性較與單一(DMC、DEC、EC)電解質來的更佳。當正極材料表面塗層Al2O3混合單一電解質DMC的情況下，不一定能有效的減少正極材料與電解質的放熱反應速率，但含有LiNi1-x-yCoxAlyO2或Coating Al2O3離子的正極材料確實能有效提升熱穩定性。

關鍵字：鋰離子電池、正極材料、電解質、起始放熱溫度

Lithium-ion battery becomes the most important energy supplier with the rapid development of the portable electric and electronic products. However overheating, fire and explosion accidents occurred from time to time owing to battery thermal runaway. One of the possible reasons is the exothermic reaction between the lithiated cathode materials and electrolytes.
In this study thermal curves of eight lithiated cathode materials reacted with different electrolytes that are commonly used in lithium-ion battery are performed in a Mettler TA-4000 System coupled with a differential scanning calorimetry (DSC822) measuring cell. Disposable crucible (ME-26732) which can withstand up to 100 bars is used for detecting thermal curves. Data are acquired and stored for further evaluation. Scanning rate is selected to be 4K min-1 in programmatic ramp up to 500℃ for the reason of sustaining better thermal equilibrium inside the crucible.
Electrolytes, namely, ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and mixtures of DMC/EC and DEC/EC with the ratio of 1：1 reacted with eight cathode materials, i.e., lithium iron phosphate (LiFePO4), lithium manganese oxide (LiMn2O4), lithium nickel manganese cobalt oxide (LiNi1/3Mn1/3Co1/3O2, NMC333), LiNi0.5Mn0.3Co0.2O2, NMC532), (LiNi0.8Co0.2O2, NCA ), etc. are measured and accessed, respectively.
Results indicate that the lowest onset temperature occurred at the reaction of lithium manganese oxide (LiMn2O4) with DMC as well as DMC/EC mixture. In addition, lithium iron phosphate (LiFePO4) reacted with electrolytes do not exhibit exothermic behaviors and turns out to have the best thermal stability than other lithited cathode materials. Furthermore electrolyte mixtures seem to have better thermal stability than the single electrolyte alone. These phenomena provide much more clear sights for searching the root causes to explain or link the incidents of overheating, fire or explosion encountered in lithium-ion batteries.

Keywords: lithiated cathode material, onset temperature, thermal instability, electrolyte

摘要
Abstract
誌謝
目錄
表目錄
圖目錄
第一章 緒論
1.1 研究背景
1.2 研究動機與目的
1.3 研究流程
第二章 文獻回顧
2.1 鋰離子電池發展簡史
2.2 鋰離子電池的基本概念及組構介紹
2.3 鋰離子電池工作原理與機制
2.4 鋰離子電池具備特點
2.5 鋰離子電池之正極材料及分子結構：
2.6 鋰離子電池負極材料相關研究
2.7 鋰離子電池之電解質相關研究
2.8 鋰離子電池之鋰鹽電解質相關研究
2.9 鋰離子電池之隔離膜
2.10 其他鋰離子電池相關文獻研究
第三章 研究方法與步驟
3.1 實驗材料
3.2 實驗藥品
3.3 實驗樣品配置
3.4 實驗儀器及設備
3.5 工作原理
3.6 實驗條件與方法
3.7 實驗流程與步驟
第四章 結果與討論
4.1 模擬鋰離子電池放電後正極材料與單一電解質之熱不穩定性
4.1.1 正極材料與單一電解質DMC之DSC測試
4.1.2 正極材料與單一電解質DEC之DSC測試
4.1.3 正極材料與單一電解質EC之DSC測試
4.1.4 正極材料與單一電解質DMC、DEC、EC之DSC比較
4.2 模擬鋰離子電池放電後正極材料與混合電解質之熱不穩定性
4.2.1 正極材料與混合電解質DMC/EC之DSC測試
4.2.2 正極材料與混合電解質DEC/EC之DSC測試
4.2.3 正極材料與混合電解質DMC/EC、DEC/EC之DSC比較
第五章 結論與建議
5.1 結論
5.2 建議
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