臺灣博碩士論文加值系統

鋰離子電池在攜帶式電子設備的小型電池市場上佔據主導地位，且成功為電動汽車和固定式儲能的首選技術。鋰鈷電池為市面上電極結構穩定性最高且研究較完整的鋰離子電池，目前研究不同快速充電方式所造成電極之影響較少，尤其具有逆還原反應的正弦波充電，因此我們利用光譜、阻抗量測分析，探討不同快速充電方式及不同次數下的電極材料完整性。
鋰鈷電池的使用壽命及安全度與電極材料的結晶度密切相關，尤其是石墨電極為關鍵。為了觀察電極材料在多次充放電循環下電極材料損壞程度，此篇論文使用商用鋰鈷電極與石墨電極的電池作為實驗樣品，分別利用恆電流-恆電壓和正弦波充電法快速對電池充電，經過循環充放電100次、300次及500次後，應用各種電化學技術及檢測儀器，如電化學阻抗圖譜、拉曼光譜儀、X光繞射儀等。通過阻抗和光譜技術分析，比較不同快速充電循環下造成阻抗差異及對電極的損壞程度。
經過SEM、XRD、Raman對電極檢測，發現電池的正極鈷酸鋰材料結構穩定對兩種充電方法在500次循環下變化不明顯，但是對於石墨電極的損壞使用CC-CV的充電法較嚴重，且生成較多的SEI膜。本篇論文呈現利用不同充電方式及多種量測分析技術審視電極材料完整性，這些經驗對於未來開發新型材料電池可能仍然適用。

Lithium-ion batteries dominate markets of small-scale batteries for the use of portable electronics and successfully serve as a top-tiered choice for electric vehicles and stationary energy storage technologies. As one type of lithium-ion batteries, lithium-cobalt batteries has the highest electrode structural stability among other batteries in the market, and are studied more extensively. To date, research regarding the impact of different fast charging methods on electrodes is deficient, especially that involves the sinusoidal wave charging with reverse reduction reaction. Therefore, we use spectrum, impedance measurement and analysis to investigate the integrity of electrode materials under different fast charging methods and times.
The longevity and safety issues of lithium-cobalt batteries are correlated with the crystallinity of electrode materials, especially graphite electrodes. In order to observe the extent of damage to electrode materials under multiple charge-discharge cycles, batteries with commercial lithium cobalt electrodes and graphite electrodes are rapidly charged via constant current-constant voltage and sinusoidal wave charging methods, respectively. After 100, 300 and 500 charge and discharge cycles, a variety of electrochemical techniques and testing apparatuses, such as electrochemical impedance spectroscopy, Raman spectrometer, and X-ray diffractometer, etc, are applied. Through the impedance and spectroscopic analysis, the difference in electrodes impedance and the extent of damage to the electrodes under different fast charging cycles were compared.
After implementing SEM, XRD and Raman counter electrode testing, it was discovered that the structures of the lithium cobalt oxide positive electrode materials in the batteries were stable, not susceptible to change under 500 cycles of both charging methods. However, the damage to the graphite electrode using the CC-CV charging method was observable, with more SEI films engendered. This paper presents a framework of applying diverse charging methods, measurements and analytic techniques to interrogate the integrity of electrode materials. The experience from this research is applicable to the development in new battery materials in the foreseeable future.

摘要 i
ABSTRACT iii
致謝 v
目錄 vi
表目錄 ix
圖目錄 x
第一章 緒論 1
1.1 前言 1
1.2 鋰離子電池 1
1.3 鋰離子電池作動機制 2
1.4 鋰離子電池材料與特性 4
1.4.1 電極 4
1.4.2 電解質(Electrolyte) 11
1.4.3 隔離膜(Separator) 13
1.5 鋰離子電池優缺點 13
1.6 固態電解質層 14
1.6.1 石墨電極的固態電解質層生成機制 14
1.6.2 石墨電極的固態電解質層組成 15
1.7 電池充電方式 17
1.7.1 恆電流-恆電壓充電法 18
1.7.2 正弦波充電法 19
1.8 研究動機 20
第二章 文獻回顧 21
2.1 電池老化 21
2.2 SEM對SEI膜之觀測 21
2.3 電化學阻抗圖譜(EIS) 23
2.3.1 等效電路模型 24
2.3.2 EIS對鋰離子電池之阻抗檢測 25
2.4 電極檢測 26
2.4.1 X光繞射儀對電極之檢測 26
2.4.2 拉曼光譜儀對電極之檢測 30
第三章 實驗流程與方法 35
3.1 實驗儀器 35
3.2 實驗流程 36
3.3 直流電源分析儀充放電參數 37
3.4 恆電位恆電流儀量測和分析技術 38
3.4.1 等效電路模型建立 39
3.5 場發射掃瞄式電子顯微鏡檢測技術 40
3.5.1 能量色散X射線光譜儀 42
3.6 X光繞射儀檢測技術 43
3.6.1 XRD數據處理 44
3.7 拉曼光譜學檢測技術 45
第四章 結果與討論 48
4.1 電池電容量 48
4.2 充放電循環溫度 50
4.3 電池阻抗 52
4.3.1 電池的奈奎斯特圖 52
4.3.2 電池之等效電路模型 55
4.4 電極之SEM圖譜 57
4.4.1 SEM之鈷酸鋰電極 57
4.4.2 EDS之鈷酸鋰電極 60
4.4.3 SEM之石墨電極 64
4.4.4 EDS之石墨電極 66
4.5 電極之XRD圖譜 69
4.5.1 XRD之鈷酸鋰電極 70
4.5.2 XRD之石墨電極 73
4.6 電極之拉曼圖譜 76
4.6.1 拉曼光譜之鈷酸鋰電極 76
4.6.2 拉曼光譜之石墨電極 79
第五章 結論 82
參考文獻 84

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