臺灣博碩士論文加值系統

本研究內容主要分為四部分 (1)以熱閉環法聚合成新型多功能型聚醯亞胺-氯離子液體; (2)聚醯亞胺-氯離子液體應用於鋰硫電池黏著劑; (3)以聚醯亞胺-氯離子液體/聚丙烯腈複合式油性黏著劑提升鋰硫電池電化學穩定度; (4)以非臨場分析探討黏著劑與電極材料交互作用。
這個研究工作以發展具有離子液體功能聚醯亞胺-氯離子液體新型黏著劑PICl-IL，透過四步再結晶方式進行單體改質和熱閉環脫水聚合。黏著劑材料PICl-IL設計的概念主要為以離子液體官能基接枝於聚醯亞胺之側鏈，使聚合物本身玻璃轉化點溫度降低，有利於側鏈離子液體結構的擺動，並可提升材料離子導電性，由NMR和FTIR分析成功證實製備出聚醯亞胺-氯離子液體高分子。而電化學分析中，首先將硫承量控制約0.96 mg/cm^2，並進行50圈充放電循環測試，仍可維持719.8 mAh/g之電容量，明顯優於商業化黏著劑PVdF及NaCMC (~540 mAh/g)。而PICl-IL具有優異的捕捉多硫化物或多硫化鋰能力，有效使陰極表面硫的利用率提高，綜合上述結果顯示聚醯亞胺-氯離子液體除了能應用於黏著劑之外，亦可同時解決硫的利用率不足之問題。
本研究進一步提出複合式油性黏著劑之應用，以提升電化學穩定度，探討不同比例複合式黏著劑效應，結果顯示黏著劑比為 PICl-IL/PAN-10 (1:1) 經50圈於0.1C充放電循環後，碳硫電極可維持801.6 mAh/g之電容量，約等於52.8 %電容維持率 ; 相較之下，優於PICl-IL黏著劑之維持率，而由於聚丙烯腈的腈基結構，使PAN與多硫化物容易產生極性間的親和力。此外添加高極性PAN有助於使導電碳材和硫粉分散均勻，補足PICl-IL分散性及黏度不足之問題，PAN也提供良好導離性，因此充放電測試中，正極材料在高速率2 C下充放電測試，可逆電容仍然可達339.2 mAh/g。
研究結果顯示PICl-IL/PAN複合黏著劑具有良好互補的功能與提升碳硫材料的穩定性。此外，亦應用同步輻射光源之X光原子吸收光譜和X光電子能譜分析黏著劑與電極材料之交互作用機制。於首圈充放電中可觀察到新型黏著劑能有效減少與電解液的反應，生成SEI沉積於陰極材料表面上，減少硫含量的損失，其PICl-IL與PAN相較於商業化黏著劑PVdF及NaCMC耐化學性極佳，除了高黏度及好的分散性和導離度，也具有捕捉多硫化物的能力，因此能更有效使鋰硫電池的電化學循環獲得更穩定之提升。

This work mainly consists of four topics: (a) synthesis of novel polyimide-Cl ionic liquid by thermal cyclodehydration, (b) application of polyimide-Cl ionic liquid as a binder for Lithium–sulfur batteries, (c) polyimide-Cl ionic liquid/PAN composite binder for enhancing electrochemical stability of lithium-sulfur batteries, and (d) the interaction mechanism between binder and electrode materials by ex-situ analysis.
First, a novel multifunctional binder comprising of polymeric ionic liquid, polyimide-chlorine ionic liquid complex coupled with chlorine anions is developed, prepared by a four-step recrystallization method through thermal cyclodehydration. The concept of synthetic structure was mainly by grafting ionic liquid functional groups on the side chain of polyimide, in order to lower down the temperature of glass transition point of polymer and facilitate the swinging of the side chain, thereby, increasing the ionic conductivity, PICl-IL were synthesized and confirmed by NMR and FTIR. The loading amount of sulfur was fixed around 0.96 mg/cm2, and the discharge capacity delivers as 719.8 mAh/g, which is better than electrode with the commercial binder (~540 mAh/g). In addition, PICl can also trap the lithium polysulfides and minimize the shuttle effect and sulfur loss.
Next, composite binder with lipophilic compound was prepared. After optimization, the fabricated composite binder PICl-IL/PAN-10 (1:1) showed better capacity retention after 50 cycles with discharging-charging rate of 0.1 C. The composite binder showed a capacity of 801.6 mAh/g and retention of 82.8% at the 50th cycle, exceeding the retention of a commercial binder. The nitrile group on PAN backbone possess good affinity towards polysulfides Li2Sn (4≤n≤8) due to the strong dipole-dipole interactions. The addition of highly polar PAN helped disperse the conductive carbon and sulfur powder, which were poorly dispersed in PICl-IL and improved insufficient viscosity of PICL-IL, as well as increased the ionic conductivity. Therefore, PICl-IL/PAN-10 (1:1) can deliver a high reversible capacity of 339.2 mAh/g at 2 C-rate.
The results show that the compound binder has a good complementary function and enhance the stability of carbon/sulfur composite. Furthermore, the synchrotron-based X-ray absorption spectroscopy (XAS) and X-ray
photoelectron spectroscopy (XPS) were used to study the interaction mechanism between binder and electrode materials. It demonstrated that new PICl-IL/PAN binder can effectively reduce the reactions with the electrolyte at the first cycle, and SEI is formed on the surface of the cathode material, and decreases the loss of sulfur.
In conclusion, the PICl-IL/PAN binder exhibits better chemical resistance and excellent functions, such as strong adhesion, good dispersion and high ionic conductivity. As a result, the composite binder is capable of effectively trapping polysulfides to improve the electrochemical performance of sulfur composite cathode. PICl-IL is thought to be a promising multifunctional binder for Li-S batteries.

摘要 I
Abstract III
致謝 V
目錄 VII
圖目錄 XIII
表目錄 XXII
符號索引 XXIV
第1章 緒論 1
1.1. 前言 1
1.2. 鋰離子二次電池的發展 3
1.3. 鋰離子二次電池的組成及機制 5
1.4. 鋰離子二次電池各元件介紹 9
1.4.1. 正極(陰極)材料 11
1.4.2. 負極(陽極)材料 16
1.4.3. 電解液 18
1.4.4. 隔離膜 24
1.4.5. 黏著劑 25
1.5. 鋰硫電池介紹 29
1.5.1. 鋰硫電池電化學機制 31
1.5.2. 限制鋰硫電池發展主要問題 37
1.6. 研究動機與目的 39
第2章 文獻回顧 43
2.1. 鋰硫電池文獻回顧 43
2.1.1. 鋰硫電極材料發展演進 43
2.2. 鋰硫穿梭效應限制的突破方法 50
2.2.1. 陰極材料設計 50
2.2.2. 陰極材料表面改質 53
2.2.3. 固態電解質摻入修飾 56
2.2.4. 黏著劑開發 58
2.3. 黏著劑材料開發之回顧 61
2.3.1. 鋰硫電池黏著劑發展 63
2.3.2. 聚丙烯腈黏著劑應用 74
2.4. 離子液體黏著劑發展 76
2.4.1. 聚醯亞胺合成相關文獻 76
2.4.2. 離子液體 (Ionic liquid, IL) 82
2.4.3. 離子液體高分子 85
2.4.4. 離子液體(PIL)黏著劑應用 88
第3章 實驗方法與儀器設備 91
3.1. 儀器設備 91
3.2. 實驗藥品 93
3.3. 實驗步驟 95
3.3.1. 碳硫陰極材料合成 95
3.3.2. 聚醯亞胺氯離子液體 (Polyimide-Cl Ionic Liquid, PICl-IL) 黏著劑 96
3.3.3. 陰極極片製備 104
3.3.4. 鈕扣型電池組裝 107
3.4. 材料結構鑑定 108
3.4.1. 核磁共振儀分析 (NMR) 108
3.4.2. 傅立葉轉換紅外線光譜儀 (FTIR) 108
3.4.3. 熱重分析儀 (TGA) 109
3.4.4. 表面積及孔徑分析儀 (BET) 109
3.5. 不同黏著劑電極分析儀器 110
3.5.1. 場發射掃描式電子顯微鏡 (FE-SEM) 110
3.5.2. 穿透式電子顯微鏡 (TEM) 110
3.5.3. 固有黏度測試 (Inherent viscosities test) 110
3.5.4. X光能量色散圖譜分析 (EDS) 111
3.5.5. X光繞射分析儀 (XRD) 112
3.5.6. 同步輻射光源軟X-ray吸收光譜 (Soft XAS) 113
3.5.7. 同步輻射光源X-ray光電子能譜 (XPS) 114
3.6. 抑制穿梭效應機制分析方法 115
3.6.1. 多硫鋰化物溶液製備方法 115
3.6.2. 紫外光-可見光光譜分析 (UV-vis) 115
3.6.3. 拉曼散射光譜分析儀 (Raman) 117
3.7. 鈕扣電池電化學效能測試 117
3.7.1. 電化學效能特性測試 117
3.7.2. 循環伏安分析 (CV) 117
3.7.3. 電化學交流阻抗 (EIS) 118
第4章 結果與討論 123
4.1. 合成新型多功能醯亞胺-氯離子液 123
4.1.1. 聚醯亞胺-氯離子液體結構鑑定 124
4.1.2. 聚醯亞胺-氯離子液體熱性質分析 143
4.1.3. 小結 147
4.2. 聚醯亞胺-氯離子液體黏著劑 148
4.2.1. 碳硫複合陰極材料鑑定 148
4.2.2. 不同黏著劑性質比較 153
4.2.3. 不同黏著劑之鈕扣型電池性能測試 162
4.2.4. 小結 171
4.3. 聚醯亞胺-氯離子液體/聚丙烯腈複合式黏著劑 173
4.3.1. 複合式黏著劑鈕扣型電池性能測試 173
4.3.2. 複合式黏著劑性質比較 188
4.3.3. 小結 201
4.4. 以非臨場分析黏著劑與電極間交互作用 202
4.4.1. XANES光譜非臨場分析 202
4.4.2. X光電子能譜表面元素非臨場分析 208
4.4.3. Soft XAS非臨場吸收光譜電子結構變化分析 216
4.4.4. 小結 219
第5章 綜合討論 220
5.1. 聚醯亞胺-氯離子液體黏著劑與商業化黏著劑分析比較 220
5.2. 聚醯亞胺-氯離子液體/聚丙烯腈複合式黏著劑分析 221
第6章 結論 222
第7章 未來展望 225
參考文獻 226
附錄 一 碳載體比表面積測定與電化學影響 240
附錄 二 硝酸鋰催化裂解反應的影響 241
附錄 三 紫外光-可見光譜定量分析多硫化鋰 242
附錄 四 變速率充放電曲線圖 243

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