臺灣博碩士論文加值系統

本研究製備P(vdf-hfp)高分子/ Pyr14TFSI離子熔液之複合膜，測試其性質並探討其做為可撓式鋰離子二次電池電解質之可行性。研究結果顯示成功製備高分子複合膜，且因熱穩定性及難燃性高之離子熔液的摻入，顯著提高此類高分子複合膜之安全性。結果亦顯示，以40wt%高分子配上0.6m離子熔液之配方(PYR14_6)所獲得之複合膜，在所致被之膠態電解質中具備最佳電化學性質。DSC測試結果顯示PYR14_6之高分子受鋰鹽影響大幅度降低Tm點、Tc點且及其對應之結晶性，7Li-NMR圖譜揭示PYR14_6中僅具一種鋰離子，亦即在該電解質中之Li+均在相同之環境下移動，無不同環境造成之阻礙，與由變溫導電度測試所得具最低活化能(2.293 KJ/mole) 之結果吻合。此外，以該膜與磷酸鋰鐵電極製備之半電池以0.2C充放電速率進行測試，電容量可達到140 mAh g-1，且經50圈充放電亦只有10%的損耗。而利用5C充放電速率進行高速充放電，電容量亦達40 mAh g-1大幅領先目前已報導之結果。最後以磷酸鋰鐵正極、碳負極及PYR14_6組成可撓式全電池，以0.2C充放電速率進行測試結果顯示，在彎曲的狀況下電容量依然有130 mAh g-1。本研究之結果顯示，所製備之含離子熔液複合膜為一有潛力之安全、可撓式膠態電解質。

Rechargeable lithium ion batteries (LIBs) have been applied in portable electronics and electricity powered transportation due to the high energy and power density. Unlike the traditional batteries packed in a cylindrical type, currently, most LIBs used in the consumer electronics (like smart phones and pads) are prismatic batteries. To meet the requirement of the electronics with particular shape such as wearable devices the flexible energy storage devices have been developed. For the safety concern, the solid electrolytes, such as polymer electrolyte, are developed to avoid leakage of liquid electrolyte. Nevertheless, the larger interfacial resistance between the solid electrolyte and electrodes and less flexibility reduced its application. Therefore, the geltype electrolytes are favored because lithium ion is more easily to transport in gel electrolyte than solid electrolyte. Yet, as reported, certain amount of the organic solvents such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC)…etc. have been usually used with polymers in the traditional gel electrolytes, causing the suspicion of solvent leakage. In this work, the solventfree polymer based ionogel electrolyte (IGE) composed of nonflammable and thermally stable NbutylNmethylpyrrolidinum bis(trifluorome thanesulfonyl) imide (PYR14TFSI) room temperature ionic liquid and polyvinylidenefluoridecohexafluoro- propylene (P(vdf-hfp)) are prepared by the solution casting method. The thermal properties are determined by the DSC measurements. And the electrical properties are investigated by the linear sweep voltammetry, cyclic voltammetry and impedance spectroscopy. It is found that the asprepared ionogel electrolytes are flexible selfstanding films with wide electrochemical windows. The best conductivity obtained at room temperature is 6.0 × 10−4 S cm−1. The highest capacity of the half-cell fabricated with the asprepared IGE achieves 143 mA h g-1 at 0.2C rate. And even after 50 cycles, the capacity retains 135 mA h g-1 at 0.2C. Besides, the capacity of the bending full-cell (LFP/PYR14_6/ Carbon) reached 130 mA h g-1 at 0.2C rate. This study reveals that the ionogel electrolyte is a promising safe electrolyte for application in the flexible LIBs.

摘要 I
Abstract II
目錄 IV
圖片索引 VII
表格索引 X
第一章　緒論 1
1.1　電池介紹 1
1.1.1　鋰離子二次電池之工作原理 3
1.1.2　正極材料 5
1.1.3　負極材料 8
1.1.4　電解質 9
1.1.5　可撓式電池 16
1.1.6　高分子材料的傳導機制 18
1.1.7　溫度效應對高分子電解質的影響 21
第二章　文獻回顧 22
2.1　研究動機 30
第三章　實驗 32
3.1　實驗藥品 32
3.2　實驗儀器 33
3.3　 實驗步驟 34
3.3.1　離子溶液合成 34
3.3.2　高分子複合膜的製備 35
3.3.3　可撓式全電池製備 37
3.4　鑑定 39
3.4.1.　傅立葉轉換紅外線光譜 (Fourier Transform Infrared Spectrometer , FT-IR) 39
3.4. 2　核磁共振儀(Nuclear Magnetic Resonance, NMR NMR) 40
3.4. 3　場發式掃描電子顯微鏡(FE-SEM) 40
3.4. 4　熱差式掃描卡計(DSC) 41
3.4.4　電化學測試 41
3.4.5　導電度測試 42
第四章　結果與討論 44
4.1　離子熔液之鑑定 44
4.1.1　紅外線光譜(IR) 44
4.1.2　核磁共振之氫譜以及碳譜(13C -NMR/1H-NMR) 46
4.2　高分子複合膜之測試 48
4.2.1　膠態高分子複合膜之可撓性 48
4.2.2　熱分析測試(DSC) 50
4.2.3　表面結構鑑定(SEM) 56
4.2.4　固態核磁共振鋰譜分析(7Li-NMR) 61
4.2.5　線性伏安掃描(LSV) 62
4.2.6　變溫導電度測試(Conductivity) 63
4.2.7　充放電測試(Capacity) 65
4.2.8　循環壽命測試(Cycle Life) 68
4.2.9　倍率放電測試(Different Rate Capacity) 70
4.2.10　交阻抗測試(Electrochemical Impedance Spectroscopy) 71
4.2.11　可撓式全電池測試(Flexible full cell testing) 73
第五章　結論 74
參考資料 76

圖片索引
圖1.1 鋰離子電池原理圖 4
圖1.2 離子熔液之種類、特性與在電化學上之應用[4] 11
圖1.3 PEO以螺旋方式包覆LiAsF6 模型 15
圖1.4 伴隨科技演進，穿戴式的電子產品逐漸展露頭角，不論是Nokia或是飛利浦公司皆提出具有撓曲性的電子產品 17
圖1.5 鋰離子在高分子中的傳導示意圖 19
圖1.6 離子在螺旋體孔道內擴散模型 20
圖 2.1在25 oC中不同莫耳數比的PEO高分子電解質之導電度 22
圖 2.2高分子和鋰離子γ-ray yield之關係圖 23
圖 2.3膠態電解質與LiCoO2之半電池測試 24
圖 2.4高分子和離子熔液組成所做的變溫導電度 25
圖2.5 Li團隊所做出膠態高分子膜之充放電數據 26
圖 2.6不同含量之PMMA混摻之高分子對離子熔液之吸附量 27
圖 2.7 Li/GPE/LFP之充放電數據 27
圖 2.8使用LiCoO2/Pvdf-IL/Li4Ti5O12全電池，再以護備機進行封裝 28
圖 3.1自製全電池 37
圖 3.2彎曲全電池狀 37
圖 3.3 FTIR原理 39
圖 3.4交流阻抗儀示意圖 43
圖4.1 Pyr14TFSI之IR光譜 44
圖4.2 Pyr14TFSI之1H-NMR 46
圖4.3 Pyr14TFSI之13C -NMR 47
圖 4.4取出之高分子薄膜 48
圖 4.5彎曲之後的高分子膜 48
圖 4.6 Polymer DSC圖 52
圖 4.7 Polymer+IL DSC圖 52
圖4.8 Polymer+Li salt DSC圖 53
圖 4.9 PYR14_3 DSC圖 54
圖4.10 PYR14_6 DSC圖 54
圖4.11 PYR14_9 DSC圖 55
圖 4.12 PYR14_12 DSC圖 55
圖 4.13 Polymer放大500倍 57
圖 4. 14 Polymer+IL放大500倍 57
圖 4.15 PYR14_3放大500倍 58
圖 4.16 PYR14_6放大500倍 59
圖 4. 17 PYR14_9放大500倍 59
圖 4. 18 PYR14_12放大500倍 60
圖 4. 19 7Li-NMR測試 61
圖 4.20線性伏安掃描 62
圖 4. 21高分子複合膜變溫導電度圖 64
圖 4.22以0.2C充放電50圈之數據 66
圖 4.23以0.2C充放電50圈之數據 66
圖 4. 24 PYR14_9 以0.2C充放電50圈之數據 67
圖 4.25 PYR14_12 以0.2C充放電50圈之數據 68
圖 4.26以0.2C充放電50圈之循環壽命圖 69
圖 4. 27利用不同速率進行充放電圖 70
圖 4. 28高分子樣品進行交流阻抗測試 72
圖 4. 29全電池進行充放電測試 73

 
表格索引
表1.1電池發展與比較[2] 2
表 2.1 高分子電解質文獻整理 28
表 3.1 藥品資訊 32
表 3.2 儀器資訊 33
表3.3實驗之配方 35
表 4.1 高分子複合膜透過DSC實驗所得數據 51
表 4.2 高分子複合膜之活化能 64
表 4.3 交流阻抗Fitting之數據 71

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