多成分高分子混合以促進鋰離子傳導之研究｜國立清華大學博碩士論文庫

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研究生：	趙嘉烺 Zhao, Jia-Lang
論文名稱：	多成分高分子混合以促進鋰離子傳導之研究 Multicomponent Polymer Blends for Enhanced Lithium-Ion Conduction
指導教授：	楊長謀 Yang, Arnold C. M.
口試委員:	鄭智嘉 Cheng, Chi-Chia 官振豐 Kuan, Zhen-Feng
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學工程學系 Materials Science and Engineering
論文出版年：	2024
畢業學年度：	112
語文別：	中文
論文頁數：	109
中文關鍵詞：	高熵高分子、相分離、離子傳導、水吸收、結晶
外文關鍵詞：	high-entropy polymer, phase separation, ion conduction, water absorption, crystallization
相關次數：	點閱：40 下載：0
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我們嘗試利用五種彼此有截然不同主鏈結構和玻璃轉換溫度、但具有高極性端官能基的高分子(PEO、PVDF-HFP、PCL、PEC、CA)，利用旋轉塗佈法製成高熵高分子薄膜，探討高熵特性影響其分子相分離、離子傳導行為、與吸水性。我們發現單成份高分子能進行結晶 (PVDF-HFP: 38%、PEO: 70%、PCL: 32%、CA: 30%)，但結晶行為會因分子混合而受到抑制，整體結晶度隨高分子成分數(n)增加而降低，當n =5時降至16%，並只出現PE0、PCL特徵結晶峰。當添加20 wt.% LiClO4時，鋰鹽結晶峰並未出現，而隨n增加，高分子結晶明顯下降，離子導電度上升。添加40 wt.% LiClO4時，鋰鹽結晶峰出現，但高分子結晶度、反而因離子吸附、破壞分子間作用的規律性、而被抑制。在過量的LiClO4添加下(40 wt.% )，部分鋰鹽析出結晶，但未析出之鋰鹽仍能提升離子導電度約一個數量級，至10-8-10-6S/cm。此時，隨n增加，鋰鹽結晶明顯下降，歸因於高熵混合效應使鋰鹽有效分散，且在n=5時，離子導電度仍遠高於成分高分子的平均期望值，顯示高熵分子分散效應，仍有效提升離子導電行為。此系統高分子皆具有環境吸水特性，吸水後導電度快速增加約5個數量級至5x10-4 S/cm (at 20wt.% 鋰鹽)。推論吸附的水分子，改變離子傳導機制，建立了能讓離子進行連續跳躍，以類似電泳方式遷移的快速通道。

We attempted to use five polymers with distinct main chain structures and glass transition temperatures, but all possessing high polarity end functional groups (PEO, PVDF-HFP, PCL, PEC, CA), to create high-entropy polymer films through the spin coating method. This approach aimed to explore how high-entropy characteristics affect molecular phase separation, ion conduction behavior, and water absorption. We found that single-component polymers could crystallize (PVDF-HFP: 38%, PEO: 70%, PCL: 32%, CA: 30%), but crystallization was suppressed due to molecular mixing, with overall crystallinity decreasing as the number of polymer components (n) increased, dropping to 16% when n=5, and only characteristic crystalline peaks of PEO and PCL appeared. When 20 wt.% LiClO4 was added, no lithium salt crystalline peaks were observed, and polymer crystallinity significantly decreased with increasing n, while ion conductivity increased. Upon adding 40 wt.% LiClO4, lithium salt crystalline peaks appeared, but polymer crystallinity was suppressed due to the ion adsorption disrupting the regularity of molecular interactions. With an excess of LiClO4 (40 wt.%), some lithium salts precipitated as crystals, but the unprecipitated lithium salts still enhanced the ion conductivity by approximately an order of magnitude, to 10-8-10-6 S/cm. As n increased, lithium salt crystallinity significantly decreased, attributed to the high-entropy mixing effect facilitating efficient dispersion of lithium salts, and at n=5, the ion conductivity remained significantly higher than the average expected value of the component polymers, indicating the effective enhancement of ion conducting behavior by the high-entropy molecular dispersion effect. All polymers in this system exhibited hygroscopic properties, and upon water absorption, conductivity rapidly increased by about five orders of magnitude to 5x10-4 S/cm (at 20wt.% lithium salt). It is inferred that the absorbed water molecules alter the ion conduction mechanism, establishing fast channels that allow ions to hop continuously, moving in a manner similar to electrophoresis.

目錄
摘要    I
Abstract    III
致謝    V
目錄    VII
圖目錄    X
第一章    簡介    1
第二章 文獻回顧    3
2-1 高熵高分子    3
2-1-1高熵高分子介紹    3
2-2 鋰離子固態電解質    5
2-1-1 鋰離子固態電解質    5
2-1-2 鋰離子傳導機制    7
2-3 橡膠態高分子(RUBBERY STATE POLYMERS)    8
2-3-1 聚乙二醇烷 (PEO)    8
2-3-2 聚偏二氟乙烯-六氟丙烯(PVDF-HFP)    9
2-3-3 聚己內酯(PCL)    10
2-3-4 聚（碳酸亞乙酯）(PEC)    11
2-4 玻璃態高分子(GLASSY STATE POLYMERS)    12
2-4-1 醋酸纖維素 (CA)    12
2-5 電化學阻抗分析圖譜原理    13
2.5.1奈奎斯特阻抗圖譜(Nyquist plot)    14
2.5.2 等效電路圖    15
第三章 實驗方法    16
3-1 實驗材料    17
3-1-1高分子材料    17
3-1-2    有機溶劑    18
3-1-3 實驗基材    18
3-2 樣品製備    19
3-2-1固態電解質膜    19
3-2-2 CR2032鈕扣電池組裝    20
3-3 量測方法    22
3-3-1 電化學阻抗量測實驗    22
3-3-2 薄膜結晶度    22
3-4 實驗儀器介紹    23
3-4-1 光學顯微鏡 (Optical microscopy, OM)    23
3-4-2 原子力顯微鏡 (Atomic force microscopy, AFM)    25
3-4-3 電化學交流阻抗分析儀(Electrochemical Impedance Spectroscopy, EIS)    27
3-4-4 X光粉末繞射儀(XRPD)    28
3-4-5 薄膜厚度輪廓測量儀(α-Step)    29
3-4-6 掃描電子顯微鏡SEM    31
第四章 結果與討論    32
4-1 高熵固態電解質薄膜表面形貌變化    32
4-1-1 光學顯微鏡影像    32
4-1-2 AFM原子力顯微鏡影像分析    38
4-1-3 SEM掃描電子顯微鏡影像分析    40
4-2高熵固態電解質結晶行為    47
4-2-1 無鋰鹽環境下的結晶度    48
4-2-2 鋰鹽環境下的結晶度    51
4-3有效離子濃度    53
4-3-1 有效離子分量計算    53
4-4高熵固態電解質離子導電性    57
4-4-1 20wt% LiClO4 1元高分子導電性    57
4-4-2 20wt% LiClO4  n=2-5 離子導電性    58
4-4-3 40wt% LiClO4  n=1 離子導電性    65
4-4-4 40wt% LiClO4  n=2-5 離子導電性    67
4-4-6 單成份比例改變對高熵環境的導電度影響    71
4-4-7 離子導電性與結晶性的關係    79
4-5吸水性固態電解質離子導電度的影響    82
4-5-1吸水性對導電度的影響    82
第五章 結論    89
第六章 參考文獻    92
附錄    95

                                

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