新型態鋰離子電池添加劑(馬來醯亞胺/雙馬來醯亞胺)研究探討

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研究生：	陳奕升 Yi-Sheng Chen
論文名稱：	新型態鋰離子電池添加劑(馬來醯亞胺/雙馬來醯亞胺)研究探討 The Investigation of New Type of Additive(N,N’-bismaleimide-4,4’-diphenylmethane and maleimide) in Lithium Ion Battery
指導教授：	陳崇賢 Chorng-Shyan Chern
口試委員:	王復民 Fu-Ming Wang 蔡大翔 Dah-Shyang Tsai
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2019
畢業學年度：	107
語文別：	中文
論文頁數：	102
中文關鍵詞：	鋰離子電池、添加劑、馬來醯亞胺、雙馬來醯亞胺
外文關鍵詞：	Lithium ion battery, Additive, Maleimide, N,N- bismaleimide-4,4-diphenylmethane
相關次數：	點閱：349 下載：0
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本研究利用示差掃描熱量分析儀(DSC)，以非恆溫反應動力學探討合成馬來醯亞胺線性添加劑( Living@ MI )和馬來醯亞胺/雙馬來醯亞胺支狀添加劑( Living@ BMI/MI )，合成反應溫度、反應放熱量以及藉由自由模型法求得反應活化能，並利用核磁共振(NMR)鑑定Living@ BMI/MI、Living@ MI添加劑的化學結構，而熱重分析(TGA)和動態光散射(DLS)，分別為測試Living@ BMI/MI以及Living@ MI添加劑耐熱性質以及Living@ BMI/MI添加劑具有Microgel顆粒性質。
另一方面的研究，將Living@ BMI/MI、Living@ MI添加劑應用於鋰離子電池，作為鋰離子電池添加劑，探討對於LiNi0.5Co0.2Mn0.3O2正極材料的影響，利用正極半電池，進行充放電(C/DC)、交流阻抗圖譜(EIS)以及循環伏安(CV)以上測試，分析這兩種添加劑添加至正極材料後，對於電池性能、電池內部阻抗以及電化學性質的影響，並通過掃描式電子顯微鏡(SEM)、能量分散光譜(EDS)，了解經充放電後的電極極片表面型態及元素組成，最後再藉由示差掃描熱量分析儀(DSC)測試電極材料的熱穩定性。本研究的實驗結果，在正極材料中添加1wt%的Living@ BMI/MI可以最有效改善正極半電池於常溫電池循環壽命衰退以及電化學反應性質，而高溫環境的充放電測則是添加1 wt%的Living@ MI表現最為優異，在電極材料的熱穩定性為0.5%的Living@ BMI/MI耐熱性質較佳。

This study used a differential scanning calorimeter (DSC) to investigate the maleimide additive (Living@ MI) and bismaleimide / maleimide additive (Living@ BMI/MI) with non-isothermal kinetics that can be understanded the reaction temperature, exotherm. the study also used the free model method to know the activation energy, and identification of chemical structure of Living@ BMI/MI, Living@ MI additive by nuclear magnetic resonance (NMR), and thermogravimetry Analysis (TGA) and dynamic light scattering (DLS), respectively, for testing Living@BMI/MI and Living@MI additive heat-resistant properties and Living@BMI/MI additive Microgel particle properties.
On the other hand, Living@BMI/MI and Living@MI additives were applied to lithium-ion batteries, We want to know the effect of LiNi0.5Co0.2Mn0.3O2 cathode material. The cathode be made to the half-cell, It was used for charging. Discharge test (C/DC), Electrochemical Impedance Spectroscopy (EIS), and cyclic voltammetry (CV) tests were performed to analyze the effects of the two additives added to the positive electrode material. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used to understand the surface morphology and elemental composition of the electrode after charge and discharge. Finally, the thermal stability of the electrode material was tested by differential scanning calorimetry (DSC). . The experimental results of this study, adding 1wt% of Living@BMI/MI to the positive electrode material can most effectively improve the cycle life degradation and electrochemical reaction properties of the positive half cell at room temperature, while the charge and discharge test in the high temperature environment is to add 1 wt. % Living@ MI is the most excellent, and the heat resistance of Living@BMI/MI with 0.5% thermal stability of the electrode material is better.

摘要    I
Abstract    II
致謝    III
目錄    IV
圖目錄    VIII
表目錄    XI
第一章、研究背景    1
1鋰離子電池    1
1.1正極材料    2
1.2電解質    2
1.3隔離膜    2
1.4負極材料    3
第二章、研究動機    4
第三章、文獻回顧    8
1隔離膜斷開技術    8
1.1微孔高分子隔離膜    9
1.2不織布纖維隔離膜    11
1.3無機複合隔離膜    12
2電解質安全性改善    13
2.1穩定的鋰鹽    14
2.2路易斯鹼穩定劑    14
2.3阻燃添加劑    16
3塗層技術保護正極材料    17
4表面活物修飾    23
第四章、研究介紹    26
1 Living@ BMI / MI反應機制    27
2 Living@ MI反應機制    28
第五章、實驗藥品和設備    29
第六章、實驗樣品製備    30
1 NMR樣品製備    30
1.1 [ BMI / MI [ 1 / 1 ( mol / mol )] / NMP ]    30
1.2 [ MI / NMP ]    30
1.3 [ BMI / NMP ]    30
2 DLS樣品製備    30
2.1 [ BMI / MI [ 1 / 1 ( mol / mol )] / NMP ]    30
2.2 [ MI / NMP ]    31
2.3 [ BMI / NMP ]    31
3 DSC樣品製備    31
3.1 [ BMI / MI [ 1 / 1 ( mol / mol )] / NMP ]    31
3.2 [ MI / NMP ]    31
3.3 [ BMI / NMP ]    32
3.4 [ BMI / MI [ 1 / 1 ( mol / mol )] / HQ / NMP ]    32
3.5 [ MI / HQ / NMP ]    32
3.6 [ BMI / HQ / NMP ]    32
4 GPC樣品製備    32
4.1 [ BMI / MI [ 1 / 1 ( mol / mol )] / NMP ]    32
4.2[ MI / NMP ]    33
4.3 [ BMI / NMP ]    33
5 TGA樣品製備    33
5.1 [ BMI / MI [ 1 / 1 ( mol / mol )] / NMP ]    33
5.2 [ MI / NMP ]    33
5.3 [ BMI ]    34
5.4 [ MI ]    34
6 Living@添加劑製備    34
6.1 [ BMI / MI [ 1 / 1 ( mol / mol )] ]    34
6.2 [ MI ]    34
6.3 [ BMI ]    34
7 電極漿料製備    35
7.1 [ LiNi0.5Co0.2Mn0.3O2 ]    35
7.2 [ Living@ BMI / MI - 0.5% / LiNi0.5Co0.2Mn0.3O2 ]    35
7.3 [ Living@ BMI / MI - 1% / LiNi0.5Co0.2Mn0.3O2 ]    35
7.4 [ Living@ BMI - 0.5% / LiNi0.5Co0.2Mn0.3O2 ]    35
7.5 [ Living@ BMI - 1% / LiNi0.5Co0.2Mn0.3O2 ]    35
7.6 [ Living@ MI - 0.5% / LiNi0.5Co0.2Mn0.3O2 ]    36
7.7 [ Living@ MI - 1% / LiNi0.5Co0.2Mn0.3O2 ]    36
8 電極極片製備    36
9 鈕扣型電池(coin cell)組裝    37
第七章、結果與討論    38
1 Living@添加劑合成熱化學分析    38
1.1 馬來醯亞胺與雙馬來醯亞胺非恆溫動力學    38
1.2 馬來醯亞胺非恆溫動力學    40
1.3 雙馬來醯亞胺非恆溫動力學    41
2 非恆溫動力學以自由模型法分析    42
2.1 非恆溫動力學雙馬來醯亞胺活化能分析    43
2.2 非恆溫動力學馬來醯亞胺活化能分析    44
2.3 非恆溫動力學馬來醯亞胺與雙馬來醯亞胺活化能分析    45
3 Living@添加劑反應機制探討    47
3.1 馬來醯亞胺與雙馬來醯亞胺反應機制分析    47
3.2 馬來醯亞胺反應機制分析    47
4 Living@添加劑NMR結構分析    48
4.1 Living@ BMI / MI 氫譜結構分析    49
4.2 Living@ MI 氫譜結構分析    50
4.3 PMI / MI 氫譜結構分析    51
5 Living@ BMI / MI添加劑 DLS粒徑分析    52
6 Living@添加劑耐熱性質分析    53
8 循環伏安(CV)分析    55
8.1 Bare NCM523    55
8.2 Living@ MI    56
8.3 Living@ BMI/MI    57
8.4 Living@ BMI/MI不同添加量對於CV分析的影響    59
9第一圈充放電曲線分析    60
10常溫充放電循環壽命圖    62
10.1 Living@ BMI/MI、Living@ MI與Living@ BMI分析    62
10.2 Living@ BMI/MI、Living@ MI與STOBA分析    63
11常溫Living@添加劑(1-50圈)充放電曲線    64
12常溫Living@添加劑(1-50圈)交流阻抗圖譜分析    66
12.1 NCM523    66
12.2 Living@ BMI/MI - 0.5%    67
12.3 Living@ BMI/MI - 1%    69
12.4 Living@ MI - 0.5%    70
12.5 Living@ MI - 1%    71
13 高溫(55oC)充放電循環壽命圖    72
13.1 Living@ BMI/MI、Living@ MI與STOBA分析    72
14 高溫(55oC)Living@添加劑充放電曲線分析    73
15 高溫(55oC)Living@添加劑交流阻抗圖譜分析    75
16 Living@ BMI/MI添加劑於不同充放電速率分析    77
17 [ Living@ 添加劑 / NCM523 ] SEM分析    78
17.1 NCM523    78
17.2 Living@ BMI/MI - 0.5%    79
17.3 Living@ BMI/MI - 1%    80
18 [ Living@添加劑 / NCM523 ] EDS分析    81
19正極極片DSC分析    82
第八章、結論    83
參考文獻    84
圖片參考    88

                                

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全文公開日期 2024/07/25 (校內網路)
全文公開日期 2024/07/25 (校外網路)
全文公開日期 2024/07/25 (國家圖書館：臺灣博碩士論文系統)

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