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研究生:吳振利
研究生(外文):Chen-L i Wu
論文名稱:鋰電池用高分子接著劑之研究
論文名稱(外文):Study on the adhesive of Lithium ion batt ery
指導教授:馬振基馬振基引用關係
指導教授(外文):Chen-Chi M.Ma
學位類別:碩士
校院名稱:國立清華大學
系所名稱:化學工程學系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:139
中文關鍵詞:接著劑鋰電池
外文關鍵詞:adhesive of lithium ion battery
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摘 要
本研究旨在探討多孔性高分子接著劑應用於Li-ion二次電池上之可行性。利用相分離的機制,來製備多孔性高分子材料(porous polymer),探討不同的溶劑利用環氧樹脂在硬化所造成的化學相分離,再以真空加熱將溶劑抽掉,以製備porous polymer。不同溶劑其本身的化學、物理性質,和環氧樹脂的相容性及環氧樹脂硬化的機制,都是影響孔隙度的參數。本研究選擇不同的溶劑在不同濃度和不同的硬化條件下製備porous polymer ,並進一步利用掃描式電子顯微鏡(SEM)來觀察孔洞大小分怖,並比較孔洞對於比表面積、密度等 的影響,並將此porous polymer 施於Li-ion 二次電池上,研究其對Li 電池性質的影響,如電容量、cycle life 等。
研究結果顯示,solvent必須是低沸點,藉由引入高分子與溶劑間的溶解度參數,可快速尋找和環氧樹脂有良好相容性solvent,以便在環氧樹脂未反應時有均勻的混合相,藉由環氧樹脂的硬化產生相分離,由於低沸點便於真空加熱除去溶劑,而良好的相容性可得均勻的分散相,將溶劑除去後可得均勻的孔洞分布。在硬化反應溫度控制的研究上,利用DSC觀察其硬化反應溫度,選擇不同的硬化溫度觀察其孔洞大小和分布的情況。在後階段的真空加熱,加熱溫度必須要高於Tg,利於溶劑的除去,藉由TGA的分析,可以得知溶劑的殘留量。由SEM圖可以觀察到其孔洞大小主要分佈在10μm,孔洞隨著溶劑濃度的增加而變大,隨著硬化溫度增高,孔洞半徑也隨之增大。
在電池性質方面, 研究結果發現具孔洞性的接著劑對於電池的 cycle life、lst irev%、及充放電的穩定性有明顯的影響,lst- irrev %≒10%,充放電的電容量比>90%,但對於整個電池的電容量有稍許的減少,當上膠面積20% (1cm2)時電容量下降約6.91% (23mAh/g)。Uni-cell 的電性可以達到1C/0.2C>95%, 2C/0.2C>90%, cycle life 也可達到1C充放300次之容量≧第一次容量之80%,且第一次容量高於C rate測試時1C容量之95%,即電池性能能已達一般商業電池之標準。
Abstract
This research intends to investigate the utilization of porous polymer for Li-ion second battery. Using phase separation method to control the porous condition. Various solvents were used to generate phase separation when epoxy was cured. The cured sample was heated in a vacuum oven to remove solvent, and formed porous polymer. In this research, various kinds of solvent、various concentrations of solvent and curing conditions were utilized to prepare porous polymer. Different chemical and physical properties of solvents, compatibility between epoxy and solvents, the curing mechanism are the parameters affect the porous structure of polymer. Scanning electron microscope (SEM) was utilized to observe the void distribution of porous polymer ,and to study the effect of porosity of polymer on the density and specific surface of polymer. The thermal degradation kinetics of porous polymer was investigated by thermogravimetric analyzer (TGA). Furthermore, the porous adhesive was applied to the Li-ion battery. The effect of adhesive on the capacity and cycle life of Li-ion battery was investigated.
Results indicate that low boiling point solvent should be used, since which can be removed easily. It is an efficient way to find the solvents which are compatible with epoxy by the solubility parameters between the polymer and solvent. Homogeneous mixture of cured epoxy will form uniform porosity.
In order to obtain uniform porosity of adhesive, the curing temperature is very critical. Results show the temperature must be moderate. The higher the temperature , the bigger the pores and the lower the degree of porosity . However, when the temperature is lower ,the pores become smaller and the degree of porosity will be increased. In this study, 75℃ was selected as the curing temperature for epoxy. In the post-cured step, the porous adhesive must be dried to dispel the solvent to obtain the open pores .The post-cured temperature must be higher than the glass transition temperature (Tg) of the polymer to dispel the solvents.
Results also show that the diameter of pores is 10μm mainly, which can be controlled by the concentration of the solvents and the curing temperature. The porous structures may be changed with different solvents, namely, THF, cyclohexane and hexane.
The battery properties such as the capacity, cycle life, charge, discharge and the 1st irrev % are affected significantly by the porous adhesive.The 1st irrev%≒10%, and the ratio of discharge to charge is over 90% in the coin-cell. While the capacity of battery decreased slightly (about 6.91%(23mAh/g)) as the coating area of adhesive reached 20%(1cm2 ). The electrical property of Uni-cell shows that 1C/0.2C>95%, 2C/0.2C>90%which, meets with the standards of the commercial grade Uni-cell..
第一章 緒論………………………………………………………. 1
1-1前言……………………………………………………….… 1
第二章 文獻回顧與理論基礎……………………………………… 5
2-1 高分子接著原理…………………………………………… 5
2-2 環氧樹脂硬化反應…………………………………………. 8
2-3 溶液熱力學-結晶理論…………………………………….. 11
2-4 溶液的選擇……………………………………………….…..21
2-5 製備porous 的方法……………………………………….…24
2-5-1相分離製程方向…………………………… …………24
2-6 電化學相關原理……………………………………………...26
2-7電化學分析法……………………………………………….. 28
2-7-1交流阻抗分析法應用……………………………….32
2-7-2交流阻抗圖譜的分析與等效電路建立…………….32
2-8 鋰電池用接著劑之文獻回顧………………………………..37
2-9接著劑回獻…………………………………………………...43
2-10相分離法製備多孔性高分子─(薄膜)文獻回顧………….46
第三章 研究目的和內容…………………………………………….50
3-1 研究目的……………………………………………………..50
3-2 研究內容……………………………………………………..51
第四章 實驗步驟、實驗流程……………………………………….53
4-1 實驗藥品和材料……………………………………………..53
4-2實驗儀器……………………………………………………...55
4-3實驗步驟…………………………………………………….58
4-4實驗方法……………………………………………………..61
4-4.1 接著劑的製備……………………………………….61
4-4.2 上膠製備程序……………………………………….62
4-4.3 DSC熱分析………………………………………….62
4-4.4 TGA 熱分析…………………………………………..63
4-4.5 掃描式電子顯微鏡(SEM)……………………………64
4-4.6 測試電池組裝………………………………………..64
4-4.7 循環伏安測試………………………………………..66
4-4.8 充放電循環測試……………………………………..67
4-4.9 交流阻抗譜測試………… ………………………..68
第五章 研究成果與討論………………………………………………70
5-1 循環伏安測試(Cyclic Voltammetry, CV)……….70
5-2 接著強度的測試………………………………………..76
5-3 solvent 對孔洞高分子的影響……………………….77
5-4 硬化溫度對孔洞的影響………………………………...82
5-5孔洞對密度的影響……………………………………….83
5-6 Coin-Cell電池測試………………………………………85
5-7 Uni-cell 電池性能試………………………………….…87
5-8 Real-cell 電池性能測試………………………………...90
第六章 研究總結論…………………………………………………..123
第七章 參考文獻…………………………………………………..…129
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