研究生: |
姚均逢 Yao, Chun-Feng |
---|---|
論文名稱: |
新型共軛高分子黏著劑之合成並應用於鋰離子電池矽基陽極 Synthesis of cyclopentadithiophene-terephthalic acid copolymers via direct arylation and saponification for use in lithium-ion batteries |
指導教授: |
堀江正樹
Horie, Masaki |
口試委員: |
蘇安仲
Su, An-Chung 游進陽 Yu, Chin-Yang |
學位類別: |
碩士 Master |
系所名稱: |
工學院 - 化學工程學系 Department of Chemical Engineering |
論文出版年: | 2017 |
畢業學年度: | 105 |
語文別: | 英文 |
論文頁數: | 59 |
中文關鍵詞: | 鋰離子電池 、共軛導電高分子 、黏著劑 |
外文關鍵詞: | Lithium-ion battery, Conjugated polymer, Binder |
相關次數: | 點閱:2 下載:0 |
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奈米矽因其較高的理論電容量(4200 mAh g-1)而成為新型的鋰離子電池陽極材料。然而在充放電過程中,奈米矽陽極巨大的體積變化使電池電容量快速損失。因此,許多團隊致力於開發多功能高分子黏著劑,改善奈米矽陽極劇烈膨脹造成的不良影響。本研究合成了包含4H-Cyclopenta[2,1-b:3,4-b']dithiophene和對苯二甲酸二甲酯或對苯二甲酸的共軛高分子黏著劑,並探討高分子支鏈對電池表現影響。對苯二甲酸二甲酯酯單元中的二甲酯基通過皂化反應轉化為羧基,使其與矽表面形成氫鍵,藉此增加電池穩定性。
Silicon (Si) has been considered to be a next generation anode material for Li-ion batteries (LIBs) because of its high specific capacity (4200 mAhg-1). Despite such high capacity, large volume expansion and pulverization on anode during electrochemical cycling causes degradation of the batteries resulting in short life-time. This thesis describes the development of new polymer binders for Si anode in LIBs. The polymer binders have been synthesized by palladium catalyzed direct arylation of 2-ethylhexyl (EH) or triethylene glycol monomethylether (EG) substituted cyclopentadithiophene (CPDT(EH) or CPDT(EG)) and dimethyl 2,5-dibromoterephthalate (dibromo-DMT) to provide P[CPDT(EH)-DMT] and P[CPDT(EG)-DMT]. After the polymerization, DMT unit is further converted into terephthalic acid (TPA) through saponification, affording P[CPDT(EH)-TPA]-17k and P[CPDT(EG)-TPA]. These polymers are used to prepare polymer-Si nanoparticle composites for use in LIBs, showing sufficient electrical conductivity, ionic conductivity, and mechanical properties. In particular, the LIBs composed of an anode of a composite of P[CPDT(EH)-TPA]-17k with Si nanoparticle performs highest capacity in all polymers, giving a specific capacity of 3900 mAh g-1 (total anode weight) in a first charging-discharging cycle and 2300 mAh g-1 in the second cycle, followed by further decrease by 83% after 50 cycles. On the other hand, P[(CPDT(EG)-TPA] reveals the best stability, in which the capacity is observed to be 3500 and 2300 mAh g-1 in the first and the second cycles, respectively, followed by decrease by 60% after 50 charging-discharging cycles. However, the LIBs composed of P[CPDT(EH)-DMT] and P[CPDT(EH)-DMT] reveal low capacity and stability. These results show that the existence of hydroxyl groups apparently improve the cycle life of LIBs. Furthermore, effects of a molecular weight of P[CPDT(EH)-TPA] on cycling performance are studied; the LIBs composed of the low molecular weight polymer binder tends to show higher specific capacity than the higher molecular weight polymers.
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