研究生: |
黃柏棋 PO-CHI HUANG |
---|---|
論文名稱: |
丙烯腈及氨酯-丙烯酸丁酯寡聚物掺和聚偏氟乙烯六氟丙烯長鏈高分子的複合電解質及其固態電池充放電 The composite electrolytes containing acrylonitrile and urethane-acrylate oligomers blended with PVdF-HFP long-chain polymer along with their solid state battery cycling |
指導教授: |
蔡大翔
Dah-Shyang Tsai |
口試委員: |
陳良益
Liang-Yih Chen 陳崇賢 Chorng-Shyan Chern |
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: | 2021 |
畢業學年度: | 109 |
語文別: | 中文 |
論文頁數: | 98 |
中文關鍵詞: | 聚丙烯腈 、氨酯-丙烯酸丁酯 、固態鋰金屬電池 、固態聚合物電解質 、複合電解質 、可逆加成-斷裂鏈轉移法 |
外文關鍵詞: | polyacrylonitrile, polyurethane acrylate, solid-state lithium-metal battery, solid polymer electrolyte, omposite electrolyte, reversible addition-fragmentation chain transfer polymerization |
相關次數: | 點閱:401 下載:4 |
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丙烯腈(AN)單體與2-丙烯酸十二烷基酯(DA) 利用可逆加成-斷裂練轉移法(RAFT)聚合成的PAN寡聚物為主體,寡聚物的分子量受RAFT聚合控制,其中最佳比例為AN:DA:RAFT:AIBN = 50:3:40:30 (w/w),並且與長鏈高分子聚偏氟乙烯-六氟丙烯共聚物(PVdF-HFP)做掺合,並加入30 wt%的雙氟磺醯亞胺鋰 (LiFSI)、10 wt%的Li6.75La3Zr1.75 Ta0.25O12 (LLZTO)與相比PAN比例為0.22之氨酯-丙烯酸丁酯(PUA),製備獨立膜材複合固態電解質。以此比例電解質做鋰金屬電池充放測試及電解質膜材特性量測,並且與未添加PUA之複合固態鋰金屬電池做比較。
對於兩種複合電解質從掃描式電子顯微鏡(SEM)下可發現皆有三明治的構造,其中以有添加PUA之複合電解質比較特別,最外層為PVdF-HFP再由PUA包覆其中,中間主要以PAN為主體形成三明治的結構,在室溫下導電率可達6×104 S cm−1,而其鋰離子遷移常數為0.343,電位窗口為4.7 V。
所使用的陰極為磷酸鋰鐵而陽極則使用鋰金屬,再將複合固態電解質放置中間組成固態鋰金屬電池,電位窗口在2.0-4.0 V,並且在室溫下以0.1 C、0.3 C、0.5 C以恆流電流進行充放電測試,其中0.1C電容量166.1 mAh g−1、0.3C電容量131.5 mAh g−1而0.5C電容量112.6 mAh g−1。
最後使用比例較高之PUA來做比較,並且在室溫下以0.5C以恆流電流進行充放電測試,電容量達118.7 mAh g−1。
Acrylonitrile(AN) is copolymerized with dodecyl acrylate(DA) using reversible addition-fragmentation chain transfer (RAFT) polymerization to control the degree of polymerization. Use RAFT polymerization to control its molecular weight, the best ratio of PAN is AN:DA:RAFT:AIBN = 50:3:40:30 (w/w), and it is combined with the long-chain polymer poly(vinylidene fluoride)-co-hexafluoropropylene (PVdF-HFP) to prepared composite solid electrolyte, and the composite solid electrolyte was used as to add 30 wt% lithium bisfluorosulfonylimide (LiFSI), 10 wt% Li6.75La3Zr1.75Ta0.25O12 (LLZTO) and PUA with a PAN ratio of 0.22 are added. . This ratio has been studied and tested for lithium metal batteries, and compared with batteries without PUA. The independent membrane electrolyte is mainly used to prove that it is an solid electrolyte.
For the two composite electrolytes, it can be found under the scanning electron microscope (SEM) that there is a sandwich structure. Among them, the composite electrolyte with added PUA is more special. The outermost layer is PVdF-HFP and then is coated with PUA. AN is used as the main body of middle to form a sandwich structure, the conductivity can reach 6×10−4 S cm−1 at room temperature, and its lithium ion transference number (tLi+) is 0.343, and the potential window (U) is 4.7 V.
Use lithium iron phosphate (LFP) as the cathode, lithium metal as the anode. The composite solid electrolyte is placed in the middle to form a solid lithium ion battery. The potential window is 2.0V-4.0V. Use 0.1 C, 0.3 C, 0.5 C to charge and discharge at room temperature. The charge and discharge test was use with a constant current. The 0.1C capacity was about 166.1 mAh g−1, the 0.3C capacity was about 131.5 mAh g−1, and the 0.5C capacity was about 112.6 mAh g−1.
At last use PUA with a ratio of 0.4 of PAN to comparison and the charge and discharge test is carried out at a constant current of 0.5C at room temperature, and the capacitance is about 118.7 mAh g−1
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