研究生: |
張娟華 Chuan-hua Chang |
---|---|
論文名稱: |
離子液體嵌入奈米碳管對電化學微電容器的儲能性質影響 Influences of ionic liquid intercalation in carbon nanotubes on the storage properties miniature electrochemical capacitor |
指導教授: |
蔡大翔
Dah-Shyang Tsai |
口試委員: |
周振嘉
Chen-chia Chou 吳溪煌 She-huang Wu |
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: | 2013 |
畢業學年度: | 101 |
語文別: | 中文 |
論文頁數: | 146 |
中文關鍵詞: | 指叉式電極 、奈米碳管 、室溫離子液體 、嵌入 、微型電化學電容器 |
外文關鍵詞: | interdigitated electrode, Carbon nanotubes, Room temperature ionic liquid, Intercalation, miniature electrochemical capacitor |
相關次數: | 點閱:333 下載:1 |
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能量與功率值為工作電壓的平方比是眾所皆知的事情,所以工作窗口的大小極大影響電容器的儲存能力。而我們將證明合適的窗口大小不再一直是影響儲存能量的唯一原因,本次研究,我們探討離子液體[EMIM][TFSI]嵌入奈米碳管對於指叉式微型電容器的能量儲存影響。
原則上,可操作電位窗口受到電解液分解限制,離子液體[EMIM][TFSI]以白金片當電極測量可用電為範圍:-1.8 2.6 V (vs. RHE)。然而,一維奈米碳管是層狀結構,奈米碳管經受陽離子[EMIM]和陰離子[TFSI] 的嵌入,導致剝離或是管破裂,嵌入的電位範圍小於離子液體[EMIM][TFSI]分解電位。我們用循環伏安探討上界與下界電位,且以拉曼光譜解析出嵌入限制電位,嵌入的上界電位決定在1.5和1.7 V (vs. RHE)之間,下界電位決定於-1.6 和-1.7 V (vs. RHE)之間,在循環穩定分析進一步驗證嵌入的上界與下界電位的影響。
當操作電位窗口2.0 V,微型電容器充放電10000圈後的保留率約100 %,代表有很好的循環穩定性,且庫倫效率也很快提升且穩定於100 %。然而,當操作電壓設在2.8 V或3.8 V,電容器的循環穩定逐漸下降,因為電極的電位已達到離子嵌入的電位境界,且奈米碳管有部分破裂。當電容器電壓設在2.8 V,正極的電位達到嵌入的上界內,且隨著圈數增加比電容值逐漸下降,在電流密度8 A g-1充放電10000圈後,保留率為90.8 % 。另外一方面,當電容器窗口設在3.8 V,而電流密度30 A g-1充放電10000圈後,保留率為77.5 %,由於循環測定中正負極都受到並非只有正極,造成低保留率。因此,電化學電容器的循環穩定性,主要是受電壓窗口,少數影響來自於電流密度,因此兩個因素能改變的正負電極的電位界限。
It is well-known that the energy and power values of an ultracapacitor are proportional to the square of its working voltage window. The size of working window influences the storage capability tremendously. As we shall demonstrate, the answer of proper window size is not a straightforward one. In this work, we investigate the influences of ionic liquid [EMIM][TFSI] intercalation in carbon nanotubes (CNT) on energy storage of a miniature electrochemical capacitor with interdigitated electrodes.
In principle, the workable potential window is governed by decomposition potential limits of the electrolyte. For ionic liquid [EMIM][TFSI], the measured potential range with a platinum working electrode is -1.8 2.6 V (vs. RHE). Nevertheless, one-dimensional CNT is a layer structure material. [EMIM] cation and [TFSI] anion may undergo intercalation into CNT, resulting in exfoliation or tube rupture. The potential range of intercalation is narrower than the decomposition limits of ionic liquid [EMIM][TFSI]. We explore the potential upper and lower limits with cyclic voltammetry and resolve the intercalation limits with Raman spectroscopy. The upper potential limit of intercalation is determined between 1.5 and 1.7 V (vs. RHE), while the lower potential limit is decided between -1.6 and -1.7 V (vs. RHE). The upper and lower potential limits for intercalation are further validated in the cycle stability analysis.
When operated in the potential window 2.0 V, the miniature ultracapacitor was charged and discharged with excellent cycle stability, typified by a retention ratio 100% after 104 cycles. Their coulombic efficiencies quickly rise up, and hold steady at 100%. However, when the applied voltage is set at 2.8 V or 3.8 V, the cycle stability of capacitor gradually declines, because the electrode potential has reached the potential limits of ion intercalation and ruptured a fraction of CNT structure. When the capacitor window is set 2.8 V, the positive electrode potential can reach the intercalation upper limit, and the capacitance value gradually decreases with increasing cycle number. The retention ratio, after 104 cycles, is 90.8% at current density 8 A g-1. On the other hand, when the capacitor window is set 3.8 V, the capacitor energy is cycled at current density 30 A g-1, the retention ratio is only 77.5% after 104 cycles. The lower retention ration results from both of the electrodes, not just positive electrode, which experienced intercalation during energy cycling. Hence the cycle stability of this electrochemical capacitor is mainly affected by the voltage window, less influenced by the current density, since both factors can change the potential boundaries of positive and negative electrodes.
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