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研究生： 張文馨
Wen-Xin Chang
論文名稱： 聚苯胺奈米複合材料的製備表徵在超級電容器的應用
Preparation and Characterization of Polyaniline Nanocomposites for Supercapacitor
指導教授： 氏原真樹
Masaki Ujihara
蘇威年
Wei-Nian Su
口試委員: 氏原真樹
Masaki Ujihara
蘇威年
Wei-Nian Su
今榮東洋子
Toyoko Imae
學位類別： 碩士
Master
系所名稱： 應用科技學院 - 應用科技研究所
Graduate Institute of Applied Science and Technology
論文出版年： 2022
畢業學年度： 110
語文別： 英文
論文頁數： 57
中文關鍵詞： 聚苯胺 、超級電容器 、印刷式導電墨水 、凝膠電解質
外文關鍵詞： Polyaniline, supercapacitors, printable conductive ink, gel electrolyte
相關次數： 點閱：371  下載：3 
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  •  上一筆

    • 近來，為了給移動裝置提供穩定的可持續能源，電池和超級電容器等儲能設備的發展逐漸成熟。本研究重點在使用聚苯胺 (PANI) 的超級電容器，並考慮了用於可穿戴超級電容器的PANI奈米複合材料。由於PANI容易形成納米纖維，相互纏繞並引發大分子沉澱，因此添加二氧化矽奈米粒子(直徑：12奈米)作為凝結核，形成具有二氧化矽-PANI殼層結構的球狀奈米粒子。利用 SEM 和 TEM進行表面分析，發現二氧化矽-PANI呈現直徑為 200-300 nm 的球狀聚集體。為了防止PANI過度聚集，在反應溶液中加入保護劑:聚(丙烯酸)(PAA)。PAA的作用與 pH 值有關，即：PAA交聯 PANI在pH 5左右時會形成凝膠；而二氧化矽-PANI顆粒直徑約20 nm的奈米分散體在pH 3以下表現穩定。將二氧化矽-PANI奈米複合材料透過瓊脂糖凝膠固定在不鏽鋼網上，並分析其電化學行為。由於PANI上的表面覆蓋了PAA進而增加了電荷轉移電阻(Rct)，但並沒有因此使溶液電阻增加。再者瓊脂糖凝膠中的二氧化矽-PANI 表現出約 100 F/g 的比電容，但二氧化矽-PANI-PAA 奈米複合材料在pH 4的電解質中量測到的比電容從約 40 F/g（含 1 wt.% PAA）降至約 6 F/g（含1.5-2.5 wt.% PAA)。另外觀察到在pH 3或更低的電解質中時，瓊脂糖凝膠會崩解。這說明瓊脂糖凝膠在酸性環境中處於不穩定的狀態，因此需要為可穿戴超級電容器的聚苯胺墨水製備穩定的凝膠電解質進行更深入的研究。

    Recently, energy storage devices such as batteries and supercapacitor has increased to stabilize sustainable energies and to use mobile tools. In this study, supercapacitors using polyaniline (PANI) are focused, and PANI nanocomposites for wearable supercapacitors were considered. Since the PANI easily forms nanofibers, which could intertwine each other and precipitate, silica nanoparticles (diameter: 12 nm) were added as template to form spherical nanoparticles with silica-PANI core-shell structure. Using SEM and TEM, the silica-PANI was found to be spherical aggregates with 200-300 nm in diameter. To prevent aggregation, a protection agent, poly(acrylic acid) (PAA) was added in the reaction solution. The role of PAA was related to the pH value: the PAA cross-linked PANI to form gel at pH 5, while the dispersion of small silica-PANI nanoparticles (diameter: ~20 nm) were stabilized at pH 3. The silica-PANI nanocomposites were immobilized by agarose gel on a stainless-mesh, and their electrochemical behaviors were analyzed. The PAA increased the charge transfer resistance due to the surface cover on PANI, but didn't largely increased the solution resistance. While the silica-PANI in agarose gel exhibited the specific capacitance of ~100 F/g, that of silica-PANI-PAA nanocomposites decreased from ~40 F/g (with 1 wt. % PAA) to ~6 F/g (with 1.5-2.5 wt. % PAA) at pH 4. At pH 3 or lower, the agarose gel was decomposed. The agarose gel was not stable in the acidic medium, and therefore further study is required to prepare stable gel electrolyte for the PANI ink for the wearable supercapacitors.

    Abstract i 摘要 ii Acknowledgements iii Contents iv List of Figures vi List of Schemes viii List of Tables ix CHAPTER 1. Introduction and Motivation 1 1.1 Classification of Supercapacitors 2 1.2 Materials for Supercapacitors 4 1.3 Preparation of PANI 6 1.4 PANI Application 10 1.5 Motivation to use PANI 12 1.6 Motivation to develop functional ink 13 CHAPTER 2. Experimental Part 14 2.1 Materials 14 2.2 Synthesis of PANI 15 2.3 In-situ polymerization of core-shell silica-PANI nanocomposite 15 2.4 In-situ polymerization of core-shell silica-PANI nanocomposite with PAA 17 2.5 Synthesis of PANI-rGO composites 17 2.6 Preparation of working electrode for electrochemical measurement 18 CHAPTER 3. Instruments and Their Principles 19 3.1 Ultraviolet–visible (UV-vis) spectroscopy 19 3.2 Scanning electron microscope (SEM) and Transmission electron microscope (TEM) 21 3.3 Cyclic Voltammetry (CV) 23 3.4 Galvanostatic charge-discharge (GCD) 24 3.5 Electrochemical impedance spectroscopy (EIS) 26 CHAPTER 4. Results and Discussion 27 4.1 Characterization of PANI 27 4.1.1 UV-vis absorption of silica-PANI core-shell nanoparticles 27 4.1.2 Morphology of silica-PANI core-shell nanoparticles 29 4.1.3 XRD analysis of PANI nanocomposites 40 4.2 Electrochemical properties of PANI nanocomposites 42 4.2.1 Electrochemical Performance of PANI nanocomposite Electrode 44 CHAPTER 5. Conclusions 51 References 53

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