本發明係有關一種具導電高分子砂紙基電極之超級電容器及其製法，尤指一種利用石墨烯/奈米碳管混合成的複合導電懸浮液滴覆在砂紙表面，得到砂紙基複合電極，製備PVA/H3PO4凝膠電解質，由砂紙基電極、凝膠電解質、隔膜、凝膠電解質及砂紙基電極組立成一砂紙基複合超級電容器的技術。The invention relates to a supercapacitor with a conductive polymer sandpaper-based electrode and a manufacturing method thereof, in particular to a composite conductive suspension liquid prepared by mixing graphene / nanocarbon tubes on the surface of the sandpaper to obtain a sandpaper-based composite electrode. PVA / H3 PO4 gel electrolyte is a sandpaper-based composite super capacitor technology composed of sandpaper-based electrodes, gel electrolytes, separators, gel electrolytes and sandpaper-based electrodes.
傳統的電子產品都有著以堅硬外殼做為硬體設計的基礎，但隨著科技的演進，軟性材料逐漸被應用到可撓式電子產品的設計上。高穩定性、平整性、可重複撓曲等特性成為軟性電子最大的優勢。為了讓軟性的電子裝置能在折疊或彎曲的工作條件下運作順暢，可撓式儲能裝置將是不可或缺的重要元件，這也是為何近幾年超級電容器成為各國不斷努力發展的目標。超級電容器，又稱為電化學電容器(electrochemical capacitor)，具有功率密度高、充電時間短、使用壽命長、温度特性好、具有高可逆性、快速充放電等優點。而透過儲能方式又可區分為兩類：電雙層電容器(electric double-layer capacitor,EDLC)和偽電容器(pseudo-capacitor)。EDLC，結構包含電極-電解質-隔膜-電解質-電極依三明治結構構成EDLC，主要是利用電極與電解質間電荷受到庫倫靜電力的作用，形成正負電分離的情形，造成電雙層並儲存淨電荷，且電解質離子不會產生化學變化。碳系材料是做為電雙層電容器最為常見的電極材料，其中以石墨烯(Graphene,G)與奈米碳管(Carbon nanotube,CNT)最受科學家歡迎。但石墨烯容易發生層層堆疊與團聚的現象，許多學者都會在分散的過程中添加奈米碳管，使其纏繞在片狀石墨烯周圍，避免其剝落與堆疊，以提高其比表面積利用率。法拉第電容器又稱為偽電容器，通常選用貴金屬、貴金屬氧化物材料、導電高分子做為電極，其儲能原理是利用外加電壓使電解質中的離子往電極與電解質的接觸面遷移，電解質離子藉由電化學反應作用被吸附到具有偽電容特性的電極。若選用比表面積較高的材料做為偽電容器的電極，則在充電時會發生較多次的電化學反應使電極儲存較多的電荷。而在放電過程中，被儲存於電極的電解質離子會以化學脫附的方式回到電解質中，展現出電容特性，因此被稱為「偽電容」。由於偽電容牽扯到電荷的轉移，所以其電荷儲存量遠大於傳統電容器和電雙層電容器，但法拉第電容器卻有著功率密度低和循環壽命短的缺點，這些缺點大大限制了它們作為超級電容器的應用。為了解決這些問題，科學家將電雙層電容器與法拉第電容器相互混合製成混合式超級電容器，以提高其電化學性能與循環壽命。Traditional electronic products have a hard shell as the basis for hardware design, but with the evolution of technology, soft materials have gradually been applied to the design of flexible electronic products. High stability, flatness, and repeatable deflection become the biggest advantages of soft electronics. In order to allow flexible electronic devices to operate smoothly under folded or curved working conditions, flexible energy storage devices will be an indispensable important component, which is why supercapacitors have become the goal of continuous efforts of countries in recent years. Supercapacitors, also known as electrochemical capacitors, have the advantages of high power density, short charging time, long service life, good temperature characteristics, high reversibility, and fast charge and discharge. Energy storage methods can be divided into two types: electric double-layer capacitors (EDLC) and pseudo-capacitors. EDLC, the structure consists of electrode-electrolyte-separator-electrolyte-electrode constitutes EDLC in a sandwich structure, which is mainly subjected to the coulomb electrostatic force by using the charge between the electrode and the electrolyteEffect, forming a situation of positive and negative electrical separation, causing an electrical double layer and storing a net charge, and the electrolyte ions will not cause chemical changes. Carbon-based materials are the most common electrode materials for electric double-layer capacitors. Among them, graphene (G) and carbon nanotubes (Carbon nanotube, CNT) are the most popular among scientists. However, graphene is prone to stacking and agglomeration. Many scholars will add nano carbon tubes in the dispersion process to make it wrap around the sheet of graphene, avoiding its peeling and stacking, to improve its specific surface area utilization. . Faraday capacitors are also called pseudocapacitors. Generally, noble metals, noble metal oxide materials, and conductive polymers are used as electrodes. The energy storage principle is to use an applied voltage to move ions in the electrolyte to the contact surface between the electrode and the electrolyte. Electrochemical reactions are adsorbed to electrodes with pseudocapacitive properties. If a material with a higher specific surface area is used as the electrode of the pseudo capacitor, more electrochemical reactions will occur during charging and the electrode will store more charge. During the discharge process, the electrolyte ions stored in the electrode will return to the electrolyte in a chemically desorbed manner, exhibiting capacitive characteristics, and are therefore called "pseudocapacitors." Due to the transfer of charge involved in pseudocapacitors, their charge storage capacity is much larger than traditional capacitors and electric double-layer capacitors, but Faraday capacitors have the disadvantages of low power density and short cycle life. These shortcomings have greatly limited their application as supercapacitors. . To solve these problems, scientists mixed electric double-layer capacitors and Faraday capacitors into hybrid supercapacitors to improve their electrochemical performance and cycle life.
最近幾年，導電高分子與碳系材料的混合電極用來做為超級電容器已引起科學家的關注，使用具有法拉第電容效應的電極材料有助於提升超級電容器的比電容量，因為在充放電的過程中會發生氧化還原反應以提升比電容量。(聚3,4-亞乙基二氧噻吩：聚苯乙烯磺酸)(PEDOT：PSS)是一種具有導電佳、加工易、成本低的導電性高分子，適合做為超級電容器的電極。但導電性高分子的可循環性差，容易產生降解反應，導致循環壽命差。然而PEDOT卻難溶解於大部分的溶劑，因此添加PSS可促使PEDOT能分散在水溶液中，得到PEDOT：PSS水溶液。但添加PSS會大幅降低PEDOT的導電性，約只剩1Scm-1。為了提升PEDOT：PSS水溶液的導電性，常見的做法是在PEDOT：PSS水溶液中添加有機溶劑，如添加乙二醇(Ethylene glycol,EG)，二甲基亞碸(Dimethyl sulfoxide,DMSO)等，以去除包覆在PEDOT周圍的PSS。研究者利用導電高分子與碳系材料的特性，結合兩者的優點做成混合電極，發現碳系材料的高循環特性可以彌補導電高分子可循環性低的缺點，而導電高分子也可以藉由法拉第電容效應提升碳系電極的比電容量，使兩者互補達到最高效益。Y.Qin等人發現增加PEDOT-PSS的含量不能提高複合材料的比電容。根據推測，雖然多壁奈米碳管(MWCNT)和PEDOT：PSS都會對比電容量有影響，但MWCNT佔主要地位，所以添加過多的PEDOT：PSS，相應地會降低MWCNT的添加量，導致複合材料的比電容量降低。因此，本發明以含有不同比例的PEDOT與石墨烯、多壁奈米碳管均勻混合製作複合導電懸浮液滴覆於砂紙上製成電極並進行比較。In recent years, the use of mixed electrodes of conductive polymers and carbon-based materials as supercapacitors has attracted the attention of scientists. The use of electrode materials with a Faraday capacitance effect can help increase the specific capacitance of supercapacitors. A redox reaction occurs during the process to increase the specific capacitance. (Poly3,4-ethylenedioxythiophene: polystyrene sulfonic acid) (PEDOT: PSS) is a conductive polymer with good conductivity, easy processing, and low cost, and is suitable as an electrode for supercapacitors. However, the conductive polymer has poor cyclability and is prone to degradation reactions, resulting in poor cycle life. However, PEDOT is difficult to dissolve in most solvents. Therefore, the addition of PSS can promote the dispersion of PEDOT in an aqueous solution to obtain a PEDOT: PSS aqueous solution. However, the addition of PSS will greatly reduce the conductivity of PEDOT, leaving only about 1Scm-1 . In order to improve the conductivity of the PEDOT: PSS aqueous solution, it is common practice to add an organic solvent to the PEDOT: PSS aqueous solution, such as adding ethylene glycol (EG), dimethyl sulfoxide (DMSO), etc. Remove the PSS that surrounds the PEDOT. Researchers have used the characteristics of conductive polymers and carbon-based materials to combine the advantages of both to make hybrid electrodes. They found that the high cycling characteristics of carbon-based materials can make up for the shortcomings of conductive polymers, and the conductive polymers can also borrow The specific capacitance of carbon-based electrodes is enhanced by the Faraday capacitance effect, so that the two are complementary to achieve the maximum benefit. Y.Qin et al. Found that increasing the content of PEDOT-PSS could not improve the specific capacitance of composite materials. It is speculated that although both multi-walled carbon nanotubes (MWCNTs) and PEDOT: PSS have an impact on the capacitance, MWCNTs are dominant, so adding too much PEDOT: PSS will correspondingly reduce the amount of MWCNTs added, leading to composite materials. The specific capacitance decreases. Therefore, in the present invention, a composite conductive suspension is dripped on sandpaper to make an electrode by uniformly mixing PEDOT containing different proportions with graphene and multi-walled carbon nanotubes to make electrodes and comparing them.
超級電容器主要是將兩片電極、電解質與隔膜以三明治結構組裝而成，在電解質的部分，又可細分為固態、液態與凝膠態。市面上主要是使用固態電解質為主，雖然固態電解質具有良好機械性質且不會有電解質洩漏的問題，但電極與電解質間卻容易造成接觸不良的缺點，進而造成比電容量降低。而液態電解質其特性卻剛好與固態電解質相反，若應用在產品上可能會有電解質洩漏的問題。因此，藉由使用凝膠態電解質來整合固態跟液態電解質的優點，凝膠態電解質擁有在電極與電解質間較佳的黏合力與液態電解質的滲透特性，且無電解質洩漏的疑慮，藉此達到安全性及提升比電容量的功效。Q.Chen等人對六種相同濃度不同的凝膠電解質(磷酸(H3PO4)、硫酸(H2SO4)、氫氧化鉀(KOH)、氫氧化鈉(NaOH)、氯化鉀(KCl)與氯化鈉(NaCl))進行電化學測試，發現磷酸(H3PO4)做為電解質時，電容量雖然沒有高於其他電解質，但其能量密度與功率密度優於其它者。因此本發明選用磷酸(H3PO4)做為主要的凝膠電解質。而T.Coskun等人為了降低H3PO4凝膠電解質的內電阻值，在凝膠電解質內添加1wt%奈米碳管，發現有添加1%奈米碳管的比電容值由原來的97F/g提高至123F/g。為了進一步提升超級電容器的儲能效益，我們亦選擇於H3PO4中添加少量多壁奈米碳管的方式製成凝膠電解質。Supercapacitors are mainly assembled by sandwiching two electrodes, an electrolyte, and a separator in a sandwich structure. The electrolyte can be subdivided into solid, liquid, and gel states. The market mainly uses solid electrolytes. Although solid electrolytes have good mechanical properties and do not have the problem of electrolyte leakage, the disadvantage of poor contact between the electrode and the electrolyte is likely to cause the specific capacitance to decrease. The characteristics of liquid electrolytes are just opposite to those of solid electrolytes. If applied to products, there may be electrolyte leakage problems. Therefore, by using the gel state electrolyte to integrate the advantages of the solid and liquid electrolytes, the gel state electrolyte has better adhesion between the electrode and the electrolyte and the permeability characteristics of the liquid electrolyte, and there is no doubt about electrolyte leakage, thereby achieving Safety and the effect of improving specific capacity. Q. Chen et al. Analyzed six different gel electrolytes (phosphoric acid (H3 PO4 ), sulfuric acid (H2 SO4 ), potassium hydroxide (KOH), sodium hydroxide (NaOH), potassium chloride ( KCl) and sodium chloride (NaCl) were electrochemically tested. It was found that when phosphoric acid (H3 PO4 ) was used as the electrolyte, although the capacitance was not higher than other electrolytes, its energy density and power density were better than others. Therefore, phosphoric acid (H3 PO4 ) is selected as the main gel electrolyte in the present invention. In order to reduce the internal resistance value of the H3 PO4 gel electrolyte, T.Coskun et al. Added 1 wt% carbon nanotubes to the gel electrolyte, and found that the specific capacitance of the 1% carbon nanotubes was increased from the original 97F. / g increased to 123F / g. In order to further improve the energy storage efficiency of supercapacitors, we also choose to add a small amount of multi-walled carbon nanotubes to H3 PO4 to make a gel electrolyte.
電雙層電容器主要是由碳系材料而組成，藉由添加具有法拉第電容效應的導電高分子PEDOT，結合兩種材料的優點製成複合電極。本發明利用砂紙做為基板，在其表面滴覆含有不同比例PEDOT之石墨烯/多壁奈米碳管(G/MWCNTs)複合導電懸浮液製作出電極，隨後比較不同PEDOT添加量對砂紙基超級電容器儲能性質之影響。為了進一步提升砂紙基超級電容器的比電容值，我們在H3PO4凝膠電解質中添加微量多壁奈米碳管，並探討添加微量多壁奈米碳管對砂紙基電極之影響。最後，利用多功能循環伏安儀進行組立後的超級電容器的電化學特性分析。The electric double-layer capacitor is mainly composed of a carbon-based material. A composite electrode is made by adding a conductive polymer PEDOT with a Faraday capacitance effect and combining the advantages of the two materials. The invention uses sandpaper as a substrate, and the surface is coated with a graphene / multi-walled carbon nanotube (G / MWCNTs) composite conductive suspension containing different proportions of PEDOT on its surface to make an electrode, and then the different amounts of PEDOT added are compared to the sandpaper based Impact of capacitor energy storage properties. In order to further improve the specific capacitance of sandpaper-based supercapacitors, we added a trace of multi-walled carbon nanotubes to the H3 PO4 gel electrolyte, and explored the effect of adding a trace of multi-walled carbon nanotubes on sandpaper-based electrodes. Finally, the multi-functional cyclic voltammetry was used to analyze the electrochemical characteristics of supercapacitors after assembly.
本發明第一目的在於提供一種(a)砂紙基電極之製備：(a1)將果膠加入於去離子水中於高於室溫的溫度下攪拌均勻，以得到果膠水溶液；(a2)將冷卻後的該果膠水溶液加入多壁奈米碳管攪拌均勻；(a3)接著透過超音波震盪，使多壁奈米碳管均勻分散在果膠水溶液中；(a4)隨後以高速離心機旋轉離心，取上層懸浮液，而得到均勻地多壁奈米碳管懸浮液；(a5)以該果膠水溶液與石墨烯混合後，以超音波震盪；(a6)隨後透過高速離心機旋轉離心，留下下層沉澱物；將下層沉澱物加入去離子水稀釋並用磁石攪拌與超音波震洗機分別處理，得到分散均勻的石墨烯懸浮液；(a7)隨後，將製備好的石墨烯懸浮液和奈米碳管懸浮液依1：5~1：10的比例均勻混合並搭配磁石攪拌機及超音波震洗機分別處理一預定時間，得到混合均勻的石墨烯/奈米碳管導電懸浮液；(a8)在具有偽電容特性的(聚3,4-亞乙基二氧噻吩：聚苯乙烯磺酸)(PEDOT：PSS)水溶液中添加二甲基亞碸(DMSO)去除PSS，以獲得一偽電容材料；(a9)再將該偽電容材料與先前製備的石墨烯/奈米碳管(G/MWCNTs)導電懸浮液以一預定比例均勻混合成聚3,4-亞乙基二氧噻吩/石墨烯/多壁奈米碳管(PEDOT/G/MWCNTs)複合導電懸浮液；(a10)藉由溶劑蒸發法，將複合導電懸浮液滴覆在一砂紙表面，以高於室溫的溫度烘烤以去除水分後，使該複合導電懸浮液中的複合導電物沉積於該砂紙上，即可得到砂紙基複合電極；(b)凝膠電解質之製備：(b1)取去離子水與聚乙烯醇(PVA)，以高於室溫的溫度加熱攪拌，以完全溶解成PVA水溶液；(b2)隨後，加入磷酸(H3PO4)均勻攪拌後，烘烤而得到聚乙烯醇/磷酸(PVA/H3PO4)凝膠電解質；以及(c)超級電容器之組立與封裝：(c1)三明治結構(砂紙基電極/凝膠電解質/隔膜/凝膠電解質/砂紙基電極)組立超級電容器；取兩片砂紙基電極表面均勻塗佈凝膠電解質後，將聚對苯二甲酸乙二酯不織布浸漬於凝膠電解質後置於砂紙基電極的中間做為隔膜，避免兩片電極接觸造成短路；隨後將超級電容器以聚乙烯薄片包覆後，用熱壓式封裝機封裝其四個邊，即可得到砂紙基複合超級電容器。The first object of the present invention is to provide (a) the preparation of sandpaper-based electrodes: (a1) adding pectin to deionized water and stirring at a temperature higher than room temperature to obtain a pectin aqueous solution; (a2) cooling The aqueous solution of pectin was added to the multi-walled carbon nanotubes and stirred well; (a3) the ultrasonic wave was then used to uniformly disperse the multi-walled carbon nanotubes in the aqueous solution of pectin; (a4) subsequent high-speed centrifugation Take the upper suspension to obtain a uniform multi-walled carbon nanotube suspension; (a5) After mixing the pectin solution with graphene, oscillate with ultrasonic waves; (a6) Rotate and centrifuge through a high-speed centrifuge, leaving Lower lower sediment; Dilute the lower sediment with deionized water and treat with magnetic stirring and ultrasonic vibration washing machine separately to obtain a uniformly dispersed graphene suspension; (a7) Then, prepare the prepared graphene suspension and Nai The rice carbon tube suspension is evenly mixed according to the ratio of 1: 5 ~ 1: 10 and processed with a magnetic stirrer and an ultrasonic vibration washer for a predetermined time to obtain a uniformly mixed graphene / nanocarbon tube conductive suspension; (a8 ) (Poly 3,4-ethylenedioxythiophene: polystyrene sulfonic acid) (PEDOT: PSS) aqueous solution was added with dimethylsulfinium (DMSO) to remove PSS to obtain a pseudocapacitor material; (a9) and The pseudocapacitor material is uniformly mixed with the previously prepared conductive suspension of graphene / nanocarbon tubes (G / MWCNTs) at a predetermined ratio to form poly 3,4-ethylenedioxythiophene / graphene / multi-wall nanometer. Carbon tube (PEDOT / G / MWCNTs) composite conductive suspension; (a10) by solvent evaporation method, the composite conductive suspension is dripped on a sandpaper surface, baked at a temperature higher than room temperature to remove moisture, and then The composite conductive substance in the composite conductive suspension is deposited on the sandpaper to obtain a sandpaper-based composite electrode; (b) Preparation of a gel electrolyte: (b1) Take deionized water and polyvinyl alcohol (PVA), and Heat and stir at room temperature to completely dissolve into a PVA aqueous solution; (b2) Then, add phosphoric acid (H3 PO4 ) and stir uniformly, and then bake to obtain polyvinyl alcohol / phosphoric acid (PVA / H3 PO4 ). Gel electrolyte; and (c) assembly and packaging of supercapacitors: (c1) sandwich structure (sandpaper-based electrode / gel electrolyte / separator / gel electrolyte / sand Paper-based electrodes) to form supercapacitors; take two pieces of sandpaper-based electrodes and evenly coat the gel electrolyte, immerse the polyethylene terephthalate non-woven fabric in the gel electrolyte and place them in the middle of the sandpaper-based electrodes as a separator. Avoid the short circuit caused by the contact between the two electrodes; then cover the supercapacitor with a polyethylene sheet and seal its four sides with a hot-press packaging machine to obtain a sandpaper-based composite supercapacitor.
本發明第二目的，在於提供一種以如請上述之製法所製得之超級電容器，其包括砂紙基電極/凝膠電解質/隔膜/凝膠電解質/砂紙基電極。A second object of the present invention is to provide a supercapacitor manufactured by the above-mentioned manufacturing method, which comprises a sandpaper-based electrode / gel electrolyte / separator / gel electrolyte / sandpaper-based electrode.
本發明第三目的，在於提供一種超級電容器，將聚對苯二甲酸乙二酯不織布浸漬於凝膠電解質後置於砂紙基電極的中間做為隔膜；超級電容器以聚乙烯薄片包覆。The third object of the present invention is to provide a supercapacitor. A polyethylene terephthalate non-woven fabric is impregnated with a gel electrolyte and placed in the middle of a sandpaper-based electrode as a separator. The supercapacitor is covered with a polyethylene sheet.
10‧‧‧砂紙基電極10‧‧‧ sandpaper-based electrode
20‧‧‧凝膠電解質20‧‧‧gel electrolyte
30‧‧‧隔膜30‧‧‧ diaphragm
40‧‧‧玻璃基板40‧‧‧ glass substrate
圖1(a)係本發明具砂紙基電極之超級電容器結構示意圖；(b)為(a)之充放電示意圖；圖2(a)係本發明石墨烯；(b)多壁奈米碳管；(c)石墨烯表面纏繞多壁奈米碳管；(d)添加1%；(e)添加3%；(f)添加5% PEDOT於石墨烯/多壁奈米碳管混合物中之SEM照片；圖3係本發明在0.02~0.20V/s掃描速度下，將四種不同電極：(a)為G/MWCNTs電極；(b)為1%PEDOT/G/MWCNTs電極；(c)為3%PEDOT/G/MWCNTs電極；(d)為5%PEDOT/G/MWCNTs電極，分別置於磷酸電解質中之循環伏安曲線，(e)為上述四種不同電極在0.02V/s掃描速度下之循環伏安曲線比較圖；(f)為四種不同電極在0.20mA恆電流下之充放電測試與內電阻分析圖；圖4係本發明含有3%PEDOT/G/MWCNTs之電極經600次循環伏安測試下之偽電容效應分析；圖5係本發明在不同掃描速率下，添加PEDOT對電極之比電容量的影響；圖6係本發明(a)為將G/MWCNTs電極置於添加不同濃度多壁奈米碳管的磷酸電解質中，在0.02V/s掃描速率下之循環伏安曲線；(b)為G/MWCNTs電極置於添加不同濃度多壁奈米碳管的磷酸電解質中，在恆電流(0.20mA)下之內電阻分析圖；圖7係本發明比較1.0%多壁奈米碳管添加之磷酸電解質，在掃描速率0.02V/s下對含有3% PEDOT/G/MWCNTs之電極的循環伏安曲線的影響；圖8係本發明(a)G/MWCNTs；(b)3%PEDOT/G/MWCNTs之砂紙基電極，在0.20mA恆電流下經2000次循環充放電測試後之結果；及圖9係本發明對具有複合式電極之可撓式砂紙基超級電容器進行快速充電後點亮功率0.06W的LED燈泡的照片(左上角插圖為未點亮LED前之照片)。Fig. 1 (a) is a schematic diagram of the structure of a supercapacitor with a sandpaper-based electrode according to the present invention; (b) is a schematic diagram of the charge and discharge of (a); Fig. 2 (a) is a graphene of the present invention; (b) a multi-walled carbon nanotube (C) Graphite surface wound multi-walled carbon nanotubes; (d) Add 1%; (e) Add 3%; (f) Add 5% PEDOT to the SEM of graphene / multi-walled carbon nanotube mixtures Photo; Figure 3 shows the present invention using four different electrodes at a scanning speed of 0.02 to 0.20 V / s: (a) G / MWCNTs electrode; (b) 1% PEDOT / G / MWCNTs electrode; (c) is 3% PEDOT / G / MWCNTs electrode; (d) cyclic voltammetry curve of 5% PEDOT / G / MWCNTs electrode respectively placed in phosphoric acid electrolyte, (e) is the scanning speed of the above four different electrodes at 0.02V / s The following cyclic voltammetry curve comparison chart; (f) is the charge and discharge test and internal resistance analysis chart of four different electrodes under a constant current of 0.20mA; Figure 4 is the electrode of the present invention containing 3% PEDOT / G / MWCNTs. Cyclic voltammetryAnalysis of the pseudo capacitance effect below; Figure 5 shows the effect of adding PEDOT on the specific capacitance of the electrode at different scan rates in the present invention; and Figure 6 shows the present invention (a) where the G / MWCNTs electrode is placed in a multi-wall with different concentrations Cyclic voltammetry curve of phosphoric electrolyte for carbon nanotubes at a scan rate of 0.02V / s; (b) G / MWCNTs electrodes were placed in phosphoric acid electrolyte with multi-walled carbon nanotubes with different concentrations, at constant current (0.20mA), the internal resistance analysis diagram; Figure 7 is a comparison of the phosphoric acid electrolyte added to the 1.0% multi-walled carbon nanotubes of the present invention at a scanning rate of 0.02V / s for an electrode containing 3% PEDOT / G / MWCNTs Effect of cyclic voltammetry curve; Figure 8 shows the results of (a) G / MWCNTs; (b) 3% PEDOT / G / MWCNTs sandpaper-based electrode after 2000 cycles of charge and discharge tests at 0.20 mA constant current And FIG. 9 is a photo of an LED light bulb with a lighting power of 0.06W after the fast charging of a flexible sandpaper-based supercapacitor with a composite electrode according to the present invention (the upper left illustration is a photo before the LED is not lit).
圖10係本發明表1導電高分子的添加對砂紙基電極比電容量的影響、表2超級電容器之比電容特性比較；及表3電解質中奈米碳管的添加對砂紙基電極比電容量的影響示意。Fig. 10 shows the effect of the addition of conductive polymer on the specific capacitance of sandpaper-based electrodes in Table 1 of the present invention, the comparison of the specific capacitance of supercapacitors in Table 2; and the specific capacitance of sandpaper-based electrodes in the addition of nanocarbon tubes in Table 3 The impact is shown.
為讓 貴審查委員能進一步瞭解本發明整體的技術特徵與達成本發明目的之技術手段，玆以具體實施例並配合圖式加以詳細說明如下：In order to allow your reviewers to further understand the overall technical features of the present invention and the technical means for achieving the purpose of the present invention, specific embodiments and drawings are described in detail as follows:
請配合參看圖1~2及圖5所示，達成本發明第一目的之具導電高分子砂紙基電極之超級電容器的製法，其具體實施例，包括以下步驟：(a)砂紙基電極之製備：(a1)將果膠加入於去離子水中於高於室溫的溫度下攪拌均勻，以得到果膠水溶液；(a2)將冷卻後的該果膠水溶液加入多壁奈米碳管攪拌均勻；(a3)接著透過超音波震盪，使多壁奈米碳管均勻分散在果膠水溶液中；(a4)隨後以高速離心機旋轉離心後，取上層懸浮液，而得到均勻地多壁奈米碳管懸浮液；(a5)以該果膠水溶液與石墨烯混合後，並以超音波震盪；(a6)隨後透過高速離心機旋轉離心，留下下層沉澱物；將下層沉澱物加入去離子水稀釋並用磁石攪拌與超音波震洗機分別處理，進而得到分散均勻的石墨烯懸浮液；(a7)隨後，將製備好的石墨烯懸浮液和奈米碳管懸浮液依1：5~1：10的比例均勻混合並搭配磁石攪拌機及超音波震洗機分別處理，得到混合均勻的石墨烯/奈米碳管導電懸浮液；(a8)在具有偽電容特性的(聚3,4-亞乙基二氧噻吩：聚苯乙烯磺酸)(PEDOT：PSS)水溶液中添加二甲基亞碸(DMSO)去除PSS，以獲得一PEDOT偽電容材料；(a9)再將該PEDOT偽電容材料與先前製備的石墨烯/奈米碳管(G/MWCNTs)導電懸浮液以一預定比例均勻混合成包括有聚3,4-亞乙基二氧噻吩/石墨烯/奈米碳管(PEDOT/G/MWCNTs)之複合導電物的複合導電懸浮液；(a10)藉由溶劑蒸發法，將該複合導電懸浮液滴覆在一砂紙表面，以高於室溫的溫度烘烤去除水分後，使該複合導電懸浮液中的複合導電物沉積於該砂紙上，即可得到砂紙基複合電極；(b)凝膠電解質之製備：(b1)取去離子水與聚乙烯醇(PVA)，以高於室溫的溫度加熱攪拌，以完全溶解成PVA水溶液；(b2)隨後，加入磷酸(H3PO4)，均勻攪拌後，經烘烤而得到聚乙烯醇/磷酸(PVA/H3PO4)凝膠電解質；以及(c)超級電容器之組立與封裝：(c1)三明治結構(砂紙基電極/凝膠電解質/隔膜/凝膠電解質/砂紙基電極)組立超級電容器；取兩片砂紙基電極表面均勻塗佈凝膠電解質後，將聚對苯二甲酸乙二酯不織布浸漬於凝膠電解質後置於砂紙基電極的中間做為隔膜，避免兩片電極接觸造成短路；隨後將超級電容器以聚乙烯薄片包覆後，用熱壓式封裝機封裝其四個邊，即可得到砂紙基複合超級電容器。Please refer to FIGS. 1 to 2 and FIG. 5 for a method for manufacturing a supercapacitor with a conductive polymer sandpaper-based electrode that achieves the first purpose of the present invention. The specific embodiment includes the following steps: (a) Preparation of sandpaper-based electrode : (A1) adding pectin to deionized water and stirring at a temperature higher than room temperature to obtain an aqueous pectin solution; (a2) adding the cooled pectin aqueous solution to a multi-walled carbon nanotube and stirring well; (a3) Ultrasonic vibration is then used to uniformly disperse the multi-walled carbon nanotubes in the aqueous pectin solution; (a4) After subsequent centrifugation with a high-speed centrifuge, the upper suspension is taken to obtain uniform multi-walled carbon nanotubes. Tube suspension; (a5) after mixing the pectin solution with graphene and oscillating with ultrasonic waves; (a6) subsequent centrifugation by high-speed centrifuge to leave the lower layer of sediment; dilute the lower layer of sediment with deionized water The magnetic stirring and ultrasonic vibration washing machine were separately processed to obtain a uniformly dispersed graphene suspension; (a7) Subsequently, the prepared graphene suspension and the nano-carbon tube suspension were prepared according to 1: 5 ~ 1: 10. Mix evenly with magnets The mixer and the ultrasonic vibration washing machine were separately processed to obtain a uniformly mixed graphene / nanometer carbon tube conductive suspension; (a8) the (poly 3,4-ethylenedioxythiophene: polybenzene) having pseudocapacitive characteristics Ethylene sulfonic acid) (PEDOT: PSS) solution was added with dimethylsulfinium (DMSO) to remove PSS to obtain a PEDOT pseudocapacitor material; (a9) the PEDOT pseudocapacitor material and the previously prepared graphene / nanometer Carbon tube (G / MWCNTs) conductive suspension is uniformly mixed at a predetermined ratio to form a composite conductive material including poly 3,4-ethylenedioxythiophene / graphene / nanometer carbon tube (PEDOT / G / MWCNTs) Composite conductive suspension; (a10) by solvent evaporation method, the composite conductive suspension is dripped on the surface of a sandpaper, and the water is baked at a temperature higher than room temperature to remove the composite conductive suspension in the composite conductive suspension; (B) Preparation of gel electrolyte: (b1) Take deionized water and polyvinyl alcohol (PVA), heat and stir at a temperature higher than room temperature, and PVA was completely dissolved into the aqueous solution; (B2) Next, phosphoric acid (H3 PO4), after uniformly stirred, obtained by baking a poly Alcohol / phosphoric acid (PVA / H3 PO4) gel electrolyte; Assembling the package and (c) a super capacitor: (c1) a sandwich structure (sandpaper yl electrode / gel electrolyte / separator / gel electrolyte / electrode group sandpaper ) Assemble supercapacitors; take two pieces of sandpaper-based electrode to evenly coat the gel electrolyte, dip the polyethylene terephthalate non-woven cloth in the gel electrolyte and place it in the middle of the sandpaper-based electrode as a separator, avoid two pieces Electrode contact caused a short circuit; after the supercapacitor was covered with a polyethylene sheet, the four sides of the supercapacitor were encapsulated with a hot-press packaging machine to obtain a sandpaper-based composite supercapacitor.
本發明一種較佳實施例中，步驟(a1)中，果膠與去離子水攪拌的溫度為50~70℃(較佳為60℃)；步驟(a4)中，高速離心機的轉速及時間分別為2500~3500rpm(較佳為3000rpm)及10~20分鐘(較佳為15分鐘)。In a preferred embodiment of the present invention, in step (a1), the temperature for stirring the pectin and deionized water is 50 to 70 ° C (preferably 60 ° C); in step (a4), the speed and time of the high-speed centrifuge They are 2500 ~ 3500rpm (preferably 3000rpm) and 10 ~ 20 minutes (preferably 15 minutes).
本發明一種較佳實施例中，步驟(a6)中，高速離心機的轉速及時間分別為3500~4500rpm(較佳為4000rpm)及10~20分鐘(較佳為15分鐘)；將下層沉澱物加入去離子水稀釋用磁石攪拌與超音波震洗機分別處理時間分別為0.5至1.5小時(較佳為1小時)。In a preferred embodiment of the present invention, in step (a6), the rotation speed and time of the high-speed centrifuge are 3500 ~ 4,500 rpm (preferably 4000 rpm) and 10-20 minutes (preferably 15 minutes); Adding deionized water to dilute with a magnetic stirrer and ultrasonic vibration washing machine, respectively, the processing time is 0.5 to 1.5 hours (preferably 1 hour).
本發明一種較佳實施例中，步驟(a10)中，烘烤的溫度及時間分別為50~70℃(較佳為60℃)及5~7小時(較佳為6小時)。In a preferred embodiment of the present invention, in step (a10), the baking temperature and time are 50 to 70 ° C (preferably 60 ° C) and 5 to 7 hours (preferably 6 hours).
本發明一種較佳實施例中，步驟(b1)中，加熱攪拌的溫度為80~90℃(較佳為85℃)。In a preferred embodiment of the present invention, in step (b1), the temperature of heating and stirring is 80-90 ° C (preferably 85 ° C).
其中，本發明一種較佳實施例中，步驟(b2)中，烘烤溫度及時間分別為50~70℃(較佳為60℃)及10~14小時(較佳為12小時)。In a preferred embodiment of the present invention, in step (b2), the baking temperature and time are 50 to 70 ° C (preferably 60 ° C) and 10 to 14 hours (preferably 12 hours).
達成本發明第二目的之實施例，以如上述本發明之方法所製成之超級電容器，其包括砂紙基電極/凝膠電解質/隔膜/凝膠電解質/砂紙基電極。To achieve the second object of the present invention, the supercapacitor manufactured by the method of the present invention as described above includes a sandpaper-based electrode / gel electrolyte / separator / gel electrolyte / sandpaper-based electrode.
請配合參看圖7~9所示，達成本發明第三目的之實施例，一種應用本發明之超級電容器，將聚對苯二甲酸乙二酯不織布浸漬於凝膠電解質後置於砂紙基電極的中間做為隔膜；超級電容器以聚乙烯薄片包覆。Please refer to Figs. 7-9. An embodiment that achieves the third object of the present invention is a supercapacitor to which the present invention is applied. A polyethylene terephthalate non-woven fabric is impregnated with a gel electrolyte and placed on a sandpaper-based electrode. The middle is the separator; the supercapacitor is covered with a polyethylene sheet.
本發明砂紙基電極之製備。本發明選用果膠做為導電懸浮液的分散劑，將果膠加入於去離子水中，並在60℃下攪拌均勻，即可得到0.5wt%果膠水溶液。將果膠水溶液放置於室溫冷卻，再將多壁奈米碳管(VGCFTM-X,Showa Denko K.K.)加入0.5wt%果膠水溶液中，並搭配磁石攪拌均勻。接著透過探針式超音波(VCX750,SONICS)震盪30分鐘，使多壁奈米碳管能均勻分散在果膠水溶液中。隨後以高速離心機在3000rpm的轉速下離心15分鐘，取上層懸浮液，即可得到均勻地多壁奈米碳管懸浮液。此外，我們利用0.5wt%果膠水溶液與石墨烯(P-ML20,Graphene)混合後，一樣以探針式超音波震盪30分鐘，隨後透過高速離心機以4000rpm的轉速離心15分鐘，留下下層沉澱物。將下層沉澱物加入去離子水稀釋並用磁石攪拌與超音波震洗機各別處理1小時，即可得到分散均勻的石墨烯懸浮液。隨後，將製備好的石墨烯懸浮液和奈米碳管懸浮液依1：5的比例均勻混合並搭配磁石攪拌機搭配超音波震洗機各別處理30分鐘，即可得到混合均勻的導電懸浮液。而為了製備複合電極，我們在具有偽電容特性的(聚3,4-亞乙基二氧噻吩：聚苯乙烯磺酸)(PEDOT：PSS)水溶液中添加0.5%的二甲基亞碸(DMSO)去除PSS後。再將其與先前製備的G/MWCNTs導電懸浮液均勻混合成含有1、3、5%之PEDOT而包含有PEDOT/G/MWCNTs複合導電物的複合導電懸浮液。藉由溶劑蒸發法，將不同比例的混合懸浮液透過微量滴管吸取3ml滴覆在砂紙(Sandpaper,1000#C,Sanlu)表面，並將其放置於60℃的真空烘箱中烘烤6小時，待水分蒸發去除後，複合導電物將沉積於砂紙上，即可得到砂紙基複合電極。Preparation of the sandpaper-based electrode of the present invention. In the present invention, pectin is selected as the dispersant of the conductive suspension, and the pectin is added to deionized water and stirred at 60 ° C. to obtain a 0.5 wt% pectin aqueous solution. The pectin aqueous solution was left to cool at room temperature, and then a multi-walled carbon nanotube (VGCF™ -X, Showa Denko KK) was added to the 0.5 wt% pectin aqueous solution, and stirred with a magnet evenly. Then, the probe-type ultrasonic wave (VCX750, SONICS) was shaken for 30 minutes, so that the multi-walled carbon nanotubes could be evenly dispersed in the aqueous pectin solution. Subsequently, the centrifuge was centrifuged at 3000 rpm for 15 minutes and the upper suspension was taken to obtain a uniform multi-walled carbon nanotube suspension. In addition, we used 0.5 wt% pectin solution to mix with graphene (P-ML20, Graphene), and then oscillated with a probe-type ultrasonic for 30 minutes, and then centrifuged at 4000 rpm for 15 minutes through a high-speed centrifuge, leaving the lower layer. Precipitate. The lower layer of sediment is diluted with deionized water and treated with a magnetic stirrer and an ultrasonic vibration washing machine for 1 hour respectively to obtain a uniformly dispersed graphene suspension. Subsequently, the prepared graphene suspension and nano carbon tube suspension are evenly mixed according to a ratio of 1: 5 and processed with a magnetic stirrer and an ultrasonic vibration washing machine respectively for 30 minutes to obtain a uniformly mixed conductive suspension. . In order to prepare a composite electrode, we added 0.5% dimethylsulfinium (DMSO) to an aqueous solution of (poly 3,4-ethylenedioxythiophene: polystyrenesulfonic acid) (PEDOT: PSS) with pseudo-capacitance characteristics. ) After removing PSS. Then it is uniformly mixed with the previously prepared G / MWCNTs conductive suspension to form a composite conductive suspension containing 1, 3, and 5% PEDOT and containing a PEDOT / G / MWCNTs composite conductive substance. By the solvent evaporation method, 3ml of the mixed suspension with different proportions was sucked on the surface of sandpaper (Sandpaper, 1000 # C, Sanlu) through a micro-dropper, and placed in a vacuum oven at 60 ° C for 6 hours, After the water is evaporated and removed, the composite conductive material will be deposited on the sandpaper to obtain a sandpaper-based composite electrode.
本發明凝膠電解質之製備。採用溶膠-凝膠法製備凝膠態電解質，先取50ml的去離子水與5g聚乙烯醇(Polyvinyl alcohol,PVA,MW：85,000~120,000,SIGMA)放置於燒杯中，於85℃下加熱攪拌，使其完全溶解成PVA水溶液。隨後，加入10g磷酸(phosphoric acid,H3PO4,SIGMA)，並利用磁石攪拌機均勻攪拌後，置於60℃真空烘箱中烘烤12小時，即可得到PVA/H3PO4凝膠電解質。隨後，添加不同比例(0.1、0.5、1.0、1.5%)的MWCNTs導電懸浮液於PVA/H3PO4凝膠電解質中。以探討不同比例MWCNTs的添加量對凝膠電解質的內電阻與比電容量之影響。Preparation of the gel electrolyte of the present invention. The gel-state electrolyte was prepared by the sol-gel method. First, 50 ml of deionized water and 5 g of polyvinyl alcohol (PVA, MW: 85,000 ~ 120,000, SIGMA) were placed in a beaker, and heated and stirred at 85 ° C. so that It was completely dissolved into an aqueous PVA solution. Subsequently, 10 g of phosphoric acid (H3 PO4 , SIGMA) was added and uniformly stirred with a magnetic stirrer, and then baked in a vacuum oven at 60 ° C. for 12 hours to obtain a PVA / H3 PO4 gel electrolyte. Subsequently, MWCNTs conductive suspensions of different ratios (0.1, 0.5, 1.0, 1.5%) were added to the PVA / H3 PO4 gel electrolyte. The effects of the addition of MWCNTs in different proportions on the internal resistance and specific capacitance of the gel electrolyte were discussed.
本發明超級電容器之組立與封裝。我們以三明治結構(砂紙基電極/凝膠電解質/隔膜/凝膠電解質/砂紙基電極)組立超級電容器。取兩片本發明所製得的砂紙基電極，分別於其表面均勻塗佈一層凝膠電解質後，將聚對苯二甲酸乙二酯(Polyethylene Terephalate,PET,Good Young Co.,Ltd.,Taiwan)不織布浸漬於凝膠電解質後置於二砂紙基電極的中間，以做為隔膜，避免兩片砂紙基電極相互接觸而造成短路，而組立成本發明之超級電容器。隨後將超級電容器以聚乙烯薄片包覆後，用熱壓式封裝機封裝其四個邊，即可得到砂紙基複合超級電容器。Assembly and packaging of the supercapacitor of the present invention. We assembled supercapacitors in a sandwich structure (sandpaper-based electrode / gel electrolyte / separator / gel electrolyte / sandpaper-based electrode). Take two pieces of the sandpaper-based electrode prepared by the present invention, and apply a layer of gel electrolyte evenly on the surface, and then apply polyethylene terephalate (Polyethylene Terephalate, PET, Good Young Co., Ltd., Taiwan) ) Non-woven fabric is impregnated with gel electrolyte and placed in the middle of two sandpaper-based electrodes as a separator to prevent two pieces of sandpaper-based electrodes from contacting each other and causing a short circuit. After the supercapacitor is covered with a polyethylene sheet, the four sides of the supercapacitor are encapsulated with a hot-press packaging machine to obtain a sandpaper-based composite supercapacitor.
本發明砂紙基電極之特性分析。利用多功能循環電性分析儀(CHI Instruments,CHI6273E)來研究電極對超級電容器的電化學性質變化。將製備好的砂紙基電極置於電三極系統中進行循環伏安(Cyclic Voltammetry,CV)分析、恆電流充放電(Constant current charge-discharge,CP)分析與循環壽命(Cycle stability)分析。電三極系統分別為參考電極(reference electrolyte,RE)為銀-氯化銀電極(Ag/AgCl electrolyte)、輔助電極(counter electrolyte,CE)為鉑金電極(Pt electrolyte)和工作電極為待測試砂紙基電極。我們以三種不同比例之含有(1、3、5%)PEDOT的PEDOT/G/MWCNTs砂紙基電極與純G/MWCNTs砂紙基電極四種做為工作電極並比較其中差異。設定掃描電壓為0至0.7V之間，掃描速率為0.02至0.20V/s，電解質分別為以1M磷酸(H3PO4)與在1M磷酸(H3PO4)中添加四種不同比例(0.1、0.5、1.0、1.5%)之多壁奈米碳管(MWCNTs)進行分析。根據Eqs.(1)-(3)可分別計算出砂紙基電極之比電容量(specific capacity,Cs)、能量密度(energy density,ED)與功率密度(power density,PD)：
式中，Cs為比電容量(F/g)；i為放電電流(mA)；m為導電層材料之重量(g)；s為掃描速率(V/s)；△V為電壓範圍差；ED為能量密度(Wh/kg)；PD為功率密度(W/kg)；t為放電時間。In the formula, Cs is the specific capacitance (F / g); i is the discharge current (mA); m is the weight of the conductive layer material (g); s is the scanning rate (V / s); △ V is the voltage range difference; ED is the energy density (Wh / kg); PD is the power density (W / kg); t is the discharge time.
電極的表面形貌。在無添加化學黏著劑的情況下，石墨烯與奈米碳管容易產生層層堆疊或團聚等問題，造成儲能效果降低。為了解決堆疊與團聚的問題，本發明利用植物果膠分別添加於石墨烯與奈米碳管中當作分散劑使用，其SEM照片，如圖2(a)(b)所示。如果單純使用石墨烯做為可撓式超級電容器之電極使用時，因石墨烯容易產生堆疊與剝落，反而無法有效利用其高比表面積的特性。而藉由添加多壁奈米碳管當作支撐架，可改善石墨烯堆疊的現象。所以我們將多壁奈米碳管與石墨烯以5：1的比例混合製成石墨烯/多壁奈米碳管導電懸浮液。由圖2(c)之SEM照片可以發現多壁奈米碳管會纏繞在石墨烯表面。多壁奈米碳管除了可避免石墨烯發生層與層之間的堆疊外，還可以做為石墨烯間的間隙子，藉由多壁奈米碳管間的連結可提高混合導電層的有效比表面積。圖2(d)(e)為石墨烯/多壁奈米碳管導電混合液中添加少量不同比例(1、3%)的PEDOT做為電極的顯微組織照片。由於PEDOT的添加量較少，導致其SEM照片與圖2(c)很相似，無法看出明顯差異。Surface morphology of the electrode. Without the addition of chemical adhesives, graphene and carbon nanotubes are prone to problems such as layer-by-layer stacking or agglomeration, which reduces the energy storage effect. In order to solve the problems of stacking and agglomeration, the present invention uses plant pectin added to graphene and nano carbon tubes as dispersants, and the SEM photos thereof are shown in FIG. 2 (a) (b). If you use graphene aloneWhen used as an electrode of a flexible supercapacitor, graphene is prone to stacking and peeling, so it cannot effectively utilize its high specific surface area. By adding multi-walled carbon nanotubes as a support frame, the phenomenon of graphene stacking can be improved. Therefore, we mixed a multi-walled carbon nanotube with graphene at a ratio of 5: 1 to make a graphene / multi-walled carbon nanotube conductive suspension. From the SEM photograph of Fig. 2 (c), it can be found that the multi-walled carbon nanotubes are entangled on the graphene surface. In addition to avoiding the stacking of graphene layers and layers, multi-walled carbon nanotubes can also be used as interstitials between graphenes. The effectiveness of mixed conductive layers can be improved by the connection between multi-walled carbon nanotubes. Specific surface area. Figures 2 (d) (e) are micrographs of a graphene / multi-walled carbon nanotube conductive mixture containing a small amount of PEDOT in different proportions (1, 3%) as an electrode. Due to the small amount of PEDOT added, the SEM photo is very similar to that in Figure 2 (c), and no obvious difference can be seen.
本發明砂紙基電極之循環伏安分析。在電三極系統中，一個理想的循環伏安曲線將呈現矩形的形狀。但是在電極與電解質接觸時會因為有接觸電阻以及電解質內電阻的存在，造成循環伏安曲線偏離理想形狀。圖3(a)是將石墨烯/奈米碳管混合的砂紙基電極置於磷酸電解質中，在0.02~0.20V/s掃描速率下所呈現的的循環伏安曲線。在不同掃面速率下進行循環伏安測試，各曲線皆為對稱的矩形形狀，顯示出石墨烯/多壁奈米碳管混合電極具有良好的可逆性與理想的電容性質。圖3(b)(c)(d)則是在石墨烯/多壁奈米碳管混合導電液中分別以1、3、5%的比例添加PEDOT的砂紙電極，並其分別置於磷酸電解質中之循環伏安曲線圖。相對於圖3(a)的石墨烯/多壁奈米碳管混合電極，添加導電高分子PEDOT的循環伏安曲線無法呈現對稱矩形。導電高分子PEDOT其偽電容效應可以透過含有3%PEDOT/G/MWCNTs砂紙基電極之循環伏安曲線(圖4)進行了解。在掃描速度0.02V/s時，含有3%PEDOT/G/MWCNTs的砂紙基電極具有偽電容效應的氧化還原特徵峰。因為氧化還原峰的存在會導致循環伏安曲線無法成為對稱矩形，但卻能大幅增加比電容量。但經過600次循環伏安特性分析後，偽電容材料會發生電化學降解，導致比電容量下降。Cyclic voltammetry analysis of the sandpaper-based electrode of the present invention. In an electric three-pole system, an ideal cyclic voltammetry curve will assume a rectangular shape. However, when the electrode is in contact with the electrolyte, the cyclic voltammetry curve deviates from the ideal shape because of the contact resistance and the internal resistance of the electrolyte. Figure 3 (a) is a cyclic voltammetry curve of a graphene / nanometer carbon tube mixed sandpaper-based electrode in a phosphoric acid electrolyte at a scanning rate of 0.02 to 0.20 V / s. Cyclic voltammetry tests were performed at different scan rates. Each curve was a symmetrical rectangular shape, showing that the graphene / multi-walled carbon nanotube hybrid electrode had good reversibility and ideal capacitance properties. Figure 3 (b) (c) (d) is a sandpaper electrode with PEDOT added to the graphene / multi-walled carbon nanotube mixed conductive liquid at a ratio of 1, 3, and 5%, respectively, and placed on the phosphate electrolyte The cyclic voltammetry graph. Compared with the graphene / multi-walled carbon nanotube hybrid electrode in Fig. 3 (a), the cyclic voltammetry curve of the conductive polymer PEDOT cannot show a symmetrical rectangle. The pseudo-capacitance effect of conductive polymer PEDOT can be understood through the cyclic voltammetry curve of a sandpaper-based electrode containing 3% PEDOT / G / MWCNTs (Figure 4). Scan speedAt 0.02V / s, the sandpaper-based electrode containing 3% PEDOT / G / MWCNTs has a redox characteristic peak with pseudocapacitive effect. Because of the existence of redox peaks, the cyclic voltammetry curve cannot be a symmetrical rectangle, but it can greatly increase the specific capacitance. However, after 600 cycles of voltammetric characteristics analysis, the pseudocapacitor material will undergo electrochemical degradation, resulting in a decrease in specific capacitance.
藉由Eq.(1)可計算出在G/MWCNTs中添加三種不同比例PEDOT與G/MWCNTs之砂紙基電極在0.02~0.20V/s掃描速率下之比電容量，其結果呈現於圖3(e)與圖10中的表1。顯示G/MWCNTs與三種不同比例(1、3、5%)PEDOT/G/MWCNTs之砂紙基電極在0.02V/s掃描速率下其比電容量分別為55,100,124,89F/g。顯然含PEDOT之砂紙基電極因具有偽電容效應，所以較G/MWCNTs之砂紙基電極具有較高之比電容量。由無添加PEDOT電極之比電容量為55F到添加3%PEDOT之比電容量值達124F，提升了125%。而含3%PEDOT者其比電容量又比另外兩者都高。此外，由Eqs.(2,3)計算可知，G/MWCNTs之砂紙基電極其比電容值在55F/g時，其能量密度與功率密度分別為3.74Wh/kg與347.90W/kg。而含1%PEDOT之砂紙基電極其比電容量為100F/g，其能量密度與功率密度分別為6.80Wh/kg與438.70W/kg；而含3%PEDOT之砂紙基電極之比電容量為124F/g，其能量密度與功率密度分別為8.43Wh/kg與542.89W/kg；而含5%PEDOT者砂紙基電極之比電容量為89F/g，其能量密度與功率密度分別為6.05Wh/kg與336.11W/kg。這顯示了含3%PEDOT之G/MWCNTs電極比其他三者更具有優異的能量密度與功率密度。With Eq. (1), the specific capacitance of the sandpaper-based electrode added with three different ratios of PEDOT and G / MWCNTs to G / MWCNTs at a scan rate of 0.02 to 0.20V / s can be calculated. The results are shown in Figure 3 ( e) Same as Table 1 in FIG. It shows that the specific capacitances of G / MWCNTs and three different ratios (1, 3, 5%) of PEDOT / G / MWCNTs sandpaper-based electrodes are 55,100,124,89F / g at a scan rate of 0.02V / s. Obviously, the sandpaper-based electrode containing PEDOT has higher specific capacitance than the sandpaper-based electrode of G / MWCNTs because of its pseudo-capacitance effect. Increased the specific capacitance from 55F without PEDOT electrodes to 124F with 3% PEDOT, an increase of 125%. Those with 3% PEDOT have higher specific capacitance than the other two. In addition, from Eqs. (2, 3) calculations, it can be known that when the specific capacitance of the sandpaper-based electrode of G / MWCNTs is 55F / g, its energy density and power density are 3.74Wh / kg and 347.90W / kg, respectively. The sandpaper-based electrode with 1% PEDOT has a specific capacitance of 100F / g, and its energy density and power density are 6.80Wh / kg and 438.70W / kg; and the specific capacitance of the sandpaper-based electrode with 3% PEDOT is 124F / g, its energy density and power density are 8.43Wh / kg and 542.89W / kg respectively; while the specific capacitance of the sandpaper-based electrode containing 5% PEDOT is 89F / g, its energy density and power density are 6.05Wh / kg and 336.11W / kg. This shows that the G / MWCNTs electrode with 3% PEDOT has better energy density and power density than the other three.
此外，由圖5可發現比電容量會隨著掃描速率的降低而增加，這表示在較低掃描速率時能驅使多的電解質離子進入電極表面，使較多的電荷吸附於電極表面而提高其比電容量。在恆定電流下，不同掃描速率間的比電容值變化量稱為電容衰退率(Attenuation rate,α)。電容衰退率越高表示電容維持率(Rate capability,β)越低，其計算方式如下：△C=|Clow-Chigh| (4)In addition, it can be found from Fig. 5 that the specific capacitance increases with the decrease of the scanning rate, which means that at a lower scanning rate, more electrolyte ions can be driven into the electrode surface, and more charges are adsorbed on the electrode surface to increase it. Specific capacitance. At a constant current, the amount of change in the specific capacitance value between different scan rates is called the capacitance decay rate (Attenuation rate,α ). The higher the capacitance decay rate is, the lower the capacitance capability rate (β ) is. The calculation method is as follows: △ C = |Clow -Chigh | (4)
β=1-α (6)β = 1-α (6)
式中，Chigh與Clow分別為測量範圍最高與最低掃描速率下的比電容量；△C為電容變化量的絕對值。透過圖5與Eqs.(4)-(6)計算可得到對應於無添加與添加1%,3%,5%PEDOT於G/MWCNTs之砂紙基電極的電容維持率分別為51.91%,40.0%,33.88%與23.60%。這意味著未添加PEDOT的砂紙基電極具有較佳的電容維持特性。經過分析，我們發現隨著降低掃描速率其比電容值會隨之增加。主因為在較低的掃描速率時，會有較多的電解質離子進入電極，使電極吸附更多的電荷。添加PEDOT之電極因其在低掃描速率時會有較高的比電容量，所以其電容變化量(△C)會比G/MWCNTs電極來得高。透過公式(6)可知，當△C越高時，其電容衰退率α也會越高，電容維持率β則越低。透過在0.20mA下測試三種不同比例PEDOT/G/MWCNTs與G/MWCNTs之砂紙基電極之恆電流充放電分析，其結果如圖3(f)所示。理想的恆電流充放電圖形呈等腰三角形，但是在放電的過程中電荷離子從電極兩端回到電解質時所會產生阻抗，此阻抗稱之為內電阻(iRdrop)。透過iRdrop值的降低，可使放電的過程中減少能量損耗與熱能的產生，進而提高比電容量。含3%PEDOT/G/MWCNTs之砂紙基電極其iRdrop為0.056v，明顯低於含5%PEDOT/G/MWCNTs電極的0.092v與G/MWCNTs電極的0.072v。電極中添加3%PEDOT者其iRdrop值較含有5%PEDOT者小，可能在於添加3%PEDOT者在恆電流測試充放電時，電荷在電解質間遇到的阻礙較少，所以iRdrop較低。此外，含有PEDOT砂紙基電極之充放電週期大於G/MWCNTs之砂紙基電極，主因是含有PEDOT之砂紙基電極所儲存的電容量較多，因此在充放電時會消耗越長的時間。由恆電流充放電試驗結果尚可看出四種電極的曲線都近似等腰三角形，顯示四種電極都具有良好的可逆性與具備快速充放電特性。。In the formula, Chigh and Clow are the specific capacitances at the highest and lowest scan rates of the measurement range respectively; △ C is the absolute value of the capacitance change. Through calculations in Figure 5 and Eqs. (4)-(6), the capacitance retention rates of the sandpaper-based electrodes corresponding to no addition and addition of 1%, 3%, and 5% PEDOT to G / MWCNTs are 51.91% and 40.0%, respectively. 33.88% and 23.60%. This means that sandpaper-based electrodes without PEDOT have better capacitance retention characteristics. After analysis, we found that the specific capacitance value increases with decreasing scan rate. The main reason is that at a lower scanning rate, more electrolyte ions enter the electrode, causing the electrode to adsorb more charge. The PEDOT-added electrode will have a higher specific capacitance at low scan rates, so its capacitance change (△ C) will be higher than that of the G / MWCNTs electrode. It can be known from the formula (6) that when ΔC is higher, the capacitance decay rateα is higher, and the capacitance retention rateβ is lower. The constant current charge-discharge analysis of sandpaper-based electrodes of three different ratios of PEDOT / G / MWCNTs and G / MWCNTs was tested at 0.20 mA. The results are shown in Figure 3 (f). The ideal constant-current charge-discharge pattern is an isosceles triangle, but during the discharge process, the charge ions will return to the electrolyte from both ends of the electrode, and this impedance is called the internal resistance (iRdrop ). By reducing the iRdrop value, the energy loss and heat generation can be reduced during the discharge process, and the specific capacitance can be improved. The iRdrop of the sandpaper-based electrode containing 3% PEDOT / G / MWCNTs was 0.056v, which was significantly lower than 0.092v of the 5% PEDOT / G / MWCNTs electrode and 0.072v of the G / MWCNTs electrode. The iRdrop value of those who added 3% PEDOT to the electrode was smaller than those who contained 5% PEDOT. It may be that those who added 3% PEDOT encountered less obstacles between the electrolytes during charge and discharge during the constant current test, so the iRdrop was lower. . In addition, the charge and discharge cycle of PEDOT sandpaper-based electrodes is longer than that of G / MWCNTs. The main reason is that the sandpaper-based electrodes containing PEDOT have a larger storage capacity, so the longer it takes to charge and discharge. From the results of the constant current charge and discharge test, it can be seen that the curves of the four electrodes are approximately isosceles triangles, showing that the four electrodes have good reversibility and fast charge and discharge characteristics. .
圖10中的表2為本發明所製備之複合式電極與其他相關研究之比較表。我們發現多數的研究者皆以電聚合與電沉積的方式製備複合電極。本發明以簡易的磁石攪拌與超音波震盪的方式製作出比電容量值達124F/g的複合式電極，此值雖非最高，但若考量製作成本與所獲得的比電容量，本發明所提供之技術明顯具有優異的市場價值。Table 2 in FIG. 10 is a comparison table of the composite electrode prepared by the present invention and other related studies. We found that most researchers have prepared composite electrodes by electropolymerization and electrodeposition. The present invention produces a composite electrode with a specific capacitance value of 124F / g in a simple magnetic stirring and ultrasonic vibration manner. Although this value is not the highest, if the production cost and the obtained specific capacitance are considered, the present invention The technology provided clearly has excellent market value.
凝膠電解質之循環伏安分析。圖6(a)為利用G/MWCNTs之砂紙基電極對磷酸電解質中添加少量多壁奈米碳管對循環伏安曲線之影響。由圖10中的表3與圖6(a)顯示出當多壁奈米碳管添加濃度分別為0.1,0.5,1.0%時，其比電容量會由55F/g提升至63,69及73F/g，且其對應於0.20mA恆電流下之內電阻值會從原先的0.072v(未添加)分別下降至0.052v、0.041v及0.028v，可以證實添加多壁奈米碳管確實能降低內電阻值(見圖6(b))。但當多壁奈米碳管添加量提升至1.5%時，其比電容量會下降至67F/g，而內電阻值會上升至0.037v。這可能是因為過量的多壁奈米碳管在電解質中發生團聚，阻礙離子的遷移。圖7為本實驗利用比電容量最高的3%PEDOT砂紙基電極搭配含有1.0%多壁奈米碳管的磷酸電解質進行循環伏安測試分析的結果，顯示其比電容量會由原本的124F/g提升到137F/g(見圖10中的表3)，提升了10.4%。Cyclic Voltammetric Analysis of Gel Electrolyte. Figure 6 (a) shows the effect of the addition of a small amount of multi-walled carbon nanotubes in phosphoric acid electrolyte on the cyclic voltammetry curve of a sandpaper-based electrode using G / MWCNTs. From Table 3 in Figure 10 and Figure 6 (a), it is shown that when the multi-wall carbon nanotubes are added at concentrations of 0.1, 0.5, and 1.0%, the specific capacitance will increase from 55F / g to 63, 69, and 73F. / g, and its internal resistance value corresponding to 0.20mA constant current will decrease from the original 0.072v (not added) to 0.052v, 0.041v and 0.028v respectively, which can confirm that the addition of multi-walled carbon nanotubes can indeed reduce Internal resistance value (see Figure 6 (b)). However, when the multi-wall carbon nanotubes are added to 1.5%, the specific capacitance will drop to 67F / g, and the internal resistance value will rise to 0.037v. This may be because excessive multi-walled carbon nanotubes agglomerate in the electrolyte, hindering the migration of ions. Figure 7 shows the results of a cyclic voltammetry test using a 3% PEDOT sandpaper-based electrode with the highest specific capacitance and a phosphate electrolyte containing 1.0% multi-walled carbon nanotubes, which shows that the specific capacitance will be changed from the original 124F / g increased to 137F / g (seeTable 3) in Figure 10, an increase of 10.4%.
超級電容器之電化學分析。本發明利用砂紙做為基板，對添加1.0%MWCNTs凝膠電解質在0.20mA恆電流下對G/MWCNTs與3%PEDOT/G/MWCNTs之砂紙基電極進行2000次循環充放電測試，其結果如圖8(a)與圖8(b)所示，顯示此二者的比電容量仍分別保有初始電容量的98%與97%，這遠高於先前單獨使用G/MWCNTs砂紙基電極的比電容保有率僅有91%之效果，驗證出此儲能元件具有優異的循環壽命與電容穩定性。本發明之所以能較過去G/MWCNTs砂紙基電極的比電容值保有率提升到98%，推測原因可能是採用探針式超音波震盪分散多壁奈米碳管與石墨烯的效果遠優於傳統的超音波槽，且磷酸電解質中添加微量的多壁奈米碳管造成內電阻的降低也起了加成的作用。如圖1及9所示，為以三明治結構超級電容器，將兩片含有3%PEDOT/G/MWCNTs凝膠電解質20做為導電層之砂紙基電極10分置於一玻璃基板40上，於二砂紙基電極10間插入浸泡過含1%MWCNTs的磷酸凝膠電解質的隔膜30，組立成可撓式砂紙基複合超級電容器後，以10V電壓進行充電後點亮工作電壓3V、功率0.06W的LED燈。Electrochemical analysis of supercapacitors. The present invention uses sandpaper as a substrate, and conducts 2,000 cycles of charge and discharge tests on G / MWCNTs and 3% PEDOT / G / MWCNTs sandpaper-based electrodes by adding 1.0% MWCNTs gel electrolyte at a constant current of 0.20 mA. The results are shown in the figure below. As shown in Figures 8 (a) and 8 (b), the specific capacitance of the two still retains 98% and 97% of the initial capacitance, respectively, which is much higher than the specific capacitance of the previous G / MWCNTs sandpaper-based electrode alone. The retention rate is only 91%, which proves that this energy storage element has excellent cycle life and capacitance stability. The reason why the present invention can increase the specific capacitance value retention rate of G / MWCNTs sandpaper-based electrodes to 98% in the past is speculated that the reason may be that the effect of dispersing multi-walled carbon nanotubes and graphene with probe-type ultrasonic vibration is much better than The traditional ultrasonic tank, and the addition of a small amount of multi-walled carbon nanotubes in the phosphoric acid electrolyte caused a reduction in the internal resistance. As shown in Figures 1 and 9, for a sandwich-type supercapacitor, two sheets of sandpaper-based electrodes containing 3% PEDOT / G / MWCNTs gel electrolyte 20 as a conductive layer are placed on a glass substrate 40. Between the sandpaper-based electrodes 10, a separator 30 impregnated with a phosphate gel electrolyte containing 1% MWCNTs is inserted to form a flexible sandpaper-based composite supercapacitor. After charging at 10V, the LED with a working voltage of 3V and a power of 0.06W is lit. light.
本發明製程技術可應用於類紙式超級電容器之製作。本發明之成品可應用於薄型化儲能裝置，或可撓式穿戴電子裝置。導電高分子PEDOT的添加是利用其偽電容效應的氧化還原峰來提升比電容量。The process technology of the invention can be applied to the manufacture of paper-like supercapacitors. The finished product of the present invention can be applied to a thin energy storage device or a flexible wearable electronic device. The addition of conductive polymer PEDOT is to use the redox peak of its pseudocapacitive effect to increase the specific capacitance.
以上所述，僅為本發明之可行實施例，並非用以限定本發明之專利範圍，凡舉依據下列請求項所述之內容、特徵以及其精神而為之其他變化的等效實施，皆應包含於本發明之專利範圍內。本發明所具體界定於請求項之結構特徵，未見於同類物品，且具實用性與進步性，已符合發明專利要件，爰依法具文提出申請，謹請 鈞局依法核予專利，以維護本申請人合法之權益。The above description is only a feasible embodiment of the present invention, and is not intended to limit the patent scope of the present invention. Any equivalent implementation of other changes based on the content, characteristics and spirit of the following claims should be It is included in the patent scope of the present invention. The structural features specifically defined in the present invention are not found in similar items, and are practical and progressive.The patent requirements were clarified, and the application was filed according to the law. I would like to request the Bureau to approve the patent in accordance with the law in order to protect the legitimate rights and interests of the applicant.
| Application Number | Priority Date | Filing Date | Title |
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| TW107140405ATWI673735B (en) | 2018-11-14 | 2018-11-14 | Supercapacitor with conductive polymer sandpaper base electrode and preparation method thereof |
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| TW107140405ATWI673735B (en) | 2018-11-14 | 2018-11-14 | Supercapacitor with conductive polymer sandpaper base electrode and preparation method thereof |
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| TW202018745A TW202018745A (en) | 2020-05-16 |
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| TW107140405ATWI673735B (en) | 2018-11-14 | 2018-11-14 | Supercapacitor with conductive polymer sandpaper base electrode and preparation method thereof |
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