本發明係有關於一種以紙為基材之超級電容器，尤指一種可在低溫環境的要求下利用簡便與低成本製備器具的基材表面改質技術。The invention relates to a paper-based supercapacitor, in particular to a substrate surface modification technology which can be used in a low temperature environment to prepare an appliance with a simple and low cost.
按習知薄型儲能裝置包括電池和超級電容器(supercapacitor)兩部分，其儲能機制略有差異。共同點在於能量提供的過程是發生在電極與電解質界面。不同點在於能量儲存與釋放的機制，以電池來說，是經由氧化還原反應的化學能轉換，能量產生於陽極與陰極之間。而超級電容器，亦可稱為電化學電容器(electrochemical supercapacitors,ES)，其能量儲存不需經由氧化還原反應，藉由電解質離子在電極與電解質界面之間的移動，將能量以純物理電荷吸附在電極表面上。因此，電池的反應時間較長，而超級電容器可以快速的充放電，所以這也是超級電容器優勢之所在。超級電容器除了具有充放電快速外，尚具有節能、使用壽命超長、安全、環保、使用溫度範圍寬、無需人工維護等優點。大部分專利技術所提出超級電容器裝置的架構包含兩個電流收集層、兩個電極，一個電解質和一個隔膜所組成，例如中華民國第I340400號專利案為可撓式超級電容結構與其製備方法，其係提供一種可撓式超級電容之可撓式電極複合層，利用金屬結構刺穿並固定其碳纖維層與金屬集電層，使電極複合層於撓曲時還能使其複合層間彼此密合。超級電容器裝置的電極製作部份，如中華民國第I247345號專利案及中華民國第I346647號專利案。中華民國第I247345號專利案所提出之可作為超高電容器電極材料的奈米複合碳材及其製法，該專利案技術提供一種多孔性碳材表面孔隙結構之改質方法，以簡易製程提高碳材之電雙層形成的表面的比例，藉由化學氣相沈積法成長奈米碳纖於碳材表面進行碳材表面改質，實驗證實此種方法可增加碳材的中孔比例，可加速離子擴散速率。因而當此表面改質的碳材用作為超高電容器的電極材料時，有助於提升電容器之電化學特性。中華民國第I346647號專利案係關於一種奈米碳管複合電極材料、其製備方法及包含其的電極，其所研發者係一種奈米碳管複合電極材料，該奈米碳管複合電極材料包括大量碳纖維及奈米碳管，其製備方法包括大量碳纖維搭接形成網路狀結構，該奈米碳管纏繞或附著於碳纖維上。由於碳纖維之直徑遠大於奈米碳管之直徑，因此該奈米碳管複合電極材料中之孔隙大於單純由奈米碳管形成之電極材料中之孔隙，電解液或者反應物很容易進入奈米碳管複合電極材料之孔隙中而與奈米碳管表面充分接觸，從而可以提高電池之容量。大部分專利技術皆有使用集電層來增加電荷收集的效果，其材料以金屬和其他導電高分子為主。其專利宣告範圍及所研發的實施方式中並無針對蘋果果膠分散奈米碳管，以溶劑蒸發法沉積在紙上之電極材料的相關應用。According to the conventional thin energy storage device, which includes a battery and a supercapacitor, the energy storage mechanism is slightly different. The commonality is that the process of energy supply occurs at the electrode-electrolyte interface. The difference lies in the mechanism of energy storage and release. In the case of a battery, it is a chemical energy conversion via a redox reaction, and energy is generated between the anode and the cathode. Supercapacitors, also known as electrochemical supercapacitors (ES), do not need to pass through the redox reaction, and the energy is adsorbed to the electrode by pure physical charge by the movement of electrolyte ions between the electrode and the electrolyte interface. On the surface. Therefore, the reaction time of the battery is long, and the supercapacitor can be quickly charged and discharged, so this is also the advantage of the supercapacitor. In addition to fast charging and discharging, supercapacitors have the advantages of energy saving, long service life, safety, environmental protection, wide temperature range, and no need for manual maintenance. The structure of the supercapacitor device proposed by most of the patented technology comprises two current collecting layers, two electrodes, an electrolyte and a diaphragm. For example, the Republic of China No. I340400 patent is a flexible supercapacitor structure and a preparation method thereof. The invention provides a flexible electrode composite layer of a flexible supercapacitor, which pierces and fixes the carbon fiber layer and the metal collector layer by using a metal structure, so that the electrode composite layer can also be made when flexingThe composite layers are in close contact with each other. The electrode fabrication part of the supercapacitor device, such as the Patent No. I247345 of the Republic of China and the Patent No. I346647 of the Republic of China. A nanocomposite carbon material which can be used as an ultrahigh capacitor electrode material and a method for preparing the same according to the Patent No. I247345 of the Republic of China, the patented technology provides a method for modifying the surface pore structure of a porous carbon material, and improves the carbon by a simple process. The ratio of the surface formed by the electric double layer of the material is modified by chemical vapor deposition to modify the surface of the carbon material on the surface of the carbon material. Experiments have confirmed that this method can increase the ratio of the mesopores of the carbon material and accelerate the ion. Diffusion rate. Therefore, when the surface-modified carbon material is used as an electrode material of an ultrahigh capacitor, it contributes to the electrochemical characteristics of the capacitor. Patent No. I346647 of the Republic of China on a nanocarbon tube composite electrode material, a preparation method thereof and an electrode comprising the same, which are developed by a carbon nanotube composite electrode material, the nano carbon tube composite electrode material comprising A large number of carbon fibers and carbon nanotubes are prepared by a large number of carbon fibers lapped to form a network structure, and the carbon nanotubes are entangled or attached to the carbon fibers. Since the diameter of the carbon fiber is much larger than the diameter of the carbon nanotube, the pore in the carbon nanotube composite electrode material is larger than the pore in the electrode material formed by the carbon nanotube, and the electrolyte or the reactant easily enters the nanocarbon. The pores of the composite electrode material are in sufficient contact with the surface of the carbon nanotubes, thereby increasing the capacity of the battery. Most of the patented technologies use collector layers to increase charge collection. The materials are mainly metals and other conductive polymers. There is no related application for the electrode material of apple pectin-dispersed carbon nanotubes deposited on paper by solvent evaporation in the scope of patent declaration and the developed embodiment.
目前習知中華民囼專利前案技術，有關於超級電容器裝置方面，例如中華民國公告號I340400及公開號201117242、200923991和200923993號等專利前案，其專利技術範疇皆鎖定製法及組裝的方式，根據查詢及分析結果，並沒有針對以紙作為基礎之超級電容器專利發表。然而有關電極的製作技術，則有如中華民國公告號I247345及I346647，及公開號201118902、201007792、201039364和200741747號等專利前案。根據查詢及分析的結果，並無相關於植物果膠作為分散劑製作導電懸浮液，並滴覆或塗佈在紙上形成導電紙，並結合固態電解質形成超級電容器，經過電化學分析可得良好電容行為與循環穩定性。At present, the Chinese patent law of the former Chinese folklore is related to the supercapacitor device.In the case of patents such as the Republic of China Announcement No. I340400 and the publications No. 201117242, 200923991 and 200923993, the patented technical scopes are locked in the way of manufacturing and assembly. According to the results of the inquiry and analysis, there is no paper-based supercapacitor. Patent publication. However, the manufacturing techniques of the electrodes are as disclosed in the Republic of China Bulletin Nos. I247345 and I346647, and the publication numbers 201118902, 201007792, 201039364 and 200741747. According to the results of the inquiry and analysis, there is no conductive suspension prepared by using plant pectin as a dispersing agent, and coated or coated on paper to form conductive paper, and combined with solid electrolyte to form a supercapacitor, good electrochemical behavior can be obtained by electrochemical analysis. With loop stability.
有鑑於此，本發明人乃積極努力投入研發，終於研發出一套確具實用功效的本發明。In view of this, the inventors have actively invested in research and development, and finally developed a set of practical inventions.
本發明主要目的，在於提供一種以紙為基材之超級電容器，提供一種製造簡便、輕量化、薄型化、具可撓性，可有效適用於可攜式電子產品，充份發揮薄型儲能裝置之效能的超極電容器及其製造方法。達成本發明目的之技術手段，係採用固定重量百分比的蘋果果膠分散奈米碳管形成奈米碳管懸浮液，並以溶劑蒸發法將懸浮液沉積在紙上形成導電紙，再以溶膠凝膠法將磷酸-聚乙烯醇製作成固態電解質。將導電紙與固態電解質熱壓封裝成超級電容器，施加電壓電流之後，利用奈米碳管的高導電性與高比表面積的特性，使得超級電容器產生充電與放電的功能。本發明是一種導電紙結合固態電解質製作成紙基超級電容器，此電容器裝置將電極與電流收集器合併並且以固態電解質取代液態電解質與隔膜，大幅減少了超級電容器的厚度。電解質與導電紙都具有良好的機械性能，造就了紙基超級電容器高撓曲性的特性。更提升超級電容器使用壽命長、安全及環保等優點。The main object of the present invention is to provide a paper-based supercapacitor, which is simple, lightweight, thin, flexible, and can be effectively applied to portable electronic products, and fully utilizes a thin energy storage device. Ultra-capacitor for its performance and its manufacturing method. The technical means for achieving the object of the present invention is to form a carbon nanotube suspension by using a fixed weight percentage of apple pectin dispersed carbon nanotubes, and depositing the suspension on paper by solvent evaporation to form conductive paper, and then using sol gel. The method produces a phosphoric acid-polyvinyl alcohol into a solid electrolyte. The conductive paper and the solid electrolyte are hot-pressed into a supercapacitor, and after applying a voltage and current, the characteristics of high conductivity and high specific surface area of the carbon nanotube are utilized, so that the supercapacitor generates charging and discharging functions. The invention relates to a conductive paper combined with a solid electrolyte to form a paper-based supercapacitor.The electrode is combined with the current collector and the liquid electrolyte and the separator are replaced by a solid electrolyte, which greatly reduces the thickness of the supercapacitor. Both electrolyte and conductive paper have good mechanical properties, resulting in high flexibility of paper-based supercapacitors. It also enhances the advantages of long life, safety and environmental protection of supercapacitors.
如第三、四圖所示，本發明所研發一種以紙為基材的超級電容器之製法，其基本技術特徵包括以下步驟：(a)將一特定量的果膠置入去離子水中加熱攪拌(具體實施例中，果膠為蘋果果膠)，使該特定量的果膠均勻溶於該特定量的去離水中而形成果膠水溶液後，將該果膠水溶液於室溫下冷卻；(b)將一特定量的多壁奈米碳管加入該果膠水溶液中，先經超音波震盪而使該多壁奈米碳管均勻分散在該果膠水溶液中；(c)以離心機使該果膠水溶液做離心旋轉一特定時間後，取該果膠水溶液上方的清液而去除下方的沉澱物，以去除多餘雜質與部份團聚的該多壁奈米碳管；(d)重複步驟(c)一特定次數，以獲得均質分散的多壁奈米碳管懸浮液；(e)以溶劑蒸發法將該多壁奈米碳管懸浮液20沉積於一紙張10上，以一特定溫度烘乾，進而形成一多壁奈米碳管導電紙30；及(f)以二個該多壁奈米碳管導電紙做30為上下電極，在該二個多壁奈米碳管導電紙30的表面塗上一層凝膠水溶液作為黏合劑40後，將一固態電解質50夾於其中，經加壓加溫固定後，即獲得一紙基超級電容器60。As shown in the third and fourth figures, the method for fabricating a paper-based supercapacitor according to the present invention has the following basic technical features:(a) placing a specific amount of pectin in deionized water and heating and stirring (in the specific embodiment, the pectin is apple pectin), so that the specific amount of pectin is uniformly dissolved in the specific amount of deionized water. After the gelatin solution is obtained, the aqueous pectin solution is cooled at room temperature; (b) a specific amount of multi-walled carbon nanotubes is added to the aqueous pectin solution, and the multi-walled nanocarbon is first oscillated by ultrasonic waves. The tube is uniformly dispersed in the aqueous pectin solution; (c) the aqueous pectin solution is centrifuged for a specific time in a centrifuge, and the supernatant above the pectin aqueous solution is taken to remove the precipitate underneath to remove excess impurities and a partially agglomerated multi-walled carbon nanotube; (d) repeating step (c) a specific number of times to obtain a homogeneously dispersed multi-walled carbon nanotube suspension; (e) solvent-evaporating the multi-walled naphthalene The carbon nanotube suspension 20 is deposited on a paper 10 and dried at a specific temperature to form a multi-walled carbon nanotube conductive paper 30; and (f) is made of two of the multi-walled carbon nanotube conductive paper 30 is an upper and lower electrode, and a surface of the two multi-walled carbon nanotube conductive paper 30 is coated with a gel aqueous solution as a viscosity. After the agent 40, 50 to a solid electrolyte interposed therein, after fixing the pressurized heating, i.e., to obtain a paper-based super capacitor 60.
為證明前述的基本技術特徵的可行性，本發明人乃投入實驗。在電極製備的實驗例中，本發明先製備奈米碳管懸浮液。本發明的奈米碳管懸浮液是由蘋果果膠來分散多壁奈米碳管所製備而成。首先，以0.5wt%蘋果果膠置入去離子水中，以磁石加熱攪拌器加熱攝氏60℃並攪拌1小時，使蘋果果膠完全溶解於去離子水中而形成果膠水溶液。當果膠溶液呈現透明且帶有淡黃色澤時，果膠即均勻溶於去離子水中。將果膠水溶液置於室溫下冷卻約2小時。將0.5g的多壁奈米碳管加入果膠水溶液中，以15000 J/min超音波震盪(機型為VCX 750，公司為SONICS)約半小時，使多壁奈米碳管分散在果膠水溶液中，再利用離心機(機型LEGEND MACH 1.6R，公司為SONICS)以4000rpm的轉速離心15分鐘，以去除多餘雜質與團聚的多壁奈米碳管。離心後，取上清液(即取果膠水溶液上方的清液)。重複離心數次，直到完全去除沉澱物，得到均質分散的奈米碳管懸浮液為止。In order to prove the feasibility of the aforementioned basic technical features, the inventors have invested in experiments. In the experimental example of electrode preparation, the present invention first prepared a carbon nanotube suspension. The carbon nanotube suspension of the present invention is prepared by dispersing a multi-walled carbon nanotube from apple pectin. First, 0.5 wt% apple pectin was placed in deionized water, heated to 60 ° C with a magnet heating stirrer and stirred for 1 hour, so that the apple pectin was completely dissolved in deionized water to form an aqueous pectin solution. When the pectin solution is transparent and has a pale yellow color, the pectin is uniformly dissolved in deionized water. The pectin aqueous solution is cooled at room temperatureAbout 2 hours. Add 0.5g of multi-walled carbon nanotubes to the pectin aqueous solution, and ultrasonically oscillate at 15000 J/min (model is VCX 750, the company is SONICS) for about half an hour to disperse the multi-walled carbon nanotubes in the pectin water. The solution was centrifuged at 4000 rpm for 15 minutes using a centrifuge (model LEGEND MACH 1.6R, company SONICS) to remove excess impurities and agglomerated multi-walled carbon nanotubes. After centrifugation, the supernatant was taken (ie, the supernatant above the pectin solution was taken). The centrifugation was repeated several times until the precipitate was completely removed to obtain a homogeneously dispersed carbon nanotube suspension.
完成上述奈米碳管懸浮液製備之後，接下來再製備奈米碳管導電紙以做為電極。本發明奈米碳管導電紙是以溶劑蒸發法將多壁奈米碳管懸浮液沉積於紙張(本發明實驗例採用影印紙)上。其紙張10被裁剪大小為4cm×7cm，邊緣1cm的部分向內對摺形成盒狀，將盒狀的紙張10放置於玻璃載片12上(請配合參看第二圖所示)。以微量吸取器(MP-100,Micropet)吸取3mL的多壁奈米碳管懸浮液20滴覆於盒狀的紙張10上，使多壁奈米碳管懸浮液20容納在盒狀紙張10的凹槽11內並完全覆蓋於紙張10表面。將玻璃載片12連同盒狀紙張10及紙張10上的多壁奈米碳管懸浮液20平放於真空烘箱中以固定溫度攝氏60℃烘乾，烘乾的溫差不大於0.5℃，整個烘烤過程約6小時，亦可形成奈米碳管導電紙30。本發明的整個流程架構，請配合參看第一、二圖所示。After the preparation of the above carbon nanotube suspension is completed, a carbon nanotube conductive paper is next prepared as an electrode. The carbon nanotube conductive paper of the present invention is a solvent-evaporating method for depositing a multi-walled carbon nanotube suspension on paper (photographed paper of the experimental example of the present invention). The paper 10 is cut to a size of 4 cm x 7 cm, and the portion of the edge 1 cm is folded inward to form a box shape, and the box-shaped paper 10 is placed on the glass slide 12 (please refer to the second figure). A 3 mL multi-walled carbon nanotube suspension 20 was pipetted onto a box-shaped paper 10 with a micropipette (MP-100, Micropet) to accommodate the multi-walled carbon nanotube suspension 20 in the box-shaped paper 10. The groove 11 is completely covered on the surface of the paper 10. The glass slide 12 together with the box-shaped paper 10 and the multi-walled carbon nanotube suspension 20 on the paper 10 are placed in a vacuum oven to be dried at a fixed temperature of 60 ° C, and the temperature difference of the drying is not more than 0.5 ° C. The baking process is about 6 hours, and the carbon nanotube conductive paper 30 can also be formed. For the entire process architecture of the present invention, please refer to the first and second figures.
在超級電容器製備的實驗例中，本發明先製備奈米碳管懸浮液。本發明的奈米碳管懸浮液是由蘋果果膠來分散多壁奈米碳管所製備而成。首先，以0.5wt%蘋果果膠置入去離子水中，以磁石加熱攪拌器加熱攝氏60℃並攪拌1小時，使蘋果果膠完全溶解於去離子水中而形成果膠水溶液。當果膠溶液呈現透明且帶有淡黃色澤時，果膠即均勻溶於去離子水中。將果膠水溶液置於室溫下冷卻約2小時。將0.5g的多壁奈米碳管加入果膠水溶液中，以15000 J/min超音波震盪(機型為VCX 750，公司為SONICS)約半小時，使多壁奈米碳管分散在果膠水溶液中，再利用離心機(機型LEGEND MACH 1.6R，公司為SONICS)以4000rpm的轉速離心15分鐘，以去除多餘雜質與團聚的多壁奈米碳管。離心後，取上清液(即取果膠水溶液上方的清液)。重複離心數次，直到完全去除沉澱物，得到均質分散的奈米碳管懸浮液為止。In the experimental example of supercapacitor preparation, the present invention first prepares a carbon nanotube suspension. The carbon nanotube suspension of the present invention is prepared by dispersing a multi-walled carbon nanotube from apple pectin. First, 0.5 wt% apple pectin was placed in deionized water, heated to 60 ° C with a magnet heating stirrer and stirred for 1 hour, so that the apple pectin was completely dissolved in deionized water to form an aqueous pectin solution. When the pectin solution is transparent and has a light yellowWhen the color is color, the pectin is uniformly dissolved in deionized water. The aqueous pectin solution was cooled at room temperature for about 2 hours. Add 0.5g of multi-walled carbon nanotubes to the pectin aqueous solution, and ultrasonically oscillate at 15000 J/min (model is VCX 750, the company is SONICS) for about half an hour to disperse the multi-walled carbon nanotubes in the pectin water. The solution was centrifuged at 4000 rpm for 15 minutes using a centrifuge (model LEGEND MACH 1.6R, company SONICS) to remove excess impurities and agglomerated multi-walled carbon nanotubes. After centrifugation, the supernatant was taken (ie, the supernatant above the pectin solution was taken). The centrifugation was repeated several times until the precipitate was completely removed to obtain a homogeneously dispersed carbon nanotube suspension.
完成上述奈米碳管懸浮液製備之後，接下來再製備奈米碳管導電紙以做為電極。本發明奈米碳管導電紙是以溶劑蒸發法將多壁奈米碳管懸浮液沉積於紙張(本發明實驗例採用影印紙)上。其紙張10被裁剪大小為4cm×7cm，邊緣1cm的部分向內對摺形成盒狀，將盒狀的紙張10放置於玻璃載片12上(請配合參看第二圖所示)。以微量吸取器(MP-100,Micropet)吸取3mL的多壁奈米碳管懸浮液20滴覆於盒狀的紙張10上，使多壁奈米碳管懸浮液20容納在盒狀紙張10的凹槽11內並完全覆蓋於紙張10表面。將玻璃載片12連同盒狀紙張10及紙張10上的多壁奈米碳管懸浮液20平放於真空烘箱中以固定溫度攝氏60℃烘乾，烘乾的溫差不大於0.5℃，整個烘烤過程約6小時，即可於紙張10上沉積多壁奈米碳管21而形成奈米碳管導電紙30。本發明的整個流程架構，請配合參看第一、二圖所示。After the preparation of the above carbon nanotube suspension is completed, a carbon nanotube conductive paper is next prepared as an electrode. The carbon nanotube conductive paper of the present invention is a solvent-evaporating method for depositing a multi-walled carbon nanotube suspension on paper (photographed paper of the experimental example of the present invention). The paper 10 is cut to a size of 4 cm x 7 cm, and the portion of the edge 1 cm is folded inward to form a box shape, and the box-shaped paper 10 is placed on the glass slide 12 (please refer to the second figure). A 3 mL multi-walled carbon nanotube suspension 20 was pipetted onto a box-shaped paper 10 with a micropipette (MP-100, Micropet) to accommodate the multi-walled carbon nanotube suspension 20 in the box-shaped paper 10. The groove 11 is completely covered on the surface of the paper 10. The glass slide 12 together with the box-shaped paper 10 and the multi-walled carbon nanotube suspension 20 on the paper 10 are placed in a vacuum oven to be dried at a fixed temperature of 60 ° C, and the temperature difference of the drying is not more than 0.5 ° C. The baking process is about 6 hours, and the multi-walled carbon nanotubes 21 can be deposited on the paper 10 to form the carbon nanotube conductive paper 30. For the entire process architecture of the present invention, please refer to the first and second figures.
完成電極製備後，再製備固態電解質。本發明實驗例中，製備固態電解質，係先配製10wt%的聚乙烯醇(Poly Vinyl Alcohol,PVA)水溶液，在攝氏60℃下，加熱攪拌2小時。使聚乙烯醇完全溶解於水中而獲得聚乙烯醇水溶液，將聚乙烯醇水溶液放置於室溫冷卻約2小時。再將1.2g的磷酸(H3PO4)加入於聚乙烯醇水溶液中攪拌12小時，使磷酸能均勻溶解在聚乙烯醇水溶液中成為凝膠電解質。再將凝膠電解質塗佈在乾淨玻璃載片表面，並置於室溫下烘乾2至3天，以去除多餘的水分，移除玻璃載片並取下薄片即可得到固態電解質。After the electrode preparation is completed, a solid electrolyte is prepared. In the experimental example of the present invention, a solid electrolyte was prepared by first preparing a 10 wt% aqueous solution of polyvinyl alcohol (Poly Vinyl Alcohol, PVA) and heating and stirring at 60 ° C for 2 hours. The polyvinyl alcohol is completely dissolved in water to obtain an aqueous solution of polyvinyl alcohol, and the aqueous solution of polyvinyl alcohol is placed in the chamber.The temperature was cooled for about 2 hours. Further, 1.2 g of phosphoric acid (H3PO4) was added to the aqueous polyvinyl alcohol solution and stirred for 12 hours to uniformly dissolve the phosphoric acid in the aqueous polyvinyl alcohol solution to form a gel electrolyte. The gel electrolyte is then coated on the surface of a clean glass slide and dried at room temperature for 2 to 3 days to remove excess moisture, the glass slide is removed and the sheet is removed to obtain a solid electrolyte.
本發明之紙基超級電容器是以多壁奈米碳管導電紙30作為上下電極，在其表面塗上一層凝膠水溶液作為黏合劑40後，將固態電解質50夾於其中，在攝氏60℃下加壓固定1小時後取出，即完成紙基超級電容器60，整個裝置架構圖，請配合參看第一至四圖所示。The paper-based supercapacitor of the present invention is a multi-walled carbon nanotube conductive paper 30 as an upper and lower electrode, and after a surface of a gel aqueous solution is applied as a binder 40, the solid electrolyte 50 is sandwiched therein at 60 ° C. After the pressure is fixed for 1 hour, the paper-based supercapacitor 60 is completed, and the entire device structure diagram is shown, please refer to the first to fourth figures.
本發明關於奈米碳管導電紙的製備技術中，其在製備多壁奈米碳管懸浮液時，將多壁奈米碳管添加果膠水溶液後分別以超音波震盪進行分散處理，多壁奈米碳管的管束除了會被剪切力打散之外，超音波震盪造成的空穴作用，會將蘋果果膠吸附於奈米碳管表面，使碳管間的凡得瓦爾引力減弱，導致碳管間的相互分離，進而形成均勻分散之奈米碳管懸浮液，請參附件1所示的影像，影像右上角照片標示為(10)者可明顯看出蘋果果膠對奈米碳管的分散效果，在室溫下靜置2個片依然保持穩定的分散。將奈米碳管懸浮液滴覆於紙張上(本發明一種較佳實施例，該紙張為市面上常用影印紙)形成導電紙，隨後將導電紙分別以掃描式電子顯微鏡與原子力顯微鏡觀察表面形貌如附件1所示之影像。藉由超音波震盪處理，使蘋果果膠附著於多壁奈米碳管表面，使得多壁奈米碳管間凡得瓦爾引力的影響降低，不易聚集形成管束，導致碳管管束直徑變小，經掃瞄式電子顯微鏡觀察，約為14-28nm之間，與原廠商提供之奈米碳管管徑(15-20 nm)相當接近，請參看附件2所示中標示(9)者為奈米碳管。這顯示蘋果果膠可有效將碳管完全分散開來，奈米碳管懸浮液已達到最佳的分散程度。經由原子力顯微鏡分析之數據，導電紙的表面傾斜度Ssk為0.386，此正值表示pectin-cp表面主要是由許多小山丘所組成。分散良好的奈米碳管懸浮液滴覆於紙張時，在溶劑蒸發後，蘋果果膠會使保持奈米碳管間的分離，導致表面沉積較均勻，表面形貌落差較小，平均粗糙度Ra為313nm，請參看第五圖所示。In the preparation technology of the carbon nanotube conductive paper, in the preparation of the multi-walled carbon nanotube suspension, the multi-walled carbon nanotubes are added with a pectin aqueous solution and then dispersed by ultrasonic vibration, and the wall is multi-walled. In addition to the tube bundle of the carbon nanotubes, the cavitation caused by ultrasonic vibration will adsorb the apple pectin on the surface of the carbon nanotubes, and the van der Waals attraction between the carbon tubes will be weakened. Lead to the separation of the carbon tubes, and then form a uniform dispersion of carbon nanotube suspension, please refer to the image shown in Annex 1, the photo in the upper right corner of the image is marked as (10), the apple pectin can be clearly seen on the carbon The dispersing effect of the tube maintains stable dispersion after standing at room temperature for 2 pieces. The carbon nanotube suspension is sprayed on the paper (in a preferred embodiment of the present invention, the paper is commonly used as a photocopying paper on the market) to form a conductive paper, and then the conductive paper is observed by a scanning electron microscope and an atomic force microscope respectively. Look at the image shown in Annex 1. Ultrasonic vibration treatment causes apple pectin to adhere to the surface of multi-walled carbon nanotubes, so that the influence of van der Waals attraction between multi-walled carbon nanotubes is reduced, and it is difficult to aggregate to form tube bundles, resulting in a smaller diameter of carbon tube bundles. Observed by a scanning electron microscope, between 14-28 nm,It is quite close to the diameter of the carbon nanotubes (15-20 nm) provided by the original manufacturer. Please refer to the label (9) shown in Appendix 2 for the carbon nanotubes. This shows that apple pectin can effectively disperse the carbon tube completely, and the carbon nanotube suspension has achieved the best dispersion. According to the data analyzed by atomic force microscopy, the surface slope Ssk of the conductive paper is 0.386, which indicates that the surface of the pectin-cp is mainly composed of many hills. When the well-dispersed carbon nanotube droplets are coated on the paper, after the solvent evaporates, the apple pectin will keep the separation between the carbon nanotubes, resulting in uniform surface deposition, small surface topography, and average roughness. Ra is 313nm, please see the fifth picture.
本發明對所研製的導電紙之導電性及彎曲做測試。測試時，係將待測物置於四點探針儀(Four Point Probes,2400)之待測平台上，探針與待測物間的距離為探針接觸到待測物後，再往下1mm即可，設定四點探針儀為四點接觸模式，電流為100mA，電阻由最小值20ohm的範圍開始測量，藉以測量值經由計算獲得待測物之片電阻(sheet resistance,Rs)。將樣品固定於剝離測試配件上，設定可撓式基板多功能試驗機(Micro-Computer Tensile Tester,JIA-802)為壓縮模式，測試深度為20mm，加壓測試速度200mm/min、慢速回升速度200mm/min，彎曲次數為100、300和500次，藉由四點探針儀測量測試前後的導電性，請參看第六圖所示。將導電紙對摺前後，以數位三用電表測試其導電性，分別為47.9ohm與45.3ohm，如附件3上、下圖所示。這二者的測試結果相當接近，表示導電紙具有相當良好的可撓性與導電穩定性，請參附件3對摺前後的示意圖。The invention tests the conductivity and bending of the developed conductive paper. During the test, the object to be tested is placed on the platform to be tested by Four Point Probes (2400). The distance between the probe and the object to be tested is 1 mm after the probe contacts the object to be tested. That is, the four-point probe is set to the four-point contact mode, the current is 100 mA, and the resistance is measured from the range of the minimum value of 20 ohm, whereby the measured value is obtained by calculation to obtain the sheet resistance (Rs) of the object to be tested. The sample was fixed on the peeling test accessory, and the Micro-Computer Tensile Tester (JIA-802) was set to a compression mode with a test depth of 20 mm, a pressurization test speed of 200 mm/min, and a slow recovery speed. 200mm/min, the number of bending times is 100, 300 and 500 times. The conductivity before and after the test is measured by a four-point probe instrument, as shown in the sixth figure. Before and after the conductive paper was folded in half, the conductivity was tested by a digital three-meter electric meter, which were 47.9 ohms and 45.3 ohms respectively, as shown in the attached figure 3 and the following figure. The test results of the two are quite close, indicating that the conductive paper has quite good flexibility and electrical stability. Please refer to the schematic diagram of the front and back of the attachment.
本發明所研製的紙基超級電容器也進行測試。測試方式係將樣品固定於儀器上，設定循環伏安儀(Cyclic voltammetry,CV,611C)為類比模式，選擇參考電極為Ag/AgCl，設定起始電壓為-0.67V，結束電壓為0.67V，掃描速率為20、40、50、60、80和100mV/s，藉以分析樣品的電容行為及儲能穩定性，請參看第七圖所示。並以C=I/sm計算其比電容值(specific capacitance,C)，I為操作電壓的相對電流，s為掃描速率，m為電極的質量。The paper-based supercapacitors developed by the present invention were also tested. The test method is to fix the sample on the instrument, set the cyclic voltammetry (Cyclic voltammetry, CV, 611C) as the analog mode, select the reference electrode as Ag/AgCl, set the starting voltage to-0.67V, end voltage is 0.67V, scan rate is 20, 40, 50, 60, 80 and 100mV / s, to analyze the sample's capacitance behavior and energy storage stability, please refer to the seventh figure. And calculate its specific capacitance (C) with C=I/sm, I is the relative current of the operating voltage, s is the scanning rate, and m is the mass of the electrode.
本發明具有以下之技術特點：The invention has the following technical features:
1．蘋果果膠作為分散劑：本發明提出以蘋果果膠作為分散劑，能將奈米碳管有效均勻分散。相較於其他分散劑，如表面活性劑和有機溶劑，蘋果果膠有較良好的分散效果，且更具環保及安全等特性。1. Apple pectin as a dispersing agent: The present invention proposes apple pectin as a dispersing agent, which can effectively and uniformly disperse the carbon nanotubes. Compared with other dispersants, such as surfactants and organic solvents, apple pectin has a better dispersion effect and is more environmentally friendly and safe.
2．固態電解質之選擇：相較於液體電解質的使用，以固態電解質作為電解質及隔膜，可有效解決洩漏與電極間接觸的問題，更具有良好的機械性質等優勢。2. The choice of solid electrolyte: Compared with the use of liquid electrolyte, solid electrolyte as electrolyte and separator can effectively solve the problem of leakage and contact between electrodes, and has good mechanical properties.
3．紙基板的選擇：以塑膠基板和玻璃基板為主的電極，前者之導電層與塑膠基板間通常藉由黏結劑予以附著，而後者之電極的撓曲性受限於玻璃基板。本發明以紙作為基板，因紙的纖維結構形成許多的毛細通道，溶液會經由纖維的毛細作用將奈米碳管吸附於紙張表層，使導電層與紙基板之間產生良好的附著。導電紙良好的撓曲性，即使將導電紙對摺都可保持相同的電阻值，紙材本身為植物纖維，具有環保與可回收之特性。3. Selection of paper substrate: an electrode mainly composed of a plastic substrate and a glass substrate. The conductive layer and the plastic substrate of the former are usually adhered by a bonding agent, and the flexibility of the latter electrode is limited to the glass substrate. In the invention, paper is used as the substrate, and a plurality of capillary channels are formed by the fiber structure of the paper, and the solution adsorbs the carbon nanotubes on the surface layer of the paper via the capillary action of the fibers, so that good adhesion between the conductive layer and the paper substrate is produced. The conductive paper has good flexibility, and even if the conductive paper is folded in half, the same resistance value can be maintained. The paper itself is a plant fiber, and has environmental protection and recyclability.
本發明藉由導電紙結合固態電解質製作成紙基超級電容器，此裝置將電極與電流收集器合併並且以固態電解質取代液態電解質與隔膜，大幅減少了超級電容器的厚度。電解質與導電紙都具有良好的機械性能，造就了紙基超級電容器高撓曲性的特性。更提升超級電容器使用壽命長、安全及環保等優點，以便未來應用於可攜式電子產品、綠能產業及薄型儲能裝置上。The invention is made into a paper-based supercapacitor by using conductive paper in combination with a solid electrolyte. The device combines the electrode with the current collector and replaces the liquid electrolyte and the diaphragm with a solid electrolyte, which greatly reduces the thickness of the supercapacitor. Both electrolyte and conductive paper have good mechanical properties, resulting in high flexibility of paper-based supercapacitors. Improve the long life, safety and environmental protection of supercapacitors for future applicationsIt is used in portable electronic products, green energy industry and thin energy storage devices.
本發明具有以下之技術功效：The invention has the following technical effects:
1．蘋果果膠對於奈米碳管是良好的分散劑，搭配超音波震盪可達到最佳的分散效果。1. Apple pectin is a good dispersant for carbon nanotubes, with ultrasonic vibration to achieve the best dispersion.
2．奈米碳管懸浮液滴覆於紙張表層後，溶液經由纖維的毛細作用將奈米碳管吸附於紙張表層，使導電層與紙基板之間產生良好的附著。2. After the droplets of the carbon nanotubes are coated on the surface layer of the paper, the solution adsorbs the carbon nanotubes on the surface layer of the paper via the capillary action of the fibers, so that a good adhesion between the conductive layer and the paper substrate is produced.
3．將導電紙多次彎曲後其電阻值相當穩定，表示紙張纖維對於滲入之奈米碳管有良好的錨定作用，和良好的撓曲性及導電性。3. After the conductive paper is bent a plurality of times, the resistance value is relatively stable, indicating that the paper fibers have a good anchoring effect on the infiltrated carbon nanotubes, and good flexibility and electrical conductivity.
4．透過循環伏安儀對紙基超級電容器進行電化學分析，發現它不但具有良好的電容行為與循環穩定性。4. Electrochemical analysis of paper-based supercapacitors by cyclic voltammetry revealed that it not only has good capacitance behavior and cycle stability.
藉由導電紙結合固態電解質製作成紙基超級電容器，具有良好的撓曲性、裝置薄型化、充放電效率快、環保及安全等優勢，未來具有應用於可攜式電子產品、綠能產業及薄型儲能裝置上之潛力。The paper-based supercapacitor is made of conductive paper combined with solid electrolyte, which has the advantages of good flexibility, thinner device, fast charge and discharge efficiency, environmental protection and safety, etc., and is applied to portable electronic products and green energy industries in the future. The potential of thin energy storage devices.
以上所述，僅為本發明之一可行實施例，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 is only one of the possible embodiments of the present invention, and is not intended to limit the scope of the patents of the present invention, and the equivalent implementations of other changes according to the contents, features and spirits of the following claims are It should be included in the scope of the patent of the present invention. The invention is specifically defined in the structural features of the request item, is not found in the same kind of articles, and has practicality and progress, has met the requirements of the invention patent, and has filed an application according to law, and invites the bureau to approve the patent according to law to maintain the present invention. The legal rights of the applicant.
10‧‧‧紙張10‧‧‧ Paper
11‧‧‧凹槽11‧‧‧ Groove
12‧‧‧玻璃載片12‧‧‧glass slides
20‧‧‧多壁奈米碳管懸浮液20‧‧‧Multi-walled carbon nanotube suspension
21‧‧‧多壁奈米碳管21‧‧‧Multi-walled carbon nanotubes
30‧‧‧多壁奈米碳管導電紙30‧‧‧Multi-walled carbon nanotube conductive paper
40‧‧‧黏合劑40‧‧‧Binder
50‧‧‧固態電解質50‧‧‧Solid electrolyte
60‧‧‧紙基超級電容器60‧‧‧paper-based supercapacitors
第一圖係本發明紙基超級電容器之電極之製作流程簡圖。The first figure is a schematic diagram of the fabrication process of the electrode of the paper-based supercapacitor of the present invention.
第二圖係本發明紙基超級電容器之電極之製作流程圖。The second figure is a flow chart for the fabrication of the electrodes of the paper-based supercapacitor of the present invention.
第三圖係本發明紙基超級電容器之製作流程簡圖。The third figure is a schematic diagram of the production process of the paper-based supercapacitor of the present invention.
第四圖係本發明紙基超級電容器之結構示意圖。The fourth figure is a schematic structural view of a paper-based supercapacitor of the present invention.
第五圖係奈米碳管導電紙表面形貌之AFM圖。The fifth picture is the AFM image of the surface morphology of the carbon nanotube conductive paper.
第六圖係奈米碳管導電紙進行多次彎曲以四點探針量測片電阻之變化圖。The sixth figure shows the variation of the sheet resistance of the carbon nanotube conductive paper by multiple bending with four-point probe.
第七圖係不同掃描速率對紙基超級電容器進行電化學分析之循環伏安分析圖。The seventh graph is a cyclic voltammetric analysis of electrochemical analysis of paper-based supercapacitors at different scan rates.
附件1係本發明均勻分散之奈米碳管懸浮液之影像。Annex 1 is an image of a uniformly dispersed carbon nanotube suspension of the present invention.
附件2係本發明奈米碳管導電紙(即紙基超級電容器之電極)表面形貌之SEM圖。Attachment 2 is an SEM image of the surface topography of the carbon nanotube conductive paper of the present invention (i.e., the electrode of a paper-based supercapacitor).
附件3係本發明奈米碳管導電紙(即紙基超級電容器之電極)對摺前後以三用電表測量電阻變化之實體圖。Attachment 3 is a physical diagram of the change in resistance of a carbon nanotube conductive paper (i.e., an electrode of a paper-based supercapacitor) of the present invention measured by a three-meter electric meter before and after folding.
10‧‧‧紙張10‧‧‧ Paper
11‧‧‧凹槽11‧‧‧ Groove
12‧‧‧玻璃載片12‧‧‧glass slides
20‧‧‧多壁奈米碳管懸浮液20‧‧‧Multi-walled carbon nanotube suspension
21‧‧‧多壁奈米碳管21‧‧‧Multi-walled carbon nanotubes
30‧‧‧多壁奈米碳管導電紙30‧‧‧Multi-walled carbon nanotube conductive paper
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW101135000ATWI525034B (en) | 2012-09-24 | 2012-09-24 | Paper-based super capacitors |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW101135000ATWI525034B (en) | 2012-09-24 | 2012-09-24 | Paper-based super capacitors |
| Publication Number | Publication Date |
|---|---|
| TW201412632Atrue TW201412632A (en) | 2014-04-01 |
| TWI525034B TWI525034B (en) | 2016-03-11 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW101135000ATWI525034B (en) | 2012-09-24 | 2012-09-24 | Paper-based super capacitors |
| Country | Link |
|---|---|
| TW (1) | TWI525034B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI559344B (en)* | 2014-10-09 | 2016-11-21 | Univ Nat Formosa | Conductive supercapacitor combined with surface roughened electrode and gel electrolyte and method for making the same |
| CN106587287A (en)* | 2016-12-19 | 2017-04-26 | 复旦大学 | Seawater purifying device based on paper base material and preparing method of seawater purifying device |
| TWI673735B (en)* | 2018-11-14 | 2019-10-01 | National Formosa University | Supercapacitor with conductive polymer sandpaper base electrode and preparation method thereof |
| CN113077990A (en)* | 2021-03-17 | 2021-07-06 | 三峡大学 | Double-potential interval activation for improving Co (OH)2Method for performance of super capacitor |
| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI559344B (en)* | 2014-10-09 | 2016-11-21 | Univ Nat Formosa | Conductive supercapacitor combined with surface roughened electrode and gel electrolyte and method for making the same |
| CN106587287A (en)* | 2016-12-19 | 2017-04-26 | 复旦大学 | Seawater purifying device based on paper base material and preparing method of seawater purifying device |
| CN106587287B (en)* | 2016-12-19 | 2020-07-03 | 复旦大学 | Seawater purification device based on paper-based material and preparation method thereof |
| TWI673735B (en)* | 2018-11-14 | 2019-10-01 | National Formosa University | Supercapacitor with conductive polymer sandpaper base electrode and preparation method thereof |
| CN113077990A (en)* | 2021-03-17 | 2021-07-06 | 三峡大学 | Double-potential interval activation for improving Co (OH)2Method for performance of super capacitor |
| Publication number | Publication date |
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| TWI525034B (en) | 2016-03-11 |
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| MM4A | Annulment or lapse of patent due to non-payment of fees |