本發明係有關一種結合表面粗糙化電極與凝膠狀電解質之可撓式超級電容器及其製法，尤指一種可藉由砂紙表面粗糙結構來提升電極基板的比表面積的超級電容器製備技術。The invention relates to a flexible supercapacitor combining a surface roughening electrode and a gel electrolyte, and a manufacturing method thereof, in particular to a supercapacitor preparation technology capable of raising a specific surface area of an electrode substrate by a rough surface of a sandpaper.
超級電容器亦稱為電化學電容器，其充放電快速、功率密度高、循環壽命長、維護成本低等性質，可視為一個理想的儲能元件。以不同電荷儲存機制可區分為電雙層電容器與法拉第電容器。電雙層電容器儲存能量透過電雙層原理，在電極與電解質界面，通過靜電累積形成電雙層如圖1所示。電雙層電容器儲能的關鍵因素在於電極材料比表面積特性，以及電極與電解質的接觸面積。按，目前超級電容器多以塊狀或圓柱狀呈現，其主要儲能之關鍵反應發生在電極與電解質界面。其中以電極之導電材料本身多孔特性吸附電荷，達到充放電效果。據查，本案相關的專利前案如下列所示：Supercapacitors, also known as electrochemical capacitors, can be regarded as an ideal energy storage component due to their fast charge and discharge, high power density, long cycle life and low maintenance cost. Different electric charge storage mechanisms can be distinguished as electric double layer capacitors and Faraday capacitors. The electric double-layer capacitor stores the energy through the electric double-layer principle, and forms an electric double layer by electrostatic accumulation at the interface between the electrode and the electrolyte as shown in FIG. 1 . The key factors for energy storage of electric double-layer capacitors are the specific surface area characteristics of the electrode material and the contact area between the electrode and the electrolyte. According to the current, supercapacitors are mostly in the form of blocks or cylinders, and the key reaction of the main energy storage occurs at the electrode-electrolyte interface. The charge is adsorbed by the porous property of the conductive material of the electrode to achieve a charge and discharge effect. According to the investigation, the relevant patent pre-cases in this case are as follows:
1.中華民國發明第I438785號『中孔碳材、其製造方法及超級電容器』，此發明提供一種含有導電材料的中孔碳材(mesoporous carbon material)之合成方法，此導電材料可埋置於碳基質(carbon matrix)內，或者設置在碳基質內中孔洞(mesopores)的內側表面的至少一部份上。中孔碳材不僅含有均勻且可控制的中孔洞，提供電子或離子擴散的通道，也含有導電金屬以及/或金屬氧化物，改善中孔碳材的導電率，在此，金屬以及/或金屬氧化物的形式可以是粒子或膜。在中孔碳材的製造過程期間，可藉由添加單壁(single-wall)以及/或多壁(multi-wall)奈米碳管(carbon nanotubes)(SCNTs或MCNTs)而提升中孔碳材的導電率，中孔碳材可用在感應器或能量儲存裝置，例如超級電容器、蓄電池以及燃料電池。1. The Republic of China invented No. I438785 "Mesoporous carbon material, its manufacturing method and supercapacitor", which provides a method for synthesizing a mesoporous carbon material containing a conductive material, which can be embedded Within the carbon matrix, or at least a portion of the inner surface of the mesopores within the carbon matrix. Mesoporous carbon materials contain not only uniform and controllable mesopores, but also electron or ion diffusion channels, as well as conductive metals and/or metal oxides to improve the conductivity of mesoporous carbon materials, where metals and/or metals oxygenThe form of the compound can be a particle or a membrane. During the manufacturing process of mesoporous carbon materials, mesoporous carbon materials can be upgraded by adding single-wall and/or multi-wall carbon nanotubes (SCNTs or MCNTs). The conductivity, mesoporous carbon material can be used in inductors or energy storage devices such as supercapacitors, batteries, and fuel cells.
2.中華民國發明第I428942號『電雙層電容器』，此發明提供一種電雙層電容器，其係由活性碳所成電極、含電解質電解液、及分隔板所成之電雙層電容器；其特徵為，電解質係咪唑鹽(Imidazolium salts)；活性碳係在水系溶劑及鹼性催化劑存在下，將分子內具有至少一個羥基之酚性化合物與醛化合物進行聚合而得的有機氣凝膠，進行碳化所得。2. The Republic of China invented No. I428942 "Electrical Double Layer Capacitor", which provides an electric double layer capacitor which is an electric double layer capacitor formed by an electrode made of activated carbon, an electrolyte containing electrolyte, and a separator; The electrolyte is an imidazolium salt; the activated carbon is an organic aerogel obtained by polymerizing a phenolic compound having at least one hydroxyl group and an aldehyde compound in the presence of an aqueous solvent and a basic catalyst. Carbonization is obtained.
3.中華民國發明第I381406號『電雙層電容器用電解液及電雙層電容器』，此發明提供一種電雙層電容器用電解液，其特徵為，在含有碳酸乙烯酯及碳酸丙烯酯之混合溶媒中，含有第四銨鹽(quaternary ammonium salt)作為電解質。此發明之電雙層電容器用電解液之黏性係數(coefficient of viscosity)低，並表現出即使於低溫區域電解液亦不會凝固之優異低溫特性，同時，於廣泛溫度範圍內顯示高電導度，且長期可靠性優異。3. Republic of China Invention No. I381406 "Electrolyte for electric double layer capacitors and electric double layer capacitors", the invention provides an electrolyte for electric double layer capacitors, characterized in that it contains a mixture of ethylene carbonate and propylene carbonate The solvent contains a quaternary ammonium salt as an electrolyte. The electrolytic double layer capacitor of the present invention has a low coefficient of viscosity and exhibits excellent low-temperature characteristics that the electrolyte does not solidify even in a low temperature region, and exhibits high electrical conductivity over a wide temperature range. And long-term reliability is excellent.
4.中華民國發明第I253091號『鹼性固態高分子電雙層電容器的製備』，此專利中，說明開發製備鹼性固態高分子電雙層電容器並與使用PP/PE不織布與KOH電解液之傳統電容器做電性性能比較，此鹼性固態高分子電容器，可以完全取代傳統電容器。因為此固態高分子電雙層電容器有很好的電容特性：即有低的歐姆阻抗、有高的功率密度、有高的比電容量、有高的充/放次數(循環壽命)、高庫倫效率等。此鹼性固態高分子電雙層電容器完全沒有一般電雙層電容器之腐蝕與漏液的問題。4. The Republic of China Invention No. I253091 "Preparation of Alkaline Solid Polymer Electric Double Layer Capacitor", which describes the development and preparation of an alkaline solid polymer electric double layer capacitor and the use of PP/PE non-woven fabric and KOH electrolyte Compared with traditional capacitors, this alkaline solid polymer capacitor can completely replace the traditional capacitor. Because this solid polymer electric double layer capacitor has good capacitance characteristics: low ohmic impedance, high power density, high specific capacitance, high charge/discharge times (cycle life), high coulomb Efficiency and so on. The alkaline solid polymer electric double layer capacitor has no problem of corrosion and leakage of the general electric double layer capacitor.
5.中華民國發明第I399239號『活性碳及其製造方法、包含活性碳之電極、及電雙層電容器』，此發明之電雙層電容器係具有：活性碳，及含有此活性碳之電極，其中活性碳係使間苯二酚類與醛化合物之環狀聚合物進行碳化而得到者。如I427651號為超級電容器：是以奈米碳管自支撐複合結構作為電極，利用奈米碳管複合結構結合所產生的複數微孔作為關鍵儲能機制。5. The Republic of China invention No. I399239 "activated carbon and its production method, an electrode comprising activated carbon, and an electric double layer capacitor", the electric double layer capacitor of the invention has activated carbon,And an electrode containing the activated carbon, wherein the activated carbon is obtained by carbonizing a cyclic polymer of a resorcinol and an aldehyde compound. For example, I427651 is a supercapacitor: it is a self-supporting composite structure of carbon nanotubes as an electrode, and the complex micropores generated by the combination of carbon nanotube composite structures are used as a key energy storage mechanism.
6.中華民國發明第I427651號『超級電容器』，是以奈米碳管自支撐複合結構作為電極，利用奈米碳管複合結構結合所產生的複數微孔作為關鍵儲能機制。6. The Republic of China invented No. I427651 "Supercapacitor", which uses a carbon nanotube self-supporting composite structure as an electrode, and utilizes the complex micropores generated by the combination of the carbon nanotube composite structure as a key energy storage mechanism.
7.中華民國發明第I407467號『電雙層電容器之電極』，是以碳材料與纖維性聚合物材料形成一漿體，再進一步沉積在基板上製作為電極，此電極因纖維性聚合物材料呈現網狀結構，最後再將其組裝成電雙層電容器。7. The Republic of China Invention No. I407467 "Electrode of Electric Double Layer Capacitor" is formed by forming a slurry of carbon material and fibrous polymer material, and further depositing it on a substrate to form an electrode, which is made of a fibrous polymer material. The mesh structure is presented and finally assembled into an electric double layer capacitor.
8.中華民國發明第I387987號『超級電容器及其製備方法』，利用奈米碳管之間凡徳瓦爾力互相吸引，緊密結合成一自支撐結構。將奈米碳管自支撐結構利用粘結劑粘附在集流層基板上作為電極。最後將兩電極、隔膜和電解液設置在一外殼內，製成一平板電容器。8. The Republic of China invented No. I387987 "Supercapacitor and its preparation method", which uses the carbon nanotubes between the carbon nanotubes to attract each other and closely combine into a self-supporting structure. The carbon nanotube self-supporting structure is adhered to the current collector substrate as an electrode by means of an adhesive. Finally, the two electrodes, the separator and the electrolyte are placed in a casing to form a plate capacitor.
9.中華民國發明第I345249號『化學電容器之製法及其結構』，將奈米碳管直接成長於金屬集流層上，優點在於可增加電容器之電極的導電度，且降低內電阻，因而大幅提昇電容器之電容量與功率。最後並將對稱之二電極夾置一電解液及一隔離膜，而得到一電雙層電容器。9. The Republic of China Invention No. I345249 "Manufacturing Method and Structure of Chemical Capacitor", which directly grows the carbon nanotubes on the metal current collector, has the advantages of increasing the conductivity of the electrodes of the capacitor and reducing the internal resistance, thus greatly Increase the capacitance and power of the capacitor. Finally, an symmetrical double electrode is sandwiched between an electrolyte and a separator to obtain an electric double layer capacitor.
10.中華民國發明第I424447號『利用奈米碳管之導電性材料及其製造方法、以及利用該材料之電雙層電容器』，將垂直配向性奈米碳管轉印到環氧樹脂組成物層上作為電極，以此電極製作電雙層電容器。10. The Republic of China Invention No. I424447 "Conductive material using a carbon nanotube, a method for producing the same, and an electric double layer capacitor using the material", transferring a vertically aligned carbon nanotube to an epoxy resin composition As the electrode on the layer, an electric double layer capacitor was fabricated using this electrode.
11.中華民國發明第I367511號『電雙層電容器用電極及電雙層電容器』，其結構具有一對石墨狀微晶碳偏極化電極用作為彼此面對的陰極和陽極而其間有一隔件。各個偏極化電極被浸漬以水性電解液或非水性電解液，且各個偏極化電極係與汲極耦接。水性電解液可提高體積電容，降低電阻率，但使用的電壓必須不高於可能發生水電解的電壓；因此，使用非水性電解液來提高能量密度。11. Republic of China Invention No. I367511 "Electrode and capacitors for electric double layer capacitorsA double-layer capacitor having a structure in which a pair of graphite-like microcrystalline carbon polarized electrodes are used as a cathode and an anode facing each other with a spacer therebetween. Each of the polarized electrodes is impregnated with an aqueous electrolyte or a non-aqueous electrolyte, and each of the polarized electrodes is coupled to the drain. The aqueous electrolyte can increase the volumetric capacitance and reduce the resistivity, but the voltage used must be no higher than the voltage at which water electrolysis can occur; therefore, a non-aqueous electrolyte is used to increase the energy density.
12.中華民國發明第I346647號『可作為超高電容器電極材料的奈米複合碳材及其製法』，對多孔碳材表面孔隙結構進行改質，實驗證實此改質方法可增加碳材的中孔比例，加速離子擴散速率，有助於提升電容器之電化學特性。12. The Republic of China invented No. I346647 "Nano-composite carbon material which can be used as an electrode material for ultra-high capacitors and its preparation method" to modify the pore structure of the porous carbon material. Experiments have confirmed that this modification method can increase the carbon material. The pore ratio, which accelerates the ion diffusion rate, helps to improve the electrochemical properties of the capacitor.
13.中華民國發明第I367511號『電雙層電容器用電極及電雙層電容器』，其結構具有一對石墨狀微晶碳偏極化電極用作為彼此面對的陰極和陽極而其間有一隔件。各個偏極化電極被浸漬以水性電解液或非水性電解液，且各個偏極化電極係與汲極耦接。水性電解液可提高體積電容，降低電阻率，但使用的電壓必須不高於可能發生水電解的電壓；因此，使用非水性電解液來提高能量密度。13. The Republic of China invented No. I367511 "Electrode for electric double-layer capacitors and electric double-layer capacitors" having a structure in which a pair of graphite-like microcrystalline carbon polarized electrodes are used as a cathode and an anode facing each other with a spacer therebetween . Each of the polarized electrodes is impregnated with an aqueous electrolyte or a non-aqueous electrolyte, and each of the polarized electrodes is coupled to the drain. The aqueous electrolyte can increase the volumetric capacitance and reduce the resistivity, but the voltage used must be no higher than the voltage at which water electrolysis can occur; therefore, a non-aqueous electrolyte is used to increase the energy density.
14.中華民國發明第I346647號『可作為超高電容器電極材料的奈米複合碳材及其製法』，對多孔碳材表面孔隙結構進行改質，實驗證實此改質方法可增加碳材的中孔比例，加速離子擴散速率，有助於提升電容器之電化學特性。14. The Republic of China invented No. I346647 "Nano-composite carbon material which can be used as an electrode material for ultra-high capacitors and its preparation method" to modify the pore structure of the porous carbon material. Experiments have confirmed that this modification method can increase the carbon material. The pore ratio, which accelerates the ion diffusion rate, helps to improve the electrochemical properties of the capacitor.
15.中華民國發明第I340400號『可撓式超級電容結構與其製備方法』，以複數釘針刺穿固定一碳纖維層與一金屬集電層，並使該碳纖維層與該金屬集電層貼合，使得電極複合層於撓曲時還能使其複合層彼此密合。15. The Republic of China invented No. I340400 "Flexible supercapacitor structure and its preparation method", which pierces and fixes a carbon fiber layer and a metal collector layer by a plurality of staples, and bonds the carbon fiber layer to the metal collector layer Therefore, the electrode composite layer can also make the composite layer close to each other when flexed.
16.中華民國發明第I438785『中孔碳材、其製造方法及超級電容器』，此發明提供一種含有導電材料的中孔碳材(mesoporous carbon material)之合成方法，此導電材料可埋置於碳基質(carbon matrix)內，或者設置在碳基質內中孔洞(mesopores)的內側表面的至少一部份上。中孔碳材不僅含有均勻且可控制的中孔洞，提供電子或離子擴散的通道，也含有導電金屬以及/或金屬氧化物，改善中孔碳材的導電率，在此，金屬以及/或金屬氧化物的形式可以是粒子或膜。在中孔碳材的製造過程期間，可藉由添加單壁(single-wall)以及/或多壁(multi-wall)奈米碳管(carbon nanotubes)(SCNTs或MCNTs)而提升中孔碳材的導電率，中孔碳材可用在感應器或能量儲存裝置，例如超級電容器、蓄電池以及燃料電池。16. Republic of China invention No. I438785 "Medium hole carbon material, its manufacturing method and superStage capacitor, the invention provides a method for synthesizing a mesoporous carbon material containing a conductive material, which may be buried in a carbon matrix or placed in a carbon matrix (mesopores) On at least a portion of the inside surface. Mesoporous carbon materials contain not only uniform and controllable mesopores, but also electron or ion diffusion channels, as well as conductive metals and/or metal oxides to improve the conductivity of mesoporous carbon materials, where metals and/or metals The form of the oxide can be a particle or a membrane. During the manufacturing process of mesoporous carbon materials, mesoporous carbon materials can be upgraded by adding single-wall and/or multi-wall carbon nanotubes (SCNTs or MCNTs). The conductivity, mesoporous carbon material can be used in inductors or energy storage devices such as supercapacitors, batteries, and fuel cells.
由上述得知，該等發明專利中並無如本發明所採用之粗糙化結構之集流層(電極基板)，該等發明專利皆是採用金屬基板或無集流層之結構製作超級電容器，僅依賴導電層之導電材料的比表面積特性實行儲能，且大多無法達到可撓效果，因此，前述專利確實無法進一步有效揭示本發明之整體的技術特徵。It is known from the above that these invention patents do not have a current collecting layer (electrode substrate) of a roughened structure as used in the present invention, and all of the invention patents are made of a metal substrate or a structure without a current collector layer. The specific surface area characteristics of the conductive material depending only on the conductive layer carry out energy storage, and most of them fail to achieve a flexible effect. Therefore, the aforementioned patent does not further effectively reveal the overall technical features of the present invention.
有鑑於此，本發明人等乃經不斷的努力研發之下，終於研發出一套可藉由砂紙表面粗糙結構做為基材以提升電極基板之比表面積的本發明。In view of the above, the present inventors have finally developed a set of the present invention which can improve the specific surface area of the electrode substrate by using a rough surface of the sandpaper as a substrate.
本發明第一目的，在於提供一種結合表面粗糙化電極與凝膠狀電解質之可撓式超級電容器，主要是利用碳化矽砂紙做為電極基板，該電極基板具備可撓性，且能增加表面積，以該電極基板做為可撓式超級電容器之電極，進而製作出可撓式超級電容器，以解決傳統習知儲能元件只能為固態且不可撓的限制，也利用砂紙表面粗糙結構增加電極與電解質間之接觸面積，促使電荷儲存量增加，並提供新技術於未來電子產品的設計與創新性應用。達成本發明第一目的所採用之技術手段，係包括二砂紙基電極、膠狀電解質、多孔隔膜及封裝薄膜。膠狀電解質分別塗覆在二砂紙基電極的內表面。多孔隔膜介置於二砂紙基電極之間的膠狀電解質中，用以隔離二砂紙基電極及傳導膠狀電解質的離子。封裝薄膜以熱壓組立方式覆設於二砂紙基電極的外表面上，藉以封裝為可撓式超級電容器。A first object of the present invention is to provide a flexible supercapacitor that combines a surface roughening electrode and a gel electrolyte, and mainly uses silicon carbide sandpaper as an electrode substrate, which has flexibility and can increase surface area. The electrode substrate is used as an electrode of a flexible supercapacitor, and then a flexible supercapacitor is fabricated to solve the limitation that the conventional energy storage component can only be solid and inflexible, and the surface roughness of the sandpaper is used to increase the electrode and The contact area between the electrolytes promotes the increase in charge storage and provides new technologies for the design of future electronic products.With innovative applications. The technical means for achieving the first object of the present invention include a sandpaper-based electrode, a gel electrolyte, a porous separator, and a package film. The gel electrolyte is coated on the inner surface of the base electrode of the sandpaper, respectively. The porous membrane is interposed in the gel electrolyte between the base electrodes of the two sandpapers to isolate the ions of the two sandpaper-based electrodes and the conductive gel electrolyte. The encapsulating film is overlaid on the outer surface of the base electrode of the grit paper by heat pressing, thereby encapsulating it as a flexible supercapacitor.
本發明第二目的，在於提供一種結合表面粗糙化電極與凝膠狀電解質之可撓式超級電容器製法，除了可藉由砂紙表面粗糙結構來提升電極基板的比表面積之外，並可藉由增加電極與電解質間之接觸面積而提升電荷儲存量，而且除可改善液態電解質容易洩漏的問題外，也能解決固態電解質接觸不良的問題，膠狀電解質易與電極間產生良好的附著性，能有效滲透於砂紙電極孔隙中，以產生更多的電荷吸附進而得到較高的比電容值。達成本發明第二目的所採用之技術手段，係以溶劑蒸發法將導電懸浮液滴覆於砂紙基板表面，經烘乾後製得砂紙基電極；將聚乙烯醇攪拌混合於去離子水以製得聚乙烯醇(PVA)水溶液，再將該PVA水溶液加入磷酸均勻混合後，進行加熱乾燥以製得膠狀電解質；以無皂乳液聚合法製得微米級微球懸浮液，並以溶劑蒸發法使微球於一基板形成自組裝排列的微球陣列，再以該PVA水溶液澆注該微球陣列縫隙中，經烘乾後將該基板取下後浸入有機溶劑中，以去微球而製得多孔隔膜；將該膠狀電解質分別塗覆在該二砂紙基電極的內表面，並於該二砂紙基電極之間位於該膠狀電解質位置介置該多孔隔膜，將封裝薄膜覆設於該二砂紙基電極的外表面上，再以熱壓組立方式製得可撓式超級電容器。A second object of the present invention is to provide a flexible supercapacitor method for combining a surface roughening electrode and a gel electrolyte, except that the surface area of the electrode substrate can be raised by a rough surface of the sandpaper, and can be increased by The contact area between the electrode and the electrolyte enhances the charge storage amount, and in addition to improving the problem that the liquid electrolyte is easily leaked, the problem of poor contact of the solid electrolyte can also be solved, and the gel electrolyte can easily form good adhesion with the electrode and can be effective. It penetrates into the pores of the sandpaper electrode to generate more charge adsorption and thus obtain a higher specific capacitance value. The technical means adopted for achieving the second object of the present invention is to deposit a conductive suspension droplet on the surface of the sandpaper substrate by solvent evaporation, and to obtain a sandpaper-based electrode after drying; mixing polyvinyl alcohol with deionized water to prepare A polyvinyl alcohol (PVA) aqueous solution is obtained, and the PVA aqueous solution is added to the phosphoric acid to be uniformly mixed, and then dried by heating to obtain a gelatinous electrolyte; the micron-sized microsphere suspension is prepared by a soap-free emulsion polymerization method, and is obtained by a solvent evaporation method. The microspheres form a self-assembled array of microspheres on a substrate, and then the PVA aqueous solution is cast into the gap of the microsphere array. After drying, the substrate is removed and immersed in an organic solvent to remove microspheres to make a porous body. a separator; respectively, coating the gel electrolyte on the inner surface of the base electrode of the two sandpaper, and interposing the porous separator between the base electrodes of the two sandpaper at the position of the gel electrolyte, and coating the package film on the sandpaper On the outer surface of the base electrode, a flexible supercapacitor is fabricated by hot pressing.
10‧‧‧砂紙基電極10‧‧‧ sandpaper base electrode
11‧‧‧砂紙基板11‧‧‧ sandpaper substrate
12‧‧‧導電層12‧‧‧ Conductive layer
20‧‧‧膠狀電解質20‧‧‧Gum electrolyte
30‧‧‧多孔隔膜30‧‧‧Polyporous membrane
31‧‧‧基板31‧‧‧Substrate
32‧‧‧微球陣列32‧‧‧microsphere array
33‧‧‧PVA水溶液33‧‧‧PVA aqueous solution
40‧‧‧封裝薄膜40‧‧‧Package film
圖1係本發明所採用之電雙層儲能原理充放電示意圖。1 is a schematic diagram of charging and discharging of the electric double-layer energy storage principle adopted by the present invention.
圖2係本發明導電混合液滴於玻璃基板表面之掃描電子顯微鏡(SEM)形貌示意圖片。2 is a scanning electron microscope (SEM) topography of the conductive mixed droplets of the present invention on the surface of a glass substrate.Italian image.
圖3係本發明之砂紙基電極製作示意圖。Fig. 3 is a schematic view showing the manufacture of a sandpaper base electrode of the present invention.
圖4係本發明藉由SEM觀察混合導電液滴覆於砂紙前後的剖面圖，右上角插圖為其相對應之表面形貌示意圖片。4 is a cross-sectional view of the present invention before and after the mixed conductive droplets are applied to the sandpaper by SEM, and the upper right corner is a schematic picture of the corresponding surface topography.
圖5係本發明之PVA多孔隔膜製作流程示意圖。Fig. 5 is a schematic view showing the production process of the PVA porous separator of the present invention.
圖6係本發明之(a)PVA包覆聚苯乙烯(PS)微球模板及(b)PS微球去除後所形成的PVA多孔隔膜的SEM圖片。Figure 6 is a SEM image of the PVA porous separator formed by (a) PVA coated polystyrene (PS) microsphere template and (b) PS microspheres removed.
圖7係本發明之可撓示超級電容器組裝結構示意圖。7 is a schematic view showing the assembled structure of the flexible supercapacitor of the present invention.
圖8係本發明之封裝後之超級電容器實施示意圖。Figure 8 is a schematic illustration of the implementation of the packaged supercapacitor of the present invention.
圖9係本發明砂紙基電極在膠狀電解質中以0.02~0.20V/s掃描速率所呈現之循環伏安曲線。Figure 9 is a cyclic voltammetry curve of a sandpaper-based electrode of the present invention in a gel electrolyte at a scan rate of 0.02 to 0.20 V/s.
圖10係本發明超級電容器在平坦彎折扭曲狀態下的循環伏安曲線示意圖。Fig. 10 is a schematic diagram showing the cyclic voltammetry curve of the supercapacitor of the present invention in a flat bending twist state.
圖11係本發明超級電容器之恆電流充放電測試示意圖。Figure 11 is a schematic diagram of a constant current charge and discharge test of the supercapacitor of the present invention.
圖12係本發明超級電容器在0.10mA恆電流下經3000次循環充放電測試示意圖。Figure 12 is a schematic diagram of the supercapacitor of the present invention subjected to 3000 cycles of charge and discharge testing at a constant current of 0.10 mA.
請參看圖1、7及圖8所示，為達成本發明第一目的之可撓式超級電容器的具體實施例，係包括二砂紙基電極10、膠狀電解質20、多孔隔膜30及封裝薄膜40等技術特徵。膠狀電解質20(如聚乙烯醇PVA/磷酸H3PO4膠狀電解質)分別塗覆在二砂紙基電極10的內表面。多孔隔膜30(如微米孔洞的PVA多孔隔膜30)則介置於二砂紙基電極10之間的膠狀電解質中，用以隔離二砂紙基電極10及傳導膠狀電解質的離子。封裝薄膜40以熱壓組立方式覆設於二砂紙基電極10的外表面上，藉以封裝成為可撓式超級電容器。具體而言，上述砂紙基電極10包含一砂紙基板11，及一覆設於砂紙基板11貼觸膠狀電解質20之表面的導電層12。至於上述封裝薄膜40的材料可以是聚醚砜(Polyethersulfone,PES)、聚對苯二甲酸乙二酯(Positron emission tomography,PET)、聚芳基酸酯(Polyarylate,PAR)、聚碳酸酯(Polycarbonate,PC)、聚乙烯(polyethylene,PE)、環烯烴共聚物(Cyclic olefin copolymer,COC)、聚甲基丙烯酸甲酯(Polymethylmethacrylate,PMMA)、聚二甲基矽氧烷(Polydimethylsiloxane,PDMS)、聚氯乙烯(Polyvinyl chloride,PVC)、尼龍Nylon或是聚氨酯(Polyurethane,PU)。Referring to FIGS. 1, 7, and 8, a specific embodiment of the flexible supercapacitor for achieving the first object of the present invention includes a sandpaper-based electrode 10, a gel electrolyte 20, a porous separator 30, and a package film 40. And other technical features. A gel electrolyte 20 such as a polyvinyl alcohol PVA/phosphoric acid H3 PO4 gel electrolyte is coated on the inner surface of the sandpaper-based electrode 10, respectively. A porous membrane 30 (e.g., a microporous PVA porous membrane 30) is interposed in a gel electrolyte between the sandpaper-based electrodes 10 for isolating the silica-based electrode 10 and the ions of the conductive gel electrolyte. The encapsulating film 40 is overlaid on the outer surface of the mica paper base electrode 10 by heat pressing, thereby encapsulating it into a flexible supercapacitor. Specifically, the sandpaper base electrode 10 includes a sandpaper substrate 11 and a conductive layer 12 that is coated on the surface of the sandpaper substrate 11 that contacts the gel electrolyte 20. The material of the above package film 40 may be polyethersulfone (PES), polyethylene terephthalate (PET), polyarylate (PAR), polycarbonate (Polycarbonate). , PC), polyethylene (PE), Cyclic olefin copolymer (COC), Polymethylmethacrylate (PMMA), Polydimethylsiloxane (PDMS), Poly Polyvinyl chloride (PVC), nylon Nylon or polyurethane (PU).
請參看圖3、5及圖7所示，為達成本發明第二目的之具體實施例，係包括砂紙基電極製備步驟、膠狀電解質製備步驟、多孔隔膜製備步驟及封裝步驟。前述各步驟詳述如后。Referring to Figures 3, 5 and 7, a specific embodiment for achieving the second object of the present invention includes a sandpaper-based electrode preparation step, a gel electrolyte preparation step, a porous membrane preparation step, and a packaging step. The foregoing steps are detailed as follows.
本發明之砂紙基電極製備步驟，請配合參看圖3所示，係以溶劑蒸發法將導電懸浮液滴覆於砂紙基板11表面，經烘乾後形成一導電層12，以製得砂紙基電極10。具體的製法，是將0.3~0.7重量份(較佳為0.5重量份(0.5g))的蘋果果膠加入95~105重量份(較佳為100重量份(100ml))的去離子水中，於攝氏55~65℃(較佳為60℃)下攪拌至均勻溶解後製得蘋果果膠水溶液，將0.3~0.7重量份(較佳為0.5重量份(0.5g))的石墨烯與0.3~0.7重量份(較佳為0.5重量份(0.5g))的奈米碳管分別加入該蘋果果膠水溶液中，以探針式超音波震碎機震盪25~35分鐘(較佳為30分鐘)，使團聚的該石墨烯與該奈米碳管均勻分散後分別形成石墨烯水溶液及奈米碳管水溶液，將該石墨烯水溶液以4000rpm的轉速攪拌離心10~20分鐘(較佳為15分鐘)，去除上清液體，取下沉物，再加入5~15重量份(較佳為10重量份(10ml))的去離子水，再以超音波震盪5~15分鐘(較佳為10分鐘)後配製成石墨烯懸浮液，將該奈米碳管水溶液以4000rpm的轉速攪拌離心10~20分鐘(較佳為15分鐘)，取得上清液做為奈米碳管懸浮液，再將該石墨烯懸浮液與該奈米碳管懸浮液混合為導電混合液12a，再將導電混合液12a滴覆於砂紙基板11表面，置於攝氏55~65℃(較佳為60℃)真空烘箱中烘乾3.5~5.5小時(較佳為4.5小時)，使砂紙基板11內表面形成導電層12，於此即可製得砂紙基電極10。The preparation step of the sandpaper base electrode of the present invention, as shown in FIG. 3, is carried out by solvent evaporation to cover the surface of the sandpaper substrate 11 by drying, and after drying, a conductive layer 12 is formed to obtain a sandpaper base electrode. 10. The specific method is that 0.3 to 0.7 parts by weight (preferably 0.5 parts by weight (0.5 g)) of apple pectin is added to 95 to 105 parts by weight (preferably 100 parts by weight (100 ml)) of deionized water. After stirring at 55-65 ° C (preferably 60 ° C) until homogeneous dissolution, an apple pectin aqueous solution is obtained, and 0.3 to 0.7 parts by weight (preferably 0.5 parts by weight (0.5 g)) of graphene and 0.3 to 0.7 are obtained. The parts by weight (preferably 0.5 parts by weight (0.5 g)) of carbon nanotubes are respectively added to the apple pectin aqueous solution, and shaken by a probe type ultrasonic vibration machine for 25 to 35 minutes (preferably 30 minutes). The agglomerated graphene and the carbon nanotube are uniformly dispersed to form a graphene aqueous solution and a carbon nanotube aqueous solution, respectively, and the graphene aqueous solution is stirred and centrifuged at 4000 rpm for 10 to 20 minutes (preferably 15 minutes). RemoveThe supernatant liquid is taken, and the sediment is removed, and then 5 to 15 parts by weight (preferably 10 parts by weight (10 ml)) of deionized water is added, and then ultrasonically oscillated for 5 to 15 minutes (preferably 10 minutes). The graphene suspension is prepared, and the nanocarbon tube aqueous solution is stirred and centrifuged at 4000 rpm for 10 to 20 minutes (preferably 15 minutes), and the supernatant liquid is taken as a carbon nanotube suspension, and the graphene is further obtained. The suspension is mixed with the carbon nanotube suspension as the conductive mixture 12a, and the conductive mixture 12a is dripped on the surface of the sandpaper substrate 11, and dried in a vacuum oven at 55-65 ° C (preferably 60 ° C). The conductive layer 12 is formed on the inner surface of the sandpaper substrate 11 at 3.5 to 5.5 hours (preferably 4.5 hours), whereby the sandpaper-based electrode 10 can be obtained.
本發明之膠狀電解質製備步驟，係將聚乙烯醇(poly(vinyl alcohol),PVA)攪拌混合於去離子水以製得PVA水溶液33，再將該PVA水溶液33加入磷酸均勻混合後，進行加熱乾燥以製得膠狀電解質。具體的製法，係取8~12重量份(較佳為10重量份(10g))的該聚乙烯醇加入95~105重量份(較佳為100重量份(100ml))該去離子水中，在攝氏55~65℃(較佳為60℃)下攪拌使其完全溶解，再於該PVA水溶液33中加入15~25重量份(較佳為20重量份(20g))的磷酸(phosphoric acid,H3PO4,SIGMA)均勻混合後，置於攝氏70~80℃(較佳為75℃)的烘箱中乾燥，以製得PVA/H3PO4膠狀電解質。The preparation process of the gel electrolyte of the present invention comprises mixing polyvinyl alcohol (poly(vinyl alcohol), PVA) in deionized water to prepare an aqueous PVA solution 33, and then uniformly adding the PVA aqueous solution 33 to the phosphoric acid, and heating. Dry to prepare a gelatinous electrolyte. In a specific preparation method, 8 to 12 parts by weight (preferably 10 parts by weight (10 g)) of the polyvinyl alcohol is added to 95 to 105 parts by weight (preferably 100 parts by weight (100 ml)) of the deionized water. The mixture is stirred at 55 to 65 ° C (preferably 60 ° C) to be completely dissolved, and then 15 to 25 parts by weight (preferably 20 parts by weight (20 g)) of phosphoric acid (H) is added to the PVA aqueous solution 33.3 PO4 , SIGMA) After uniformly mixing, it is dried in an oven at 70 to 80 ° C (preferably 75 ° C) to prepare a PVA/H3 PO4 gel electrolyte.
本發明之多孔隔膜製備步驟，請配合參看圖5所示，係以無皂乳液聚合法製得微米級微球懸浮液，並以溶劑蒸發法使微球於一基板31形成自組裝排列的微球陣列32，再以該PVA水溶液33澆注該微球陣列32縫隙中，經烘乾後將該基板31取下後浸入有機溶劑中，以去微球而製得多孔隔膜30。具體的製法，是分別將8~12重量份(較佳為10重量份(10g))的苯乙烯(Styrene)、85~95重量份(較佳為100重量份(100ml))的去離子水以及0.003~0.008重量份(較佳為5重量份(5mg))的聚二甲基矽氧烷(4-styrenesulfonic acid sodium salt,NaSS)置於第一容器(四頸瓶)內加熱攪拌，反應過程在一迴流冷凝管和氮氣環境下進行，當反應溫度達到攝氏65~75℃(較佳為70℃)時，加入0.05~0.1重量份(較佳為0.087重量份(0.087g))的過硫酸鉀(potassium persulfate,KPS)進行聚合反應23~25小時(較佳為24小時)，以製得粒徑約2mm之聚苯乙烯(PS)微球懸浮液，再取2重量份(較佳為2重量份(2ml))的該微球懸浮液與10~20重量份(較佳為15重量份(15ml))的無水乙醇(Ethyl Alcohol)置於第二容器(如燒杯)中，經超音波震盪5~15分鐘(較佳為10分鐘)，以製得聚苯乙烯(PS)微球稀釋溶液，在室溫下，將該聚苯乙烯(PS)微球稀釋溶液注入該基板31中，以旋轉式震盪培養機以30rpm轉速下旋轉乾燥25~35分鐘(較佳為30分鐘)，再置於攝氏55~65℃(較佳為60℃)烘箱中烘乾15~25分鐘(較佳為20分鐘)，以去除多餘乙醇，使各聚苯乙烯微球自組裝排列成緊密堆積的聚苯乙烯微球陣列32，再以8~12重量百分比(wt%)(較佳為10wt%)的該PVA水溶液33澆注於該聚苯乙烯微球陣列32縫隙，置於攝氏55~65℃(較佳為60℃)烘箱中烘乾後形成PVA包覆層33a，再將PVA包覆層33a所包覆之聚苯乙烯微球陣列32的基板31取下，並將PVA包覆層33a浸於甲苯溶劑而去除聚苯乙烯微球，以製得到具微米孔洞的PVA多孔隔膜30。In the preparation process of the porous membrane of the present invention, please refer to FIG. 5, the micron-sized microsphere suspension is prepared by soap-free emulsion polymerization, and the microspheres are formed into a self-assembled microsphere by a solvent evaporation method on a substrate 31. The array 32 is further filled with the PVA aqueous solution 33 into the gap of the microsphere array 32. After drying, the substrate 31 is removed and immersed in an organic solvent to remove the microspheres to obtain a porous separator 30. The specific preparation method is 8 to 12 parts by weight (preferably 10 parts by weight (10 g)) of styrene (Styrene), 85 to 95 parts by weight (preferably 100 parts by weight (100 ml)) of deionized water, respectively. And 0.003 to 0.008 parts by weight (preferably 5 parts by weight (5 mg)) of polydimethyl siloxane (4-styrenesulfonic)The acid sodium salt (NaSS) is placed in a first vessel (four-necked flask) and stirred under a reflux condenser and a nitrogen atmosphere. When the reaction temperature reaches 65-75 ° C (preferably 70 ° C) Adding 0.05 to 0.1 part by weight (preferably 0.087 part by weight (0.087 g)) of potassium persulfate (KPS) for polymerization for 23 to 25 hours (preferably 24 hours) to obtain a particle size of about 2 mm of polystyrene (PS) microsphere suspension, and then 2 parts by weight (preferably 2 parts by weight (2 ml)) of the microsphere suspension and 10-20 parts by weight (preferably 15 parts by weight (15 ml) )) Ethanol Alcohol is placed in a second container (such as a beaker) and ultrasonically shaken for 5 to 15 minutes (preferably 10 minutes) to prepare a polystyrene (PS) microsphere dilution solution. The polystyrene (PS) microsphere dilution solution is injected into the substrate 31 at room temperature, and rotated by a rotary shaker at 30 rpm for 25 to 35 minutes (preferably 30 minutes), and then placed. Drying in an oven at 55-65 ° C (preferably 60 ° C) for 15 to 25 minutes (preferably 20 minutes) to remove excess ethanol, so that the polystyrene microspheres are self-assembled into closely packed aggregates. The ethylene microsphere array 32 is further poured into the gap of the polystyrene microsphere array 32 in an amount of 8-12 weight percent (wt%) (preferably 10 wt%) of the PVA aqueous solution 33, and is placed at 55 to 65 ° C. Preferably, the PVA coating layer 33a is formed by drying in an oven at 60 ° C, and the substrate 31 of the polystyrene microsphere array 32 coated with the PVA coating layer 33a is removed, and the PVA coating layer 33a is immersed in The polystyrene microspheres were removed by a toluene solvent to obtain a PVA porous separator 30 having micropores.
本發明之封裝步驟，係將膠狀電解質分別塗覆在二砂紙基電極10的內表面，並於二砂紙基電極10之間位於膠狀電解質位置介置一多孔隔膜30，如圖7所示，將此三明治結構(砂紙/混合導電物/膠狀電解質/多孔隔膜30/凝膠電解質/混合導電物/砂紙)，將封裝薄膜40覆設於二砂紙基電極10的外表面上，再以熱壓組立方式製得可撓式超級電容器。具體實施例中，上述封裝薄膜40係選用聚對苯二甲酸乙二酯(Positron emission tomography,PET)。整個超級電容器結構之示意圖則如圖8所示。In the encapsulation step of the present invention, a gel electrolyte is separately coated on the inner surface of the grit paper base electrode 10, and a porous membrane 30 is placed between the grit paper base electrodes 10 at the position of the gel electrolyte, as shown in FIG. It is shown that the sandwich structure (sandpaper/mixed conductive material/gel electrolyte/porous separator 30/gel electrolyte/mixed conductive material/sand paper) is coated on the outer surface of the sandpaper base electrode 10, and then A flexible supercapacitor is produced by a hot press assembly method. In a specific embodiment, the package film 40 is made of polyethylene terephthalate (Positron emission tomography,PET). A schematic diagram of the entire supercapacitor structure is shown in FIG.
為了評估砂紙電極之電化學特性，本發明進行了電化學特性測試，係利用恆電位儀(Logic SP-150)進行循環伏安、恆電流充放電與循環壽命測試。在電三極系統中，以凝膠電解質或液態電解質進行電化學分析，分別以砂紙電極、鉑Pt與銀Ag/氯化銀AgCl做為工作電極、輔助電極與參考電極。砂紙電極在凝膠電解質中以0.02~0.20V/s掃描速率及0.0~0.6V之電壓範圍進行循環伏安分析。此外，以恆定電流(0.08~0.50mA)對砂紙電極進行恆電流充放電進行測試。在電三極系統中，根據以下方程式(1)，砂紙基電極10之比電容值等於其電容量除以工作電極上活性物質重量。In order to evaluate the electrochemical characteristics of the sandpaper electrode, the present invention conducted electrochemical property testing using a potentiostat (Logic SP-150) for cyclic voltammetry, constant current charge and discharge, and cycle life testing. In the electric triode system, electrochemical analysis was carried out with a gel electrolyte or a liquid electrolyte, with a sandpaper electrode, platinum Pt and silver Ag/silver chloride AgCl as working electrodes, auxiliary electrodes and reference electrodes, respectively. The sandpaper electrode was subjected to cyclic voltammetry analysis in a gel electrolyte at a scan rate of 0.02 to 0.20 V/s and a voltage range of 0.0 to 0.6 V. In addition, constant current charging and discharging were performed on the sandpaper electrode with a constant current (0.08 to 0.50 mA). In the electric three-pole system, according to the following equation (1), the specific capacitance value of the sandpaper-based electrode 10 is equal to its capacitance divided by the weight of the active material on the working electrode.
其中i為放電電流(A)，m為電極材料質量(g)，S為掃描速率(V/s)，△V為電壓範圍(V)。圖2係本發明導電混合液滴於玻璃基板表面之SEM形貌示意圖片。圖4係本發明藉由SEM觀察混合導電液滴覆於砂紙前後的剖面圖，右上角插圖為其相對應之表面形貌示意圖片。圖6係本發明之(a)PVA包覆PS微球模板及(b)PS微球去除後所形成的PVA多孔隔膜的SEM圖片。圖9為砂紙基電極10在膠狀電解質中，以0.02~0.20V/s掃描速率所呈現之循環伏安曲線，各曲線呈現對稱矩形，表示砂紙電極具備良好可逆性和理想的電容特性。藉由方程式(1)計算出之比電容值最高達550F/g。圖10為細砂紙基電極10製作之可撓式超級電容器在平坦、彎折、扭曲的狀態下的循環伏安曲線，三者之電化學特性並無明顯差異，顯示此元件具有良好可撓特性。而在不同恆定電流下進行充放電測試其結果，如圖11所示，曲線含有內電阻(iRdrop)。在恆定電流增加時造成內電阻增加，而較低的內電阻能防止充放電時過多的能量損耗與不必要的熱能產生，促使比電容值下降。且可明顯觀察到恆定電流增加造成充放電時間變短，但曲線仍然維持一類三角形，顯示此超級電容器具有良好可逆性與具備快速充放電特性。圖12為超級電容器在0.10mA恆電流下經3000次循環充放電測試後其比電容值仍保有初始電容值的91%，顯示該元件具有優異的循環壽命與穩定性。於具體的實測實施例中，係以3V電壓對單一可撓式超級電容器(spec：2cm×4cm×0.67mm,thickness：0.66mm)進行快速充電後得以點亮發光二極體(LED)之實證，顯示此儲能元件具有實際應用潛力。Where i is the discharge current (A), m is the electrode material mass (g), S is the scan rate (V/s), and ΔV is the voltage range (V). 2 is a schematic view showing the SEM topography of the conductive mixed droplets of the present invention on the surface of a glass substrate. 4 is a cross-sectional view of the present invention before and after the mixed conductive droplets are applied to the sandpaper by SEM, and the upper right corner is a schematic picture of the corresponding surface topography. 6 is a SEM picture of the PVA porous separator formed by (a) PVA-coated PS microsphere template and (b) PS microspheres removed. Fig. 9 is a cyclic voltammetry curve of the sandpaper-based electrode 10 in a gel electrolyte at a scanning rate of 0.02 to 0.20 V/s, and each curve exhibits a symmetrical rectangle, indicating that the sandpaper electrode has good reversibility and ideal capacitance characteristics. The specific capacitance value calculated by equation (1) is up to 550 F/g. Figure 10 is a cyclic voltammetry curve of a flexible supercapacitor made of a fine sandpaper-based electrode 10 in a flat, bent, and twisted state. The electrochemical characteristics of the three are not significantly different, indicating that the component has good flexibility. . The result of the charge and discharge test at different constant currents, as shown in Fig. 11, the curve contains an internal resistance (iRdrop ). When the constant current increases, the internal resistance increases, and the lower internal resistance prevents excessive energy loss and unnecessary heat energy generation during charging and discharging, causing the specific capacitance value to decrease. It can be clearly observed that the constant current increase causes the charge and discharge time to become shorter, but the curve still maintains a kind of triangle, indicating that the supercapacitor has good reversibility and fast charge and discharge characteristics. Figure 12 shows that the supercapacitor retains 91% of the initial capacitance value after 3000 cycles of charge and discharge testing at a constant current of 0.10 mA, indicating that the component has excellent cycle life and stability. In a specific measured embodiment, an empirical demonstration is performed to illuminate a light-emitting diode (LED) by rapidly charging a single flexible supercapacitor (spec: 2 cm × 4 cm × 0.67 mm, thickness: 0.66 mm) with a voltage of 3 V. Shows that this energy storage component has practical application potential.
因此，藉由上述之具體實施例說明，本發明確實具有下列所述的特點：Thus, by way of the specific embodiments described above, the present invention does have the following features:
1.本發明砂紙基電極之表面不同於傳統電極，傳統電極僅藉由導電材料本身多孔特性儲存電荷，基板僅做為支撐體或電流傳導層，而本發明藉由砂紙表面粗糙結構結合導電材料多孔特性，增加電極與電解質間之接觸面積，促使在相同面積下之電極能夠儲存更多電荷，進而提升超級電容器之電荷儲存量。1. The surface of the sandpaper-based electrode of the present invention is different from the conventional electrode. The conventional electrode only stores the electric charge by the porous property of the conductive material itself, and the substrate is only used as a support or a current conducting layer, and the present invention combines the conductive material by the rough surface structure of the sandpaper. The porous property increases the contact area between the electrode and the electrolyte, so that the electrode under the same area can store more charge, thereby increasing the charge storage capacity of the supercapacitor.
2.本發明之膠狀電解質可以取代傳統之固態與液態電解質，由於膠狀電解質對電極具有強的黏合力並能有效滲入電極材料的孔隙中，故而在充放電時，電極與電解質較不會發生接觸不良。2. The gel electrolyte of the present invention can replace the traditional solid and liquid electrolytes. Since the gel electrolyte has strong adhesion to the electrode and can effectively penetrate into the pores of the electrode material, the electrode and the electrolyte are less likely to be charged and discharged. Poor contact occurred.
3.本發明藉由簡單低成本方式製作多孔隔膜，且利用生物可分解之材料製作，故而可以降低對環境之衝擊。3. The present invention produces a porous membrane by a simple and low-cost method, and is made of a biodegradable material, so that the impact on the environment can be reduced.
4.本發明所製備之可撓式超級電容器，在快速充電後得以點亮LED做為實證，未來可應用於穿戴式或可撓式電子產品中，進而提供一項新的設計概念與提升能源科技一項新的技術。4. The flexible supercapacitor prepared by the invention can be illuminated by LED after rapid charging, and can be applied in wearable or flexible electronic products in the future, thereby providing a new design.Concept and a new technology for energy technology.
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 is only a possible embodiment 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 should be It is included in 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‧‧‧砂紙基電極10‧‧‧ sandpaper base electrode
20‧‧‧膠狀電解質20‧‧‧Gum electrolyte
30‧‧‧多孔隔膜30‧‧‧Polyporous membrane
| Application Number | Priority Date | Filing Date | Title |
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| TW103135207ATWI559344B (en) | 2014-10-09 | 2014-10-09 | Conductive supercapacitor combined with surface roughened electrode and gel electrolyte and method for making the same |
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| TW103135207ATWI559344B (en) | 2014-10-09 | 2014-10-09 | Conductive supercapacitor combined with surface roughened electrode and gel electrolyte and method for making the same |
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| TW201614697A TW201614697A (en) | 2016-04-16 |
| TWI559344Btrue TWI559344B (en) | 2016-11-21 |
| Application Number | Title | Priority Date | Filing Date |
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| TW103135207ATWI559344B (en) | 2014-10-09 | 2014-10-09 | Conductive supercapacitor combined with surface roughened electrode and gel electrolyte and method for making the same |
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| TWI718733B (en)* | 2019-03-28 | 2021-02-11 | 薩摩亞商美科米尚技術有限公司 | Method of liquid assisted binding |
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| TWI673735B (en)* | 2018-11-14 | 2019-10-01 | National Formosa University | Supercapacitor with conductive polymer sandpaper base electrode and preparation method thereof |
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