TWI464762B - Super capacitor - Google Patents
Super capacitor Download PDFInfo
- Publication number
- TWI464762B TWI464762B TW096151263A TW96151263A TWI464762B TW I464762 B TWI464762 B TW I464762B TW 096151263 A TW096151263 A TW 096151263A TW 96151263 A TW96151263 A TW 96151263A TW I464762 B TWI464762 B TW I464762B
- Authority
- TW
- Taiwan
- Prior art keywords
- carbon nanotube
- supercapacitor
- nanotube film
- carbon
- carbon nanotubes
- Prior art date
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Description
本發明涉及一種超級電容器，尤其涉及一種基於奈米碳管的超級電容器。 The present invention relates to a supercapacitor, and more particularly to a carbon nanotube-based supercapacitor.
超級電容器(supercapacitor)，又叫電化學電容器、電雙層電容器。超級電容器具有較高的比功率和較長的循環壽命，工作溫度範圍寬。在移動通訊、資訊技術、電動汽車、航空航天和國防科技等方面都有著極其重要和廣闊的應用前景。 Supercapacitor, also known as electrochemical capacitors, electric double layer capacitors. Supercapacitors have high specific power and long cycle life with a wide operating temperature range. It has extremely important and broad application prospects in mobile communication, information technology, electric vehicles, aerospace and defense technology.
先前的超級電容器一般包括電極、隔膜和電解液溶液，該電極和隔膜都設置在該電解液溶液中。該電極包括一集電體及設置在該集電體上的電極材料。先前超級電容器的製備方法通常係將電極材料充分研磨後，在其中加入一定量的粘結劑攪拌均勻，再通過模壓法、冷等靜壓法、熱等靜壓法等壓制方法壓制在泡沫鎳、石墨片、鎳片、鋁片或銅片等集電體上，即可製成一定形狀的電極；然後將電極設置在含隔膜的電解液溶液中即可製成超級電容器。該製備方法較複雜。 Previous supercapacitors typically included an electrode, a membrane, and an electrolyte solution, both of which were disposed in the electrolyte solution. The electrode includes a current collector and an electrode material disposed on the current collector. In the prior art, the preparation method of the supercapacitor is generally after the electrode material is sufficiently ground, a certain amount of the binder is added thereto and stirred uniformly, and then pressed in the foamed nickel by a compression method such as a compression method, a cold isostatic pressing method or a hot isostatic pressing method. On the current collectors such as graphite sheets, nickel sheets, aluminum sheets or copper sheets, electrodes of a certain shape can be formed; and then the electrodes are placed in an electrolyte solution containing a separator to form a supercapacitor. This preparation method is complicated.
超級電容器中影響其容量的決定因素係電極材料。理想的電極材料要求結晶度高、導電性好、比表面積大、微孔集中在一定的範圍內(要求微孔大於2奈米)。先前的超級電容器中電極材料主要有：活性碳系列和過渡金屬氧化物系列。活性碳系列的材料導電 性較差，採用活性碳系列的材料作電極的電容器等效串聯電阻大。而且該活性碳系列的比表面積實際利用率不超過30%，電解質離子難以進入。過渡金屬氧化物用作電極材料在提高超級電容器的容量方面具有良好的效果，但其成本太高，無法推廣使用。 The determinant of the influence of its capacity in supercapacitors is the electrode material. The ideal electrode material requires high crystallinity, good electrical conductivity, large specific surface area, and micropores are concentrated in a certain range (required micropores greater than 2 nm). The electrode materials of the previous supercapacitors mainly include: activated carbon series and transition metal oxide series. Active carbon series materials are conductive Poorly, the capacitor with the activated carbon series as the electrode has a large equivalent series resistance. Moreover, the actual utilization ratio of the specific surface area of the activated carbon series does not exceed 30%, and electrolyte ions are difficult to enter. The use of a transition metal oxide as an electrode material has a good effect in increasing the capacity of a supercapacitor, but its cost is too high to be promoted.
奈米碳管(Carbon Nanotube,CNT)的出現為超級電容器的開發提供了新的機遇。奈米碳管係一種奈米級無縫管狀石墨結構碳材料，管徑為幾奈米到幾十奈米，管長為幾微米到幾十微米。奈米碳管比表面積大，結晶度高，導電性好，管內外徑可通過合成工藝加以控制，可使比表面利用率達到100%，因而可以成為一種理想的超級電容器材料。 The emergence of carbon nanotubes (CNTs) provides new opportunities for the development of supercapacitors. The carbon nanotube is a nano-scale seamless tubular graphite structure carbon material with a diameter ranging from several nanometers to several tens of nanometers and a tube length of several micrometers to several tens of micrometers. The carbon nanotube has a large specific surface area, high crystallinity and good electrical conductivity. The inner and outer diameters of the tube can be controlled by a synthetic process, and the specific surface utilization rate can be 100%, so that it can be an ideal supercapacitor material.
奈米碳管用作超級電容器材料的研究最早見諸於Chunming Niu等的報導(請參見High power electrochemical capacitors based on carbon nanotube electrodes,Apply Physics Letter,Chunming Niu et al.,vol 70,p1480-1482(1997))。他們將純的多壁奈米碳管粉末製成薄膜電極後，封裝制得一超級電容器。在該薄膜電極的製備方法中，由於所用的奈米碳管原料為粉末狀，極易發生團聚，製成的薄膜電極中奈米碳管分佈不均勻且無序排列，故需要對奈米碳管進行化學改性。然而，即使經過化學改性後的奈米碳管仍然會出現團聚現象，造成所制得的薄膜電極韌性差，容易斷裂，影響了超級電容器的性能。 The use of carbon nanotubes as supercapacitor materials was first reported in Chunming Niu et al. (see High power electrochemical capacitors based on carbon nanotube electrodes, Applied Physics Letter, Chunming Niu et al., vol 70, p1480-1482 (1997). )). They made a pure multi-walled carbon nanotube powder into a thin film electrode and packaged it to make a supercapacitor. In the preparation method of the thin film electrode, since the raw material of the carbon nanotube used is powdery, agglomeration is extremely likely to occur, and the carbon nanotubes in the prepared thin film electrode are unevenly distributed and disorderly arranged, so that it is necessary to have a nano carbon. The tube is chemically modified. However, even if the chemically modified carbon nanotubes still have agglomeration, the resulting film electrode has poor toughness and is easily broken, which affects the performance of the supercapacitor.
有鑒於此，提供一種具有電容量高和功率密度大的超級電容器實為必要。 In view of this, it is necessary to provide a supercapacitor having a high capacitance and a large power density.
一種超級電容器，其包括：一第一電極，一第二電極，一第一集 電體，一第二集電體，一隔膜，一電解液溶液和一外殼。所述電解液溶液設置在該外殼內。所述第一集電體和第二集電體間隔設置在所述電解液溶液內。所述第一電極包括一第一奈米碳管薄膜結構並設置在所述第一集電體表面。所述第二電極包括一第二奈米碳管薄膜結構並設置在所述第二集電體表面。所述隔膜設置在所述的第一電極和第二電極之間，並分別與所述第一電極和第二電極間隔設置。所述的第一奈米碳管薄膜結構和第二奈米碳管薄膜結構中均包括至少一奈米碳管層，該奈米碳管層包括多個沿同一方向定向排列的奈米碳管。 A supercapacitor comprising: a first electrode, a second electrode, and a first set The electric body, a second current collector, a diaphragm, an electrolyte solution and an outer casing. The electrolyte solution is disposed within the outer casing. The first current collector and the second current collector are disposed in the electrolyte solution at intervals. The first electrode includes a first carbon nanotube film structure and is disposed on a surface of the first current collector. The second electrode includes a second carbon nanotube film structure and is disposed on a surface of the second current collector. The diaphragm is disposed between the first electrode and the second electrode and is spaced apart from the first electrode and the second electrode, respectively. The first carbon nanotube film structure and the second carbon nanotube film structure each include at least one carbon nanotube layer, and the carbon nanotube layer comprises a plurality of carbon nanotubes aligned in the same direction .
與先前技術相比較，所述的超級電容器具有以下優點：其一，奈米碳管具有良好的導電性能且本身的比表面積大，制得的超級電容器具有較高的比電容量和電導率；其二，由於奈米碳管陣列中奈米碳管生長均勻，因而所製備的奈米碳管薄膜結構中的奈米碳管分散均勻，且製備方法簡單，易於實際應用；其三，該奈米碳管薄膜結構包括多個首尾相連且定向排列的奈米碳管，相鄰的奈米碳管之間具有多個微孔結構，使得奈米碳管薄膜結構中形成大量的均勻且規則分佈的微孔結構，這有利於充分的利用奈米碳管的表面微孔結構，使之成為導電性良好的電荷通路。 Compared with the prior art, the supercapacitor has the following advantages: First, the carbon nanotube has good electrical conductivity and has a large specific surface area, and the obtained supercapacitor has high specific capacitance and electrical conductivity; Secondly, due to the uniform growth of the carbon nanotubes in the carbon nanotube array, the carbon nanotubes in the prepared carbon nanotube film structure are uniformly dispersed, and the preparation method is simple and easy to be practically applied; The carbon nanotube film structure comprises a plurality of carbon nanotubes connected end to end and oriented, and a plurality of microporous structures between adjacent carbon nanotubes, so that a large number of uniform and regular distributions are formed in the carbon nanotube film structure. The microporous structure facilitates the full utilization of the surface microporous structure of the carbon nanotubes, making it a conductive path with good conductivity.
10‧‧‧超級電容器 10‧‧‧Supercapacitors
101‧‧‧第一電極 101‧‧‧First electrode
102‧‧‧第二電極 102‧‧‧second electrode
103‧‧‧第一集電體 103‧‧‧First current collector
104‧‧‧第二集電體 104‧‧‧Second current collector
105‧‧‧隔膜 105‧‧‧Separator
106‧‧‧電解液 106‧‧‧ electrolyte
107‧‧‧外殼 107‧‧‧Shell
第1圖係本技術方案實施例的超級電容器的結構示意圖。 FIG. 1 is a schematic structural view of a supercapacitor according to an embodiment of the present technical solution.
第2圖係本技術方案實施例獲得的奈米碳管薄膜的掃描電鏡照片。 Fig. 2 is a scanning electron micrograph of a carbon nanotube film obtained in an embodiment of the present technical solution.
第3圖係本技術方案實施例的超級電容器的製備方法的流程示意圖。 FIG. 3 is a schematic flow chart of a method for preparing a supercapacitor according to an embodiment of the present technical solution.
第4圖係本技術方案實施例的超級電容器的恒流充放電曲線。 Fig. 4 is a graph showing a constant current charge and discharge curve of the supercapacitor of the embodiment of the present technical solution.
以下將結合附圖詳細說明本技術方案超級電容器及其製備方法。 The supercapacitor of the present technical solution and a method of manufacturing the same will be described in detail below with reference to the accompanying drawings
請參閱圖1，本技術方案實施例提供一種超級電容器10，該超級電容器具有平板型的結構，包括：一第一電極101，一第二電極102，一第一集電體103，一第二集電體104，一隔膜105，一電解液溶液106和一外殼107。所述電解液溶液106設置在該外殼107內。所述第一集電體103和第二集電體104間隔設置在所述電解液溶液106內。所述第一電極101包括一第一奈米碳管薄膜結構並設置在所述第一集電體103表面。所述第二電極102包括一第二奈米碳管薄膜結構並設置在所述第二集電體104表面。所述隔膜105設置在所述的第一電極101和第二電極102之間，並分別與所述第一電極101和第二電極102間隔設置。所述的第一奈米碳管薄膜結構和第二奈米碳管薄膜結構中均包括至少一奈米碳管層，該奈米碳管層包括多個沿同一方向定向排列的奈米碳管。 Referring to FIG. 1 , an embodiment of the present invention provides a supercapacitor 10 having a flat type structure, including: a first electrode 101 , a second electrode 102 , a first collector 103 , and a second The current collector 104, a diaphragm 105, an electrolyte solution 106 and a casing 107. The electrolyte solution 106 is disposed within the outer casing 107. The first current collector 103 and the second current collector 104 are spaced apart from each other in the electrolyte solution 106. The first electrode 101 includes a first carbon nanotube film structure and is disposed on a surface of the first current collector 103. The second electrode 102 includes a second carbon nanotube film structure and is disposed on the surface of the second current collector 104. The diaphragm 105 is disposed between the first electrode 101 and the second electrode 102 and is spaced apart from the first electrode 101 and the second electrode 102, respectively. The first carbon nanotube film structure and the second carbon nanotube film structure each include at least one carbon nanotube layer, and the carbon nanotube layer comprises a plurality of carbon nanotubes aligned in the same direction .
所述奈米碳管薄膜結構包括一奈米碳管層或者至少兩個重疊設置的奈米碳管層，每個奈米碳管層中奈米碳管沿同一方向定向排列。所述至少兩個重疊設置的奈米碳管層中相鄰的兩個奈米碳管層中的奈米碳管排列方向具有一交叉角度α，0°≦α≦90°，具體可依據實際需求製備。相鄰兩個奈米碳管層之間通過凡德瓦爾力緊密結合。所述至少兩個重疊設置的奈米碳管層中的奈米碳管之間具有多個微孔結構，該微孔結構均勻且規則分佈於奈米碳管薄膜結構中，其中微孔直徑為1奈米~0.5微米。所述奈米碳管層包括一奈米碳管薄膜或者至少兩個平行且無間隙鋪設的奈米碳管薄 膜。所述奈米碳管薄膜包括多個首尾相連且定向排列的奈米碳管束，該奈米碳管束包括多個長度相等且相互平行排列的奈米碳管。所述奈米碳管薄膜中的奈米碳管束的長度基本相同，奈米碳管束之間通過凡德瓦爾力緊密連接。請參閱圖2，所述奈米碳管薄膜包括多個奈米碳管片段，每個奈米碳管片段具有大致相等的長度且每個奈米碳管片段由多個相互平行的奈米碳管束構成，奈米碳管片段兩端通過凡德瓦爾力相互連接。 The carbon nanotube film structure comprises a carbon nanotube layer or at least two overlapping carbon nanotube layers, and the carbon nanotubes in each carbon nanotube layer are aligned in the same direction. The arrangement of the carbon nanotubes in the adjacent two carbon nanotube layers in the at least two overlapping carbon nanotube layers has an intersection angle α, 0° ≦ α ≦ 90°, depending on the actual Demand preparation. The adjacent two carbon nanotube layers are tightly bonded by Van der Waals force. The carbon nanotubes in the at least two overlapping carbon nanotube layers have a plurality of microporous structures between them, and the microporous structures are uniformly and regularly distributed in the carbon nanotube film structure, wherein the micropore diameter is 1 nm ~ 0.5 microns. The carbon nanotube layer comprises a carbon nanotube film or at least two carbon nanotubes which are laid in parallel and without gaps. membrane. The carbon nanotube film comprises a plurality of end-to-end and aligned carbon nanotube bundles, the bundle comprising a plurality of carbon nanotubes of equal length and arranged in parallel with each other. The lengths of the carbon nanotube bundles in the carbon nanotube film are substantially the same, and the nanotube bundles are closely connected by van der Waals force. Referring to FIG. 2, the carbon nanotube film comprises a plurality of carbon nanotube segments, each of the carbon nanotube segments having substantially equal lengths and each of the carbon nanotube segments being composed of a plurality of mutually parallel nanocarbons. The tube bundle is formed, and the carbon nanotube segments are connected to each other by Van der Waals force.
所述奈米碳管薄膜的厚度為0.5奈米~100微米。該奈米碳管薄膜中的奈米碳管為單壁奈米碳管、雙壁奈米碳管及多壁奈米碳管中的一種。該奈米碳管的長度為50微米~5毫米。當所述奈米碳管薄膜中的奈米碳管為單壁奈米碳管時，該單壁奈米碳管的直徑為0.5奈米~50奈米。當所述奈米碳管薄膜中的奈米碳管為雙壁奈米碳管時，該雙壁奈米碳管的直徑為1.0奈米~50奈米。當所述奈米碳管薄膜中的奈米碳管為多壁奈米碳管時，該多壁奈米碳管的直徑為1.5奈米~50奈米。 The carbon nanotube film has a thickness of from 0.5 nm to 100 μm. The carbon nanotubes in the carbon nanotube film are one of a single-walled carbon nanotube, a double-walled carbon nanotube, and a multi-walled carbon nanotube. The carbon nanotubes have a length of 50 microns to 5 mm. When the carbon nanotubes in the carbon nanotube film are single-walled carbon nanotubes, the single-walled carbon nanotubes have a diameter of 0.5 nm to 50 nm. When the carbon nanotubes in the carbon nanotube film are double-walled carbon nanotubes, the double-walled carbon nanotubes have a diameter of 1.0 nm to 50 nm. When the carbon nanotubes in the carbon nanotube film are multi-walled carbon nanotubes, the multi-walled carbon nanotubes have a diameter of 1.5 nm to 50 nm.
所述的隔膜105為玻璃纖維或者聚合物膜，其允許上述電解液溶液106中的電解質離子流通而阻止所述第一電極101和第二電極102相接觸。 The separator 105 is a glass fiber or a polymer film that allows electrolyte ions in the electrolyte solution 106 to circulate to prevent the first electrode 101 and the second electrode 102 from coming into contact.
所述的電解液溶液106為氫氧化納水溶液、氫氧化鉀水溶液、硫酸水溶液、硝酸水溶液、高氯酸鋰的碳酸丙烯酯溶液、四氟硼酸四乙基銨的碳酸丙烯酯溶液，或以上任意組合的混合液。 The electrolyte solution 106 is a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a sulfuric acid aqueous solution, a nitric acid aqueous solution, a lithium chlorate propylene carbonate solution, a tetraethylammonium tetrafluoroborate propylene carbonate solution, or any of the above. Combined mixture.
所述的外殼107為玻璃外殼或者不銹鋼外殼。 The outer casing 107 is a glass outer casing or a stainless steel outer casing.
所述集電體的材料可為石墨、鎳、鋁或銅等等，該集電體可為一 金屬基板，優選為銅片。該集電體的形狀大小不限，可依據實際需要進行改變。上述奈米碳管薄膜結構本身具有較強的粘性，故作為電極的奈米碳管薄膜結構可以直接粘附在所述集電體的表面，或將所述奈米碳管薄膜結構通過一粘結劑粘附在所述集電體的表面。 The material of the current collector may be graphite, nickel, aluminum or copper, etc., and the current collector may be one The metal substrate is preferably a copper sheet. The shape and size of the current collector are not limited, and can be changed according to actual needs. The above-mentioned carbon nanotube film structure itself has strong viscosity, so that the carbon nanotube film structure as an electrode can directly adhere to the surface of the current collector, or pass the carbon nanotube film structure through a viscosity The junction adheres to the surface of the current collector.
所述超級電容器10中的第一集電體103和第二集電體104均為一可選擇的結構，因為奈米碳管薄膜結構具有良好的導電性能和一定的自支撐性及穩定性，實際應用時，可直接在該奈米碳管薄膜結構表面塗覆一層導電膠而不需要上述的集電體。 The first current collector 103 and the second current collector 104 in the ultracapacitor 10 are both an optional structure, because the carbon nanotube film structure has good electrical conductivity and a certain self-supporting property and stability. In practical applications, a layer of conductive paste can be directly coated on the surface of the carbon nanotube film structure without the above-mentioned current collector.
可以理解，該超級電容器的結構類型不限，還可以係硬幣型或者捲繞型。 It can be understood that the structure type of the supercapacitor is not limited, and it is also possible to be a coin type or a winding type.
請參閱圖2，本技術方案實施例提供一種製備上述超級電容器10的方法，具體包括以下步驟： Referring to FIG. 2, an embodiment of the present technical solution provides a method for preparing the above supercapacitor 10, which specifically includes the following steps:
步驟一：提供一第一集電體103和一第二集電體104。 Step 1: A first current collector 103 and a second current collector 104 are provided.
本技術方案實施例的集電體優選為一銅片，該銅片的面積與奈米碳管陣列面積基本相同。 The current collector of the embodiment of the present technical solution is preferably a copper sheet having an area substantially the same as that of the carbon nanotube array.
步驟二：製備至少一奈米碳管薄膜。 Step 2: Prepare at least one carbon nanotube film.
該奈米碳管薄膜的製備方法包括以下步驟： The preparation method of the carbon nanotube film comprises the following steps:
(1)提供一奈米碳管陣列形成於一基底，優選地，該陣列為超順排奈米碳管陣列。 (1) Providing a carbon nanotube array formed on a substrate, preferably the array is a super-sequential carbon nanotube array.
本實施例中，超順排奈米碳管陣列的製備方法採用化學氣相沈積法，其具體步驟包括：(a)提供一平整基底，該基底可選用P型 或N型矽基底，或選用形成有氧化層的矽基底，本實施例優選為採用4英寸的矽基底；(b)在基底表面均勻形成一催化劑層，該催化劑層材料可選用鐵(Fe)、鈷(Co)、鎳(Ni)或其任意組合的合金之一；(c)將上述形成有催化劑層的基底在700℃~900℃的空氣中退火約30分鐘~90分鐘；(d)將處理過的基底置於反應爐中，在保護氣體環境下加熱到500℃~740℃，然後通入碳源氣體反應約5分鐘~30分鐘，生長得到超順排奈米碳管陣列，其高度為50微米~5毫米。該超順排奈米碳管陣列為至少兩個彼此平行且垂直於基底生長的奈米碳管形成的純奈米碳管陣列。通過上述控制生長條件，該超順排奈米碳管陣列中基本不含有雜質，如無定型碳或殘留的催化劑金屬顆粒等。該奈米碳管陣列中的奈米碳管彼此通過凡德瓦爾力緊密接觸形成陣列。該奈米碳管陣列的面積與上述基底面積基本相同。 In this embodiment, the method for preparing the super-sequential carbon nanotube array adopts a chemical vapor deposition method, and the specific steps thereof include: (a) providing a flat substrate, the substrate may be selected from a P-type Or an N-type ruthenium substrate, or a ruthenium substrate formed with an oxide layer, in this embodiment, a 4-inch ruthenium substrate is preferably used; (b) a catalyst layer is uniformly formed on the surface of the substrate, and the catalyst layer material may be iron (Fe). One of alloys of cobalt (Co), nickel (Ni) or any combination thereof; (c) annealing the substrate on which the catalyst layer is formed in air at 700 ° C to 900 ° C for about 30 minutes to 90 minutes; (d) The treated substrate is placed in a reaction furnace, heated to 500 ° C to 740 ° C in a protective gas atmosphere, and then reacted with a carbon source gas for about 5 minutes to 30 minutes to grow a super-aligned carbon nanotube array. The height is 50 microns to 5 mm. The super-sequential carbon nanotube array is an array of pure carbon nanotubes formed by at least two carbon nanotubes that are parallel to each other and perpendicular to the substrate. The super-sequential carbon nanotube array contains substantially no impurities such as amorphous carbon or residual catalyst metal particles, etc., by controlling the growth conditions described above. The carbon nanotubes in the array of carbon nanotubes are in close contact with each other to form an array by van der Waals force. The area of the carbon nanotube array is substantially the same as the area of the substrate described above.
上述碳源氣可選用乙炔、乙烯、甲烷等化學性質較活潑的碳氫化合物，本實施例優選的碳源氣為乙炔；保護氣體為氮氣或惰性氣體，本實施例優選的保護氣體為氬氣。 The above carbon source gas may be selected from acetylene, ethylene, methane and other chemically active hydrocarbons. The preferred carbon source gas in this embodiment is acetylene; the shielding gas is nitrogen or an inert gas, and the preferred shielding gas in this embodiment is argon. .
可以理解，本實施例提供的奈米碳管陣列不限於上述製備方法，也可為石墨電極恒流電弧放電沈積法、鐳射蒸發沈積法等。 It can be understood that the carbon nanotube array provided in this embodiment is not limited to the above preparation method, and may be a graphite electrode constant current arc discharge deposition method, a laser evaporation deposition method or the like.
(2)採用一拉伸工具拉取上述奈米碳管陣列從而獲得一奈米碳管薄膜。 (2) Pulling the above-mentioned carbon nanotube array with a stretching tool to obtain a carbon nanotube film.
本實施例中，採用一拉伸工具拉取上述奈米碳管陣列從而獲得一奈米碳管薄膜的方法包括以下步驟：(a)從上述奈米碳管陣列中選定一定寬度的多個奈米碳管束片斷；(b)以一定速度沿基本垂直於奈米碳管陣列生長方向拉伸該多個奈米碳管束片斷，獲 得一連續的奈米碳管薄膜，該奈米碳管薄膜中奈米碳管的排列方向平行於奈米碳管薄膜的拉伸方向。 In this embodiment, the method for drawing the carbon nanotube array by using a stretching tool to obtain a carbon nanotube film comprises the steps of: (a) selecting a plurality of nades of a certain width from the array of carbon nanotubes; a carbon nanotube bundle segment; (b) stretching the plurality of carbon nanotube bundle segments at a constant speed along a growth direction substantially perpendicular to the carbon nanotube array growth direction A continuous carbon nanotube film is obtained, and the arrangement of the carbon nanotubes in the carbon nanotube film is parallel to the stretching direction of the carbon nanotube film.
在上述拉伸過程中，該多個奈米碳管束片斷在拉力作用下沿拉伸方向逐漸脫離基底的同時，由於凡德瓦爾力作用，該選定的多個奈米碳管束片斷分別與其他奈米碳管束片斷首尾相連地連續地被拉出，從而形成一奈米碳管薄膜。該奈米碳管薄膜為定向排列的多個奈米碳管束首尾相連形成的具有一定寬度的奈米碳管薄膜。 During the above stretching process, the plurality of carbon nanotube bundle segments are gradually separated from the substrate in the stretching direction under the action of the tensile force, and the selected plurality of carbon nanotube bundle segments are respectively associated with the other naphthalenes due to the van der Waals force. The carbon nanotube bundle segments are continuously pulled out end to end to form a carbon nanotube film. The carbon nanotube film is a carbon nanotube film having a certain width formed by connecting a plurality of aligned carbon nanotube bundles end to end.
步驟二中直接拉伸獲得的定向排列的奈米碳管薄膜具有較好的均勻性，即具有均勻的厚度及均勻的導電性能。同時該直接拉伸獲得奈米碳管薄膜的方法簡單快速，適宜進行工業化應用。 The aligned carbon nanotube film obtained by direct stretching in the second step has better uniformity, that is, has uniform thickness and uniform electrical conductivity. At the same time, the direct stretching method for obtaining the carbon nanotube film is simple and rapid, and is suitable for industrial application.
步驟三：將至少一奈米碳管薄膜鋪設在所述第一集電體103和第二集電體104的表面分別形成一奈米碳管薄膜結構。 Step 3: laying at least one carbon nanotube film on the surfaces of the first current collector 103 and the second current collector 104 to form a carbon nanotube film structure.
所述將至少一奈米碳管薄膜分別鋪設在第一集電體103和第二集電體104的表面分別形成一奈米碳管薄膜結構的方法包括以下步驟：提供一基板；將至少一個奈米碳管薄膜鋪設於基板表面，去除基板外多餘的奈米碳管薄膜；移除基板，形成一自支撐的奈米碳管薄膜結構；將該奈米碳管薄膜結構鋪設在所述集電體的表面。由於本實施例提供的超順排奈米碳管陣列中的奈米碳管非常純淨，且由於奈米碳管本身的比表面積非常大，故該奈米碳管薄膜本身具有較強的粘性，該奈米碳管薄膜可利用其本身的粘性直接粘附於基板。 The method for respectively forming at least one carbon nanotube film on the surfaces of the first current collector 103 and the second current collector 104 to form a carbon nanotube film structure respectively comprises the steps of: providing a substrate; at least one The carbon nanotube film is laid on the surface of the substrate to remove excess carbon nanotube film outside the substrate; the substrate is removed to form a self-supporting carbon nanotube film structure; and the carbon nanotube film structure is laid in the set The surface of the electric body. Since the carbon nanotubes in the super-sequential carbon nanotube array provided by the embodiment are very pure, and since the specific surface area of the carbon nanotube itself is very large, the carbon nanotube film itself has strong viscosity. The carbon nanotube film can be directly adhered to the substrate by its own viscosity.
上述基板也可選用一框架結構，上述奈米碳管薄膜可利用其本身的粘性直接粘附於固定框架結構，使奈米碳管薄膜的四周通過固 定框架結構固定，該奈米碳管薄膜的中間部分懸空；奈米碳管薄膜黏附在框架結構表面，框架結構外多餘的奈米碳管薄膜部分可以用小刀刮去；移除框架結構，得到一自支撐的奈米碳管薄膜結構；將該奈米碳管薄膜結構鋪設在所述集電體的表面。 The substrate may also be selected from a frame structure, and the carbon nanotube film may be directly adhered to the fixed frame structure by its own viscosity, so that the periphery of the carbon nanotube film is solidified. The fixed frame structure is fixed, and the middle portion of the carbon nanotube film is suspended; the carbon nanotube film adheres to the surface of the frame structure, and the excess portion of the carbon nanotube film outside the frame structure can be scraped off with a small knife; a self-supporting carbon nanotube film structure; the carbon nanotube film structure is laid on the surface of the current collector.
本實施例中，上述基板或框架結構的大小可依據實際需求確定。當基板或框架結構的寬度大於上述奈米碳管薄膜的寬度時，可以將至少兩個奈米碳管薄膜平行且無間隙或/和重疊鋪設於基板或框架結構上，形成一奈米碳管薄膜結構。所述至少兩個重疊設置的奈米碳管薄膜中的奈米碳管之間具有多個微孔結構，該微孔結構均勻且規則分佈於奈米碳管薄膜結構中，其中微孔直徑為1奈米~0.5微米。 In this embodiment, the size of the above substrate or frame structure can be determined according to actual needs. When the width of the substrate or the frame structure is larger than the width of the carbon nanotube film, at least two carbon nanotube films may be laid on the substrate or the frame structure in parallel without gaps or/and overlapping to form a carbon nanotube. Film structure. The carbon nanotubes in the at least two overlapping carbon nanotube films have a plurality of microporous structures between them, and the micropores are uniformly and regularly distributed in the carbon nanotube film structure, wherein the micropore diameter is 1 nm ~ 0.5 microns.
可以理解，還可以將至少一個奈米碳管薄膜直接鋪設在所述集電體的表面。或者將至少兩個奈米碳管薄膜平行且無間隙或/和重疊鋪設在所述集電體的表面。所述至少兩個重疊設置的奈米碳管薄膜中的奈米碳管之間具有多個微孔結構，該微孔結構均勻且規則分佈於奈米碳管薄膜結構中，其中微孔直徑為1奈米~0.5微米。所述的奈米碳管薄膜結構具有很好的粘性，故上述奈米碳管薄膜結構可以利用自身的粘性比較牢固地固定於所述集電體的表面。進一步，還可以通過一導電粘結劑將上述奈米碳管薄膜結構固定於所述集電體的表面。 It will be appreciated that at least one carbon nanotube film may also be laid directly on the surface of the current collector. Alternatively, at least two carbon nanotube films are laid parallel and without gaps or/and overlaps on the surface of the current collector. The carbon nanotubes in the at least two overlapping carbon nanotube films have a plurality of microporous structures between them, and the micropores are uniformly and regularly distributed in the carbon nanotube film structure, wherein the micropore diameter is 1 nm ~ 0.5 microns. The carbon nanotube film structure has good viscosity, so that the above-mentioned carbon nanotube film structure can be relatively firmly fixed to the surface of the current collector by its own viscosity. Further, the above-mentioned carbon nanotube film structure may be fixed to the surface of the current collector by a conductive adhesive.
另外，上述奈米碳管薄膜結構可直接使用，或者也可使用有機溶劑處理後再使用。使用有機溶劑處理所述奈米碳管薄膜結構的過程包括：通過試管將有機溶劑滴落在奈米碳管薄膜結構表面浸潤整個奈米碳管薄膜結構，或者將整個奈米碳管薄膜結構浸入盛有 有機溶劑的容器中浸潤。該有機溶劑為揮發性有機溶劑，如乙醇、甲醇、丙酮、二氯乙烷或氯仿，本技術方案實施例中採用乙醇。所述的奈米碳管薄膜結構經有機溶劑浸潤處理後，在揮發性有機溶劑的表面張力的作用下，奈米碳管薄膜中平行的奈米碳管片斷會部分聚集成奈米碳管束。因此，該奈米碳管薄膜結構表面體積比小，無粘性，且具有良好的機械強度及韌性。 Further, the above-mentioned carbon nanotube film structure may be used as it is, or may be used after being treated with an organic solvent. The process of treating the carbon nanotube film structure with an organic solvent comprises: dipping the organic solvent onto the surface of the carbon nanotube film structure through a test tube to infiltrate the entire carbon nanotube film structure, or immersing the entire carbon nanotube film structure Surprise The organic solvent is infiltrated in a container. The organic solvent is a volatile organic solvent such as ethanol, methanol, acetone, dichloroethane or chloroform, and ethanol is used in the embodiment of the present invention. After the nanocarbon tube film structure is infiltrated by an organic solvent, the parallel carbon nanotube fragments in the carbon nanotube film partially aggregate into the carbon nanotube bundle under the surface tension of the volatile organic solvent. Therefore, the carbon nanotube film structure has a small surface volume ratio, is non-tacky, and has good mechanical strength and toughness.
步驟四：提供一隔膜105，將上述兩個分別覆蓋有奈米碳管薄膜結構的第一集電體103和第二集電體104間隔地設置在該隔膜105的兩側，並裝入一外殼107中。 Step 4: providing a separator 105, and disposing the two first current collectors 103 and the second current collector 104 respectively covered with the carbon nanotube film structure on both sides of the diaphragm 105, and inserting a In the outer casing 107.
將上述兩個分別覆蓋有奈米碳管薄膜結構的第一集電體103和第二集電體104間隔設置，並將所述隔膜105設置在所述兩個分別覆蓋有奈米碳管薄膜結構的第一集電體103和第二集電體104之間。本技術方案實施例採用無紡布作為隔膜105。 Disposing the two first current collectors 103 and the second current collectors 104 respectively covered with the carbon nanotube film structure, and placing the separators 105 on the two carbon nanotube films respectively covered Between the first current collector 103 and the second current collector 104 of the structure. The embodiment of the technical solution uses a nonwoven fabric as the separator 105.
所述超級電容器電極10中的第一集電體103和第二集電體104為一可選擇的結構，因為奈米碳管薄膜具有良好的導電性能和一定的自支撐性及穩定性，實際應用時，可直接在該奈米碳管薄膜結構表面塗覆一層導電膠而不需要上述的第一集電體103和第二集電體104。 The first current collector 103 and the second current collector 104 in the supercapacitor electrode 10 are an optional structure because the carbon nanotube film has good electrical conductivity and a certain self-supporting property and stability. When applied, a layer of conductive paste may be directly coated on the surface of the carbon nanotube film structure without the first current collector 103 and the second current collector 104 described above.
步驟五：提供一電解液溶液106，將該電解液溶液106注入進上述外殼107中，封裝制得一超級電容器10。 Step 5: An electrolyte solution 106 is provided, and the electrolyte solution 106 is injected into the outer casing 107 to form a supercapacitor 10.
該電解液溶液106注入進該外殼107中，上述兩個分別覆蓋有奈米碳管薄膜結構的第一集電體103和第二集電體104及隔膜105均設置在該電解液溶液106中。整個超級電容器10的封裝過程都在充 滿惰性氬氣的手套乾燥箱中進行。 The electrolyte solution 106 is injected into the outer casing 107, and the two first current collectors 103 and the second current collectors 104 and 105 each covered with a carbon nanotube film structure are disposed in the electrolyte solution 106. . The packaging process of the entire supercapacitor 10 is in charge It is carried out in a glove drying oven filled with inert argon.
請參閱圖4，該圖係本技術方案實施例的超級電容器在電流為3毫安培時的充放電循環曲線圖。從圖中可以看出，該充放電曲線具有明顯的近似三角形對稱分佈，在恒流充放電的條件下，電壓隨時間變化具有明顯的線性關係。這表明該超級電容器電極反應的可逆性很好。經恒流放電測試得出該電流強度下該超級電容器的比電容量大於100法/克。 Please refer to FIG. 4 , which is a graph of charge and discharge cycle of the supercapacitor of the embodiment of the present invention at a current of 3 milliamperes. It can be seen from the figure that the charge-discharge curve has a distinct approximation of the triangular symmetry. Under the condition of constant current charge and discharge, the voltage has a significant linear relationship with time. This indicates that the reluctance of the supercapacitor electrode reaction is very good. The constant current discharge test shows that the specific capacitance of the supercapacitor is greater than 100 law / gram at the current intensity.
該超級電容器10採用了上述的奈米碳管薄膜結構作為電極。該奈米碳管薄膜結構中奈米碳管分佈均勻，相鄰的奈米碳管之間具有多個微孔結構，其中微孔直徑為1奈米~0.5微米。所述奈米碳管薄膜結構在作為超級電容器的電極時，具有很高的比表面積利用率，且製備方法簡單，易於實際的應用。 The supercapacitor 10 employs the above-described carbon nanotube film structure as an electrode. In the carbon nanotube film structure, the carbon nanotubes are uniformly distributed, and the adjacent carbon nanotubes have a plurality of microporous structures, wherein the micropores have a diameter of 1 nm to 0.5 μm. The carbon nanotube film structure has high specific surface area utilization when used as an electrode of a supercapacitor, and has a simple preparation method and is easy to be practically applied.
綜上所述，本發明確已符合發明專利之要件，遂依法提出專利申請。惟，以上所述者僅為本發明之較佳實施例，自不能以此限制本案之申請專利範圍。舉凡熟悉本案技藝之人士援依本發明之精神所作之等效修飾或變化，皆應涵蓋於以下申請專利範圍內。 In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by persons skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims.
10‧‧‧超級電容器 10‧‧‧Supercapacitors
101‧‧‧第一電極 101‧‧‧First electrode
102‧‧‧第二電極 102‧‧‧second electrode
103‧‧‧第一集電體 103‧‧‧First current collector
104‧‧‧第二集電體 104‧‧‧Second current collector
105‧‧‧隔膜 105‧‧‧Separator
106‧‧‧電解液 106‧‧‧ electrolyte
107‧‧‧外殼 107‧‧‧Shell
Claims (12)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW096151263A TWI464762B (en) | 2007-12-31 | 2007-12-31 | Super capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW096151263A TWI464762B (en) | 2007-12-31 | 2007-12-31 | Super capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW200929292A TW200929292A (en) | 2009-07-01 |
| TWI464762B true TWI464762B (en) | 2014-12-11 |
Family
ID=44864438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW096151263A TWI464762B (en) | 2007-12-31 | 2007-12-31 | Super capacitor |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI464762B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2671236B1 (en) * | 2011-02-04 | 2019-11-06 | Vishay Sprague, Inc. | Hermetically sealed electrolytic capacitor |
| CN103187586B (en) | 2011-12-28 | 2016-01-20 | 清华大学 | Lithium ion battery |
| CN103187575B (en) | 2011-12-28 | 2015-11-25 | 清华大学 | The preparation method of film lithium ion battery |
| CN103187573B (en) | 2011-12-28 | 2016-01-20 | 清华大学 | Lithium ion cell electrode |
| CN103187572B (en) | 2011-12-28 | 2016-01-20 | 清华大学 | Film lithium ion battery |
| CN103187574B (en) | 2011-12-28 | 2015-07-29 | 清华大学 | The preparation method of lithium ion cell electrode |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317809A (en) * | 2000-04-12 | 2001-10-17 | 李永熙 | Super-grade capacitor for electrode of using new material and its mfg. method |
| JP2007145634A (en) * | 2005-11-25 | 2007-06-14 | National Institute Of Advanced Industrial & Technology | Double-walled carbon nanotube, bulk structure of the same, method and apparatus for producing them, and applications of the nanotube and bulk structure |
| CN1982209A (en) * | 2005-12-16 | 2007-06-20 | 清华大学 | Carbon nano-tube filament and its production |
-
2007
- 2007-12-31 TW TW096151263A patent/TWI464762B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317809A (en) * | 2000-04-12 | 2001-10-17 | 李永熙 | Super-grade capacitor for electrode of using new material and its mfg. method |
| JP2007145634A (en) * | 2005-11-25 | 2007-06-14 | National Institute Of Advanced Industrial & Technology | Double-walled carbon nanotube, bulk structure of the same, method and apparatus for producing them, and applications of the nanotube and bulk structure |
| CN1982209A (en) * | 2005-12-16 | 2007-06-20 | 清华大学 | Carbon nano-tube filament and its production |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200929292A (en) | 2009-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Salvatierra et al. | Graphene carbon nanotube carpets grown using binary catalysts for high-performance lithium-ion capacitors | |
| Zhang et al. | 3D superelastic graphene aerogel-nanosheet hybrid hierarchical nanostructures as high-performance supercapacitor electrodes | |
| Notarianni et al. | Synthesis and applications of carbon nanomaterials for energy generation and storage | |
| CN101471184B (en) | Super capacitor | |
| CN101425380B (en) | Super capacitor and preparing method therefor | |
| CN101425381B (en) | Super capacitor and preparing method therefor | |
| Zeiger et al. | Carbon onions for electrochemical energy storage | |
| Cao et al. | Three-dimensional graphene materials: preparation, structures and application in supercapacitors | |
| Mao et al. | A review of electrospun carbon fibers as electrode materials for energy storage | |
| Niu et al. | A “skeleton/skin” strategy for preparing ultrathin free-standing single-walled carbon nanotube/polyaniline films for high performance supercapacitor electrodes | |
| Chen et al. | Carbon nanomaterials for high-performance supercapacitors | |
| Zhu et al. | CoO nanoflowers woven by CNT network for high energy density flexible micro-supercapacitor | |
| Liu et al. | Lithiation-induced embrittlement of multiwalled carbon nanotubes | |
| Raffaelle et al. | Carbon nanotubes for power applications | |
| Zhang et al. | Flexible three-dimensional carbon cloth/carbon fibers/NiCo2O4 composite electrode materials for high-performance all-solid-state electrochemical capacitors | |
| Dang et al. | Long-life electrochemical supercapacitor based on a novel hierarchically carbon foam templated carbon nanotube electrode | |
| TWI464762B (en) | Super capacitor | |
| KR20130018744A (en) | Spiral wound electrical devices containing carbon nanotube-infused electrode materials and methods and apparatuses for production thereof | |
| JP5253943B2 (en) | Conductive material and method for producing the same | |
| US20140166496A1 (en) | Method for producing shaped graphene sheets | |
| He et al. | A large area, flexible polyaniline/buckypaper composite with a core–shell structure for efficient supercapacitors | |
| JP6556923B2 (en) | Battery electrode manufacturing method | |
| US20080225464A1 (en) | Supercapacitors and Methods of Manufacturing Same | |
| Du et al. | One-step detonation-assisted synthesis of Fe 3 O 4-Fe@ BCNT composite towards high performance lithium-ion batteries | |
| TWI387987B (en) | Super capacitor and method for making the same |