201133524 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種超級電容器，尤其涉及一種基於奈米碳 管之超級電容器。 [先前技術] [0002] 超級電容器（supercapac i tor )屬於雙電層電容器，具 有較高的比功率和較長的循環壽命，工作溫度範圍寬等 特點；因此，於移動通訊、資訊技術、電動汽車、航空 ^ 航天和國防科技等領域都有著極其重要和廣闊的應用前 ❹ 景。 [0003] 先前之超級電容器一般包括兩個電極、隔膜和電解液， 該兩個電極和隔膜都設置於該電解液中；該兩個電極均 包括一集電體以及設置於該集電體上的電極材料。其中 *影響該超級電容益容ΐ的決定因素係電極材料。理想 之電極材料應具有結晶度高、導電性好、比表面積大、 微孔集中於一範圍内（要求微孔大於2nm)等特點。先前之 超級電容電極材料主要有.活性碳糸列和過渡金屬氧 化物系列。活性碳系列的材料導電性較差，其作為電極 會使電容器之等效串聯電阻較大；而且該活性碳系列的 比表面積實際利用率不超過30%，電解液與該活性碳系列 之電極難以充分接觸，因此，採用該活性碳系列材料作 為電極之超級電容器的容量較小。過渡金屬氧化物用作 電極材料於提高超級電容器之容量方面雖具有良好的效 果，但其成本太高，無法推廣使用。 [0004] 奈米碳管（Carbon Nanotube，CNT )係一種奈米級無 099107618 表單編號A0101 第3頁/共31頁 0992013736-0 201133524 缝管狀石墨結構的碳材料，其具有比表面積大，結晶度 高，導電性好，奈米碳管之内外徑可通過合成工藝加以 控制的特點，而且其比表面利用率可達到1 0 0%，因而可 以成為一種理想之超級電容器材料。奈米碳管用作超級 電容器材料之研究最早見諸於Chunming Niu等的報導（ 請參見High power electrochemical capacitors based on carbon nanotube electrodes, Apply Physics Letter, Chunming Niu et a 1. , vol 70, pl480-1482(1 997))。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。由於該薄膜 電極係採用奈米碳管粉末作為原料製備的，而奈米碳管 粉末極易發生團聚，這使得該薄膜電極不能充分發揮奈 米碳管之性能，影響了電容器之性能，限制了電容器容 量的提高。 [0005] 為此，南京大學之張劍榮等人於2005年3月16日公開的， 公開號為CN 159421 2A的中國大陸發明專利申請公開說 明書中提供了 一種超級電容器電極材料無定形二氧化錳/ 多壁奈米碳管複合物。該無定形二氧化錳/多壁奈米碳管 複合物中之奈米碳管之直徑係20至40奈米，長度係200奈 米至5微米，無定形二氧化錳負載於奈米碳管表面。該二 氧化錳/多壁奈米碳管複合物作為超級電容器之電極，雖 然可以使得超級電容器之比電容得到提高，但由於該二 氧化錳/多壁奈米碳管複合結構為粉末狀，其用作電極時 需要金屬集電體。然而，所述之金屬集電體之質量一般 比較重，因此使得所述超級電容器之質量比較重，從而 099107618 表單編號A0101 第4頁/共31頁 0992013736-0 201133524 [0006] [0007] ❹ [0008]201133524 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a supercapacitor, and more particularly to a supercapacitor based on a carbon nanotube. [Prior Art] [0002] Supercapacitor (supercapac i tor) is an electric double layer capacitor with high specific power, long cycle life, wide operating temperature range, etc.; therefore, in mobile communication, information technology, electric Automotive, aerospace, aerospace and defense technologies all have extremely important and broad application prospects. [0003] The prior supercapacitor generally comprises two electrodes, a diaphragm and an electrolyte, both of which are disposed in the electrolyte; the two electrodes each comprise a current collector and are disposed on the current collector Electrode material. Among them * the determinant of the influence of the supercapacitor is the electrode material. The ideal electrode material should have the characteristics of high crystallinity, good electrical conductivity, large specific surface area, and micropores concentrated in a range (requiring micropores greater than 2 nm). Previous supercapacitor electrode materials mainly include active carbon enthalpy and transition metal oxide series. The material of the activated carbon series has poor conductivity, and the equivalent series resistance of the capacitor is large as an electrode; and the actual utilization ratio of the specific surface area of the activated carbon series is not more than 30%, and the electrolyte and the electrode of the activated carbon series are difficult to be sufficient. Contact, therefore, the capacity of the supercapacitor using the activated carbon series material as an electrode is small. The use of transition metal oxides as electrode materials has a good effect in increasing the capacity of supercapacitors, but its cost is too high to be promoted. [0004] Carbon Nanotube (CNT) is a nanometer without 099107618 Form No. A0101 Page 3 / Total 31 Pages 0992013736-0 201133524 Carbon material with a tubular graphite structure, which has a large specific surface area and crystallinity High, good conductivity, the inner and outer diameters of the carbon nanotubes can be controlled by the synthesis process, and its specific surface utilization can reach 100%, so it can be an ideal supercapacitor material. The research on the use of carbon nanotubes as a supercapacitor material was first reported in Chunming Niu et al. (See High power electrochemical capacitors based on carbon nanotube electrodes, Apply Physics Letter, Chunming Niu et a 1. , vol 70, pl480-1482 ( 1 997)). They made a pure multi-walled carbon nanotube powder into a thin film electrode and packaged it to make a supercapacitor. Since the film electrode is prepared by using carbon nanotube powder as a raw material, and the carbon nanotube powder is highly prone to agglomeration, the film electrode cannot fully exert the performance of the carbon nanotube, affecting the performance of the capacitor, and limiting Increase in capacitor capacity. [0005] For this purpose, a supercapacitor electrode material amorphous manganese dioxide is provided in the Chinese Mainland Patent Application Publication No. WO 159421 2A, published on March 16, 2005, by the same. Multi-walled carbon nanotube composite. The carbon nanotubes in the amorphous manganese dioxide/multi-walled carbon nanotube composite have a diameter of 20 to 40 nm, a length of 200 nm to 5 μm, and an amorphous manganese dioxide supported on the carbon nanotube. surface. The manganese dioxide/multi-walled carbon nanotube composite as an electrode of a supercapacitor can improve the specific capacitance of the supercapacitor, but since the composite structure of the manganese dioxide/multi-walled carbon nanotube is powdery, A metal current collector is required for use as an electrode. However, the quality of the metal current collector is generally relatively heavy, thus making the quality of the supercapacitor relatively heavy, thus 099107618 Form No. A0101 Page 4 / Total 31 Page 0992013736-0 201133524 [0006] [0007] ❹ [ 0008]
[0009] [0010] 使得所述超級電容器之總能量密度及總功率密度降低。 【發明内容】 有鑒於此，確有必要提供一種具有較高的總能量密度及 總功率密度的超級電容器。 一種超級電容器，其包括：一第一電極；一第二電極， 該第二電極與所述第一電極間隔設置；一隔膜，該隔膜 設置於所述第一電極與第二電極之間；以及一電解液， 所述第一電極、第二電極及隔膜均設置於該電解液中， 其中，所述第一電極為一奈米碳管複合結構，該奈米碳 管複合結構為一自支撐結構，且包括一奈米碳管結構及 設置於該奈米碳管結構表面的奈米級顆粒。 與先前技術相比較，本發明提供的超級電容器中之第一 電極為奈米碳管複合結構，該奈米碳管複合結構具有自 支撐之特點，可以直接作為超級電容器之電極，不需要 金屬集電體，因此，使得超級電容器具有較大的總能量 密度及總功率密度。 【實施方式】 下面將結合附圖及具體實施例，對本發明提供的超級電 容器作進一步的詳細說明。 請參閱圖1，本發明第一實施例提供一種超級電容器10， 該超級電容器為平板型結構，包括：一第一電極101，一 第二電極102，一隔膜105，一電解液106和一外殼107。 所述電解液106設置於所述外殼107内。所述第一電極 101、第二電極102以及所述隔膜105均設置於所述電解 099107618 表單編號A0101 第5頁/共31頁 0992013736-0 201133524 。戶斤述隔膜设置於所述第一電極ιοί和第一 液106内r 。子間，並分別與所述第一電極1 〇 1和第二電極 電極1〇2& 102間睬設置。 [0011] 禮極101為一奈米碳管複合結構，該奈米碳管複 ^ ·\ \^ hS ^2* 所迷弟 合結構A 置於該条 奈米破f 述奈米，级 米碳管複 述奈米媒· 成的，该 廣狀或膜狀結構，其包括一奈米碳管結構及設 米破管結構表面的奈米級顆粒。具體地，所述 鱗構係由若干奈米碳管組成的自支樓結構，所 賴粒設置於所述若干奈米碳管之表面。所述奈 合，结構包括複數個微孔，該複數個微孔係由所 管結構中之若干奈米碳管之間存在的間隙而形 微孔的尺寸不大於10微米，該複數個微孔佔所[0010] [0010] The total energy density and total power density of the supercapacitor are reduced. SUMMARY OF THE INVENTION In view of the above, it is indeed necessary to provide a supercapacitor having a high total energy density and a total power density. A supercapacitor comprising: a first electrode; a second electrode, the second electrode being spaced apart from the first electrode; a diaphragm disposed between the first electrode and the second electrode; An electrolyte, the first electrode, the second electrode and the separator are all disposed in the electrolyte, wherein the first electrode is a carbon nanotube composite structure, and the carbon nanotube composite structure is a self-supporting The structure comprises a carbon nanotube structure and nano-sized particles disposed on the surface of the carbon nanotube structure. Compared with the prior art, the first electrode in the supercapacitor provided by the invention is a carbon nanotube composite structure, and the carbon nanotube composite structure has the characteristics of self-supporting, and can be directly used as an electrode of a supercapacitor, and does not require a metal set. The electric body thus makes the supercapacitor have a larger total energy density and a total power density. [Embodiment] The super capacitor provided by the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. Referring to FIG. 1 , a first embodiment of the present invention provides a supercapacitor 10 having a flat structure including a first electrode 101 , a second electrode 102 , a diaphragm 105 , an electrolyte 106 , and an outer casing . 107. The electrolyte 106 is disposed within the outer casing 107. The first electrode 101, the second electrode 102, and the diaphragm 105 are all disposed on the electrolysis 099107618 Form No. A0101 Page 5 of 31 0992013736-0 201133524. The diaphragm is disposed in the first electrode ιοί and the first liquid 106. Between the sub-electrodes, and between the first electrode 1 〇 1 and the second electrode electrode 1〇2 & 102, respectively. [0011] ritual pole 101 is a carbon nanotube composite structure, the carbon nanotube complex ^ · \ \^ hS ^ 2 * the fascinating structure A is placed in the section of the nano-fractured nanometer, grade meters The carbon tube repeats the nano-media, the broad or membranous structure, which comprises a carbon nanotube structure and nano-scale particles on the surface of the rice-breaking structure. Specifically, the squama structure is a self-supporting structure composed of a plurality of carbon nanotubes, and the granules are disposed on the surface of the plurality of carbon nanotubes. The structure includes a plurality of micropores, and the plurality of micropores are formed by a gap existing between a plurality of carbon nanotubes in the tube structure, and the size of the micropores is no more than 10 micrometers, and the plurality of micropores occupy Place
述奈來碳管妨構的大部分體積°所述複數個微孔的存在 使得所述条米碳管複合結構的比表面積比較大’可以促 進該超级電容器10的快速充放電，進而提高該超級電容 器10的比電容量。 [0012] [0013] 099107618The majority of the volume of the carbon nanotubes is discussed. The presence of the plurality of micropores makes the specific surface area of the carbon nanotube composite structure relatively large, which can promote rapid charging and discharging of the supercapacitor 10, thereby improving the super The specific capacitance of the capacitor 10. [0013] 099107618
所述奈米破管結構係自支撐結構，即為奈米碳管結構不 需要大面積的載體支揮，而只要:;相對兩邊提供支樓力即 能整體上懸空而保持自身狀態’也就是說，將該奈米碳 管結構置於（或固定於）間隔設置的兩個支撐體上時， 位於兩個支撐體之間的奈米碳管結構能夠懸空保持自身 狀態。所述自支推主要通過奈米碳管結構中存在連續的 通過范德瓦爾力首尾相連延伸排列的奈米碳管而實現。 所述奈米碳管結構為一層狀或膜狀結構，其包括至少一 奈米碳管膜，至少一奈米碳管線狀結構或其組合。當所 述奈米碳管結構包括複數個奈米碳管膜時，該奈米碳管 表單編號A0101 第6頁/共31頁 0992013736-0 201133524 Ο [0014] 膜可以基本平行無間隙共面設置或層疊設置。當所述奈 米碳管結構僅包括一奈米碳管線狀結構時，該奈米碳管 線狀結構可以折疊或纏繞成一層狀奈米碳管結構。當所 述奈米碳管結構包括複數個奈米碳管線狀結構時，該複 數個奈米碳管線狀結構可以平行設置、交叉設置或編織 成一層狀奈米碳管結構。當所述奈米碳管結構包括奈米 碳管膜及奈米碳管線狀結構時，可以將奈米碳管線狀結 構β又置於奈米碳管膜的至少一個表面。由於該奈米礙管 結構中之奈米碳管具有很好的柔韌性，使得該奈米碳管 結構具有报好的柔韌性’可以彆曲折疊成任意形狀而不 易破裂。 所述奈米碳管膜由若干奈米碳管組成；，該奈米碳管膜中 大多數奈米碳管之延伸方向基本平行於該奈米碳管膜的 表面。所述奈米碳管膜中之奈米碳管無序排列或有序排 列。所謂無序排列係指奈米碳管之排列方向無規則。所 謂有序排列係指奈米碳管之排列方向有規則。具體地， ο 當奈米碳管結構包括無序排列的奈米碳管時，奈米碳管 相互纏繞或者各向同性排列；當奈米碳管結構包括有序 排列的奈米碳管時，奈米碳管沿一個方向或者複數個方 向擇優取向排列。所謂“擇優取向”係指所述奈米碳管 結構中之大多數奈米碳管於一個方向或幾個方向上具有 較大的取向幾率；即，該奈米碳管結構中之大多數奈米 碳管之轴向基本沿同一方向或幾個方向延伸。所述奈米 碳管膜包括奈米碳管拉膜、奈米碳管碾壓膜和奈米碳管 絮化膜。 099107618 表單編號Α0101 第7頁/共31頁 0992013736-0 201133524 [0015] 該奈米碳管結構中之奈米碳管包括單壁奈米碳管、雙壁 奈米碳管及多壁奈米碳管中之一種或多種。所述單壁奈 米碳管之直徑為〇. 5奈米至50奈米，雙壁奈米碳管之直徑 為1.0奈米至50奈米，多壁奈米碳管之直徑為1.5奈米至 50奈米。所述奈米碳管之長度大於50微米。優選地，該 奈米碳管之長度優選為200微米至900微米。 [0016] 所述奈米碳管拉膜係由若干奈米碳管組成的自支撐結構 。所述若干奈米碳管沿同一方向擇優取向排列。該奈米 碳管拉膜中大多數奈米碳管之整體延伸方向基本朝同一 方向。而且，所述大多數奈米碳管之整體延伸方向基本 平行於奈米碳管拉膜的表面。進一步地，.所述奈米碳管 拉膜中多數奈米碳管係通過范德瓦爾力首尾相連。具體 地，所述奈米碳管拉膜中基本朝同一方向延伸的大多數 奈米碳管中每一奈米碳管與於延伸方向上相鄰的奈米碳 管通過范德瓦爾力首尾相連。當然，所述奈米碳管拉膜 中存在少數隨機排列的奈米碳管，這些奈米碳管不會對 奈米碳管拉膜中大多數奈米碳管之整體取向排列構成明 顯影響。所述奈米碳管拉膜不需要大面積的載體支撐， 而只要相對兩邊提供支撐力即能整體上懸空而保持自身 膜狀狀態，即將該奈米碳管膜置於（或固定於）間隔一 定距離設置的兩個支撐體上時，位於兩個支撐體之間的 奈米碳管膜能夠懸空保持自身膜狀狀態。 [0017] 具體地，所述奈米碳管拉膜中基本朝同一方向延伸的多 數奈米碳管，並非絕對的直線狀，可以適當的彎曲；或 者並非完全按照延伸方向上排列，可以適當的偏離延伸 099107618 表單編號A0101 第8頁/共31頁 0992013736-0 201133524 [0018] Ο [0019] Ο [0020] 099107618 方向。因此’不能排除奈米碳管拉膜的基本朝同一方向 ^伸的多數奈米碳管中並列的奈米碳管之間可能存在部 分接觸。 具體地，所述奈米碳管拉膜包括複數個連續且定向排列 的’丁:米碳管片段。該複數個奈米碳管片段通過范德瓦爾 ^尾相連母一奈米碳管片段包括複數個相互平行的 奈米普，該複數個相互平行的奈米碳管通過范德瓦爾 力緊密結合。該奈米碳管片段具有任意的長度、厚度、 句勻ϋ及形狀。該奈米碳管拉膜中之奈米碳管沿同一方 向擇優取向排列。 該奈米碳管拉财之奈米碳管之間形成複數個微孔該 複數個微孔佔據該奈米碳管拉膜的大部分_，如，微 孔的體積可以達到奈米碳管拉膜體積的7〇%。所述奈米碳 管拉膜可通過從奈米碳管陣列直接拉取獲得。單層奈米 碳管拉膜的厚度可為〇·5奈米至1〇〇微米。可以理/，通 過將複數個奈米碳管賴平行且無_共_設或/和= 疊鎖設’可以製備不同面積與厚度的奈米碳管結構。當 奈米碳管結構包括複數個層疊設置的奈米碳管拉膜時Υ 相鄰的奈米碳管拉膜中之奈米碳管之排列方向形成一夾 角a，（TS«S90。。所述奈米碳管拉臈的結構及其製備 方法請參見范守善等人於2008年8月16日公開的第 200833862號中華民國公開專利申請公佈本。 所述奈米碳管碾壓膜由均勻分佈的複數個奈米碳管組成 ’該複數個奈米碳管無序、沿同一方向或不同方向擇優 取向排列，該複數個奈米碳管之轴向沿同_方向戍不门 表單編號A0101 第9頁/共31頁 0992013736-0 201133524 方向延伸。所述奈米碳管碾壓膜中之奈米碳管相互部分 交疊，並通過范德瓦爾力相互吸引，緊密結合，從而形 成一自支撐結構。另外，所述奈米碳管碾壓膜越厚，越 有利於其具有自支撐功能，如奈米碳管碾壓膜的厚度大 於1微米時，就具有良好的自支撐功能。所述奈米碳管碾 壓膜可通過碾壓一奈米碳管陣列獲得。該奈米碳管陣列 形成於一基底表面，所製備的奈米碳管碾壓膜中之奈米 碳管與該奈米碳管陣列之基底的表面成一夾角/3，其中 ，/9大於等於0度且小於等於15度（0°$/9^15°)。優選 地，所述奈米碳管碾壓膜中之奈米碳管之轴向基本平行 於該奈米碳管碾壓膜的表面。依據碾壓的方式不同，該 奈米碳管碾壓膜中之奈米碳管具有不同的排列形式。所 述奈米碳管碾壓膜的面積和厚度不限，可根據實際需要 選擇。所述奈米碳管碾壓膜的面積與奈米碳管陣列的尺 寸基本相同。所述奈米碳管碾壓膜厚度與奈米碳管陣列 的高度以及碾壓的壓力有關，可為1微米〜1毫米。所述奈 米碳管碾壓膜及其製備方法請參見范守善等人於2009年1 月1日公開的第200900348號中華民國專利申請公佈本。 [0021] 所述奈米碳管絮化膜包括相互纏繞的奈米碳管，該奈米 碳管長度可大於10釐米。所述奈米碳管之間通過范德瓦 爾力相互吸引、纏繞形成網路狀結構，以形成一自支撐 的奈米碳管絮化膜。另外，所述奈米碳管絮化膜越厚， 越有利於其具有自支撐功能，如奈米碳管絮化膜的厚度 大於1微米時，就具有良好的自支撐功能。所述奈米碳管 絮化膜各向同性。所述奈米碳管絮化膜中之奈米碳管為 099107618 表單編號A0101 第10頁/共31頁 0992013736-0 201133524 [0022] θ [0023] Ο 099107618 均勻分佈，無規則排列，形成大量的微孔結構。可以理 解，所述奈米碳管絮化膜的長度、寬度和厚度不限，可 根據實際需要選擇。所述奈米碳管絮化膜的厚度為1微米 至1毫米，優選為100微米。所述奈米碳管絮化膜及其製 備方法請參見2008年11月16日公開的第200844041號中 華民國專利申請公佈本。 所述奈米碳管線狀結構包括至少一個奈米碳管線，該奈 米碳管線可為一非扭轉之奈米碳管線或扭轉的奈米碳管 所述非扭轉之奈米碳管線由若干奈米碳管組成，該若干 奈米碳管之轴向基本沿平行於該非扭轉之奈米碳管線軸 向方向延伸。非扭轉之奈米碳管線可通過將奈米碳管拉 膜通過有機溶劑處理得到。具體地，該奈米碳管拉膜包 括複數個連續且定向排列的奈米碳管片段。該複數個奈 米碳管片段通過范德瓦爾力首尾相連。每一奈米碳管片 段包括複數個相互平行並通過范德瓦爾力緊密結合的奈 米碳管。該奈米碳管片段具有任意的長度、厚度、均勻 性及形狀。該非扭轉之奈米碳管線長度不限，直徑為0. 5 奈米至1毫米。具體地，可將有機溶劑浸潤所述奈米碳管 拉膜的整個表面，於揮發性有機溶劑揮發時產生的表面 張力之作用下，奈米碳管拉膜中之相互平行的複數個奈 米碳管通過范德瓦爾力緊密結合，從而使奈米碳管拉膜 收縮為一非扭轉之奈米碳管線。該有機溶劑為揮發性有 機溶劑，如乙醇、甲醇、丙酮、二氯乙烷或氣仿，本實 施例中採用乙醇。通過有機溶劑處理的非扭轉奈米碳管 表單編號Α0101 第11頁/共31頁 0992013736-0 201133524 線與未經有機溶劑處理的奈米碳管膜相比，比表面積減 小，黏性降低。 [0024] 所述扭轉的奈米碳管線由若干奈米碳管組成，該若干奈 米碳管之軸向繞該扭轉的奈米碳管線的軸向方向螺旋延 伸。該奈米碳管線可採用一機械力將所述奈米碳管拉膜 兩端沿相反方向扭轉獲得。進一步地，可採用一揮發性 有機溶劑處理該扭轉的奈米碳管線。於揮發性有機溶劑 揮發時產生的表面張力的作用下，處理後的扭轉的奈米 碳管線中相鄰的奈米碳管通過范德瓦爾力緊密結合，使 扭轉的奈米碳管線的比表面積減小，密度及強度增大。 [0025] 所述奈米碳管線及其製備方法請參見2008年11月21曰公 告的，公告號為1303239的中華民國專利公告本；以及於 2009年7月21日公告的，公告號為1312337的中華民國專 利公告本。 [0026] 當所述奈米碳管線狀結構包括複數個奈米碳管線時，該 複數個奈米碳管線平行設置組成一束狀結構或該複數個 奈米碳管線相互扭轉組成一絞線結構。另外，所述奈米 碳管線中相鄰奈米碳管間存在間隙，故該奈米碳管線狀 結構具有大量微孔，且微孔的孔徑約小於10微米。 [0027] 所述奈米級顆粒設置於所述若干奈米碳管之表面。具體 地，所述奈米級顆粒可以間隔地形成於每一個奈米碳管 之表面；也可以連續地設置於每一個奈米碳管之表面以 形成一層，並包覆於奈米碳管之表面。所述奈米級顆粒 能夠促進所述超級電容器10的快速充放電，進而提高該 099107618 表單編號A0101 第12頁/共31頁 0992013736-0 201133524 Ο 超級電谷|§ 10的電容。所述奈米級顆粒不與所述電解液 106發生化學反應；優選地，該奈米級顆粒為奈米級金屬 氧化物顆粒、奈米級金屬顆极或兩者之組合物。所述奈 米級金屬氧化物顆粒為二氧化猛顆粒（Μη。。、四氧化三 钻顆粒（C〇3〇4)、一氧化鎳顆粒（Ni〇)、氧化釕顆粒 (Ru〇2)及氧化銥顆粒（Ir〇2)中之一種或幾種。所述奈米 級金屬顆粒為銅顆粒、鎳顆粒、金顆粒、銀顆粒、鈀顆 粒、釘顆粒、始及铑顆粒中之一種或幾種。所述奈米級 顆粒的大小範圍為1奈米_1〇〇奈米；優選地，所述奈米級 顆粒的範圍為1奈米-50奈米。所述奈米級顆粒於所述奈 米碳管複合結構中之質量百分含量大於〇且小於1〇〇%，優 選地’所述奈米級金屬顆粒於所述奈米碳管複合結構中 之質量百分含量大於5〇%且小於70%。 [0028] Ο 請參閱圖2至圖4，本實施例中，所述第一電極1〇1為奈米 碳管複合結構110 ^所述奈米碳管複合結構110由二十層 層疊設置的奈米碳管拉膜組成的一奈米碳管結構及設 置於該奈米碳管結構表面的奈米級金屬氡化物顆粒丨14組 成。每一層奈米碳管拉膜112由若干奈米碳管Η 22組成， 且相鄰的奈米碳管拉膜中之奈米碳管1122的軸向之間的 夾角為90。。該二十層層疊設置的奈米碳管拉膜112的厚 度大約為500奈米，其表面密度大約為27微克/平方釐米 ’其方塊電阻為5〇歐。所述奈米級金屬氧化物顆粒114為 Μη〇2顆粒，Μη〇2顆粒間隔分佈於每一個奈米碳管Π22的 表面，且於該奈米碳管複合結搆110中之質量百分含量大 約為62%，該Μη〇2顆粒的大小約為5奈米。因此，該奈米 099107618 表單編號Α0101 第13頁/共31頁 0992013736-0 201133524 碳管複合結構110為一奈米碳管/ Mn〇2複合結構。 [0029] 所述第二電極102的材料與第一電極101的材料可以相同 ，也可以為其他的電極材料，如活性炭、過渡金屬氧化 物等。本實施例中，所述第二電極102的材料與第一電極 101的材料相同，均為奈米碳管複合結構110。由於奈米 碳管複合結構110具有自支撐的特點，所以其作為電極應 用到該超級電容器10時，不需要另外的集電體，其自身 就可以作為集電體。 [0030] 所述隔膜105為玻璃纖維或者聚合物膜，其允許所述電解 液106中之電解質離子流通而阻止所述第一電極101和第 二電極1 0 2相接觸。 [0031] 所述電解液106為氫氧化納水溶液、氫氧化鉀水溶液、硫 酸水溶液、破酸水溶液、硫酸鈉.水溶液、硫酸鉀水溶液 、高氣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。本實施例中 ，所述電解液106為0.5摩爾/升的硫酸納溶液。 [0032] 所述外殼107為玻璃外殼或者不銹鋼外殼。本實施例中， 所述外殼107為玻璃。 [0033] 可以理解，該超級電容器之結構類型不限，還可以係硬 幣型電容器或者繞卷型溶劑電容器。 [0034] 對本實施例提供的超級電容器1 0進行工作電性能測試， 請參閱圖8-10，結果表明：本實施例中之超級電容器10 具有較高充放電效率和比電容量，較好的穩定性，及良 好的循環充放電性能。其中，該超級電容器10於10安/克 099107618 表單編號A0101 第14頁/共31頁 0992013736-0 201133524 電流之情況下，其充放電時間大於120秒；平均質量比電 容量大約為508法/克，體積比電容量大約為800法/立方 釐米。當該超級電容器10經過2500次循環後，其比電容 量的損失不超過4. 5%。經過計算，該超級電容器10的能 量密度大約為30瓦•小時/千克，功率密度大約為110千 瓦/千克。 [0035] Ο 請參閱圖5，本發明第二實施例提供一種超級電容器20， 該超級電容器20的結構與第一實施例提供的超級電容器 10的結構基本相同。該超級電容器20也為平板型超級電 容器，其包括：一第一電極201，一第二電極202，一隔 膜205，一電解液206和一外殼207。所述超級電容器20 與所述超級電容器10的不同之處在於：所述第一電極201 及第二電極202的材料與第一實施例中之第一電極101及 第二電極1〇2的材料不同，所述電解液206為1摩爾/升的 氫氧化鉀溶液。The nano-tube-breaking structure is a self-supporting structure, that is, the carbon nanotube structure does not require a large-area carrier, but as long as: the supporting force is provided on both sides to be suspended and maintained in its own state. When the carbon nanotube structure is placed (or fixed) on the two support bodies arranged at intervals, the carbon nanotube structure located between the two supports can be suspended to maintain its own state. The self-supporting is mainly achieved by the presence of a continuous carbon nanotube in the structure of the carbon nanotube structure extending end to end by van der Waals force. The carbon nanotube structure is a layered or membranous structure comprising at least one carbon nanotube film, at least one nanocarbon line structure or a combination thereof. When the carbon nanotube structure comprises a plurality of carbon nanotube membranes, the carbon nanotube form number A0101 Page 6 of 31 0992013736-0 201133524 Ο [0014] The membrane can be arranged substantially parallel without gaps Or cascading settings. When the carbon nanotube structure includes only one nanocarbon line-like structure, the carbon nanotube linear structure can be folded or wound into a layered carbon nanotube structure. When the carbon nanotube structure comprises a plurality of nanocarbon line-like structures, the plurality of nanocarbon line-like structures may be arranged in parallel, crosswise or woven into a layer of carbon nanotube structure. When the carbon nanotube structure comprises a carbon nanotube film and a nanocarbon line-like structure, the nanocarbon line-like structure β can be placed on at least one surface of the carbon nanotube film. Due to the excellent flexibility of the carbon nanotubes in the nano-tube structure, the carbon nanotube structure has a good flexibility, which can be folded into any shape without being broken. The carbon nanotube membrane is composed of a plurality of carbon nanotubes; the majority of the carbon nanotubes in the carbon nanotube membrane extend substantially parallel to the surface of the carbon nanotube membrane. The carbon nanotubes in the carbon nanotube film are randomly or orderedly arranged. The so-called disordered arrangement means that the arrangement direction of the carbon nanotubes is irregular. The so-called ordered arrangement means that the arrangement of the carbon nanotubes is regular. Specifically, when the carbon nanotube structure includes a disordered arrangement of carbon nanotubes, the carbon nanotubes are entangled or isotropically aligned; when the carbon nanotube structure includes an ordered arrangement of carbon nanotubes, The carbon nanotubes are arranged in a preferred orientation in one direction or in a plurality of directions. By "preferable orientation" is meant that most of the carbon nanotubes in the carbon nanotube structure have a greater probability of orientation in one direction or in several directions; that is, most of the naphthalene carbon nanotube structures The axial direction of the carbon nanotubes extends substantially in the same direction or in several directions. The carbon nanotube film comprises a carbon nanotube film, a carbon nanotube film and a carbon nanotube film. 099107618 Form No. 1010101 Page 7 of 31 0992013736-0 201133524 [0015] The carbon nanotubes in the carbon nanotube structure include single-walled carbon nanotubes, double-walled carbon nanotubes and multi-walled nanocarbons. One or more of the tubes. The diameter of the single-walled carbon nanotube is 〇. 5 nm to 50 nm, the diameter of the double-walled carbon nanotube is 1.0 nm to 50 nm, and the diameter of the multi-walled carbon tube is 1.5 nm. Up to 50 nm. The length of the carbon nanotubes is greater than 50 microns. Preferably, the length of the carbon nanotubes is preferably from 200 microns to 900 microns. [0016] The carbon nanotube film is a self-supporting structure composed of a plurality of carbon nanotubes. The plurality of carbon nanotubes are arranged in a preferred orientation along the same direction. Most of the carbon nanotubes in the carbon nanotube film are oriented in the same direction. Moreover, the overall extension direction of the majority of the carbon nanotubes is substantially parallel to the surface of the carbon nanotube film. Further, most of the carbon nanotubes in the carbon nanotube film are connected end to end by van der Waals force. Specifically, each of the plurality of carbon nanotubes extending substantially in the same direction in the carbon nanotube film is connected end to end with a carbon nanotube adjacent to the extending direction by van der Waals force . Of course, there are a small number of randomly arranged carbon nanotubes in the carbon nanotube film, and these carbon nanotubes do not significantly affect the overall orientation of most of the carbon nanotubes in the carbon nanotube film. The carbon nanotube film does not need a large-area support, and as long as the support force is provided on both sides, it can be suspended and maintained in a self-membranous state, that is, the carbon nanotube film is placed (or fixed) at intervals. When the two supports are disposed at a certain distance, the carbon nanotube film located between the two supports can be suspended to maintain the self-membrane state. [0017] Specifically, a plurality of carbon nanotubes extending substantially in the same direction in the carbon nanotube film are not absolutely linear and may be appropriately bent; or are not completely aligned in the extending direction, and may be appropriately Deviation extension 099107618 Form number A0101 Page 8 / Total 31 page 0992013736-0 201133524 [0018] Ο [0019] Ο [0020] 099107618 Direction. Therefore, there may be partial contact between the carbon nanotubes juxtaposed in the majority of the carbon nanotubes in which the carbon nanotube film is stretched in the same direction. Specifically, the carbon nanotube film comprises a plurality of continuous and aligned 'D:: carbon nanotube segments. The plurality of carbon nanotube segments are connected to each other by a van der Waals end comprising a plurality of mutually parallel nanotubes, and the plurality of mutually parallel carbon nanotubes are tightly bound by van der Waals forces. The carbon nanotube segments have any length, thickness, sentence uniformity and shape. The carbon nanotubes in the carbon nanotube film are arranged in a preferred orientation in the same direction. The plurality of micropores are formed between the nano carbon tubes of the carbon nanotubes, and the plurality of micropores occupy most of the nano carbon film. For example, the volume of the micropores can reach the carbon nanotubes. 7〇% of the membrane volume. The carbon nanotube film can be obtained by directly drawing from a carbon nanotube array. The thickness of the single-layered carbon nanotube film can be from 5 nm to 1 μm. It is possible to prepare carbon nanotube structures of different areas and thicknesses by arranging a plurality of carbon nanotubes in parallel and without _ _ _ or / and = stacking '. When the carbon nanotube structure comprises a plurality of laminated carbon nanotube films, the arrangement direction of the carbon nanotubes in the adjacent carbon nanotube film forms an angle a, (TS «S90. For the structure of the carbon nanotubes and the preparation method thereof, please refer to the publication of the publication of the Chinese Patent Publication No. 200833862, published on August 16, 2008 by Fan Shoushan et al. The carbon nanotube film is uniformly distributed. The plurality of carbon nanotubes are composed of 'the plurality of carbon nanotubes are disordered and arranged in the same direction or in different directions. The axial direction of the plurality of carbon nanotubes is the same as the direction of the _ direction. Form No. A0101 9 pages/total 31 pages 0992013736-0 201133524 Direction extension. The carbon nanotubes in the carbon nanotube film are partially overlapped with each other and are attracted to each other by van der Waals force, and tightly combined to form a self-supporting In addition, the thicker the carbon nanotube rolled film is, the more advantageous it is to have a self-supporting function, such as the thickness of the carbon nanotube rolled film is greater than 1 micrometer, and has a good self-supporting function. Nano carbon tube rolling film can be crushed by one Obtained by a carbon nanotube array. The carbon nanotube array is formed on a surface of the substrate, and the carbon nanotubes in the prepared carbon nanotube rolled film are at an angle to the surface of the substrate of the carbon nanotube array/3 Wherein /9 is greater than or equal to 0 degrees and less than or equal to 15 degrees (0°$/9^15°). Preferably, the axial direction of the carbon nanotubes in the carbon nanotube rolled film is substantially parallel to the The surface of the carbon nanotube rolled film. The carbon nanotubes in the carbon nanotube rolled film have different arrangement according to the manner of rolling. The area and thickness of the carbon nanotube rolled film It is not limited, and may be selected according to actual needs. The area of the carbon nanotube film is substantially the same as the size of the carbon nanotube array. The thickness of the carbon nanotube film and the height of the carbon nanotube array and The pressure of the rolling is related to 1 micron to 1 mm. The carbon nanotube film and the preparation method thereof can be found in the publication of the patent application of the Republic of China on January 1, 2009, by Fan Shoushan et al. [0021] The carbon nanotube flocculation membrane comprises intertwined carbon nanotubes, the carbon nanotubes The degree may be greater than 10 cm. The carbon nanotubes are mutually attracted and entangled by a van der Waals force to form a network structure to form a self-supporting carbon nanotube flocculation film. The thicker the tube flocculation membrane, the more favorable it is to have a self-supporting function. For example, when the thickness of the carbon nanotube flocculation membrane is larger than 1 micrometer, it has a good self-supporting function. Same as the same. The carbon nanotubes in the carbon nanotube flocculation film are 099107618 Form No. A0101 Page 10 / Total 31 Pages 0992013736-0 201133524 [0022] θ [0023] Ο 099107618 Uniform distribution, irregular arrangement, formation A large number of microporous structures. It can be understood that the length, width and thickness of the carbon nanotube film are not limited and can be selected according to actual needs. The carbon nanotube flocculation film has a thickness of from 1 μm to 1 mm, preferably 100 μm. For the carbon nanotube flocculation film and the preparation method thereof, please refer to the publication of the Chinese Patent Application No. 200844041 published on November 16, 2008. The nanocarbon pipeline-like structure comprises at least one nanocarbon pipeline, which may be a non-twisted nano carbon pipeline or a twisted carbon nanotube, the non-twisted nanocarbon pipeline The carbon nanotubes are formed, and the axial directions of the plurality of carbon nanotubes extend substantially in an axial direction parallel to the non-twisted nanocarbon pipeline. The non-twisted nanocarbon line can be obtained by treating the carbon nanotube membrane with an organic solvent. Specifically, the carbon nanotube film comprises a plurality of continuous and aligned carbon nanotube segments. The plurality of carbon nanotube segments are connected end to end by Van der Waals force. Each carbon nanotube segment includes a plurality of carbon nanotubes that are parallel to each other and are tightly coupled by van der Waals forces. The carbon nanotube segments have any length, thickness, uniformity, and shape. 5纳米至1毫米。 The non-twisted nano carbon line length is not limited, the diameter is 0.5 to 1 mm. Specifically, the organic solvent may be used to impregnate the entire surface of the carbon nanotube film, and under the action of the surface tension generated by the volatilization of the volatile organic solvent, a plurality of nanometers parallel to each other in the carbon nanotube film are drawn. The carbon tube is tightly coupled by van der Waals force, thereby shrinking the carbon nanotube film into a non-twisted nano carbon line. The organic solvent is a volatile organic solvent such as ethanol, methanol, acetone, dichloroethane or gas, and ethanol is used in this embodiment. Non-twisted carbon nanotubes treated with organic solvents Form No. 1010101 Page 11 of 31 0992013736-0 201133524 The wire has a reduced specific surface area and reduced viscosity compared to the carbon nanotube film which has not been treated with organic solvents. [0024] The twisted nanocarbon line is composed of a plurality of carbon nanotubes, and the axial directions of the plurality of carbon nanotubes spirally extend around the axial direction of the twisted nanocarbon line. The nanocarbon line can be obtained by twisting both ends of the carbon nanotube film in the opposite direction by a mechanical force. Further, the twisted nanocarbon line can be treated with a volatile organic solvent. Under the action of the surface tension generated by the volatilization of the volatile organic solvent, the adjacent carbon nanotubes in the treated twisted nanocarbon pipeline are tightly bonded by van der Waals force, so that the specific surface area of the twisted nanocarbon pipeline Decrease, increase in density and strength. [0025] The nano carbon pipeline and the preparation method thereof can be referred to the announcement of the Republic of China patent publication No. 1303, published on November 21, 2008; and announced on July 21, 2009, the announcement number is 1312337. The Republic of China patent notice. [0026] When the nanocarbon line-like structure includes a plurality of nano carbon pipelines, the plurality of nanocarbon pipelines are arranged in parallel to form a bundle structure or the plurality of nanocarbon pipelines are twisted to each other to form a stranded structure. . In addition, there is a gap between adjacent carbon nanotubes in the nanocarbon pipeline, so the nanocarbon pipeline-like structure has a large number of micropores, and the pore diameter of the micropores is less than about 10 μm. [0027] The nano-sized particles are disposed on a surface of the plurality of carbon nanotubes. Specifically, the nano-sized particles may be formed on the surface of each of the carbon nanotubes at intervals; or may be continuously disposed on the surface of each of the carbon nanotubes to form a layer and coated on the carbon nanotubes. surface. The nano-sized particles are capable of promoting rapid charge and discharge of the supercapacitor 10, thereby increasing the capacitance of the 099107618 Form No. A0101 Page 12 of 31 0992013736-0 201133524 超级 Super Valley | § 10. The nano-sized particles do not chemically react with the electrolyte 106; preferably, the nano-sized particles are nano-sized metal oxide particles, nano-sized metal particles or a combination of the two. The nano-sized metal oxide particles are oxidized granules (Μη., osmium trioxide particles (C〇3〇4), nickel pentoxide particles (Ni〇), cerium oxide particles (Ru〇2) and One or more of cerium oxide particles (Ir〇2). The nano-sized metal particles are one or more of copper particles, nickel particles, gold particles, silver particles, palladium particles, nail particles, and bismuth particles. The size of the nano-sized particles ranges from 1 nanometer to 1 nanometer; preferably, the nano-sized particles range from 1 nanometer to 50 nanometers. The mass percentage of the carbon nanotube composite structure is greater than 〇 and less than 1%, preferably the mass percentage of the nano-sized metal particles in the nano-carbon tube composite structure is greater than 5〇 % and less than 70%. [0028] Ο Referring to FIG. 2 to FIG. 4, in the embodiment, the first electrode 1〇1 is a carbon nanotube composite structure 110. The carbon nanotube composite structure 110 is composed of A carbon nanotube structure composed of twenty layers of stacked carbon nanotube film and a nano-sized metal crucible disposed on the surface of the carbon nanotube structure The composition of the particles 丨14. Each layer of the carbon nanotube film 112 is composed of a plurality of carbon nanotubes 22, and the angle between the axial directions of the carbon nanotubes 1122 in the adjacent carbon nanotube film is 90. The twenty-layer laminated carbon nanotube film 112 has a thickness of about 500 nm and a surface density of about 27 μg/cm 2 and a sheet resistance of 5 Å. The oxide particles 114 are Μη〇2 particles, and the Μη〇2 particles are spaced apart on the surface of each of the carbon nanotubes 22, and the mass percentage in the carbon nanotube composite structure 110 is about 62%. The size of the 〇2 particle is about 5 nm. Therefore, the nano 099107618 form number Α 0101 page 13 / total 31 page 0992013736-0 201133524 The carbon tube composite structure 110 is a carbon nanotube / Mn 〇 2 composite structure. The material of the second electrode 102 may be the same as the material of the first electrode 101, or may be other electrode materials, such as activated carbon, transition metal oxide, etc. In the embodiment, the material of the second electrode 102 The same as the material of the first electrode 101, both of which are carbon nanotubes Structure 110. Since the carbon nanotube composite structure 110 is self-supporting, when it is applied as an electrode to the supercapacitor 10, an additional current collector is not required, and it can be used as a current collector by itself. The separator 105 is a glass fiber or a polymer film that allows electrolyte ions in the electrolyte 106 to circulate to prevent the first electrode 101 and the second electrode 102 from contacting. [0031] The electrolyte 106 is An aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of sulfuric acid, an aqueous solution of an aqueous acid, an aqueous solution of sodium sulfate, an aqueous solution of potassium sulfate, a solution of propylene carbonate of lithium percarbonate, a solution of propylene carbonate of tetraethylammonium tetrafluoroborate, or A mixture of any combination of the above. In this embodiment, the electrolyte solution 106 is a 0.5 mol/liter sodium sulphate solution. [0032] The outer casing 107 is a glass outer casing or a stainless steel outer casing. In this embodiment, the outer casing 107 is glass. [0033] It can be understood that the structure of the supercapacitor is not limited, and it may also be a coin type capacitor or a wound type solvent capacitor. [0034] The working electrical performance test is performed on the supercapacitor 10 provided in this embodiment. Referring to FIG. 8-10, the result shows that the supercapacitor 10 in the embodiment has higher charging and discharging efficiency and specific capacitance, and is better. Stability, and good cycle charge and discharge performance. Wherein, the supercapacitor 10 has a charge/discharge time of more than 120 seconds in the case of 10 amp/g 099107618 form number A0101 page 14 / 31 page 0992013736-0 201133524; the average mass ratio capacitance is about 508 law / gram The volumetric specific capacitance is approximately 800 laws/cm 3 . 5%。 When the supercapacitor 10 after 2,500 cycles, the loss of its specific capacitance does not exceed 4.5%. The supercapacitor 10 has been calculated to have an energy density of approximately 30 watts per hour per kilogram and a power density of approximately 110 kilowatts per kilogram.第二 Referring to FIG. 5, a second embodiment of the present invention provides a supercapacitor 20 having a structure substantially the same as that of the supercapacitor 10 provided in the first embodiment. The supercapacitor 20 is also a flat type super capacitor comprising a first electrode 201, a second electrode 202, a separator 205, an electrolyte 206 and a casing 207. The supercapacitor 20 is different from the supercapacitor 10 in that the materials of the first electrode 201 and the second electrode 202 are the same as those of the first electrode 101 and the second electrode 1〇2 in the first embodiment. The electrolyte 206 is a 1 mol/L potassium hydroxide solution.
[0036] G 所述第一電極201及第二電極202均為奈米碳管複合結構 210 ’該奈米碳管複合結構210具體凊參閱圖6及圖7，所 述奈米碳管複合結構210由二十層奈米碳管拉膜212組成 的一奈米碳管結構及設置於該奈米碳管結構表面的奈米 級金屬氧化物顆粒214組成。每個奈米碳管拉膜212由若 干奈米碳管2122組成。所述奈米碳管結構的具體結構與 第一實施例中之奈米碳管複合結構110中之奈米碳管結構 相同。所述奈米級金屬氧化物顆粒214為C〇 〇顆粒， C〇3〇4顆粒間隔設置於每一個奈米碳管2122的表面，且於 該奈米碳管複合結構210中之質量百分含量大約為54%， 099107618 表單編號A0101 窠15頁/共31頁 0992013736-0 201133524 該(：〇,0,顆粒的尺寸大小約為10奈米。因此，該奈米碳管 3 4 複合結構210為一奈米碳管/ C〇90/複合結構。 [0037] 對本實施例提供的超級電容器20進行工作性能測試，請 參閱圖8-10。該超級電容器20於10安/克電流的情況下 ，其充放電時間大於45秒；該超級電容器20的瞬間比電 容量比較高超過1100法/克。當該超級電容器20經過 2500次循環後，其比電容量的損失不超過4. 5% ;因此， 該超級電容器20的穩定性比較好。經過計算：該超級電 容器20的平均質量比電容量大约為302法/克，體積比電 容量大約為470法/立方釐米。 [0038] 本發明第三實施例也提供一超級電容器，該超級電容器 與第二實施例提供的超級電容器20基本相同。不同之處 在於，該第三實施例提供的超級電容器中之第一電極及 第二電極的材料與第二實施例的超級電容器20中之第一 電極201及第二電極202的材料不同。該第三實施例中之 第一電極及第二電極的材料為奈米碳管/NiO複合結構。 該奈米碳管/ N i 0複合結構與第二實施例中之奈米碳管複 合結構210相似；不同之處在於，該奈米碳管/NiO複合結 構中之奈米級金屬氧化物顆粒與奈米碳管複合結構210中 之奈米級金屬氧化物顆粒214不同。本實施例中之奈米級 金屬氧化物顆粒為NiO顆粒，NiO顆粒於該奈米碳管/NiO 複合結構中之質量百分含量大約為5Γ/。。對採用該奈米碳 管/NiO複合結構的超級電容器進行工作性能測試，請參 閱圖8-10。該第三實施例提供的超級電容器於10安/克電 流之情況下，其充放電時間大於30秒；其瞬間質量比電 099107618 表單編號A0101 第16頁/共31頁 0992013736-0 201133524 容重較向’超過1500法/克。當該超級電容器經過2500 次循環後，其比電容量的損失也不超過4. 5%，故其穩定 性比較好。經過計算：該第三實施例提供的超級電容器 之平均質量比電容量大約為336法/克，體積比電容量大 約為530法/立方釐米。 [0039] Ο ❹ 本發明實施例提供的超級電容器具有以下優點：第一， 所述超級電容器之電極由於採用具有自支撐功能的奈米 破賞複合結構，所以不需要另外之集電體，該奈米碳管 複合結構本身就可以作為集電體，從而簡化了超級電容 器之結構。且該奈來碳管複合結構的質量要小於金屬集 電體之質置，因此採用該奈米碳管複合結'構.的超級電容 器具有較高的總能量密度及總功率密度:，尤其係採用奈 米碳管/ 1111〇2複合結構之超級電容器。第二，所述奈米 破賞複合結構包括大量微孔，該大量微孔之存在增大了 该奈米碳管複合結構之比表面積，使得所述電解液與該 条米碳管複合結構充分接觸，從而可以促進超級電容器 快速充放電，進而提高超級電容器之電容量。第三，本 發明實施例提供的超級電容器經過25〇〇次循環後，其比 電容量的損失也不超過4. 5%，實驗證明，該超級電容器 之穩定性比較好。 [0040] 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内》 099107618 表單煸號A0101 第17頁/共31頁 0992013736-0 201133524 【圖式簡單說明】 [刪1] 圖1係本發明第一實施例提供的超級電容器之結構示意圖 〇 [0042] 圖2係本發明第一實施例中採用的奈米碳管複合結構的電 子顯微鏡掃描照片。 [0043] 圖3係本發明第一實施例中採用的奈米碳管複合結構的俯 視圖。 [0044] 圖4係本發明第一實施例中採用的奈米碳管複合結構中之 單根奈米碳管之透射電子顯微鏡照片。 [0045] 圖5係本發明第二實施例提供的超級電容器之結構示意圖 〇 [0046] 圖6係本發明第二實施例中採用的奈米碳管複合結構的俯 視圖。 [0047] 圖7係本發明第二實施例中採用的奈米碳管複合結構中之 單根奈米碳管透射電子顯微鏡照片。 [0048] 圖8係於10毫壓/秒之掃描速度下，本發明第一實施例、 第二實施例及第三實施例提供的超級電容器之電壓-比電 流曲線圖。 [0049] 圖9係於10安/克之比電流下，本發明第一實施例、第二 實施例及第三實施例提供的超級電容器之充放電曲線圖 〇 [0050] 圖10係於30安/克之比電流下，本發明第一實施例、第二 實施例及第三實施例提供的超級電容器之循環次數-比電 099107618 表單編號A0101 第18頁/共31頁 0992013736-0 201133524 容量曲線圖。 【主要元件符號說明】 [0051] [0052] [0053] [0054] [0055] 〇 [0056] [0057] [0058] [0059] [0060] 〇 超級電容器：10，20 第一電極：101，201 第二電極：102，202 隔膜：105，205 電解液：106，206 外殼：107，207 奈米碳管複合結構：110，210 奈米碳管拉膜：112，212 奈米碳管.：1122，2122 奈米級金屬氧化物顆粒：114，214 099107618 表單編號Α0101 第19頁/共31頁 0992013736-0[0036] G, the first electrode 201 and the second electrode 202 are both a carbon nanotube composite structure 210. The carbon nanotube composite structure 210 is specifically referred to FIG. 6 and FIG. 210 is composed of a carbon nanotube structure composed of twenty layers of carbon nanotube film 212 and nano-sized metal oxide particles 214 disposed on the surface of the carbon nanotube structure. Each of the carbon nanotube membranes 212 is composed of a plurality of carbon nanotubes 2122. The specific structure of the carbon nanotube structure is the same as that of the carbon nanotube composite structure 110 in the first embodiment. The nano-sized metal oxide particles 214 are C 〇〇 particles, and the C 〇 3 〇 4 particles are disposed on the surface of each of the carbon nanotubes 2122, and the mass percentage in the carbon nanotube composite structure 210 The content is about 54%, 099107618 Form No. A0101 窠 15 pages / Total 31 pages 0992013736-0 201133524 The (: 〇, 0, particle size is about 10 nm. Therefore, the carbon nanotube 3 4 composite structure 210 It is a carbon nanotube / C〇90 / composite structure. [0037] The performance test of the supercapacitor 20 provided in this embodiment is performed, please refer to FIG. 8-10. The supercapacitor 20 is at a current of 10 amps per gram. The 5%; the charge and discharge time is greater than 45 seconds; the ultracapacitor 20 is more than 1100 gram / gram of the instantaneous capacity. When the supercapacitor 20 after 2500 cycles, the loss of specific capacitance does not exceed 4.5%; Therefore, the stability of the ultracapacitor 20 is relatively good. It is calculated that the average mass ratio of the supercapacitor 20 is about 302 laws/g, and the volume specific capacity is about 470 laws/cm 3 . The third embodiment also provides a supercapacitor The supercapacitor is substantially the same as the supercapacitor 20 provided in the second embodiment, except that the material of the first electrode and the second electrode in the supercapacitor provided by the third embodiment is different from the supercapacitor of the second embodiment. The materials of the first electrode 201 and the second electrode 202 are different. The material of the first electrode and the second electrode in the third embodiment is a carbon nanotube/NiO composite structure. The carbon nanotube / N i The composite structure of 0 is similar to the carbon nanotube composite structure 210 of the second embodiment; the difference is that the nano-scale metal oxide particles and the carbon nanotube composite structure 210 in the carbon nanotube/NiO composite structure The nano-sized metal oxide particles 214 are different. The nano-sized metal oxide particles in this embodiment are NiO particles, and the mass percentage of NiO particles in the carbon nanotube/NiO composite structure is about 5 Γ/ For the performance test of the supercapacitor using the carbon nanotube/NiO composite structure, please refer to FIG. 8-10. The supercapacitor provided by the third embodiment is charged and discharged at a current of 10 amp/g. Time is greater than 30 seconds; its instantaneous mass ratio is 099107618 Form No. A0101 Page 16 / Total 31 Pages 0992013736-0 201133524 The weight-to-weight ratio is more than 1500°/g. When the supercapacitor passes 2500 cycles, its specific capacitance loss is also It does not exceed 4.5%, so its stability is better. It is calculated that the average mass-to-capacitance of the supercapacitor provided by the third embodiment is about 336 methods/g, and the volume-to-capacity is about 530 methods/cm3. . [0039] The supercapacitor provided by the embodiment of the present invention has the following advantages: First, since the electrode of the supercapacitor adopts a nano-recovery composite structure having a self-supporting function, an additional current collector is not required. The carbon nanotube composite structure itself can be used as a current collector, which simplifies the structure of the supercapacitor. Moreover, the quality of the carbon nanotube composite structure is smaller than that of the metal current collector, so the supercapacitor using the carbon nanotube composite junction has a higher total energy density and total power density: A supercapacitor with a carbon nanotube/1111〇2 composite structure. Second, the nano-reward composite structure includes a plurality of micropores, and the presence of the plurality of micropores increases the specific surface area of the carbon nanotube composite structure, so that the electrolyte and the carbon nanotube composite structure are sufficient Contact, which can promote the rapid charge and discharge of the supercapacitor, thereby increasing the capacitance of the supercapacitor. In the third embodiment, the supercapacitor provided by the embodiment of the present invention has a loss of specific capacitance of less than 4.5% after 25 cycles. The experiment proves that the stability of the supercapacitor is better. [0040] In summary, the present invention has indeed met the requirements of the invention patent, and the patent application is filed 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 changes made by those who are familiar with the skill of the present invention in accordance with the spirit of the present invention shall be covered by the following patent application. 099107618 Form No. A0101 Page 17 / Total 31 Pages 0992013736-0 201133524 [Simple diagram DESCRIPTION OF THE DRAWINGS [Deleted 1] Fig. 1 is a schematic view showing the structure of a supercapacitor according to a first embodiment of the present invention. [0042] Fig. 2 is an electron microscope scanning photograph of a composite structure of a carbon nanotube used in the first embodiment of the present invention. 3 is a top plan view showing a composite structure of a carbon nanotube used in the first embodiment of the present invention. 4 is a transmission electron micrograph of a single carbon nanotube in a carbon nanotube composite structure used in the first embodiment of the present invention. 5 is a schematic structural view of a supercapacitor provided by a second embodiment of the present invention. [0046] FIG. 6 is a plan view showing a composite structure of a carbon nanotube used in a second embodiment of the present invention. 7 is a transmission electron micrograph of a single carbon nanotube in a carbon nanotube composite structure used in a second embodiment of the present invention. 8 is a voltage-ratio current graph of the supercapacitor provided by the first embodiment, the second embodiment, and the third embodiment of the present invention at a scanning speed of 10 milliseconds per second. 9 is a charge and discharge graph of a supercapacitor provided by the first embodiment, the second embodiment, and the third embodiment of the present invention at a specific current of 10 amps/g. [0050] FIG. 10 is a 30 amp. The ratio of the number of cycles of the supercapacitor provided by the first embodiment, the second embodiment and the third embodiment of the present invention is greater than that of the electric current 099107618 Form No. A0101 Page 18 of 31 Page 99992013736-0 201133524 Capacity graph . [Main component symbol description] [0055] [0055] [0058] [0060] [0060] [0060] 〇 supercapacitor: 10, 20 first electrode: 101, 201 Second electrode: 102,202 Diaphragm: 105,205 Electrolyte: 106,206 Enclosure: 107,207 Carbon nanotube composite structure: 110,210 Nano carbon tube film: 112,212 carbon tube.: 1122, 2122 nano-sized metal oxide particles: 114, 214 099107618 Form number Α 0101 Page 19 / Total 31 pages 0992013736-0