200844046 九、發明說明： 【發明所屬之技術領域】 本發明涉及一種奈米碳管薄片的製備方法，尤其涉及 種複合金屬的奈米碳管薄片的製備方法。 【先前技術】 « 1991年曰本科學家ii：)’ima首次發現奈米碳管 jCarbcm NanQtube，OT)以來’以奈純管為代表的奈 =材料以其獨特的結構和性質引起了人們極大的關注。近 成年來Ik著奈米石厌官及奈米材料研究的不斷深入，其廣 闊應用前景不_現出來。例如，由於奈米碳f所呈有= 獨特的電磁學、光學、力學、化學性能等，大量有關1在 =發射電子源、感·、新型辟材料、 域的應用研究不斷被報導。 玎計寺項 具體t = 奈米碳#實際應用的—種重要形式。 物心膜已被研究用作場發射源、光電和生 = 池電極'吸波材料、水淨化材 屬齡在夺著奈米石炭管的製備技術的發展，將金 的導電中形成薄片有利於進-步利用奈米碳管 複合金屬的奈米碳㈣片的製備方法- 充的2將金屬複合在奈米辭或=填 上述^麵的奈米奸料的製備方法 雜、製備效率較低;同時，所製備的奈米•薄Γ;=. f\ 200844046 、—口的比例小、不易控制，且複合不均勻。 管薄！種料^率較高且製備的奈米石山 :i屬複合的比例可以控制二厌 方法實為必要。 犬專片的製備 【發明内容】 -種奈米碳管薄片的製備方法，包括 管原料加入到含有全^ 夺不米碳 理獲得太m★ 料的浴液中亚進行絮化處 、不“厌g絮狀結構；添加還原劑 =述奈米碳管絮狀結構從溶液中分離：該： 只石反S絮狀結構定型處理以獲得奈米碳管薄片。、^丁 所述的奈米碳管原料的製備包括以 -奈米細列;以及使奈米碳管陣列脫離== 得奈米碳管原料。 底獲 所述的絮化處理的方法包括超聲 高強度㈣。 以處理或 所述的金屬包括金、銀、銅、鋁或銦。 所述的含有金屬離子的溶液為銀氨溶液。 所述的還原劑包括乙搭、葡萄糖或甲搭。 所述的分離奈米碳管絮狀結構的方法具體包括 以下步驟：將上述含有奈米碳管絮狀結構的溶液倒入 放有濾紙的漏斗t;並通過抽氣裝置從漏斗嘴抽氣從 而獲得分離的奈米碳管絮狀結構。 所述的疋型處理具體包括以下步驟··將上述奈米 碳管絮狀結構置於-容器中，·將奈米碳管絮狀結ς按 200844046 疋形狀攤開；施加一定壓力於攤開的奈米石與管絮 構，以及，將洛劑烘乾或等溶劑自然揮發後獲得 奈米碳管薄片。 所述的奈米碳管薄片為1微米至2毫米。 、相較於先前技術，所述的奈米碳管薄片的製備方 ^具有以下優點：其―’採用原位還原的方法使得金 !能心!1且緊密的複合在奈米碳管表面，且製備的 奈米石反官薄片中金屬複合的比例可以控制，工序朽 單，易於實際應用；其二，通過將奈米碳管原料騎 絮化處理後使奈米碳管相互纏繞，形成的奈米碳管薄 片具有报好的章刀性。 【實施方式】 :了將結合_對本發明作進—步之詳細說明。 明茶閱圖1，本實施例奈米碳管薄片的製備方法主 要包括以下步驟： 、步驟一·提供-奈米碳管陣列，優選地，該陣列 為超順排奈米碳管陣列。 本貝把例中纟米石厌官陣列的製備方法採用化學 氣相沉積法’其具體㈣包括：（a)提供—平整基底， 該基底可選用P型或N型石夕基底，或選用形成有氧化 層的石夕基底’本實施例優選為採用4英寸的石夕基底； (b)在基底表面均勻形成—催化劑層，該催化劑層 材料可選用鐵（Fe)、始（⑻、錄㈤或其任意組 合的合金之-；（C)將上述形成有催化劑層的基底在 200844046 700〜900°C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°C，然後通入碳源氣體反應約5〜3〇分鐘， 生長得到奈米碳管陣列，其高度大於1〇〇微米。該奈 米碳管陣列為多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，由於生成的奈米碳管 長度較長，部分奈米碳管會相互纏繞。通過上述控制 生長條件，该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。本實施 例中碳源氣可選用乙块等化學性f較活潑的碳氫化 合物’保護諸可義氮氣、氨氣或惰性氣體。可以 理解的係’本實_提供的奈米料㈣秘於上述 製備方法。 其⑼一·便示米碳管陣列脫離基底，獲得奈米碳 & 料。 :實施例優選採用刀片或其他工具將奈米碳管從 ΐ:伴：：獲仔奈米碳管原料，其中奈米碳管-定程 又上保持相互纏繞的狀態。 子的步-驟訂述奈米碳管祕添加縣有金屬離 處理獲得含有奈米碳管絮狀 溶劑可選用任何含有金屬離 金屬絡離子的溶液，如 、翻、：未i屬顆粒或 施例優選採用含有銀離銀；錢銦等。本實 卞的銀虱/谷液。該銀氨溶液的 200844046 可^過在雜銀溶液中逐滴加人氨水，邊_振 盥，至最初產生的沉澱溶解為止得到溶液。該銀氨溶 液中含有弱氧化性的銀氨絡離子（Ag(腿3)/)。 絮化處理可通過採用超聲波分散處理或高強度攪 二等方去優远地，本實施例採用超聲波分散〜3〇 刀知由於奈米兔官具有極大的比表面積，奈米碳管 之間2較大的凡德瓦爾力。上述絮化處理並不會將 示米厌g原料中的奈米碳管完全分散在溶劑中，溶劑 卡的奈米碳管之間通過凡德瓦爾力相互吸引、纏繞， 形成網路狀結構，進而形成奈米碳管絮狀結構。銀氨 溶液中的銀氨絡離子在絮化處理後均勻分散在奈米 碳管絮狀結構中。 上步驟四：往上述溶液中添加還原劑，反應過程中 不知攪拌，使金屬離子還原成金屬附著在奈米碳管上 獲得複合有金屬的奈米碳管絮狀結構。 遂原劑的選擇與上述金屬離子溶液相對應，本實 轭例中還原劑包括乙醛、葡萄糖或甲醛等。利用還 原d的還原作用使銀氨絡離子巾的銀離子被還原成 金屬附者在奈米碳管上。優選地，本實施例採用將乙 搭/容液逐滴加入還原銀氨絡離子。可以理解，加入還 原劑=量與料中金屬離子的濃度有關。如果金屬離 子的濃度越高，則加入還原劑的量越多。 请蒼閱圖2’為本實施例中附著有金屬的奈米碳管 絮狀、、、。構示思圖。由於本實施例採用原位還原反應的 200844046 方法，金屬不係直接通過機械_的方法加入，而係 通過金屬離子還原成金屬的方式可使金屬與奈米碳 管的結合非常緊密，且分散均勻，金屬包覆在奈米碳 管表面或填充在奈米碳管之間的空隙中。可以理解， 本實施例中可通過控制溶液中金屬離子的濃度來控 制奈米複管絮狀結構中複合金屬的比例 : 的濃度越高’則奈米碳管絮狀結構中複合金屬= 的奈米碳管絮狀結構 絮狀結構定型處理以 步驟五··將上述複合有金屬 從浴劑中分離，並對該奈米碳管 獲得奈米碳管薄片。 七紅”、㈣T刀腎米碳管絮狀結構的方法呈體 判上述含有奈米碳管絮狀結構的溶: 放有錢的料中；靜置乾燥-段時間從而卿 为離的奈米碳管絮狀結構。 &仔 定型處理具體包括以下步驟^ =吉構置於二容器中」將奈米碳管絮狀=按;= 構大攤開’知加一定壓力於攤開的奈米碳狀： 構，以及，將奈米碳管絮壯0士 m 、 糸狀、、、口 等溶劑自然揮發後獲得奈米碳管》c谷劑烘乾或 實施例可通過控制奈米碳管絮狀結構：解’本 控制奈米碳管薄片的厚度和面心。^的面積來 大，則奈米碳管薄片的厚度和面密^就^的面積越 例中獲得的奈米碳管薄片的厚度： ’、：本實施 丄儆未至2毫米。 11 200844046 、另外，上述分離與定型處理步驟也可直接噢過抽 濾的方式獲得奈米碳管薄片，具體包括以下步驟：提 供一微孔攄膜及-抽氣漏斗；將上述含有奈米碳管絮 狀結構的㈣經賴孔伽倒人抽氣料巾，·抽濾並 乾燥後獲得奈米碳管薄片。該微孔濾㈣—表面光 滑、孔㈣G. 22微米的濾'膜。由於㈣方式本身將 ^-較大的氣虔作用于奈米碳管絮狀結構，該奈米 2絮狀結構經過抽濾、會直接形成_均勾的奈米碳 吕薄片由於微孔濾、膜表面光滑，該奈米碳管薄 片容易剝離。 閱圖3,為本實施例製備的複合金屬的奈米碳 :溥片二可以理解，本實施例可通過控制複合金屬的 不米石厌官絮狀結構攤片的面積來控制奈米碳管薄片 的厚度和面黯。攤（的面積越大，則奈米碳管薄片 的厚度和面錢朗小。本實施彳种麟的奈米碳管 薄片的厚度為1微米至2毫米。 本實施例中奈米碳管薄片的製備方法具有以下優 =其-，採用原位還原的方法使得金屬能夠均句且 緊岔的複合在奈米碳管表面，且製備的奈米碳管薄片 中金屬複合的比例可以控制，卫序簡單，易於實於處 用：ΐ二，通過將奈米碳管原料進行絮化處理後：; 未石反官相互纏繞’形成的奈米碳”片具有很好的韋刃 綜上所述，本發明確已符合發明專利之要件，遂 12 200844046 依法提出專利申請。惟，以上所述者僅為本發男之較 佳實施例，自不能以此限制本案之申請專利範圍。舉 凡沾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。 【圖式簡單說明】 、圖1係本發明實施例奈米碳管薄片的製備方法的 流程示意圖。 圖2係本發明實施例獲得的複合金屬的奈米碳管 絮狀結構的照片。 圖3係本發明實施例獲得的奈米碳管薄片的照片。 【主要元件符號說明】 益 13200844046 IX. Description of the Invention: [Technical Field] The present invention relates to a method for preparing a carbon nanotube sheet, and more particularly to a method for preparing a composite metal carbon nanotube sheet. [Prior Art] «In 1991, Sakamoto scientist ii:) 'ima first discovered the carbon nanotubes jCarbcm NanQtube, OT) Since the nep = representative of the Nai tube, the material has caused great people with its unique structure and properties. attention. In recent years, Ik has been deeply researched in the research of nano-stone and anaesthetic materials and nano materials, and its broad application prospects are not emerging. For example, due to the unique electromagnetic, optical, mechanical, and chemical properties of nanocarbon f, a large number of applications related to 1 in the emission electron source, sensation, new materials, and domains have been reported.玎计寺 Item Specific t = Nano carbon # Practical application - an important form. The pericardium has been studied as a field emission source, photoelectric and raw = pool electrode 'absorber material, water purification material age is in the development of the nano carboniferous tube preparation technology, the formation of gold in the conductive sheet is beneficial to enter -Preparation method of nano carbon (four) sheet using nano carbon tube composite metal - Filling 2 method for preparing metal nano-composite in nano-word or filling the above-mentioned surface, and preparation efficiency is low; At the same time, the prepared nano thinner; =. f\ 200844046, the ratio of the mouth is small, difficult to control, and the composite is uneven. Thin tube! The high rate of seed material and the prepared nano-rock mountain: the proportion of i-complex can control the second-negative method is really necessary. Preparation of dog-specific film [Summary of the invention] - A method for preparing a carbon nanotube sheet, comprising adding a tube raw material to a bath containing a total amount of carbon in the bath to obtain a floc, not "厌g floc structure; addition of reducing agent = said nano carbon tube floc structure separated from the solution: the: stone anti-S flocculation structure shaping treatment to obtain the carbon nanotube sheet. The preparation of the carbon tube raw material comprises a column of - nano columns; and the carbon nanotube array is detached from the == carbon nanotube raw material. The method for obtaining the flocculation treatment includes ultrasonic high intensity (4). The metal includes gold, silver, copper, aluminum or indium. The metal ion-containing solution is a silver ammonia solution. The reducing agent includes ethylene, glucose or meth. The method for forming a structure specifically includes the steps of: pouring the above solution containing a carbon nanotube floc structure into a funnel t containing a filter paper; and pumping air from the funnel through an air suction device to obtain a separated carbon nanotube floc The 疋 type processing specifically includes the following steps · Place the above-mentioned carbon nanotube floc structure in a container, and spread the carbon nanotube floc in the shape of 200844046; apply a certain pressure to the spread of the nano-stone and tube structure, and The carbon nanotube sheet is obtained by drying the agent or evaporating the solvent, etc. The carbon nanotube sheet is 1 micrometer to 2 mm. Compared with the prior art, the carbon nanotube sheet is The preparation method has the following advantages: it adopts the method of in-situ reduction to make gold! The core 1 is tightly compounded on the surface of the carbon nanotube, and the ratio of the metal composite in the prepared nano stone reverse sheet can be controlled. The process is easy to use in practical use; the second is to make the carbon nanotubes of the carbon nanotubes entangled by the flocculation treatment of the carbon nanotube raw materials, and the formed carbon nanotube sheets have the good knife-knife property. 】 : The detailed description of the invention will be described in conjunction with the present invention. The preparation method of the carbon nanotube sheet of the present embodiment mainly comprises the following steps: Step 1 · Providing - a carbon nanotube array, Preferably, the array is a super-sequential carbon nanotube array Benbe uses the chemical vapor deposition method for the preparation of the glutinous rice ruthenium array. The specific (4) includes: (a) providing a flat substrate, the substrate may be selected from a P-type or N-type stone substrate, or The embodiment of the invention is preferably a 4-inch stone substrate; (b) a catalyst layer is uniformly formed on the surface of the substrate, and the catalyst layer material can be selected from iron (Fe), beginning ((8), recorded (5) - an alloy of any combination thereof; (C) annealing the substrate on which the catalyst layer is formed in air at 200844046 700 to 900 ° C for about 30 minutes to 90 minutes; (d) placing the treated substrate in the reaction In the furnace, it is heated to 500 to 740 ° C in a protective gas atmosphere, and then reacted with a carbon source gas for about 5 to 3 minutes to grow to obtain a carbon nanotube array having a height greater than 1 μm. The carbon nanotube array is a plurality of pure carbon nanotube arrays formed of carbon nanotubes that are parallel to each other and perpendicular to the substrate. Due to the long length of the formed carbon nanotubes, some of the carbon nanotubes are entangled with each other. The super-sequential carbon nanotube array is substantially free of impurities such as amorphous carbon or residual catalyst metal particles by the above controlled growth conditions. In the present embodiment, the carbon source gas may be treated with a chemically active hydrocarbon such as a block b to protect the nitrogen, ammonia or inert gas. It is understood that the nanomaterial (4) provided by the present invention is secretive to the above preparation method. The (9) one shows that the carbon nanotube array is separated from the substrate to obtain a nano carbon & The embodiment preferably uses a blade or other tool to hold the carbon nanotubes from the crucible: with: a carbon nanotube raw material, wherein the carbon nanotubes are kept in a state of being intertwined. The step of the sub-step is to describe the carbon nanotubes in the county. There is a metal separation treatment to obtain a solvent containing a carbon nanotube. Any solution containing a metal-free metal ion can be used, such as, turning, not The example preferably uses silver-containing silver; indium and the like. This is the silver 虱 / 谷液. The 200804046 solution of the silver ammonia solution can be added dropwise to the ammonia solution in a solution of the ammonia solution, and the solution is obtained until the initially generated precipitate is dissolved. The silver ammonia solution contains a weakly oxidizing silver ammine complex ion (Ag (leg 3)/). The flocculation treatment can be carried out by using ultrasonic dispersion treatment or high-strength stirring. The present embodiment uses ultrasonic dispersion to disperse ~3 knives. Since the nano rabbit has a large specific surface area, between the carbon nanotubes 2 Larger van der Waals force. The above flocculation treatment does not completely disperse the carbon nanotubes in the rice raw material in the solvent, and the carbon nanotubes of the solvent card are attracted and entangled by the van der Waals force to form a network structure. Further, a carbon nanotube floc structure is formed. The silver ammine complex ions in the silver ammonia solution are uniformly dispersed in the nano carbon tube floc structure after the flocculation treatment. Step 4: Adding a reducing agent to the above solution, and stirring is not known during the reaction, so that the metal ions are reduced to a metal attached to the carbon nanotubes to obtain a metal-filled carbon nanotube floc structure. The selection of the bismuth agent corresponds to the above metal ion solution, and the reducing agent in the conjugate example includes acetaldehyde, glucose or formaldehyde. The reduction of the silver ions of the silver-ammonium iontophore is reduced by the reduction of the reducing element d to the metal attached to the carbon nanotubes. Preferably, this embodiment employs the dropwise addition of the ethylene/capacitor to the reduced silver ammine complex ions. It will be appreciated that the amount of reducing agent added is related to the concentration of metal ions in the feed. If the concentration of the metal ions is higher, the amount of the reducing agent added is increased. Please refer to Fig. 2' for the carbon nanotubes to which the metal is attached in the present embodiment. Construct a thought. Since the method of in situ reduction reaction of 200844046 is used in this embodiment, the metal is not directly added by the mechanical method, but the metal is reduced to metal by the metal ion, and the metal and the carbon nanotube are very tightly combined and uniformly dispersed. The metal is coated on the surface of the carbon nanotube or filled in the space between the carbon nanotubes. It can be understood that in this embodiment, the ratio of the metal ions in the solution can be controlled to control the proportion of the composite metal in the floc structure of the nano tube: the higher the concentration, the composite metal in the floc structure of the carbon nanotubes. The rice carbon tube floc structure flocculation structure is shaped and processed in step 5. The composite metal is separated from the bath, and the carbon nanotube sheet is obtained from the carbon nanotube. The method of "four red" and (four) T-knife kidney-carbon tube floc structure is judged by the above-mentioned solution containing the floc structure of the carbon nanotubes: in the rich material; the drying is allowed to dry for a period of time. Carbon tube floc structure. & Attenuation treatment specifically includes the following steps ^ = Jiji placed in two containers" will be carbon nanotubes = press; = structure spread out 'know a certain pressure on the spread of the Nai The carbon-like shape of the rice is as follows: and the carbon nanotubes of the carbon nanotubes are naturally volatilized to obtain the carbon nanotubes, or the examples can be controlled by controlling the nanocarbon. Tube floc structure: solution 'this control of the thickness and face of the carbon nanotube sheet. When the area of ^ is large, the thickness of the carbon nanotube sheet and the area of the surface of the carbon nanotube sheet are the thickness of the carbon nanotube sheet obtained in the example: ',: This embodiment is less than 2 mm. 11 200844046 In addition, the above separation and sizing treatment steps can also directly obtain the carbon nanotube sheets by means of suction filtration, and specifically include the following steps: providing a microporous ruthenium membrane and a pumping funnel; (4) The tube-shaped structure of the tube is immersed in a ventilated towel, and the carbon nanotube sheet is obtained by suction filtration and drying. The microporous filter (four) - surface smooth, pore (four) G. 22 micron filter 'membrane. Since the (4) method itself will act on the nano-carbon tube floc structure, the nano- 2 floc structure will be directly formed by suction filtration, and the nano-carbon flakes will be formed directly due to microfiltration. The surface of the film is smooth, and the carbon nanotube sheet is easily peeled off. Referring to Figure 3, the nano-carbon of the composite metal prepared in the present embodiment: the bracts 2 can be understood, the present embodiment can control the carbon nanotubes by controlling the area of the composite metal non-mysterite floc structure. The thickness and face of the sheet. The larger the area of the booth, the smaller the thickness and the surface of the carbon nanotube sheet. The thickness of the carbon nanotube sheet of the present invention is 1 micrometer to 2 mm. The carbon nanotube sheet in this embodiment The preparation method has the following advantages: - the in-situ reduction method enables the metal to be uniformly and tightly laminated on the surface of the carbon nanotube, and the proportion of the metal composite in the prepared carbon nanotube sheet can be controlled. The order is simple and easy to use: ΐ二, after the nano carbon tube raw material is flocculated:; the non-stone anti-details are formed by the 'nano carbon' sheet formed by the well-being The present invention has indeed met the requirements of the invention patent, and 遂12 200844046 filed a patent application according to law. However, the above is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application in this case. The equivalent modifications or variations of the present invention in light of the spirit of the present invention are intended to be included in the scope of the following claims. [FIG. 1] FIG. 1 is a method for preparing a carbon nanotube sheet according to an embodiment of the present invention. Process Fig. 2 is a photograph of a composite metal carbon nanotube floc structure obtained in an embodiment of the present invention. Fig. 3 is a photograph of a carbon nanotube sheet obtained in an embodiment of the present invention.