201016598 .九、發明說明： 【發明所屬之技術領域】 本發明涉及一種奈米複合材料及其製備方法，尤其涉 及一種基於奈米碳管的奈米碳管複合材料及其製備方法。 【先前技術】 奈米碳管具有優良的機械和光電性能，被認為係複合 材料的理想添加物。目前，奈米碳管已經可和其他的材料 ©形成各種各樣的複合材料，如高分子複合材料、陶瓷複合 材料、層狀複合材料、摻雜複合材料以及碳/碳物複合材料 等。這些複合材料在增強纖維、新型催化劑和奈米電子器 件等方面具有潛在的應用前景，成為世界科學研究的熱點 (Ajjayan P.M., Stephan 0., Colliex C., Tranth D. Science. 1994,265,1212-1215: Calvert P., Nature, 1999，399, 210-211)。 目前，以奈米碳管為基體的複合材料主要通過直接複 @合方法和表面改性複合方法製備。其中，直接複合方法係 將奈米顆粒通過一定方法如塗敷或喷塗的方法形成在奈米 碳管的表面，在奈米碳管表面形成一層奈米顆粒的膜。這 種方法操作相對簡單，然採用此方法製備奈米碳管複合材 料時，由於奈米碳管多以奈米碳管粉末的形式存在，奈米 碳管本身容易發生團聚，故無法控制製備的奈米碳管複合 材料中的奈米材料在奈米碳管表面的分佈，奈米顆粒和奈 米碳管在複合材料中的分佈不均勻。 為解決奈米碳管的團聚問題，通常將將奈米碳管表面 6 201016598 ，，二改性之後再將奈米碳管與其他奈米顆粒複合。對奈米 •碳管表面進行改性的方法通常採賴奈米礙管分散於^酸 及石肖酉文等強氧化性酸或表面活性劑中，這種方法可在一定 程度上解決奈米碳管團聚的問題，然，由於通過強酸處理， =使？所述奈米碳f受到-定程度的破壞，且使用表面活 '劑處理會使得表面活性劑在最終的奈米碳管複合材料中 不易除去，很大程度上影響了奈米碳管複合材料的性能。 *另，上述兩種方法製備的奈米碳管複合材料令，奈米 鬱碳管之間沒有形成一個整體的奈米碳管結構，使奈米碳管 複合材料的機械強度和勤性較1，無》充分發揮奈米碳 的良好性能。 有鑒於此，提供一種以奈米碳管為基體、機械強度較 大、韌性較好的複合材料及其製備方法實為必要。 【發明内容】 一種奈米碳管複合材料，其包括：複數個奈米碳管和 ，，個奈米顆粒，其中，所述複數個奈米碳管形成一奈米 碜碳管結構，該奈米顆粒分佈於該奈米碳管結構中。 一種奈米碳管複合材料的製備方法，其包括以下步 驟：製備-奈米碳管結構；提供一奈米顆粒預製體；將夺 米碳管結構與奈来顆粒預製體複合，形成奈米顆粒於奈米 碳管結構中。 相較於先前技術，所述之奈米碳管複合材料及其製備 方法具有以下優點：其-’由於所述奈求碳管複合材料中 的奈米碳管相互連接形成-奈米碳管結構，使得奈米碳管 複合材料的機械強度較大，韌性較好。其二，由於採用奈 米碳管結構作為骨架，#而使得所述之奈米<管複合材^ 201016598 .具有良好的導電性，充分發揮了奈米碳管的導電性能。 .三，所述奈米碳管複合材料的製備方法無需對奈米碳管表 面進行處s，故不會對奈来碳管造成破壞。 【實施方式】 提供的的奈米 以下將結合附圖詳細說明本技術方案 碳管複合材料。 ~ 請參閱® 1，纟技術方案實施例提供一種奈米竣管複 0材料1G其包括—奈米碳管結構16及複數個奈米顆粒 ❹18。所述奈米碳管結構16包括複數個奈米碳管相互連接 形成，所述奈米顆粒18均勻地附著在奈米碳管的表面。 進一步地，所述奈米碳管和奈米顆粒18可均勻分佈於所 述奈米碳管複合材料10中。 所述奈米碳管複合材料10進一步包括複數個微孔 20，該微孔20為奈米碳管之間的間隙、奈米碳管與奈米 顆粒18之間的間隙或奈米顆粒18之間的間隙。所述微 孔20的孔徑為0.3奈米-5毫米。所述奈米碳管複合材料 ❹10中的微孔20使奈米碳管複合材料1〇具有一定的通透 性和較.尚的比表面積。 所述奈米碳管結構16中的奈米碳管有序或無序排 列’具體地’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。奈米碳管之間相互吸引、相互搭接 或纏繞形成一形狀嫁定的穩定結構。在所述之奈米破管複 合材料10中’奈米碳管結構16起到了骨架作用，用於支 8 201016598 -撐奈米顆粒18。奈米碳管結構16包括至少一層奈米碳管 -膜’該奈米碳管膜包括複數個均勻分佈的奈米碳^= 複數個均句分佈的奈米碳管有序排職無序㈣， 不米碳管之間通過凡德瓦爾力連接。該奈米碳管 碳管絮化膜、奈米碳管礙壓膜或奈米碳管拉優選ς:、 =奈米碳管結構16為一自支揮的結構，具體地優=支 種情況:奈米碳管結構16完全不需要基底支 ρ 7G全獨立自支撐存在；奈米碳管結構16的一部分 ©要一個或複數個支撐點，其餘部分可懸空設置，且且 穩定的結構。 八有 請參見圖2,所述奈米碳管絮化膜為各向同性 t複數個無序排列且均勻分佈的奈之 :::德瓦爾力相互吸引、相互缠繞。故， =有很好的柔㈣，可彎曲折叠成任意形狀而不破裂， 所ΐίί好的自支雜能，可無需基底支撐，自支撐存在。 所述不米碳管絮化膜的厚度為i微米_2毫米。 參 米碳管礙壓膜包括均勾分佈的奈求碳管，奈米 麗：：二：方向或不同方向擇優取向排列。該奈米碳管碾 ，中u碳管與奈米碳管礙壓膜的表面成—夾角α， ^中，《大於等於零度且小於等於15度（〇加15。）。優選 膜=奈米碳管礙壓膜中的奈米碳管平行於奈米碳管儀 ί;:”。依據礙壓的方式不同，該奈米碳管礙麼臈中 忐=入奴官具有不同的排列形式。具體地，奈米碳管可各 擇：ί排列；當沿不同方向㈣時’奈米碳管沿不同方向 向排列，請參見圖3,奈米碳管在奈米碳管礙壓膜 中了>。-固定方向擇優取向排列，請參見圖4，奈米碳管 9 201016598 碾壓膜中的奈米碳管可沿不同方向擇優取向排列。所述奈 .米碳管碾壓膜中的奈米碳管部分交疊。所述奈米碳管碾壓 膜中奈米破營之間通過凡德瓦爾力相互吸引，緊密結合， 使得該奈米碳官礦壓膜具有很好的柔韌性，可彎曲折疊成 任意形狀而不破裂。且由於奈米碳管碾壓膜中的奈米碳管 之間通過凡德瓦爾力相互吸引，緊密結合，使奈米碳管碾 壓膜為一自支撐的結構，可無需基底支撐，自支撐存在。 所述碾壓膜的厚度為ΟΛ微米-5毫米。201016598. IX. INSTRUCTIONS: TECHNICAL FIELD The present invention relates to a nano composite material and a preparation method thereof, and more particularly to a carbon nanotube composite material based on a carbon nanotube and a preparation method thereof. [Prior Art] The carbon nanotubes have excellent mechanical and photoelectric properties and are considered to be ideal additives for composite materials. At present, carbon nanotubes can be combined with other materials to form a variety of composite materials, such as polymer composites, ceramic composites, layered composites, doped composites and carbon/carbon composites. These composite materials have potential applications in reinforcing fibers, novel catalysts, and nanoelectronic devices, and have become hotspots in scientific research in the world (Ajjayan PM, Stephan 0., Colliex C., Tranth D. Science. 1994, 265, 1212). -1215: Calvert P., Nature, 1999, 399, 210-211). At present, composite materials based on carbon nanotubes are mainly prepared by direct recombination method and surface modification composite method. Among them, the direct composite method is to form a film of nano particles on the surface of a carbon nanotube by forming a nano particle on the surface of a carbon nanotube by a method such as coating or spraying. This method is relatively simple to operate. However, when the carbon nanotube composite material is prepared by this method, since the carbon nanotubes are mostly in the form of a carbon nanotube powder, the carbon nanotubes themselves are prone to agglomeration, so the preparation cannot be controlled. The distribution of nanomaterials in the carbon nanotube composite on the surface of the carbon nanotubes, the distribution of nanoparticles and carbon nanotubes in the composite is not uniform. In order to solve the agglomeration problem of the carbon nanotubes, the carbon nanotube surface 6 201016598, and the second modification are usually combined with the other nano particles. The method for modifying the surface of the carbon nanotubes is usually carried out by dispersing the nanoparticles in a strong oxidizing acid or surfactant such as acid and stone, which can solve the carbon nanotubes to some extent. The problem of reunion, of course, due to strong acid treatment, = make? The nanocarbon f is destroyed to a certain extent, and the use of a surface active agent makes the surfactant difficult to remove in the final carbon nanotube composite, which greatly affects the carbon nanotube composite. Performance. * In addition, the carbon nanotube composites prepared by the above two methods do not form a monolithic carbon nanotube structure between the carbon nanotubes, so that the mechanical strength and flexibility of the carbon nanotube composites are 1 , no" to give full play to the good performance of nano carbon. In view of this, it is necessary to provide a composite material having a nano-carbon tube as a base, a relatively high mechanical strength, and a good toughness, and a preparation method thereof. SUMMARY OF THE INVENTION A carbon nanotube composite material includes: a plurality of carbon nanotubes and, a plurality of nano particles, wherein the plurality of carbon nanotubes form a nano-carbon tube structure, the The rice particles are distributed in the carbon nanotube structure. A method for preparing a carbon nanotube composite material, comprising the steps of: preparing a carbon nanotube structure; providing a nanoparticle preform; and combining the carbon nanotube structure with the Nailai pellet preform to form a nanoparticle In the carbon nanotube structure. Compared with the prior art, the carbon nanotube composite material and the preparation method thereof have the following advantages: - because the carbon nanotubes in the carbon nanotube composite material are interconnected to form a carbon nanotube structure The carbon nanotube composite material has high mechanical strength and good toughness. Secondly, since the carbon nanotube structure is used as the skeleton, the nano-tube composite material 201016598 has good electrical conductivity and fully exerts the conductivity of the carbon nanotube. 3. The preparation method of the carbon nanotube composite material does not require the surface of the carbon nanotube to be damaged, so that the carbon nanotubes are not damaged. [Embodiment] Provided Nano Hereinafter, the carbon nanotube composite material of the present technical solution will be described in detail with reference to the accompanying drawings. ~ Refer to the ® 1, 纟 technical solution embodiment provides a nano 竣 tube complex 0 material 1G which includes a carbon nanotube structure 16 and a plurality of nano particles ❹18. The carbon nanotube structure 16 includes a plurality of carbon nanotubes connected to each other, and the nanoparticles 18 are uniformly attached to the surface of the carbon nanotubes. Further, the carbon nanotubes and nanoparticles 18 may be uniformly distributed in the carbon nanotube composite 10. The carbon nanotube composite 10 further includes a plurality of micropores 20 which are gaps between the carbon nanotubes, a gap between the carbon nanotubes and the nanoparticles 18, or nanoparticles 18 The gap between them. The pores 20 have a pore diameter of from 0.3 nm to 5 mm. The micropores 20 in the carbon nanotube composite material 使10 provide a certain permeability and a relatively specific surface area for the carbon nanotube composite material. The ordered or disordered arrangement of the carbon nanotubes in the carbon nanotube structure 16 'specifically' when the carbon nanotube structure comprises a disordered arrangement of carbon nanotubes, the carbon nanotubes are intertwined or oriented Isotropic arrangement; 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. The carbon nanotubes are attracted to each other, overlap each other or entangled to form a stable structure of a shape. In the nanotube breaking composite material 10, the nanocarbon tube structure 16 serves as a skeleton for the branch 8 201016598 - the nanoparticle 18. The carbon nanotube structure 16 includes at least one layer of carbon nanotube-membrane. The carbon nanotube membrane includes a plurality of uniformly distributed nanocarbons. ^ A plurality of uniform distributions of carbon nanotubes are ordered and disordered (4) , the carbon nanotubes are connected by Van der Waals force. The carbon nanotube carbon nanotube flocculation membrane, the carbon nanotube membrane or the carbon nanotube is preferably ς:, = the carbon nanotube structure 16 is a self-supporting structure, specifically the superiority = the branch condition The carbon nanotube structure 16 does not require the substrate support ρ 7G to be completely independent and self-supporting; a part of the carbon nanotube structure 16 has one or a plurality of support points, and the rest can be suspended and has a stable structure. VIII. Referring to Fig. 2, the carbon nanotube flocculation membrane is isotropic, and a plurality of disordered and uniformly distributed ::: Deval force attracts each other and entangles each other. Therefore, = has a very soft (four), can be bent into any shape without breaking, so that the good self-supporting energy can be self-supported without the support of the base. The thickness of the carbon nanotube film is i microns 2 mm. The barrier film of the carbon nanotubes includes a carbon tube with a uniform distribution of the carbon nanotubes, and the nanometer:: two: the direction or the orientation of the different orientations. The carbon nanotubes of the carbon nanotubes and the surface of the carbon nanotubes of the carbon nanotubes are at an angle α, ^, "greater than or equal to zero degrees and less than or equal to 15 degrees (〇 15). Preferably, the carbon nanotubes in the membrane = nanocarbon tube is parallel to the carbon nanotubes;:". Depending on the way of the pressure barrier, the carbon nanotubes are impeding Different arrangements. Specifically, the carbon nanotubes can be selected: ί arrangement; when the carbon nanotubes are arranged in different directions along different directions (four), please refer to Figure 3, the carbon nanotubes in the carbon nanotubes In the pressure film, the orientation is preferred. Please refer to Figure 4. The carbon nanotubes in the laminated film of 201016598 can be arranged in different orientations. The carbon nanotubes in the rolled film partially overlap. The nano-carbon nanotubes in the laminated film are mutually attracted by the van der Waals force and closely combined, so that the nano-carbon official ore film has Very flexible, can be bent and folded into any shape without breaking. And because the carbon nanotubes in the carbon nanotube film are attracted to each other through the van der Waals force, the carbon nanotubes are crushed. The lamination film is a self-supporting structure, which can be self-supported without substrate support. The thickness of the laminated film is ΟΛ microns - 5 mm.
請參見圖5,所述奈米碳管拉膜包括複數個首尾相連 且沿拉伸方向擇優取向排列的奈米碳管。所述奈米碳管 均勻分佈，且平行於奈米碳管膜表面。所述奈米碳管膜 中的奈米碳管之間通過凡德瓦爾力連接。一方面，首尾 相連的奈米碳管之間通過凡德瓦爾力連接，另一方面， 平行的奈米碳管之間部分亦通過凡德瓦爾力結合，故， 該奈米碳管膜具有-定㈣_，可料折疊成任意形 狀而不破裂。所述奈米碳管拉膜的厚度為〇.5 〇〇 微米。 ， 所述奈士碳管結構16可進一步包括至少兩個重疊言 置的奈米叙官膜。可以理解，由於奈米碳管結構中的崔 米碳管膜可重疊設置，故’上述奈米碳管結構16的 限，可根據實際需要製成具有任意厚度的奈米碳管、㈣ 16。當奈^官結構16包括複數個重疊設置的奈米碳管击 膜時，相鄰的奈米碳管拉膜中的奈米碳管 一夾角 β，0°邻$90°。 j 所述奈：碳管包括單壁奈来碳管、雙壁奈米碳管幻 壁奈米碳管中的-種或幾種。單壁奈米碳管的直徑為〇. 201016598 .奈米〜50奈米，雙壁奈米碳管的直徑為1〇奈米〜5〇卉 .多壁奈米碳管的直徑為1.5奈米〜5G奈米。所述夺米 =度在5〇奈米到1〇毫米之間，優選地，奈米碳^ 度為200微米-900微米。 的長 所述奈米顆粒18可附著在奈米碳管結構16中 碳管的表面，當奈米碳管結構16包括多 =顆粒18顆可填充於相鄰的奈米碳管膜=碳： 戶18可相互獨立保持奈米顆粒18的高比表面積 斤攻不未顆粒18之間也可相互接觸。 所述奈米顆粒18包括奈米纖維、奈米管、夺 5 =奈米線各種形態的奈米顆粒中的-種或幾種。夺 金屬奈米顆粒、非金屬奈米顆粒、合金奈米Referring to FIG. 5, the carbon nanotube film comprises a plurality of carbon nanotubes connected end to end and arranged in a preferred orientation along the stretching direction. The carbon nanotubes are evenly distributed and parallel to the surface of the carbon nanotube film. The carbon nanotubes in the carbon nanotube membrane are connected by van der Waals force. On the one hand, the end-to-end carbon nanotubes are connected by van der Waals force, and on the other hand, the parallel carbon nanotubes are also combined by van der Waals force, so the carbon nanotube film has - Set (4) _, can be folded into any shape without breaking. The thickness of the carbon nanotube film is 〇.5 微米 microns. The carbon nanotube structure 16 may further comprise at least two overlapping nano-films. It can be understood that since the Cui carbon tube membranes in the carbon nanotube structure can be overlapped, the above-mentioned carbon nanotube structure 16 can be made to have carbon nanotubes of any thickness and (IV) 16 according to actual needs. When the nanostructures 16 comprise a plurality of stacked carbon nanotube membranes, the carbon nanotubes in the adjacent carbon nanotubes are at an angle β, 0° adjacent to $90°. j The nai: carbon tube includes one or several types of single-walled carbon nanotubes and double-walled nanocarbon tubes. The diameter of a single-walled carbon nanotube is 〇. 201016598 . Nano ~ 50 nm, the diameter of the double-walled carbon nanotube is 1 〇 nanometer ~ 5 〇 hui. The diameter of the multi-walled carbon nanotube is 1.5 nm. ~5G nano. The rice recovery is between 5 nanometers and 1 millimeter, and preferably, the carbon carbonity is 200 micrometers to 900 micrometers. The long nanoparticles 18 can be attached to the surface of the carbon nanotubes in the carbon nanotube structure 16, when the carbon nanotube structure 16 comprises multiple = particles 18 can be filled in adjacent carbon nanotube membranes = carbon: The households 18 can independently maintain the high specific surface area of the nanoparticles 18 and the particles 18 can also contact each other. The nanoparticles 18 include nanofibers, nanotubes, or a variety of nanoparticles of various forms of the nanowires. Metal nanoparticle, non-metallic nanoparticle, alloy nano
St二二物奈米顆粒及聚合物奈米顆粒中的-種或 it顆：，二：18可為銅奈米顆粒、鋅奈米顆粒、 ❹ 粒、聚苯胺奈米顆粒或= 奈米顆 U的粒徑為0.3奈㈣5(/奈米。=等太。/述奈米顆粒 攻.=:複合材料101的質量百分含量為〇 〇ι %~9妙。 碳管相===複合材料10中的奈米 1有Μ = ϊ 構18’奈米碳管結構18 導電性，故，奈米碳管複合材料1G具有良好的 ；，可用作電極材料、感測器、電& ^4, ： 10 奈米碳管複合材料10的咏类而接“有複數個微孔20， 能力，故，太乎雄與、t入^表積較大，具有較強的吸附 '丁、未碳吕複合材料10還可用作催化劑的載體或 11 201016598 .其他材料的支撐體。 請參見圖6，本技術方案實施例提供一種製備上述奈 米碳管複合材料的方法，其具體包括以下步驟： 步驟一、製備一奈米碳管結構。 製備奈米碳管結構的方法具體包括 以下步驟： (一）製備一奈米碳管膜，所述奈米碳管膜包括複數 個均勻V佈的奈米碳管，該複數個均勻分佈的奈米碳管 有序或無序分佈’奈米碳管之間通過凡德瓦爾力相互連 ©接。該奈米碳管骐可為奈米碳管絮化膜、奈米碳管碾壓 膜或奈米碳管拉膜。 根據奈米碳管膜的不同，所述奈米碳管膜的製備方法 包括：絮化法、碾壓法、直接拉膜法等。 所述絮化法製備奈米碳管膜的方法具體包括以 驟： 首先’提供一奈米碳管原料。 —所述不#碳S原料可為通過化學氣相沈積法、石墨電 參極恒流祕放電沈積法或㈣蒸發沈積法等St-two-nanoparticles and polymer-nanoparticles of the species or it:: two: 18 can be copper nanoparticles, zinc nanoparticles, cerium particles, polyaniline nanoparticles or = nano particles The particle size of U is 0.3 Na (4) 5 (/nano. = et al. / Nai granule attack. =: The mass percentage of composite 101 is 〇〇ι %~9 Miao. Carbon tube phase === compound The nano 1 in the material 10 has Μ = ϊ 18' carbon nanotube structure 18 conductivity, so the carbon nanotube composite 1G has good; can be used as electrode material, sensor, electricity & ^4, : 10 The carbon nanotube composite material 10 of the scorpion is connected with "a plurality of micropores 20, the ability, therefore, too male and male, t into the ^ table product is large, with strong adsorption 'd, The carbon-free composite material 10 can also be used as a carrier for the catalyst or as a support for other materials. Referring to FIG. 6 , an embodiment of the present technical solution provides a method for preparing the above-described carbon nanotube composite material, which specifically includes the following Step: Step 1: Prepare a carbon nanotube structure. The method for preparing a carbon nanotube structure specifically includes the following steps: (1) preparing a nai a carbon tube membrane comprising a plurality of carbon nanotubes of uniform V cloth, the plurality of uniformly distributed carbon nanotubes being ordered or disorderly distributed between the carbon nanotubes and the van der Waals The carbon nanotubes may be a carbon nanotube membrane, a carbon nanotube membrane or a carbon nanotube membrane. The nanotube is different according to the carbon nanotube membrane. The preparation method of the carbon tube membrane comprises: a flocculation method, a rolling method, a direct film drawing method, etc. The method for preparing the carbon nanotube film by the flocculation method specifically comprises the steps of: first providing a nano carbon tube raw material. - the non-carbon S material may be by chemical vapor deposition, graphite electric parametric constant current flow discharge deposition method or (four) evaporation deposition method, etc.
備的奈米碳管。 A 本實施例中，採用刀片或其他工具將上述定向排列的 奈米碳^陣列從基底料，獲得—奈米碳管原料。優選 地，所述之奈米碳管的長度大於100微米。 、 ,、人將上述不米碳管原料添加到 化處理獲得-奈米碳管絮狀結構。 财1進仃务、 本技術方案實施例卜溶劑可選用水、易揮發 溶劑等。絮化處理可通過採用超聲波分散處：： 揽拌等方法。優選地’本技術方案實施例採用超聲波= 12 201016598 •散10分鐘〜30分鐘。由於奈米碳管具有極大的比表面積， -相互纏繞的奈米碳管之間具有較大的凡德瓦爾力。上述 絮化處理並不會將該奈米碳管原料中的奈米碳管完全分 散在溶劑中，奈米碳管之間通過凡德瓦爾力相互吸引、 纏繞，緊密結合。 再次’將上述奈米碳管絮狀結構從溶劑中分離，並對 該奈米碳管絮狀結構定型處理以獲得一奈米碳管絮化 膜。 、 參 本技術方案實施例中，所述之分離奈米碳管絮狀结構 的方法具體包括以下步驟：將上述含有奈米碳管絮狀結 構的溶劑倒入一放有濾紙的漏斗中；靜置乾燥一段時間 從而獲得一分離的奈米碳管絮狀結構。 本技術方案實施例中，所述之奈米碳管絮狀結構的定 型處理過程具體包括以下纟驟：將上述奈米碳管絮狀結 構置於一容器中，·將該奈米碳管絮狀結構按照預定形狀 攤開；施加一定壓力於攤開的奈米碳管絮狀結構；以及， ❹將該奈米碳管絮狀結構中殘留的溶劑烘乾或等溶劑自然 揮發後獲得一奈米碳管絮化膜。由於，奈米碳管之間通 過凡德瓦爾力相互吸引、相互纏繞，故，奈米碳管絮化 膜具有很好的柔韌性，可彎曲折疊成任意形狀而不破 裂，且具有較好的自支撐性能，可無需基底支撐，自支 撐存在。 可以理解，本技術方案實施例可通過控制該奈米碳管 絮狀結構攤開的面積來控制該奈米碳管絮化膜的厚度和 麵密度。奈米碳管絮狀結構攤開的面積越大，則該奈米 碳管絮化膜的厚度和麵密度就越小。 13 201016598 * 另，上述分離與定型處理奈米碳管絮狀結構的步驟也 .可直接通過抽濾的方式實現，具體包括以下步驟：提供 一微孔濾膜及一抽氣漏斗；將上述含有奈米碳管絮狀鈐 構的溶劑經過該微孔濾膜倒入該抽氣漏斗中；抽濾並^ 燥後獲得一奈米碳管絮化膜。該微孔濾膜為一表面^ 滑、孔徑為0.22微米的濾膜。由於抽濾方式本身將提供 一較大的氣壓作用於該奈米碳管絮狀結構，該奈米碳^ 絮狀結構經過抽濾會直接形成一均勻的奈米碳管絮化 ⑩膜。且，由於微孔濾膜表面光滑，該奈米碳管絮化膜容 易剝離。 所述直接拉膜法製備奈米碳管膜的方法具體包括以 下步驟： 首先，提供一奈米碳管陣列形成於一基底，該陣列為 超順排的奈米碳管陣列。 該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 φ型或N型矽基底，或選用形成有氧化層的矽基底，本技 術方案實施例優選為採用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)、銘（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7〇〇C 〜9〇〇t>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5〇〇β(： 〜74(rc，然後通入 碳源氣體反應約5分鐘〜30分鐘，生長得到奈米碳管陣 列。該奈米碳管陣列為複數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 201016598 •長條件，該定向排列的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。 本技術方案實施例提供的奈米碳管陣列為單壁奈米 ，管陣列、雙壁奈米碳管陣列及多壁奈米碳管陣列;^的 種。所述奈米碳管的直徑為〇.5奈米〜50奈米，長度大 於50微米。本實施例中，奈米碳管的長度優選為1〇〇〜9〇〇 微求。 本技術方案實施例中碳源氣可選用乙炔、乙烯、甲烷 ❹等化學性質較活潑的碳氫化合物，本技術方案實施例優 選的碳源氣為乙炔；保護氣體為氮氣或惰性氣體，本技 術方案實施例優選的保護氣體為氬氣。 可以理解，本技術方案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。 其次，採用一拉伸工具從奈米碳管陣列中拉取奈米碳 管獲得至少一奈米碳管拉膜。 ❿ 該奈米碳管膜的製備過程具體包括以下步驟：該奈米 碳管膜係從超順排奈米碳管陣列中直接拉取獲得，其製備 方法具體包括以下步驟：（a)採用一拉伸工具選取該超 順排奈米碳管陣列中的部分奈米碳管，本實施例優選為 採用具有一定寬度的膠帶接觸奈米碳管陣列以選定一定 寬度的部分奈米碳管；（b)以一定的速度沿基本垂直於 超順排奈米碳管陣列生長方向拉伸該部分奈米碳管，形 成一連續的奈米碳管拉膜。且由於奈米碳管拉膜中的奈； 米碳管之間通過凡德瓦爾力相互吸引，緊密結合，使^ 米碳管拉膜为一自支撑的结构，无需基底支撑，可自支 15 201016598 撑存在。 在上述拉伸過程中，在拉力作用下超順排奈米碳管陣 列中的部分奈米碳管沿拉伸方向逐漸脫離基底的同時，由 於凡德瓦爾力作用，該超順排奈米碳管陣列t的其他奈米 碳管首尾相連地連續地被拉出，從而形成一奈米碳管拉 膜。該奈米碳管拉膜包括複數個奈米碳管首尾相連且沿 拉伸方向定向排列。該奈米碳管拉膜的寬度與超順排= 米碳管陣列的尺寸（直徑/寬度）有關，該奈米碳管拉膜的^ ©度與超順排奈米碳管陣列的高度有關。 所述碾壓法製備奈米碳管膜的方法具體包括以下 驟： 首先，於一基底生長一奈米碳管陣列。 所述奈米碳管陣列優選為一超順排的奈米碳管陣 列。所述奈米碳管陣列與上述奈米碳管陣列的製備方法 相同。 ' 其次，採用一施壓裝置，擠壓上述奈米碳管陣列獲得 ❹一奈米碳管碾壓膜，其具體過程為： 該施壓裝置施加一定的壓力於上述奈米碳管陣列 上。在施壓的過程中，奈米碳管陣列在壓力的作用下會 與生長的基底分離，從而形成由複數個奈米碳管組成的 奈米碳管碾壓膜，且所述之複數個奈米碳管基本上與奈 米碳管碾壓膜的表面平行。由於奈米碳管碾壓膜中的奈 米碳管之間通過凡德瓦爾力相互吸引’緊密結合，使奈 米碳管碾壓膜為一自支撐的結構，可無需基底支撐，自 支撐存在。 16 201016598 ^ 本技術方案實施例中，施壓裝置為一壓頭，壓頭表面 *光滑’壓頭的形狀及擠壓方向決定製備的奈米碳管碾壓 膜中奈米礙官的排列方式。具體地，當採用平面壓頭沿 垂直於上述奈米碳管陣列生長的基底的方向擠壓時，可 獲得奈米碳官為各向同性排列的奈米碳管碾壓膜；當採 用滾軸狀壓頭沿某一固定方向碾壓時，可獲得奈米碳管 沿該固定方向取向排列的奈米碳管碾壓膜；當採用滚軸 狀壓頭沿不同方向碾壓時，可獲得奈米碳管沿不同方向 ❹取向排列的奈米碳管礙壓膜。 (二）利用上述奈米碳管膜製備奈米碳管結構。 所述奈米碳管膜可直接作為奈米碳管結構。 進一步，還可將至少兩層奈米碳管膜重疊鋪設得到一 奈米碳管結構。該奈米碳管結構中，奈米碳管膜的層數 不限，具體可依據實際需求製備。當奈米碳管結構包括 至少兩層重疊設置的奈米碳管拉膜時，奈米碳管拉臈之 間可沿任意角度重疊鋪設，相鄰的奈米碳管拉膜中的夯 _米碳管的排列方向形成一夾角P，OYPgO。。 不 步驟二：提供一可形成奈米顆粒的預製體。 所述預製體為該奈米顆粒所對應的物質、該物 形成的溶液或該物質的前驅反應物。 所述奈米顆粒所對應的物質包括金屬、非金屬、人 金、金屬氧化物或聚合物。具體地，金屬可包括鋼： 或鈷等，非金屬可包括碳粒或金剛石，合金可包括 金或鋁合金，金屬氧化物可包括氧化銅或氧化鋅、二 物可包括聚苯胺或聚吼咯。 1口 17 201016598 • 所述奈米顆粒所對應的物質的溶液為將該材料溶解 ，於溶劑中制得。所述溶劑可為水、酸、域、有機物^可 溶解該固態的材料的溶劑，其具體根據該材料而定。 、所述該奈米顆粒所對應的物質的前驅反應物為可通 過化學反應生成該材料的反應物，該反應物可為氣熊、 液態或處於溶液中，反應完成後所生成的該物質為熊 =式，並可通過一定方法如洗滌、過濾等從反應體系= 分離出來。 碳管::;料將奈米碳管結構與預製體複合，得到-奈米 當預製體為該奈米顆粒所對應的物質時， 可採取不同方法使奈…= 興不未顆粒預製體複合。當該物質為氣態物質時， 附等方法在奈米碳管結構中形成奈米顆粒； 管結構中形成奈米顆粒；當該物質為 ^不未奴 參 蒸鑛，等方法在奈米碳管結構中、形成奈時米顆液粒可採用 田^製體為該㈣顆粒對應的物質所形成的溶液 時，^求碳管結構與預製體複合的方法包括以下步驟： 先，採用該溶液浸潤該奈米碳管結構。將夺米碳典 j浸入到該該溶液令或將該 至二 碳管結構的表面直至其浸潤該奈米碳管結構奈未 將浸潤後的奈米碳管結構置於一 冷液中的溶劑揮發或蒸發， 使 該材料以奈米顆掄的" 不未奴管結構，此時， ' /式附著於奈米碳管結構中的奈米 18 201016598 •喊管的表面。 田預製體為奈米顆粒對 用化學氣相沈積法、雷赞絲”、物質的反應前驅體時，可採 濺射顆粒形成於奈助:碳積二冓電^ 種領域，如支撐nr電m管複/材料可應用於各 料或導電材料等。 +材料、感測器、電磁遮罩材 ⑩點·^之Γ米碳管複合材料及其製備方法具有以下優 © .其一，由於所述奈米 連接形成一牟乎磁與紝接 們竹T町不木碳管相互 I序排歹"右：： 該奈求碳管結射的奈米碳管 輕t排或有序排列，使得奈米碳管複合材料的機械強度 二韌性較好，克服了奈米碳管易團聚的缺點。1二， 用奈米碳管結構作為骨架，從而使得所述之ς米碳 :材料具有良好的導電性，充分發揮了奈米碳管的導 =性能。其三，所述奈米碳管複合材料的製備方法無需高 / 皿過程或對奈米碳管表面進行處理，故不會對奈采碳管造 響成破壞。 g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。舉凡習知本案技藝 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係本技術方案實施例的提供的奈米碳管複合材料 的結構示意圖。 19 201016598 描電的奈米^絮化媒的掃 圖3為本技術方案實施例提供的包括沿不同方向擇 取向排列的奈米碳管的奈米碳管碾壓膜的掃描電鏡照片。 圖4為本技術方案實施例提供的包括沿同—方向擇優 取向排列的奈米碳管的奈米碳管碾壓膜的掃描電鏡照片。 圖5係本技術方案實施例提供的奈米碳管拉獏的掃描 電鏡照片。 參 16係本技術方案實施例提供的奈米碳管複合材料的 製備方法的流程圖。 ’、 【主要元件符號說明】 奈米碳管複合材料 奈米碳管結構 奈米顆粒 微孔 Φ 10 16 18 20 20Prepared carbon nanotubes. In the present embodiment, the aligned nanocarbon array is obtained from the substrate by a blade or other tool to obtain a carbon nanotube raw material. Preferably, the carbon nanotubes have a length greater than 100 microns. ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, For the first time, the solvent of the present invention is water, volatile solvent, and the like. The flocculation treatment can be carried out by using ultrasonic dispersion:: mixing. Preferably, the embodiment of the present technical solution uses ultrasonic = 12 201016598 • 10 minutes to 30 minutes. Since the carbon nanotubes have a very large specific surface area, there is a large van der Waals force between the intertwined carbon nanotubes. The above flocculation treatment does not completely disperse the carbon nanotubes in the carbon nanotube raw material in the solvent, and the carbon nanotubes are attracted to each other by the van der Waals force, and are tightly bonded. Again, the above carbon nanotube floc structure is separated from the solvent, and the carbon nanotube floc structure is shaped to obtain a carbon nanotube flocculation membrane. In the embodiment of the technical solution, the method for separating the carbon nanotube floc structure comprises the following steps: pouring the solvent containing the carbon nanotube floc structure into a funnel with a filter paper; The drying is carried out for a period of time to obtain a separate carbon nanotube floc structure. In the embodiment of the technical solution, the shaping process of the nano carbon tube floc structure specifically includes the following steps: placing the carbon nanotube floc structure in a container, and the carbon nanotube The structure is spread according to a predetermined shape; a certain pressure is applied to the expanded carbon nanotube floc structure; and, ❹, the residual solvent in the nano carbon tube floc structure is dried or the solvent is naturally volatilized to obtain a Rice carbon tube flocculation membrane. Because the carbon nanotubes are mutually attracted and intertwined by van der Waals force, the carbon nanotube film has good flexibility, can be bent and folded into any shape without cracking, and has better Self-supporting performance, without the need for substrate support, self-supporting. It will be appreciated that embodiments of the present technical solution can control the thickness and areal density of the carbon nanotube flocculation membrane by controlling the area in which the carbon nanotube floc is spread. The larger the area in which the carbon nanotube floc structure is spread, the smaller the thickness and areal density of the carbon nanotube flocculation film. 13 201016598 * In addition, the above steps of separating and shaping the carbon nanotube floc structure can also be directly carried out by suction filtration, specifically comprising the steps of: providing a microporous membrane and an extraction funnel; The solvent of the carbon nanotube floc structure is poured into the suction funnel through the microporous membrane; after suction filtration and drying, a carbon nanotube flocculation membrane is obtained. The microporous membrane is a membrane having a smooth surface and a pore size of 0.22 μm. Since the suction filtration method itself will provide a large gas pressure to the carbon nanotube floc structure, the nano carbon foam structure will directly form a uniform carbon nanotube flocculation membrane 10 by suction filtration. Moreover, since the surface of the microporous membrane is smooth, the carbon nanotube flocculation membrane is easily peeled off. The method for preparing a carbon nanotube film by the direct drawing method specifically comprises the following steps: First, an array of carbon nanotubes is provided on a substrate, which is a super-aligned array of carbon nanotubes. The method for preparing the 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 φ type or N type ruthenium substrate, or a ruthenium formed with an oxide layer may be selected. The substrate, the embodiment of the technical solution preferably adopts a 4 inch germanium substrate; (b) uniformly forms a catalyst layer on the surface of the substrate, and the catalyst layer material may be selected from iron (Fe), indium (Co), nickel (Ni) or One of the alloys of any combination; (c) annealing the substrate on which the catalyst layer is formed in air of 7 〇〇C to 9 〇〇t>c for about 30 minutes to 90 minutes; (d) placing the treated substrate In a reaction furnace, in a protective gas atmosphere, heat to 5 〇〇β (: ～74 (rc, then pass through a carbon source gas for about 5 minutes to 30 minutes to grow to obtain a carbon nanotube array. The carbon nanotube) The array is a plurality of pure carbon nanotube arrays formed of carbon nanotubes that are parallel to each other and perpendicular to the substrate. The above-mentioned controlled growth of the carbon nanotube array is substantially free of impurities as described above. Amorphous carbon or residual catalyst metal Particles, etc. The carbon nanotube array provided by the embodiments of the present technical solutions is a single-walled nano tube, a tube array, a double-walled carbon nanotube array, and a multi-walled carbon nanotube array; The diameter of the carbon nanotubes is 〇5 nm to 50 nm, and the length is greater than 50 μm. In the present embodiment, the length of the carbon nanotubes is preferably 1 〇〇 9 9 。. A chemically active hydrocarbon such as acetylene, ethylene or methane oxime may be used. The preferred carbon source gas in the embodiment of the technical solution is acetylene; the shielding gas is nitrogen or an inert gas, and the preferred shielding gas in the embodiment of the present technical solution is argon. It should be understood that the carbon nanotube array provided by the embodiments of the present technical solution is not limited to the above preparation method, and may also be a graphite electrode constant current arc discharge deposition method, a laser evaporation deposition method, etc. Secondly, a stretching tool is used from the bottom. The carbon nanotube array is pulled to obtain at least one carbon nanotube film. 制备 The preparation process of the carbon nanotube film specifically includes the following steps: the carbon nanotube film is from super-shoring nanocarbon Direct pull in the tube array Obtaining, the preparation method comprises the following steps: (a) selecting a part of the carbon nanotubes in the super-sequential carbon nanotube array by using a stretching tool, and in this embodiment, preferably contacting the nanometer with a tape having a certain width. The carbon tube array selects a portion of the carbon nanotubes of a certain width; (b) stretches the portion of the carbon nanotubes at a certain speed along a growth direction substantially perpendicular to the super-sequential carbon nanotube array to form a continuous nanotube Carbon tube is pulled. Because of the naphthalene in the carbon nanotube film; the carbon nanotubes are attracted to each other by the van der Waals force, and the carbon nanotubes are a self-supporting structure without the substrate support. , can be self-supporting 15 201016598 support. During the above stretching process, part of the carbon nanotubes in the super-aligned carbon nanotube array under tension is gradually separated from the substrate in the stretching direction, due to Van der Waals force As a function, the other carbon nanotubes of the super-sequential carbon nanotube array t are continuously pulled out end to end to form a carbon nanotube film. The carbon nanotube film comprises a plurality of carbon nanotubes connected end to end and oriented in a stretching direction. The width of the carbon nanotube film is related to the size of the super-sequence = carbon nanotube array (diameter/width), and the degree of the film of the carbon nanotube is related to the height of the super-sequential carbon nanotube array. . The method for preparing a carbon nanotube film by the rolling method specifically comprises the following steps: First, an array of carbon nanotubes is grown on a substrate. The carbon nanotube array is preferably a super-aligned array of carbon nanotubes. The carbon nanotube array is the same as the above-described method for preparing a carbon nanotube array. Secondly, using a pressure applying device, the carbon nanotube array is extruded to obtain a tantalum carbon nanotube rolled film, and the specific process is as follows: The pressing device applies a certain pressure to the carbon nanotube array. During the pressing process, the carbon nanotube array is separated from the growing substrate by pressure, thereby forming a carbon nanotube rolled film composed of a plurality of carbon nanotubes, and the plurality of nanotubes are described. The carbon nanotubes are substantially parallel to the surface of the carbon nanotube rolled film. Because the carbon nanotubes in the carbon nanotube film are mutually attracted by the van der Waals force, the carbon nanotube film is a self-supporting structure, which can be self-supported without substrate support. . 16 201016598 ^ In the embodiment of the technical solution, the pressing device is an indenter, and the shape of the indenter surface *the shape of the indenter and the direction of extrusion determine the arrangement of the nanometer in the prepared carbon nanotube film . Specifically, when a planar indenter is pressed in a direction perpendicular to a substrate grown by the above-described carbon nanotube array, a nanocarbon tube laminated film having an isotropic carbon nanotube is obtained; when a roller is used When the pressure head is rolled in a certain fixed direction, a carbon nanotube film which is aligned along the fixed direction of the carbon nanotubes can be obtained; when the roller-shaped indenter is rolled in different directions, the naphthalene can be obtained. The carbon nanotubes are arranged in different directions and arranged in a carbon nanotube barrier film. (2) The carbon nanotube structure is prepared by using the above carbon nanotube film. The carbon nanotube film can be directly used as a carbon nanotube structure. Further, at least two layers of carbon nanotube membranes may be overlapped to obtain a carbon nanotube structure. In the carbon nanotube structure, the number of layers of the carbon nanotube film is not limited, and can be prepared according to actual needs. When the carbon nanotube structure comprises at least two layers of carbon nanotube film which are arranged in an overlapping manner, the carbon nanotubes can be laid at any angle and overlapped, and the 奈_米 in the adjacent carbon nanotube film is laminated. The arrangement direction of the carbon tubes forms an angle P, OYPgO. . No. Step 2: Provide a preform that can form nanoparticle. The preform is a substance corresponding to the nanoparticle, a solution formed by the substance, or a precursor reactant of the substance. Substances corresponding to the nanoparticles include metals, non-metals, human gold, metal oxides or polymers. Specifically, the metal may include steel: or cobalt or the like, the non-metal may include carbon particles or diamond, the alloy may include gold or aluminum alloy, the metal oxide may include copper oxide or zinc oxide, and the second material may include polyaniline or polyfluorene. . 1 port 17 201016598 • A solution of the substance corresponding to the nanoparticle is prepared by dissolving the material in a solvent. The solvent may be water, an acid, a domain, an organic substance, a solvent which can dissolve the solid material, depending on the material. The precursor reactant of the substance corresponding to the nanoparticle is a reactant capable of generating the material by a chemical reaction, and the reactant may be a gas bear, a liquid or in a solution, and the substance formed after the reaction is completed is Bear = type, and can be separated from the reaction system by certain methods such as washing, filtration, and the like. The carbon tube::; the material is combined with the preform of the carbon nanotube structure to obtain - nano when the preform is the material corresponding to the nanoparticle, the different methods can be used to make the nano...= Xingbui granule prefabricated composite . When the substance is a gaseous substance, the attachment method forms nano particles in the carbon nanotube structure; the nano-particles are formed in the tube structure; when the substance is a non-nano-salt steamed, the method is in the carbon nanotube In the structure, when the Naibei rice liquid particle is used as the solution formed by the material corresponding to the (4) particle, the method for compounding the carbon tube structure and the preform includes the following steps: First, the solution is infiltrated The carbon nanotube structure. Immersing the carbon meter j into the solution or causing the surface of the carbon nanotube structure to be infiltrated until the carbon nanotube structure is infiltrated by the solvent in which the infiltrated carbon nanotube structure is placed in a cold liquid. Or evaporate, so that the material is in the form of a nanometer 不 不 不 不 , , , , , , , , , , 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着When the prefabricated body is a reaction precursor of nanoparticle to chemical vapor deposition, Rezans, or a substance, the sputtered particles can be formed in the field of carbon nano-electricity, such as supporting nr electricity. m tube complex / material can be applied to various materials or conductive materials, etc. + material, sensor, electromagnetic shielding material 10 points · ^ glutinous carbon tube composite material and its preparation method have the following advantages. The nano-connected to form a magnetic and splicing bamboo T-machi non-wood carbon tube mutual I-sequence 歹; right:: The carbon nanotubes of the carbon nanotubes are lightly t-ordered or ordered The nano-carbon tube composite material has better mechanical strength and toughness, and overcomes the disadvantages of easy agglomeration of the carbon nanotubes. First, the carbon nanotube structure is used as a skeleton, so that the glutinous rice carbon material has Good conductivity, fully exerting the conductivity of the carbon nanotubes. Third, the preparation method of the carbon nanotube composite does not require high/dish process or treatment of the surface of the carbon nanotube, so it will not The carbon nanotubes are damaged into damage. g In summary, the invention has indeed met the requirements of the invention patent. The patent application is filed 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 of the present invention. Anyone skilled in the art can assist in the spirit of the present invention. The modification or change of the effect should be included in the following patent application. [Simplified description of the drawings] Fig. 1 is a schematic structural view of a carbon nanotube composite material provided by an embodiment of the present technical solution. 19 201016598 Scanning electron micrograph of the carbon nanotubes including the carbon nanotubes arranged in different directions according to the embodiment of the present invention is provided in the embodiment of the present invention. FIG. 4 is a schematic diagram of the embodiment of the present invention. A scanning electron micrograph of a carbon nanotube rolled film including carbon nanotubes arranged in a preferred orientation along the same direction. Figure 5 is a scanning electron micrograph of a carbon nanotube pulling provided by an embodiment of the present technical solution. A flow chart of a method for preparing a carbon nanotube composite material provided by an embodiment of the present technical solution. ', [Key element symbol description] Nano carbon tube composite material carbon nanotube structure nanometer Microporous Φ 10 16 18 20 20