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TWI419921B - Method for making carbon nanotube composite structure - Google Patents

Method for making carbon nanotube composite structure Download PDF

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TWI419921B
TWI419921B TW99122583A TW99122583A TWI419921B TW I419921 B TWI419921 B TW I419921B TW 99122583 A TW99122583 A TW 99122583A TW 99122583 A TW99122583 A TW 99122583A TW I419921 B TWI419921 B TW I419921B
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carbon nanotube
carbon
polymer
graphite
preparing
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TW201202320A (en
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Kai Liu
Kai-Li Jiang
ying-hui Sun
Shou-Shan Fan
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Hon Hai Prec Ind Co Ltd
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奈米碳管複合結構之製備方法 Method for preparing nano carbon tube composite structure

本發明涉及一種奈米碳管複合結構之製備方法。 The invention relates to a preparation method of a carbon nanotube composite structure.

奈米碳管係一種由石墨烯片卷成之中空管狀物。奈米碳管具有優異之力學、熱學及電學性質,其應用領域非常廣闊。例如,奈米碳管可用於製作場效應電晶體、原子力顯微鏡針尖、場發射電子槍、奈米模板等。上述技術中奈米碳管之應用主要係奈米碳管在微觀尺度上之應用,操作較困難。故,使奈米碳管具有宏觀尺度之結構並在宏觀上應用具有重要意義。 The carbon nanotube is a hollow tube rolled from a graphene sheet. Nano carbon tubes have excellent mechanical, thermal and electrical properties and are used in a wide range of applications. For example, carbon nanotubes can be used to make field effect transistors, atomic force microscope tips, field emission electron guns, nano templates, and the like. The application of the carbon nanotubes in the above technology is mainly the application of the carbon nanotubes on the microscopic scale, and the operation is difficult. Therefore, it is of great significance to make the carbon nanotubes have a macroscopic structure and to be applied at a macroscopic level.

姜開利等人於2002年成功地從一奈米碳管陣列拉取獲得一具有宏觀尺度之奈米碳管線,具有請參見文獻“Spinning Continuous Carbon Nanotube Yarns”,Nature,V419,P801。所述奈米碳管線由複數首尾相連且基本沿同一方向擇優取向排列之奈米碳管組成。 In 2002, Jiang Kaili and others successfully extracted a nanometer carbon pipeline with a macroscopic scale from a carbon nanotube array, see "Spinning Continuous Carbon Nanotube Yarns", Nature, V419, P801. The nanocarbon pipeline is composed of a plurality of carbon nanotubes connected end to end and arranged in a preferred orientation along the same direction.

然,所述奈米碳管線中之奈米碳管之間之結合力較弱,故,所述奈米碳管線之機械性能還需進一步提高。 However, the bonding force between the carbon nanotubes in the nanocarbon pipeline is weak, so the mechanical properties of the nanocarbon pipeline need to be further improved.

有鑒於此,提供一種製備具有良好機械性能之奈米碳管複合結構之方法實為必要。 In view of this, it is necessary to provide a method for preparing a carbon nanotube composite structure having good mechanical properties.

一種奈米碳管複合結構之製備方法,其包括如下步驟:提供一奈米碳管結構,所述奈米碳管結構包括複數奈米碳管通過凡得瓦力連接;所述奈米碳管結構中複合一聚合物;以及石墨化複合在所述奈米碳管結構中之聚合物,使該聚合物石墨化為一石墨結構。 A method for preparing a carbon nanotube composite structure, comprising the steps of: providing a carbon nanotube structure, wherein the carbon nanotube structure comprises a plurality of carbon nanotubes connected by van der Waals; the carbon nanotube a composite-polymer in the structure; and a graphitized polymer compounded in the carbon nanotube structure to graphitize the polymer into a graphite structure.

相較於先前技術,所述製備方法通過石墨化複合在所述奈米碳管結構中之聚合物之方式,在該奈米碳管結構中填充並複合一石墨結構。所述石墨結構可與所述奈米碳管結構通過碳碳鍵結合,從而可提高奈米碳管之間之結合力,使所述奈米碳管複合結構之具有優異之機械性能。 In contrast to the prior art, the preparation method fills and composites a graphite structure in the carbon nanotube structure by graphitizing a polymer compounded in the carbon nanotube structure. The graphite structure can be bonded to the carbon nanotube structure through carbon-carbon bonds, thereby improving the bonding force between the carbon nanotubes and the excellent mechanical properties of the carbon nanotube composite structure.

圖1為一奈米碳管絮化膜之掃描電鏡照片。 Figure 1 is a scanning electron micrograph of a carbon nanotube film.

圖2為一奈米碳管碾壓膜之掃描電鏡照片。 Figure 2 is a scanning electron micrograph of a carbon nanotube rolled film.

圖3為一奈米碳管拉膜之掃描電鏡照片。 Figure 3 is a scanning electron micrograph of a carbon nanotube film.

圖4為一奈米碳管交叉膜之掃描電鏡照片。 Figure 4 is a scanning electron micrograph of a carbon nanotube cross film.

圖5為一非扭轉之奈米碳管線之掃描電鏡照片。 Figure 5 is a scanning electron micrograph of a non-twisted nanocarbon pipeline.

圖6為一扭轉之奈米碳管線之掃描電鏡照片。 Figure 6 is a scanning electron micrograph of a twisted nanocarbon line.

以下將結合附圖對本發明作進一步詳細之說明。 The invention will be further described in detail below with reference to the accompanying drawings.

本發明實施例提供一奈米碳管複合結構之製備方法,其具體包括如下步驟:步驟S10,提供一奈米碳管結構,所述奈米碳管結構包括複數奈米碳管通過凡得瓦力(Van der Waals attractive force)連接; 步驟S20,所述奈米碳管結構中複合一聚合物;以及步驟S30,石墨化複合有聚合物之奈米碳管結構,使所述聚合物石墨化為一石墨結構。 The embodiment of the present invention provides a method for preparing a carbon nanotube composite structure, which specifically includes the following steps: Step S10, providing a carbon nanotube structure, the carbon nanotube structure including a plurality of carbon nanotubes passing through the van der Waals Van der Waals attractive force connection; Step S20, compounding a polymer in the carbon nanotube structure; and step S30, graphitizing the polymerized carbon nanotube structure to graphitize the polymer into a graphite structure.

在步驟S10中,所述奈米碳管結構為由複數奈米碳管通過凡得瓦力彼此相連構成之一奈米碳管骨架,所述奈米碳管骨架可為膜狀結構、線狀結構或者其他形狀之結構。所述奈米碳管結構為一奈米碳管自支撐結構,所謂“自支撐”即該奈米碳管結構無需通過設置於一基體表面,即邊緣或者相對端部提供支撐而其未得到支撐之其他部分能保持自身特定之形狀。由於該自支撐之奈米碳管結構中大量之奈米碳管通過凡得瓦力相互吸引,從而使該奈米碳管結構具有特定之形狀,形成一自支撐結構。通常,所述自支撐之奈米碳管結構中距離在0.2奈米到9奈米之間之奈米碳管之數量較多,這部分奈米碳管之間具有較大之凡得瓦力,從而使得所述奈米碳管結構僅通過凡得瓦力即可形成自支撐結構。 In step S10, the carbon nanotube structure is composed of a plurality of carbon nanotubes connected to each other by a van der Waals force to form a carbon nanotube skeleton, and the carbon nanotube skeleton may be a membrane structure or a linear structure. Structure or other shape structure. The carbon nanotube structure is a self-supporting structure of a carbon nanotube, and the so-called "self-supporting" means that the carbon nanotube structure does not need to be supported by being disposed on a surface of the substrate, that is, the edge or the opposite end is not supported. The rest of the part can maintain its own specific shape. Since a large number of carbon nanotubes in the self-supporting carbon nanotube structure are attracted to each other by van der Waals force, the carbon nanotube structure has a specific shape to form a self-supporting structure. Generally, the number of carbon nanotubes in the self-supporting carbon nanotube structure between 0.2 nm and 9 nm is large, and the portion of the carbon nanotubes has a large van der Waals force. So that the carbon nanotube structure can form a self-supporting structure only by van der Waals force.

所述奈米碳管結構可包括一奈米碳管膜結構,所述奈米碳管膜結構為一具有複數微孔之膜狀結構。所述微孔由複數奈米碳管通過凡得瓦力相互連接而形成,形成所述微孔之奈米碳管可處於同一平面,也可處於不同平面。該微孔之尺寸在1奈米到500奈米之間。所述奈米碳管膜結構之結構不限,僅能形成複數上述微孔即可。優選地,所述奈米碳管膜結構可為一自支撐結構,從而該奈米碳管膜結構可作為所述奈米碳管複合結構之骨架。所謂“自支撐”即該奈米碳管膜結構無需通過設置於一基體表面,也能保持自身特定之形狀。由於該自支撐之奈米碳管膜結構包括大量之奈米碳管通過凡得瓦力相互吸引,從而使該奈米碳管膜結構具有特定 之形狀,形成一自支撐結構。 The carbon nanotube structure may include a carbon nanotube membrane structure, and the carbon nanotube membrane structure is a membrane-like structure having a plurality of micropores. The micropores are formed by interconnecting a plurality of carbon nanotubes by van der Waals force, and the carbon nanotubes forming the micropores may be in the same plane or in different planes. The size of the micropores is between 1 nm and 500 nm. The structure of the carbon nanotube membrane structure is not limited, and only a plurality of the above micropores can be formed. Preferably, the carbon nanotube membrane structure may be a self-supporting structure such that the carbon nanotube membrane structure can serve as a skeleton of the carbon nanotube composite structure. The so-called "self-supporting" means that the carbon nanotube film structure can maintain its own specific shape without being disposed on a surface of a substrate. Since the self-supporting carbon nanotube membrane structure comprises a large number of carbon nanotubes attracted to each other by van der Waals force, the carbon nanotube membrane structure is specific The shape forms a self-supporting structure.

所述奈米碳管膜結構可包括至少一奈米碳管膜,當所述奈米碳管膜結構包括複數奈米碳管膜時,該複數奈米碳管膜層疊設置,相鄰之奈米碳管膜之間通過凡得瓦力相結合。 The carbon nanotube membrane structure may include at least one carbon nanotube membrane, and when the carbon nanotube membrane structure comprises a plurality of carbon nanotube membranes, the plurality of carbon nanotube membranes are stacked, adjacent to each other The carbon nanotube membranes are combined by van der Waals force.

請參閱圖1,所述奈米碳管膜可為一奈米碳管絮化膜,該奈米碳管絮化膜為將一奈米碳管原料,如一超順排陣列,絮化處理獲得之一自支撐之奈米碳管膜。該奈米碳管絮化膜包括相互纏繞且均勻分佈之奈米碳管。奈米碳管之長度大於10微米,優選為200微米到900微米,從而使奈米碳管相互纏繞在一起。所述奈米碳管之間通過凡得瓦力相互吸引、分佈,形成網路狀結構。由於該自支撐之奈米碳管絮化膜中大量之奈米碳管通過凡得瓦力相互吸引並相互纏繞,從而使該奈米碳管絮化膜具有特定之形狀,形成一自支撐結構。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均勻分佈,無規則排列,形成大量尺寸在1奈米到500奈米之間之間隙或微孔。所述奈米碳管絮化膜之面積及厚度均不限,厚度大致在0.5奈米到100微米之間。 Referring to FIG. 1, the carbon nanotube film can be a carbon nanotube flocculation membrane, and the carbon nanotube membrane is obtained by flocculation treatment of a carbon nanotube raw material, such as a super-aligned array. A self-supporting carbon nanotube film. The carbon nanotube flocculation membrane comprises carbon nanotubes which are intertwined and uniformly distributed. The length of the carbon nanotubes is greater than 10 microns, preferably from 200 microns to 900 microns, such that the carbon nanotubes are intertwined with one another. The carbon nanotubes are attracted to each other by van der Waals forces to form a network structure. Since the large number of carbon nanotubes in the self-supporting carbon nanotube flocculation membrane are mutually attracted and intertwined by van der Waals force, the carbon nanotube flocculation membrane has a specific shape to form a self-supporting structure. . The carbon nanotube flocculation membrane is isotropic. The carbon nanotubes in the carbon nanotube flocculation membrane are uniformly distributed and randomly arranged to form a plurality of gaps or micropores having a size ranging from 1 nm to 500 nm. The area and thickness of the carbon nanotube flocculation membrane are not limited, and the thickness is approximately between 0.5 nm and 100 μm.

所述奈米碳管膜可為一奈米碳管碾壓膜,該奈米碳管碾壓膜為通過碾壓一奈米碳管陣列獲得之一種具有自支撐性之奈米碳管膜。該奈米碳管碾壓膜包括均勻分佈之奈米碳管,奈米碳管沿同一方向或不同方向擇優取向排列。所述奈米碳管碾壓膜中之奈米碳管相互部分交疊,並通過凡得瓦力相互吸引,緊密結合,使得該奈米碳管膜具有很好之柔韌性,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之奈米碳管之間通過凡得瓦力相互吸引,緊密結合,使奈米碳管碾壓膜為一自支撐之結構。所述奈米碳 管碾壓膜中之奈米碳管與形成奈米碳管陣列之生長基底之表面形成一夾角β,其中,β大於等於0度且小於等於15度,該夾角β與施加在奈米碳管陣列上之壓力有關,壓力越大,該夾角越小,優選地,該奈米碳管碾壓膜中之奈米碳管平行於該生長基底排列。該奈米碳管碾壓膜為通過碾壓一奈米碳管陣列獲得,依據碾壓之方式不同,該奈米碳管碾壓膜中之奈米碳管具有不同之排列形式。具體地,奈米碳管可無序排列;請參閱圖2,當沿不同方向碾壓時,奈米碳管沿不同方向擇優取向排列;當沿同一方向碾壓時,奈米碳管沿一固定方向擇優取向排列。該奈米碳管碾壓膜中奈米碳管之長度大於50微米。該奈米碳管碾壓膜之面積與奈米碳管陣列之尺寸基本相同。該奈米碳管碾壓膜厚度與奈米碳管陣列之高度以及碾壓之壓力有關,可為0.5奈米到100微米之間。可以理解,奈米碳管陣列之高度越大而施加之壓力越小,則製備之奈米碳管碾壓膜之厚度越大;反之,奈米碳管陣列之高度越小而施加之壓力越大,則製備之奈米碳管碾壓膜之厚度越小。所述奈米碳管碾壓膜之中之相鄰之奈米碳管之間具有一定間隙,從而在奈米碳管碾壓膜中形成複數尺寸在1奈米到500奈米之間之間隙或微孔。 The carbon nanotube film may be a carbon nanotube rolled film, which is a self-supporting carbon nanotube film obtained by rolling a carbon nanotube array. The carbon nanotube rolled film comprises uniformly distributed carbon nanotubes, and the carbon nanotubes are arranged in the same direction or in different directions. The carbon nanotubes in the carbon nanotube rolled film partially overlap each other and are attracted to each other by the van der Waals force, and the carbon nanotube film has good flexibility and can be bent and folded into Any shape without breaking. Moreover, since the carbon nanotubes in the carbon nanotube rolled film are attracted to each other by the van der Waals force, the carbon nanotube film is a self-supporting structure. The nanocarbon The carbon nanotubes in the tube-rolled film form an angle β with the surface of the growth substrate forming the carbon nanotube array, wherein β is greater than or equal to 0 degrees and less than or equal to 15 degrees, and the angle β is applied to the carbon nanotubes The pressure on the array is related. The larger the pressure, the smaller the angle. Preferably, the carbon nanotubes in the carbon nanotube rolled film are aligned parallel to the growth substrate. The carbon nanotube rolled film is obtained by rolling a carbon nanotube array, and the carbon nanotubes in the carbon nanotube rolled film have different arrangement forms according to the manner of rolling. Specifically, the carbon nanotubes can be arranged in disorder; referring to FIG. 2, when rolling in different directions, the carbon nanotubes are arranged in different directions; when crushed in the same direction, the carbon nanotubes are along a The orientation is preferred and the orientation is preferred. The length of the carbon nanotubes in the carbon nanotube rolled film is greater than 50 microns. The area of the carbon nanotube rolled film is substantially the same as the size of the carbon nanotube array. The thickness of the carbon nanotube film is related to the height of the carbon nanotube array and the pressure of the rolling, and may be between 0.5 nm and 100 μm. It can be understood that the larger the height of the carbon nanotube array and the lower the pressure applied, the greater the thickness of the prepared carbon nanotube rolled film; on the contrary, the smaller the height of the carbon nanotube array, the more the applied pressure Large, the smaller the thickness of the prepared carbon nanotube rolled film. a gap between adjacent carbon nanotubes in the carbon nanotube film, thereby forming a plurality of gaps between 1 nm and 500 nm in the carbon nanotube film Or micropores.

所述奈米碳管膜可為一奈米碳管拉膜,且此時所述奈米碳管膜結構至少包括兩層奈米碳管拉膜。請參見圖3,所述形成之奈米碳管拉膜係由若干奈米碳管組成之自支撐結構。所述若干奈米碳管為沿該奈米碳管拉膜之長度方向擇優取向排列。所述擇優取向係指在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。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之表面。進一步地,所述奈米碳管拉膜中多數奈米碳管 係通過凡得瓦力首尾相連。具體地,所述奈米碳管拉膜中基本朝同一方向延伸之大多數奈米碳管中每一奈米碳管與在延伸方向上相鄰之奈米碳管通過凡得瓦力首尾相連。當然,所述奈米碳管拉膜中存在少數偏離該延伸方向之奈米碳管,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。所述自支撐為奈米碳管拉膜不需要大面積之載體支撐,而僅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,即將該奈米碳管拉膜置於(或固定於)間隔一定距離設置之兩個支撐體上時,位於兩個支撐體之間之奈米碳管拉膜能夠懸空保持自身膜狀狀態。所述自支撐主要通過奈米碳管拉膜中存在連續之通過凡得瓦力首尾相連延伸排列之奈米碳管而實現。具體地,所述奈米碳管拉膜中基本朝同一方向延伸之多數奈米碳管,並非絕對之直線狀,可適當之彎曲;或者並非完全按照延伸方向上排列,可適當之偏離延伸方向。故,不能排除奈米碳管拉膜之基本朝同一方向延伸之多數奈米碳管中並列之奈米碳管之間可能存在部分接觸。 The carbon nanotube film may be a carbon nanotube film, and at this time, the carbon nanotube film structure comprises at least two layers of carbon nanotube film. Referring to FIG. 3, the formed 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 length of the carbon nanotube film. The preferred orientation means that the overall extension direction of most of the carbon nanotubes in the carbon nanotube film is substantially 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 drawn It is connected end to end by Van der Waals. Specifically, each of the carbon nanotubes of the majority of the carbon nanotubes extending substantially in the same direction in the carbon nanotube film is connected end to end with the carbon nanotubes adjacent in the extending direction by van der Waals force . Of course, there are a few carbon nanotubes in the carbon nanotube film that deviate from the extending direction. These carbon nanotubes do not constitute an obvious alignment of the majority of the carbon nanotubes in the carbon nanotube film. influences. The self-supporting carbon nanotube film does not need a large-area carrier support, but only provides support force on both sides, and can be suspended in the whole to maintain its own film state, that is, the carbon nanotube film is placed (or When fixed on two supports arranged at a certain distance, the carbon nanotube film located between the two supports can be suspended to maintain its own film state. The self-supporting is mainly achieved by the presence of a continuous carbon nanotube in the carbon nanotube film which is continuously arranged by van der Waals. Specifically, the majority of the 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 deviated from the extending direction. . Therefore, it may not be possible to exclude partial contact between the carbon nanotubes juxtaposed in the majority of the carbon nanotubes extending substantially in the same direction.

具體地,該奈米碳管拉膜包括複數連續且定向排列之奈米碳管片段。該複數奈米碳管片段通過凡得瓦力首尾相連。每一奈米碳管片段由複數相互平行之奈米碳管組成。該奈米碳管片段具有任意之長度、厚度、均勻性及形狀。該奈米碳管拉膜具有較好之透光性,可見光透過率可達到75%以上。 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 consists of a plurality of carbon nanotubes that are parallel to each other. The carbon nanotube segments have any length, thickness, uniformity, and shape. The carbon nanotube film has good light transmittance and the visible light transmittance can reach more than 75%.

當所述奈米碳管膜結構包括多層奈米碳管拉膜時,相鄰兩層奈米碳管拉膜中之擇優取向排列之奈米碳管之間形成一交叉角度α,α大於等於0度小於等於90度(0° α 90°)。請參閱圖4,優選地,為提高所述奈米碳管膜之強度,所述交叉角度α大致為90 度,即相鄰兩層奈米碳管拉膜中之奈米碳管之排列方向基本垂直,形成一交叉膜。所述複數奈米碳管拉膜之間或一個奈米碳管拉膜之中之相鄰之奈米碳管之間具有一定間隙,從而在奈米碳管結構中形成複數均勻分佈,無規則排列,尺寸在1奈米到500奈米之間之間隙或微孔。 When the carbon nanotube film structure comprises a multi-layered carbon nanotube film, a preferred angle between the adjacent two layers of carbon nanotube film forming a cross angle α, α is greater than or equal to 0 degrees is less than or equal to 90 degrees (0° α 90°). Referring to FIG. 4, preferably, to increase the strength of the carbon nanotube film, the intersection angle α is approximately 90. Degree, that is, the arrangement direction of the carbon nanotubes in the adjacent two layers of carbon nanotube film is substantially perpendicular to form a cross film. There is a gap between the adjacent carbon nanotube film or between adjacent carbon nanotubes in a carbon nanotube film, thereby forming a plurality of uniform distributions in the carbon nanotube structure, without rules Arranged, with a size between 1 nm and 500 nm or a micropore.

所述奈米碳管結構可包括至少一奈米碳管線結構,當所述奈米碳管結構包括複數奈米碳管線結構時,所述複數奈米碳管線可相互平行、纏繞或編織設置。所述奈米碳管線結構包括至少一奈米碳管線,所述奈米碳管線包括複數奈米碳管通過凡得瓦力相互連接且基本沿所述奈米碳管線之軸向延伸。當所述奈米碳管線結構包括複數奈米碳管線時,所述複數奈米碳管線可相互平行或纏繞設置。所述奈米碳管線之結構不限,優選地,所述奈米碳管線為一自支撐結構。所謂“自支撐”即該奈米碳管線無需通過設置於一基體表面,也能保持自身特定之形狀。由於該自支撐之奈米碳管線中大量之奈米碳管通過凡得瓦力相互吸引,從而使該奈米碳管線結構具有特定之形狀,形成一自支撐結構。通常,所述奈米碳管線中之奈米碳管之間具有較大之凡得瓦力,從而使得所述奈米碳管膜結構僅通過凡得瓦力即可形成所述自支撐結構。當所述奈米碳管線結構包括複數奈米碳管線時,所述複數奈米碳管線可相互平行或纏繞設置,相鄰之間之奈米碳管線同過凡得瓦力連接。 The carbon nanotube structure may include at least one nanocarbon pipeline structure, and when the carbon nanotube structure includes a plurality of nanocarbon pipeline structures, the plurality of carbon nanotube pipelines may be disposed in parallel, wound or braided with each other. The nanocarbon pipeline structure includes at least one nanocarbon pipeline including a plurality of carbon nanotubes interconnected by van der Waals and extending substantially along an axial direction of the nanocarbon pipeline. When the nanocarbon line structure includes a plurality of nanocarbon lines, the plurality of carbon carbon lines may be disposed in parallel or wound with each other. The structure of the nanocarbon pipeline is not limited. Preferably, the nanocarbon pipeline is a self-supporting structure. The so-called "self-supporting" means that the nanocarbon pipeline can maintain its own specific shape without being disposed on a surface of a substrate. Since a large number of carbon nanotubes in the self-supporting nanocarbon pipeline are attracted to each other by van der Waals force, the nanocarbon pipeline structure has a specific shape to form a self-supporting structure. Typically, there is a large van der Waals force between the carbon nanotubes in the nanocarbon line such that the carbon nanotube film structure forms the self-supporting structure only by van der Waals. When the nanocarbon pipeline structure comprises a plurality of carbon nanotubes, the plurality of carbon nanotubes may be arranged in parallel or wound with each other, and the adjacent nanocarbon pipelines are connected to the van der Waals force.

所述奈米碳管線可為將一奈米碳管拉膜經過處理形成之線結構,所述奈米碳管拉膜之處理方法包括用揮發性有機溶劑浸潤處理或機械扭轉處理。所述揮發性有機溶劑浸潤處理可通過試管將有機溶劑滴落在奈米碳管拉膜表面浸潤整個奈米碳管拉膜,或者,也 可將上述形成有奈米碳管拉膜之固定框架整個浸入盛有有機溶劑之容器中浸潤。該揮發性有機溶劑為乙醇、甲醇、丙酮、二氯乙烷或氯仿,本實施例中採用乙醇。所述有機溶劑在揮發時產生之張力使所述奈米碳管拉膜收縮形成所述奈米碳管線。請參閱圖5,通過揮發性有機溶劑浸潤處理所得到之奈米碳管線為一非扭轉之奈米碳管線,該非扭轉之奈米碳管線包括複數沿奈米碳管線長度方向排列之奈米碳管。具體地,該非扭轉之奈米碳管線包括複數奈米碳管通過凡得瓦力首尾相連且沿奈米碳管線軸向擇優取向排列。所述機械扭轉處理可通過採用一機械力將所述奈米碳管拉膜兩端沿相反方向扭轉。請參閱圖6,通過機械扭轉處理而得到之奈米碳管線為一扭轉之奈米碳管線,該扭轉之奈米碳管線包括複數繞奈米碳管線軸向螺旋排列之奈米碳管。具體地,該扭轉之奈米碳管線包括複數奈米碳管通過凡得瓦力首尾相連且沿奈米碳管線軸向呈螺旋狀延伸。可以理解,也可對獲得之奈米碳管拉膜同時或者依次進行有機溶劑揮發性有機溶劑浸潤處理或機械扭轉處理來獲得所述扭轉之奈米碳管線。 The nano carbon pipeline may be a wire structure formed by processing a carbon nanotube film, and the treatment method of the carbon nanotube film comprises a volatile organic solvent infiltration treatment or a mechanical torsion treatment. The volatile organic solvent infiltration treatment may drip the organic solvent on the surface of the carbon nanotube film by a test tube to infiltrate the entire carbon nanotube film, or The above-mentioned fixing frame in which the carbon nanotube film is formed may be entirely immersed in a container containing an organic solvent to be infiltrated. The volatile organic solvent is ethanol, methanol, acetone, dichloroethane or chloroform, and ethanol is used in this embodiment. The tension generated by the organic solvent upon volatilization causes the carbon nanotube film to shrink to form the nanocarbon line. Referring to FIG. 5, the nano carbon line obtained by the volatile organic solvent infiltration treatment is a non-twisted nano carbon line, and the non-twisted nano carbon line includes a plurality of nano carbons arranged along the length of the nano carbon line. tube. Specifically, the non-twisted nanocarbon pipeline includes a plurality of carbon nanotubes connected end to end by van der Waals force and arranged in an axially preferred orientation along the nanocarbon pipeline. The mechanical torsion treatment may be performed by twisting both ends of the carbon nanotube film in the opposite direction by using a mechanical force. Referring to FIG. 6, the nano carbon line obtained by the mechanical torsion treatment is a twisted nano carbon line, and the twisted nano carbon line includes a plurality of carbon nanotubes arranged in an axial spiral arrangement around the carbon carbon line. Specifically, the twisted nanocarbon pipeline includes a plurality of carbon nanotubes connected end to end by van der Waals force and extending helically along the axial direction of the carbon nanotubes. It can be understood that the twisted nanocarbon pipeline can also be obtained by simultaneously or sequentially performing an organic solvent volatile organic solvent wetting treatment or a mechanical torsion treatment on the obtained carbon nanotube film.

在步驟S20中,所述奈米碳管結構中複合所述聚合物之方法不限,僅能夠使所述聚合物與所述奈米碳管結構中之複數奈米碳管複合,並在所述複數奈米碳管與聚合物之間形成複數共價鍵即可。具體地,使所述奈米碳管結構複合有聚合物之方法可進一步包括如下步驟:S21,將所述奈米碳管結構浸潤在一聚合物溶液中以與所述聚合物複合。 In the step S20, the method of compounding the polymer in the carbon nanotube structure is not limited, and only the polymer can be compounded with the plurality of carbon nanotubes in the carbon nanotube structure, and It is sufficient to form a complex covalent bond between the plurality of carbon nanotubes and the polymer. Specifically, the method of compounding the carbon nanotube structure with a polymer may further include the step of: S21, impregnating the carbon nanotube structure in a polymer solution to recombine with the polymer.

在步驟S21中,所述聚合物溶液可通過將所述聚合物直接熔融或將所述聚合物溶解於一溶劑而得到。在本實施例中,所述聚合物 溶液通過將該聚合物溶解於一有機溶劑而得到。所述聚合物之種類與性質不限,可根據實際需求而選擇。所述聚合物可包括聚丙烯腈(Polyacrylonitrile,PAN)、聚乙烯醇(polyvinyl alcohol,PVA)、聚丙烯(Polypropylene,PP)、聚苯乙烯(Polystyrene,PS)、聚氯乙烯(Polyvinylchlorid,PVC)及聚對苯二甲酸乙二酯(Polyethylene terephthalate,PET)中之任意一種或任意組合。所述聚合物之聚合度也可根據實際操作而選擇。優選地,所述聚合物之聚合度在1500到3500之間,從而使得所述聚合物既可被溶解,又可與奈米碳管又保持一定之浸潤性。所述聚合物溶液中之聚合物之品質百分比根據聚合物及有機溶劑之不同而不同,通常,所述聚合物溶液中之聚合物之品質百分比大致在1%到9%之間。所述有機溶劑用於溶解所述聚合物,並能夠與所述奈米碳管浸潤,從而能夠使所述聚合物充分複合到所述奈米碳管結構中甚至複合到所述奈米碳管結構中之奈米碳管內部。優選地,所述有機溶劑在能能溶解所述聚合物之同時,還具有較大之表面張力。具體地,可選擇表面張力大於20毫牛每米且對奈米碳管之接觸角小於90度之有機溶劑。所述有機溶劑可包括二甲基亞碸(Dimethyl Sulphoxide,DMSO)、二甲基甲醯胺(Dimethyl Formamide,DMF)、2,5-二甲基呋喃(2,5-dimethyl furan)及N-甲基吡咯烷酮(N-methyl-2-pyrrolidone,NMP)中之任意一種或組合。由於所述有機溶劑之溶解能力根據聚合物之不同而不同,故,所述有機溶劑之選擇還需根據具體之聚合物而選擇。譬如,當所述聚合物為聚乙烯醇時,所述有機溶劑可選擇二甲基亞碸。所述二甲基亞碸之表面張力大致為43.54毫牛每米且對奈米碳管之接觸角大致為110度。所述有機溶劑對奈米碳管之 接觸角越小,所述聚合物對所述奈米碳管結構之浸潤性越好,所述聚合物與所述奈米碳管結構結合越緊密。所述有機溶劑之表面張力越大,所述聚合物對所述奈米碳管結構之浸潤性越好,使所述奈米碳管結構收縮之能力越強,所述聚合物與所述奈米碳管結構結合越緊密。 In step S21, the polymer solution can be obtained by directly melting the polymer or dissolving the polymer in a solvent. In this embodiment, the polymer The solution is obtained by dissolving the polymer in an organic solvent. The type and nature of the polymer are not limited and can be selected according to actual needs. The polymer may include polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC). And any one or any combination of polyethylene terephthalate (PET). The degree of polymerization of the polymer can also be selected according to the actual operation. Preferably, the degree of polymerization of the polymer is between 1500 and 3500 such that the polymer is both soluble and maintains a certain wettability with the carbon nanotubes. The percentage by mass of the polymer in the polymer solution varies depending on the polymer and the organic solvent. Generally, the percentage of the polymer in the polymer solution is approximately between 1% and 9%. The organic solvent is used to dissolve the polymer and is capable of being wetted with the carbon nanotubes, thereby enabling the polymer to be sufficiently compounded into the carbon nanotube structure or even composited to the carbon nanotube Inside the carbon nanotubes in the structure. Preferably, the organic solvent has a large surface tension while being capable of dissolving the polymer. Specifically, an organic solvent having a surface tension greater than 20 millinewtons per meter and a contact angle to the carbon nanotubes of less than 90 degrees can be selected. The organic solvent may include Dimethyl Sulphoxide (DMSO), Dimethyl Formamide (DMF), 2,5-dimethyl furan, and N- Any one or combination of N-methyl-2-pyrrolidone (NMP). Since the dissolving power of the organic solvent varies depending on the polymer, the selection of the organic solvent is also selected depending on the specific polymer. For example, when the polymer is polyvinyl alcohol, the organic solvent may be selected from dimethyl hydrazine. The surface tension of the dimethyl hydrazine is approximately 43.54 milli-Nilometers per meter and the contact angle to the carbon nanotubes is approximately 110 degrees. The organic solvent to the carbon nanotube The smaller the contact angle, the better the wettability of the polymer to the carbon nanotube structure, and the closer the polymer binds to the carbon nanotube structure. The greater the surface tension of the organic solvent, the better the wettability of the polymer to the carbon nanotube structure, the stronger the ability to shrink the structure of the carbon nanotube, the polymer and the naphthalene The tighter the carbon nanotube structure is combined.

當所述奈米碳管結構為奈米碳管膜結構時,所述聚合物溶液浸潤所述奈米碳管膜結構後,部分聚合物溶液將滲透到所述奈米碳管膜結構之微孔中並與所述奈米碳管膜結構中之奈米碳管接觸。所述聚合物溶液中之有機溶劑蒸發後,其中之聚合物將與所述奈米碳管接觸緊密接觸並形成共價鍵。且,當所述聚合物溶液填滿所述微孔後,還可在所述奈米碳管膜結構相對之兩個表面形成兩層聚合物溶液層。所述聚合物溶液層中之有機溶劑蒸發後,兩層聚合物層將形成在所述兩個表面並將所述奈米碳管膜結構夾持其中,形成一層狀結構。 When the carbon nanotube structure is a carbon nanotube film structure, after the polymer solution infiltrates the carbon nanotube film structure, a part of the polymer solution will penetrate into the structure of the carbon nanotube film. The pores are in contact with the carbon nanotubes in the carbon nanotube membrane structure. After the organic solvent in the polymer solution is evaporated, the polymer therein will be in intimate contact with the carbon nanotube and form a covalent bond. Moreover, after the polymer solution fills the micropores, two layers of polymer solution may be formed on opposite surfaces of the carbon nanotube film structure. After the organic solvent in the polymer solution layer is evaporated, two polymer layers will be formed on the two surfaces and the carbon nanotube film structure is sandwiched therein to form a layered structure.

當所述奈米碳管結構包括至少一奈米碳管線結構時,所述聚合物溶液滲透在所述奈米碳管線結構中之間隙中,並與該奈米碳管線結構中之奈米碳管浸潤。所述聚合物溶液中之有機溶劑蒸發後,所述聚合物溶液中之聚合物將纏繞或包覆所述奈米碳管線結構中首尾相連之奈米碳管形成複數聚合物纖維,或填滿所述奈米碳管線結構中之間隙,形成一個整體之聚合物結構。 When the carbon nanotube structure includes at least one nanocarbon pipeline structure, the polymer solution penetrates into a gap in the nanocarbon pipeline structure and is in combination with nanocarbon in the nanocarbon pipeline structure Tube infiltration. After the organic solvent in the polymer solution is evaporated, the polymer in the polymer solution will wrap or coat the carbon nanotubes connected end to end in the nanocarbon pipeline structure to form a plurality of polymer fibers, or fill up The gaps in the nanocarbon line structure form a unitary polymer structure.

在步驟S20中,也可通過原位聚合之方式使所述奈米碳管結構複合有聚合物。具體地,使所述奈米碳管結構複合有聚合物之方法可進一步包括如下步驟:S121,將所述奈米碳管結構浸潤在一聚合物單體溶液中;以及S122,使該聚合物單體產生聚合反應,該 聚合物單體聚合反應後成為聚合物與所述奈米碳管結構複合。 In step S20, the carbon nanotube structure may also be compounded with a polymer by in-situ polymerization. Specifically, the method of compounding the carbon nanotube structure with a polymer may further include the steps of: S121, impregnating the carbon nanotube structure in a polymer monomer solution; and S122, making the polymer The monomer generates a polymerization reaction, which After polymerization of the polymer monomer, the polymer is combined with the carbon nanotube structure.

在步驟S121及S122中,所述聚合物單體可包括丙烯腈、乙烯醇、丙烯、苯乙烯、氯乙烯或對苯二甲酸乙二酯。所述聚合物單體經過聚合後生成聚丙烯腈、聚乙烯醇、聚丙烯、聚苯乙烯、聚氯乙烯或聚對苯二甲酸乙二酯。 In steps S121 and S122, the polymer monomer may include acrylonitrile, vinyl alcohol, propylene, styrene, vinyl chloride or ethylene terephthalate. The polymer monomer is polymerized to form polyacrylonitrile, polyvinyl alcohol, polypropylene, polystyrene, polyvinyl chloride or polyethylene terephthalate.

聚合物單體在同一有機溶劑中之溶解度要大於該聚合物單體對應之聚合物在該有機溶劑中之溶解度。故,通過原位聚合之方式使所述奈米碳管結構複合有聚合物之方法,相對於將奈米碳管結構直接浸潤在所述聚合物溶液中使所述聚合物與所述奈米碳管結構複合之方法,能夠使所述聚合物之選擇範圍更廣。 The solubility of the polymer monomer in the same organic solvent is greater than the solubility of the polymer corresponding to the polymer monomer in the organic solvent. Therefore, the method of compounding the carbon nanotube structure with a polymer by in-situ polymerization is performed by directly impregnating the carbon nanotube structure in the polymer solution to make the polymer and the nanometer. The carbon tube structure composite method enables a wider selection of the polymer.

在步驟S30中,所述石墨化之方法不限,僅能夠使複合在奈米碳管結構之聚合物形成石墨結構,且不破壞所述奈米碳管結構即可。具體之,所述石墨化之方法可包括如下步驟:S31,將所述複合有聚合物之奈米碳管結構在空氣中加熱使所述聚合物進行預氧化;以及S32,將預氧化後之聚合物放置於一真空環境或惰性氣體環境高溫石墨化。 In the step S30, the method of graphitization is not limited, and only the polymer compounded in the carbon nanotube structure can be formed into a graphite structure without destroying the carbon nanotube structure. Specifically, the method for graphitizing may include the following steps: S31, heating the polymerized carbon nanotube structure in air to pre-oxidize the polymer; and S32, pre-oxidizing The polymer is placed in a vacuum environment or an inert gas atmosphere for high temperature graphitization.

在步驟S31中,所述預氧化之溫度大致在200度到300度之間。 In step S31, the pre-oxidation temperature is approximately between 200 and 300 degrees.

在步驟S32中,所述真空環境或惰性氣體環境用於獲得低氧或絕氧環境,從而使得所述奈米碳管結構在高溫時不被氧化。當選擇真空環境時,所述真空環境中之大氣壓小於5*10-2帕,優選地,所述真空環境中之大氣壓小於5*10-5帕。當選擇惰性氣體環境時,所述惰性氣體包括氬氣、氮氣等。 In step S32, the vacuum environment or inert gas environment is used to obtain a low oxygen or anaerobic environment such that the carbon nanotube structure is not oxidized at high temperatures. When a vacuum environment is selected, the atmospheric pressure in the vacuum environment is less than 5*10 -2 Pa, preferably, the atmospheric pressure in the vacuum environment is less than 5*10 -5 Pa. When an inert gas atmosphere is selected, the inert gas includes argon gas, nitrogen gas, or the like.

所述複合在奈米碳管結構中之聚合物在石墨化過程中去掉大部分之氮、氫及氧,形成所述石墨結構。且在石墨化過程中石墨結構與奈米碳管結構之間形成有複數碳碳鍵,使所述石墨結構與奈米碳管結構複合形成所述奈米碳管複合結構。所述碳碳鍵既可通過碳化所述共價鍵而形成,也可通過在高溫時使石墨結構中之碳原子與奈米碳管結構中之碳原子晶格重組時而形成。所述碳碳鍵包括在碳-碳原子間形成之sp2或sp3鍵。具體地,所述碳碳鍵包括在碳-碳原子間形成之sp2或sp3鍵。在奈米碳管複合結構中,由於所述奈米碳管結構為一自支撐結構,該奈米碳管結構為由複數奈米碳管通過凡得瓦力相互連接形成之奈米碳管骨架,而所述石墨結構則填充在該奈米碳管骨架中,且通過碳碳鍵及凡得瓦力與所述奈米碳管骨架緊密結合。 The polymer compounded in the carbon nanotube structure removes most of the nitrogen, hydrogen and oxygen during the graphitization process to form the graphite structure. And a plurality of carbon-carbon bonds are formed between the graphite structure and the carbon nanotube structure during the graphitization process, and the graphite structure is combined with the carbon nanotube structure to form the carbon nanotube composite structure. The carbon-carbon bond may be formed either by carbonizing the covalent bond or by recombining carbon atoms in the graphite structure with carbon atoms in the carbon nanotube structure at a high temperature. The carbon-carbon bond includes an sp 2 or sp 3 bond formed between carbon-carbon atoms. Specifically, the carbon-carbon bond includes an sp 2 or sp 3 bond formed between carbon-carbon atoms. In the carbon nanotube composite structure, since the carbon nanotube structure is a self-supporting structure, the carbon nanotube structure is a carbon nanotube skeleton formed by interconnecting a plurality of carbon nanotubes by van der Waals force. And the graphite structure is filled in the carbon nanotube skeleton, and is tightly bonded to the carbon nanotube skeleton by a carbon-carbon bond and a van der Waals force.

所述石墨結構之具體形態與石墨化時之具體工藝有關。譬如,高溫石墨化之溫度通常在2000度以上,為達到不同之石墨化效果,加熱到所述溫度之時間可根據實際需要而選擇。當加熱速度較快時,所述聚合物容易石墨化為石墨片段。所述石墨片段包括至少一石墨烯(Graphene),當所述石墨片段包括複數石墨烯時,所述複數石墨烯之間通過碳碳鍵結合。所述碳碳鍵包括在碳-碳原子間形成之sp2或sp3鍵。具體地,所述碳碳鍵包括在碳-碳原子間形成之sp2或sp3鍵。當加熱速度較緩慢時,所述聚合物容易石墨化為石墨纖維。所述石墨纖維為所述聚合物纖維去掉大部分之氮、氫及氧而形成。所述石墨纖維又稱高模量碳纖維,該石墨纖維為分子結構已石墨化、含碳量在99%以上具有層狀六方晶格石墨結構之纖維。 The specific form of the graphite structure is related to the specific process at the time of graphitization. For example, the temperature of high temperature graphitization is usually above 2000 degrees. In order to achieve different graphitization effects, the time to heat to the temperature can be selected according to actual needs. When the heating rate is fast, the polymer is easily graphitized into graphite fragments. The graphite segment includes at least one graphene (Graphene), and when the graphite segment includes a plurality of graphenes, the plurality of graphenes are bonded by carbon-carbon bonds. The carbon-carbon bond includes an sp2 or sp3 bond formed between carbon-carbon atoms. Specifically, the carbon-carbon bond includes an sp2 or sp3 bond formed between carbon-carbon atoms. When the heating rate is slow, the polymer is easily graphitized into graphite fibers. The graphite fibers are formed by removing most of the nitrogen, hydrogen, and oxygen from the polymer fibers. The graphite fiber is also called a high modulus carbon fiber, and the graphite fiber is a fiber having a molecular structure that has been graphitized and has a layered hexagonal lattice graphite structure with a carbon content of 99% or more.

所述石墨結構之具體形態還與所述奈米碳管結構之結構有關。當所述奈米碳管結構包括複數微孔時,所述聚合物容易石墨化為複數石墨片段。當所述奈米碳管結構包括複數首尾相連且基本沿同一方向延伸之複數奈米碳管時,所述聚合物容易石墨化為複數石墨纖維。 The specific form of the graphite structure is also related to the structure of the carbon nanotube structure. When the carbon nanotube structure includes a plurality of micropores, the polymer is easily graphitized into a plurality of graphite fragments. When the carbon nanotube structure comprises a plurality of complex carbon nanotubes connected end to end and extending substantially in the same direction, the polymer is easily graphitized into a plurality of graphite fibers.

具體地,當所述奈米碳管結構包括至少一奈米碳管膜結構時,填充在所述奈米碳管膜結構微孔中之聚合物被石墨化為石墨片段。相鄰之石墨片段之間通過碳碳結合從而形成所述石墨結構。填充在所述奈米碳管膜結構之微孔中之石墨片段並不一定能完全填滿所述微孔,通常,所述複數石墨片段附著在奈米碳管之管壁上或包覆於奈米碳管之部分表面,且通過碳碳鍵與所述奈米碳管結合。即,由所述奈米碳管膜結構與石墨結構複合形成之奈米碳管複合結構基本由奈米碳管與石墨片段組成,所述奈米碳管與所述石墨片段通過碳碳鍵及凡得瓦力結合。 Specifically, when the carbon nanotube structure includes at least one carbon nanotube film structure, the polymer filled in the micropores of the carbon nanotube film structure is graphitized into graphite fragments. Adjacent graphite segments are bonded by carbon and carbon to form the graphite structure. The graphite fragments filled in the micropores of the carbon nanotube membrane structure do not necessarily completely fill the micropores. Usually, the plurality of graphite fragments are attached to the wall of the carbon nanotube or coated with A portion of the surface of the carbon nanotube is bonded to the carbon nanotube by a carbon-carbon bond. That is, the carbon nanotube composite structure formed by the composite of the carbon nanotube film structure and the graphite structure is basically composed of a carbon nanotube and a graphite segment, and the carbon nanotube and the graphite segment pass through a carbon-carbon bond. Get the combination of Wahli.

當所述奈米碳管膜結構相對之兩個表面具有兩層聚合物層時,所述聚合物層在石墨化後在該奈米碳管膜結構兩側形成兩層石墨層,從而形成一具有層狀結構之奈米碳管複合結構。且,填充在所述奈米碳管膜結構兩側之石墨片段與分佈在該奈米碳管膜結構兩側之石墨片段通過碳碳鍵結合形成一整體結構。此時,所述奈米碳管膜結構可被所述石墨結構完全包覆,複合在所述石墨結構之內部。故,從宏觀上看,所述石墨結構為一海綿狀結構,且將所述奈米碳管膜結構包埋其中。或者說,該複數奈米碳管以自支撐之奈米碳管膜結構之形式設置於該石墨結構中,且所述石墨結構與所述複數奈米碳管通過凡得瓦力及碳碳鍵相結合。 When the carbon nanotube film structure has two polymer layers on opposite surfaces, the polymer layer forms two graphite layers on both sides of the carbon nanotube film structure after graphitization, thereby forming a A carbon nanotube composite structure having a layered structure. Moreover, the graphite fragments filled on both sides of the carbon nanotube film structure and the graphite fragments distributed on both sides of the carbon nanotube film structure are combined by carbon-carbon bonds to form a unitary structure. At this time, the carbon nanotube film structure may be completely coated by the graphite structure and composited inside the graphite structure. Therefore, from a macroscopic point of view, the graphite structure is a sponge-like structure, and the carbon nanotube film structure is embedded therein. In other words, the plurality of carbon nanotubes are disposed in the graphite structure in the form of a self-supporting carbon nanotube film structure, and the graphite structure and the plurality of carbon nanotubes pass the van der Waals and carbon-carbon bonds. Combine.

所述奈米碳管複合結構包括由複數奈米碳管形成之奈米碳管膜結構及填充在該奈米碳管膜結構中之複數石墨片段。所述複數奈米碳管之間除了用凡得瓦力結合之外,還可通過所述石墨片段緊密結合,從而增加了所述複數奈米碳管之間之結合力,提高了所述奈米碳管複合結構之機械性能。而所述石墨片段與所述奈米碳管結構具有較小之密度且均為碳素材料,故,由複數石墨片段與複數奈米碳管複合形成之奈米碳管複合結構具有密度小、耐腐蝕、耐潮等優點。 The carbon nanotube composite structure includes a carbon nanotube film structure formed of a plurality of carbon nanotubes and a plurality of graphite fragments filled in the carbon nanotube film structure. In addition to being combined with van der Waals force, the plurality of carbon nanotubes can be tightly bonded by the graphite fragments, thereby increasing the bonding force between the plurality of carbon nanotubes and improving the naphthalene Mechanical properties of the carbon nanotube composite structure. The graphite segment and the carbon nanotube structure have a small density and are both carbon materials. Therefore, the carbon nanotube composite structure formed by combining the plurality of graphite segments and the plurality of carbon nanotubes has a small density. Corrosion resistance, moisture resistance and other advantages.

當所述奈米碳管結構包括至少一奈米碳管線結構時,所述聚合物既可通過石墨化為複數石墨片段,又可石墨化為複數石墨纖維。具體地,如果在石墨化之方法中,通過快速加熱之方式進行石墨化,所述聚合物將被石墨化為複數石墨片段。所述石墨片段與所述奈米碳管線結構通過碳碳鍵結合形成奈米碳管複合結構。而如果在石墨化之方法中,通過緩慢加熱之方式進行石墨化,則所述聚合物將被石墨化為複數石墨纖維。所述石墨纖維與所述奈米碳管通過凡得瓦力及碳碳鍵結合。所述石墨纖維結構中之複數石墨纖維之間通過碳碳鍵或凡得瓦力相互結合,並形成一個整體結構。 When the carbon nanotube structure comprises at least one nanocarbon line structure, the polymer can be graphitized into a plurality of graphite fragments and graphitized into a plurality of graphite fibers. Specifically, if graphitization is carried out by rapid heating in the method of graphitization, the polymer will be graphitized into a plurality of graphite fragments. The graphite segment and the nanocarbon pipeline structure are combined by carbon-carbon bonds to form a carbon nanotube composite structure. Whereas in the method of graphitization, graphitization is carried out by slow heating, the polymer will be graphitized into a plurality of graphite fibers. The graphite fibers and the carbon nanotubes are bonded by van der Waals and carbon-carbon bonds. The plurality of graphite fibers in the graphite fiber structure are bonded to each other by a carbon-carbon bond or a van der Waals force, and form a unitary structure.

在同一奈米碳管線中之複數奈米碳管基本沿奈米碳管線之軸向延伸,故,纏繞或包覆所述複數奈米碳管之石墨纖維也基本沿所述奈米碳管線之軸向延伸。具體地,當所述奈米碳管線中之複數奈米碳管通過凡得瓦力首尾相連且基本沿奈米碳管線軸向呈螺旋狀延伸,則所述石墨纖維也基本沿奈米碳管線軸向呈螺旋狀延伸。當所述奈米碳管線中之複數奈米碳管通過凡得瓦力首尾相連且沿 奈米碳管線軸向擇優取向排列,則所述石墨纖維也基本沿所述奈米碳管線軸向擇優取向排列。在同一奈米碳管線或奈米碳管線結構中之石墨纖維即可通過凡得瓦力結合也可通過碳碳鍵結合,優選地,在同一奈米碳管線中之石墨纖維通過碳碳鍵結合。 The plurality of carbon nanotubes in the same nanocarbon pipeline extend substantially along the axial direction of the nanocarbon pipeline, so that the graphite fibers wound or coated with the plurality of carbon nanotubes are also substantially along the nanocarbon pipeline. Axial extension. Specifically, when the plurality of carbon nanotubes in the nanocarbon pipeline are connected end to end by van der Waals force and extend substantially spirally along the axial direction of the nanocarbon pipeline, the graphite fiber is also substantially along the nanocarbon pipeline. The axial direction extends in a spiral shape. When the plurality of carbon nanotubes in the nanocarbon pipeline are connected end to end by van der Waals force The nanocarbon pipelines are arranged in an axially preferred orientation, and the graphite fibers are also arranged substantially in an axially preferred orientation along the nanocarbon pipeline. The graphite fibers in the same nanocarbon pipeline or nanocarbon pipeline structure can be bonded by van der Waals force or by carbon-carbon bonds. Preferably, the graphite fibers in the same nanocarbon pipeline are bonded by carbon-carbon bonds. .

所述奈米碳管複合結構也可看作由石墨纖維及奈米碳管兩種碳素材料複合而成。具體地,所述奈米碳管複合結構可包括複數石墨纖維,每一石墨纖維均包覆或纏繞有複數首尾相連之奈米碳管。所述複數奈米碳管通過凡得瓦力首尾相連且沿該石墨纖維軸向延伸。所述複數石墨纖維可相互平行、纏繞或編織設置。所述複數石墨纖維之間可通過凡得瓦力或碳碳鍵結合形成所述石墨纖維結構。 The carbon nanotube composite structure can also be regarded as a composite of two carbon materials of graphite fiber and carbon nanotube. Specifically, the carbon nanotube composite structure may include a plurality of graphite fibers each coated or wound with a plurality of carbon nanotubes connected end to end. The plurality of carbon nanotubes are connected end to end by van der Waals force and extend axially along the graphite fiber. The plurality of graphite fibers may be disposed in parallel, wound or woven with each other. The graphite fiber structure may be formed by combining van der Waals or carbon-carbon bonds between the plurality of graphite fibers.

所述奈米碳管複合結構包括由複數奈米碳管形成之奈米碳管線結構及分佈在該奈米碳管線結構中之石墨纖維。所述複數奈米碳管之間除了用凡得瓦力結合之外,還可通過所述石墨纖維緊密結合,從而增加了所述複數奈米碳管之間之結合力,提高了所述奈米碳管複合結構之機械性能,尤其能提高沿所述奈米碳管線結構軸向方向之機械性能。而所述石墨纖維與所述奈米碳管結構具有較小之密度且均為碳素材料,故,由複數石墨纖維與複數奈米碳管複合形成之奈米碳管複合結構具有密度小、耐腐蝕、耐潮等優點。 The carbon nanotube composite structure includes a nanocarbon pipeline structure formed of a plurality of carbon nanotubes and a graphite fiber distributed in the nanocarbon pipeline structure. In addition to being combined with van der Waals force, the plurality of carbon nanotubes can be tightly bonded by the graphite fibers, thereby increasing the bonding force between the plurality of carbon nanotubes and improving the naphthalene The mechanical properties of the carbon nanotube composite structure, in particular, can improve the mechanical properties along the axial direction of the nanocarbon pipeline structure. The graphite fiber and the carbon nanotube structure have a small density and are both carbon materials. Therefore, the carbon nanotube composite structure formed by combining the plurality of graphite fibers and the plurality of carbon nanotubes has a small density. Corrosion resistance, moisture resistance and other advantages.

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內。 In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by those skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims.

Claims (13)

一種奈米碳管複合結構之製備方法,其包括如下步驟:提供一奈米碳管結構,所述奈米碳管結構為一自支撐結構,所述奈米碳管結構包括複數奈米碳管通過凡得瓦力連接;於所述奈米碳管結構中複合一聚合物;以及石墨化複合在所述奈米碳管結構中之聚合物,使該聚合物石墨化為一石墨結構。 A method for preparing a carbon nanotube composite structure, comprising the steps of: providing a carbon nanotube structure, the carbon nanotube structure is a self-supporting structure, and the carbon nanotube structure comprises a plurality of carbon nanotubes By polymerizing with a van der Waals force; compounding a polymer in the carbon nanotube structure; and graphitizing the polymer compounded in the carbon nanotube structure to graphitize the polymer into a graphite structure. 如請求項1所述之奈米碳管複合結構之製備方法,其中,所述奈米碳管結構與該聚合物複合之方法具體包括如下步驟:將所述奈米碳管結構浸潤在一聚合物溶液中以與所述聚合物複合。 The method for preparing a carbon nanotube composite structure according to claim 1, wherein the method for compounding the carbon nanotube structure with the polymer specifically comprises the step of: infiltrating the carbon nanotube structure into a polymerization. The solution is complexed with the polymer. 如請求項2所述之奈米碳管複合結構之製備方法,其中,所述聚合物溶液包括有機溶劑,該有機溶劑對奈米碳管之接觸角小於90度。 The method for preparing a carbon nanotube composite structure according to claim 2, wherein the polymer solution comprises an organic solvent, and the contact angle of the organic solvent to the carbon nanotubes is less than 90 degrees. 如請求項3所述之奈米碳管複合結構之製備方法,其中,所述有機溶劑之表面張力大於等於20毫牛每米。 The method for producing a carbon nanotube composite structure according to claim 3, wherein the organic solvent has a surface tension of 20 mN/m or more. 如請求項1所述之奈米碳管複合結構之製備方法,其中,所述奈米碳管結構與該聚合物複合之方法具體包括如下步驟:將所述奈米碳管結構浸潤在一聚合物單體溶液中;以及使該聚合物單體產生聚合反應,該聚合物單體聚合反應後成為聚合物與所述奈米碳管結構複合。 The method for preparing a carbon nanotube composite structure according to claim 1, wherein the method for compounding the carbon nanotube structure with the polymer specifically comprises the step of: infiltrating the carbon nanotube structure into a polymerization. And reacting the polymer monomer, and polymerizing the polymer monomer to form a polymer and recombining with the carbon nanotube structure. 如請求項1所述之奈米碳管複合結構之製備方法,其中,所述聚合物包括聚丙烯腈、聚乙烯醇、聚丙烯、聚苯乙烯、聚 氯乙烯或聚對苯二甲酸乙二酯。 The method for preparing a carbon nanotube composite structure according to claim 1, wherein the polymer comprises polyacrylonitrile, polyvinyl alcohol, polypropylene, polystyrene, poly Vinyl chloride or polyethylene terephthalate. 如請求項1所述之奈米碳管複合結構之製備方法,其中,所述奈米碳管結構包括一奈米碳管膜結構,所述奈米碳管膜結構具有複數微孔。 The method for preparing a carbon nanotube composite structure according to claim 1, wherein the carbon nanotube structure comprises a carbon nanotube membrane structure, and the carbon nanotube membrane structure has a plurality of micropores. 如請求項7所述之奈米碳管複合結構之製備方法,其中,所述奈米碳管膜結構包括一絮化膜、一碾壓膜或至少兩層奈米碳管拉膜。 The method for preparing a carbon nanotube composite structure according to claim 7, wherein the carbon nanotube membrane structure comprises a flocculation membrane, a milled membrane or at least two layers of carbon nanotube membranes. 如請求項7所述之奈米碳管複合結構之製備方法,其中,所述微孔由複數奈米碳管通過凡得瓦力相互連接而形成,所述微孔之尺寸在1奈米到500奈米之間。 The method for preparing a carbon nanotube composite structure according to claim 7, wherein the micropores are formed by connecting a plurality of carbon nanotubes through a van der Waals force, and the pore size is from 1 nm to 1 nm. Between 500 nm. 如請求項7所述之奈米碳管複合結構之製備方法,其中,所述石墨結構包括複數石墨片段填充在所述微孔中,所述複數石墨片段之間通過碳碳鍵結合,所述石墨片段與所述奈米碳管結構中通過碳碳鍵及凡得瓦力結合。 The method for preparing a carbon nanotube composite structure according to claim 7, wherein the graphite structure comprises a plurality of graphite fragments filled in the micropores, and the plurality of graphite fragments are bonded by carbon-carbon bonds, The graphite fragments are combined with the carbon nanotube bonds and van der Waals in the carbon nanotube structure. 如請求項1所述之奈米碳管複合結構之製備方法,其中,所述奈米碳管結構包括一奈米碳管線結構,複數奈米碳管線結構相互平行、纏繞或編織設置。 The method for preparing a carbon nanotube composite structure according to claim 1, wherein the carbon nanotube structure comprises a nano carbon pipeline structure, and the plurality of nanocarbon pipeline structures are arranged in parallel, wound or woven with each other. 如請求項11所述之奈米碳管複合結構之製備方法,其中,所述奈米碳管線結構包括複數奈米碳管通過凡得瓦力首尾相連且沿所述奈米碳管線軸向延伸。 The method for preparing a carbon nanotube composite structure according to claim 11, wherein the nanocarbon pipeline structure comprises a plurality of carbon nanotubes connected end to end by van der Waals force and extending axially along the nanocarbon pipeline . 如請求項11所述之奈米碳管複合結構之製備方法,其中,所述石墨結構包括複數石墨纖維沿所述奈米碳管線結構纏繞或包覆所述複數奈米碳管。 The method for preparing a carbon nanotube composite structure according to claim 11, wherein the graphite structure comprises a plurality of graphite fibers wound or coated around the plurality of carbon nanotube structures.
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