TW201348126A - Nano-metal-carbon tube composite, method for preparing the same and conductive substrate containing nano-carbon tube - Google Patents
Nano-metal-carbon tube composite, method for preparing the same and conductive substrate containing nano-carbon tube Download PDFInfo
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本發明是有關於一種奈米碳管及其製法，特別是指一種含有金屬的奈米碳管。 The invention relates to a carbon nanotube and a preparation method thereof, in particular to a carbon nanotube containing metal.
氧化銦錫(Indium tin oxide，簡稱ITO)透明導電膜具有高透光性及良好導電性，因此被廣泛應用於觸控面板、發光二極體、太陽能電池等領域。然，一般ITO透明導電膜的製程需經高溫處理(230℃以上)且製程繁雜，以及氧化銦錫成本高，再者，ITO透明導電膜無法形成於以塑膠為材質的軟性基板上，因ITO透明導電膜的高溫製程會導致軟性基板產生熱膨脹現象或損傷，不符合業者的使用效益及成本效益。因此，逐漸地被奈米碳管或導電高分子材料所取代。 Indium tin oxide (ITO) transparent conductive film has high light transmittance and good electrical conductivity, and is widely used in touch panels, light-emitting diodes, solar cells and the like. However, the process of the general ITO transparent conductive film needs to be processed at a high temperature (above 230 ° C) and the process is complicated, and the cost of indium tin oxide is high. Furthermore, the ITO transparent conductive film cannot be formed on a soft substrate made of plastic material, because of ITO. The high-temperature process of the transparent conductive film may cause thermal expansion or damage of the flexible substrate, which is inconsistent with the use efficiency and cost-effectiveness of the operator. Therefore, it is gradually replaced by a carbon nanotube or a conductive polymer material.
其中，奈米碳管由於具有特殊的機械強度、高導電性及優越的化學穩定性，因此深受各領域研究者廣泛的注意。但奈米碳管的導電性相較於ITO的導電性仍有些差距，目前改善方式大多是添加金屬粒子或導電高分子材料，來提升並改善其導電性。然，該改善方式容易存在有相容性及分散性等問題，因此提升導電性的效益有限，同時，易造成透明度的損失。 Among them, carbon nanotubes have attracted extensive attention from researchers in various fields due to their special mechanical strength, high electrical conductivity and superior chemical stability. However, the conductivity of the carbon nanotubes is still somewhat different from that of the ITO. Currently, most of the improvement methods are the addition of metal particles or conductive polymer materials to enhance and improve the conductivity. However, this improvement method is prone to problems such as compatibility and dispersibility, so the benefit of improving conductivity is limited, and at the same time, transparency loss is easily caused.
有鑑於上述，仍有需要發展出一種導電性及透明性佳的導電膜，且該導電膜可用低溫製程來製備，以符合業者所需。 In view of the above, there is still a need to develop a conductive film having good conductivity and transparency, and the conductive film can be prepared by a low temperature process to meet the needs of the industry.
因此，本發明之第一目的，即在提供一種高導電性的奈米金屬碳管複合材。 Accordingly, a first object of the present invention is to provide a highly conductive nano metal carbon tube composite.
於是，本發明奈米金屬碳管複合材，包含：複數個經改質奈米碳管，每一個經改質奈米碳管含有複數個官能基團；及複數個奈米金屬團，每一個奈米金屬團是連結於每一個經改質奈米碳管中之至少一官能基團上，且兩相鄰的經改質奈米碳管透過至少一個奈米金屬團而彼此相互連結。 Thus, the nano metal carbon tube composite of the present invention comprises: a plurality of modified carbon nanotubes, each modified carbon nanotube containing a plurality of functional groups; and a plurality of nano metal clusters, each The nano metal cluster is bonded to at least one functional group in each of the modified carbon nanotubes, and the two adjacent modified carbon nanotubes are connected to each other through at least one nano metal cluster.
本發明之第二目的，即在提供一種奈米金屬碳管複合材的製備方法。 A second object of the present invention is to provide a method for preparing a nano metal carbon tube composite.
於是，本發明奈米金屬碳管複合材的製備方法，包含以下步驟：步驟(a)：提供複數個的經改質奈米碳管，每一個經改質奈米碳管含有複數個官能基團；步驟(b)：提供複數個金屬離子，與該等經改質奈米碳管上的官能基團連結並獲得一混合物；步驟(c)：將該混合物加入一還原劑中以使該等金屬離子進行還原反應，形成複數個具有奈米金屬粒子的奈米碳管；步驟(d)：將該等具有奈米金屬粒子的奈米碳管施予一加熱處理，即可獲得奈米金屬碳管複合材。 Therefore, the preparation method of the nano metal carbon tube composite of the present invention comprises the following steps: Step (a): providing a plurality of modified carbon nanotubes, each of which has a plurality of functional groups. a step (b): providing a plurality of metal ions, linking with the functional groups on the modified carbon nanotubes to obtain a mixture; and step (c): adding the mixture to a reducing agent to make the The metal ions are subjected to a reduction reaction to form a plurality of carbon nanotubes having nano metal particles; and step (d): the carbon nanotubes having the nano metal particles are subjected to a heat treatment to obtain a nanometer. Metal carbon tube composite.
本發明之第三目的，即在提供一種具有高導電性的奈米碳管導電基板。 A third object of the present invention is to provide a carbon nanotube conductive substrate having high conductivity.
於是，本發明奈米碳管導電基板，包含：一基材；及一奈米金屬碳管複合材，形成於該基材上；其中，該奈米金屬碳管複合材包含複數個經改質奈米碳管，每一個經改質奈米碳管含有複數個官能基團；及複數個奈米金屬團，每一個奈米金屬團是連結於每一個經改質奈米碳管中之至少一官能基團上，且兩相鄰的經改質奈米碳管透過至少一個奈米金屬團而彼此相互連結。 Therefore, the carbon nanotube conductive substrate of the present invention comprises: a substrate; and a nano metal carbon tube composite formed on the substrate; wherein the nano metal carbon tube composite comprises a plurality of modified materials a carbon nanotube, each modified carbon nanotube containing a plurality of functional groups; and a plurality of nano metal clusters, each of which is bonded to each of the modified carbon nanotubes On the monofunctional group, two adjacent modified carbon nanotubes are connected to each other through at least one nano metal cluster.
本發明之功效在於：該奈米金屬碳管複合材透過經改質奈米碳管上的官能基團，使奈米金屬團均勻分佈並吸附在經改質奈米碳管的官能基團上而不聚集或堆積，同時，透過奈米金屬團連結使該等經改質奈米碳管彼此間緊密堆疊，提升電子傳遞效率，繼而使該奈米金屬碳管複合材具有較佳的導電性。 The effect of the invention is that the nano metal carbon tube composite penetrates the functional group on the modified carbon nanotube to uniformly distribute the nano metal cluster and adsorb on the functional group of the modified carbon nanotube. Without gathering or accumulating, at the same time, the modified carbon nanotubes are closely stacked with each other through the nano metal group to enhance the electron transfer efficiency, and then the nano metal carbon tube composite has better conductivity. .
本發明高導電性的奈米金屬碳管複合材，包含：複數個經改質奈米碳管，每一個經改質奈米碳管含有複數個官能基團；及複數個奈米金屬團，每一個奈米金屬團是連結於每一個經改質奈米碳管中之至少一官能基團上，且兩相鄰的經改質奈米碳管透過至少一個奈米金屬團而彼此相互連結。 The highly conductive nano metal carbon tube composite of the present invention comprises: a plurality of modified carbon nanotubes, each modified carbon nanotube containing a plurality of functional groups; and a plurality of nano metal clusters, Each of the nano metal clusters is bonded to at least one functional group in each of the modified carbon nanotubes, and the two adjacent modified carbon nanotubes are connected to each other through at least one nano metal cluster .
較佳地，該等官能基團為一可提供電子的基團。 Preferably, the functional groups are a group capable of providing an electron.
較佳地，該等官能基團包含至少一種由下列所構成群組的基團：酸酐基、羧基、羥基、醯基及胺基。更佳地， 該等官能基團為酸酐基。 Preferably, the functional groups comprise at least one group consisting of an acid anhydride group, a carboxyl group, a hydroxyl group, a thiol group and an amine group. More preferably, These functional groups are anhydride groups.
較佳地，該奈米金屬團包含至少一種由下列所構成群組的金屬：銀、錫及鎘。 Preferably, the nanometal cluster comprises at least one metal consisting of the following: silver, tin and cadmium.
該等經改質奈米碳管的製備方法可採用以往的方式，例如，將改質劑與奈米碳管透過自由基反應，而讓改質劑鍵結在奈米碳管上。 The preparation method of the modified carbon nanotubes can be carried out in a conventional manner. For example, the modifier is reacted with a carbon nanotube by a radical reaction, and the modifier is bonded to the carbon nanotube.
該奈米碳管可單獨或混合使用，且該奈米碳管包含但不限於單層奈米碳管(single-walled CNTs)、雙層奈米碳管(double-walled CNTs)、多層奈米碳管(multiple-walled CNTs)或奈米碳繩(rope CNTs)等。較佳地，該奈米碳管為單層奈米碳管。該改質劑為一可提供電子的化合物且能與奈米金屬團連結即可，較佳地，該改質劑為一包含至少一種由下列所構成群組的基團的改質劑，且該基團為酸酐基、羧基、羥基、醯基或胺基。該改質劑可單獨或混合使用，且該改質劑包含但不限於順丁烯二酸酐(maleic anhydride)、甲基丙烯酸-2-羥基乙酯(2-hydroxyethyl methacrylate)，或亞胺乙二酸(iminodiacetic acid)與縮水甘油甲基丙烯酸酯(glycidyl methacrylate)反應後的化合物等。 The carbon nanotubes may be used singly or in combination, and the carbon nanotubes include, but are not limited to, single-walled CNTs, double-walled CNTs, and multilayer nanometers. Multiple-walled CNTs or rope CNTs. Preferably, the carbon nanotube is a single layer of carbon nanotubes. The modifier is an electron-donating compound and can be bonded to a nano metal group. Preferably, the modifier is a modifier comprising at least one group consisting of the following groups, and The group is an acid anhydride group, a carboxyl group, a hydroxyl group, a mercapto group or an amine group. The modifier may be used singly or in combination, and the modifier includes, but is not limited to, maleic anhydride, 2-hydroxyethyl methacrylate, or imine ethylene. A compound obtained by reacting an acid (iminodiacetic acid) with glycidyl methacrylate.
該奈米金屬碳管複合材可做為顯示裝置(如液晶顯示裝置)或觸控裝置(如觸控面板)中的透明導電膜的材料。 The nano metal carbon tube composite material can be used as a material of a transparent conductive film in a display device (such as a liquid crystal display device) or a touch device (such as a touch panel).
本發明奈米金屬碳管複合材的製備方法，包含以下步驟：步驟(a)：提供複數個的經改質奈米碳管，每一個經改質奈米碳管含有複數個官能基團； 步驟(b)：提供複數個金屬離子，與該等經改質奈米碳管上的官能基團連結並獲得一混合物；步驟(c)：將該混合物加入一還原劑中以使該等金屬離子進行還原反應，形成複數個具有奈米金屬粒子的奈米碳管；步驟(d)：將該等具有奈米金屬粒子的奈米碳管施予一加熱處理，即可獲得奈米金屬碳管複合材。 The method for preparing a nano metal carbon tube composite according to the present invention comprises the following steps: Step (a): providing a plurality of modified carbon nanotubes, each modified carbon nanotube containing a plurality of functional groups; Step (b): providing a plurality of metal ions, linking with functional groups on the modified carbon nanotubes to obtain a mixture; and step (c): adding the mixture to a reducing agent to make the metals The ions are subjected to a reduction reaction to form a plurality of carbon nanotubes having nano metal particles; and step (d): the carbon nanotubes having the nano metal particles are subjected to a heat treatment to obtain a nano metal carbon Tube composite.
該加熱處理主要是使奈米金屬粒子彼此相互熔融，繼而使該等經改質奈米碳管彼此緊密堆疊，提升電子傳遞效率，繼而使該奈米金屬碳管複合材具有較佳的導電性。 The heat treatment is mainly to melt the nano metal particles with each other, and then the heat-modified carbon nanotubes are closely stacked with each other to improve the electron transfer efficiency, and then the nano metal carbon tube composite has better conductivity. .
較佳地，還包含一於步驟(c)前進行的清洗處理步驟。該清洗處理步驟可採以往的方式，目地在於清洗掉未連結在經改質奈米碳管的官能基團上的金屬離子，以利步驟(c)能將連結在經改質奈米碳管的官能基團上的金屬離子還原成奈米等級的金屬粒子。 Preferably, a cleaning treatment step performed before step (c) is further included. The cleaning treatment step can be carried out in the conventional manner, and the purpose is to wash away the metal ions not attached to the functional groups of the modified carbon nanotubes, so that the step (c) can be bonded to the modified carbon nanotubes. The metal ions on the functional groups are reduced to metal particles of the nanometer grade.
較佳地，該金屬離子與經改質奈米碳管上的官能基團的連結方式是螯合方式。 Preferably, the manner in which the metal ion is bonded to the functional group on the modified carbon nanotube is a chelation mode.
該經改質奈米碳管及官能基團如同上述，故不再贅述。該金屬離子並無特別的限制，依所需的奈米金屬碳管複合材的特性(如導電性)進行選擇即可，較佳地，該金屬離子包含至少一種由下列所構成群組的化合物：銀離子、錫離子及鎘離子。該金屬離子的來源只要是能夠提供金屬離子的金屬源皆可，如本發明具體例中的銀離子是由硝酸銀所提供；錫離子是由二氯化錫水合物所提供。該還原劑可單 獨或混合使用，且該還原劑包含至少一種由下列所構成群組的化合物：硼氫化鈉(NaBH4)、次磷酸鈉(NaH2PO2．H2O)、二鹽酸肼(N2H4．2HCl)及水合肼(N2H4．H2O)。本發明的具體例中是使用硼氫化鈉。 The modified carbon nanotubes and functional groups are as described above, and therefore will not be described again. The metal ion is not particularly limited and may be selected depending on the characteristics (e.g., conductivity) of the desired nano metal carbon tube composite. Preferably, the metal ion contains at least one compound consisting of the following groups; : Silver ions, tin ions and cadmium ions. The source of the metal ion may be any metal source capable of providing a metal ion, and the silver ion in the specific example of the present invention is provided by silver nitrate; the tin ion is provided by tin dichloride hydrate. The reducing agent may be used singly or in combination, and the reducing agent comprises at least one compound consisting of sodium borohydride (NaBH 4 ), sodium hypophosphite (NaH 2 PO 2 .H 2 O), bismuth dihydrochloride (N 2 H 4 .2 HCl) and hydrazine hydrate (N 2 H 4 .H 2 O). In a specific example of the invention, sodium borohydride is used.
該加熱處理可採用以往的方式，以能使奈米金屬粒子彼此間相互熔融的方式即可。較佳地，該加熱處理的操作溫度範圍120℃~200℃。 This heat treatment may be carried out in a conventional manner so that the nano metal particles can be mutually melted. Preferably, the heat treatment has an operating temperature range of 120 ° C to 200 ° C.
本發明高導電度的奈米碳管導電基板，包含：一基材；及一奈米金屬碳管複合材，形成於該基材上；其中，該奈米金屬碳管複合材包含複數個經改質奈米碳管，每一個經改質奈米碳管含有複數個官能基團；及複數個奈米金屬團，每一個奈米金屬團是連結於每一個經改質奈米碳管中之至少一官能基團上，且兩相鄰的經改質奈米碳管透過至少一個奈米金屬團而彼此相互連結。 The high conductivity carbon nanotube conductive substrate of the present invention comprises: a substrate; and a nano metal carbon tube composite formed on the substrate; wherein the nano metal carbon tube composite comprises a plurality of The modified carbon nanotubes each of which contains a plurality of functional groups; and a plurality of nano-metal clusters, each of which is bonded to each of the modified carbon nanotubes At least one functional group, and two adjacent modified carbon nanotubes are connected to each other through at least one nano metal cluster.
該等經改質奈米碳管、官能基團及奈米金屬團如同上述，故不再贅述。該基材的材質為玻璃、塑膠或矽。該基材可選自於應用在顯示裝置或觸控裝置中的無鹼玻璃、鈉鈣玻璃、強化玻璃(Pyrex玻璃)、石英玻璃、表面上已附著透明導電膜的玻璃或表面上已附著彩色層的玻璃等之基材及用於固體攝影元件等之光電變換元件基板(如：矽基板)等。該基材亦可選自於應用在軟性電子裝置(如電子紙或紙喇叭)中的軟性基板如聚對苯二甲酸乙二醇酯(polyethylene terephthalate，簡稱PET)材質的基材、聚醯亞胺(polyimide ，簡稱PI)材質的基材、聚碳酸酯(polycarbonate，簡稱PC)材質的基材等。 The modified carbon nanotubes, functional groups and nano-metal clusters are as described above and will not be described again. The substrate is made of glass, plastic or enamel. The substrate may be selected from the group consisting of alkali-free glass, soda-lime glass, reinforced glass (Pyrex glass), quartz glass, glass having a transparent conductive film attached to the surface or a surface on which a color is attached. A substrate such as a layer of glass or a photoelectric conversion element substrate (for example, a germanium substrate) used for a solid-state imaging device or the like. The substrate may also be selected from a flexible substrate such as polyethylene terephthalate (PET), which is used in a flexible electronic device such as an electronic paper or a paper horn. Amine , referred to as PI) material base material, polycarbonate (polycarbonate, PC) substrate.
該奈米金屬碳管複合材形成於該基材上的方式可採一般的方式，如藉由旋轉塗佈或流延塗佈、輥式塗佈或往印塗佈等塗佈方法，故不再贅述。 The nano metal carbon tube composite material is formed on the substrate in a general manner, such as by spin coating or cast coating, roll coating or printing, etc. Let me repeat.
相較於以往的ITO透明導電膜，本發明奈米金屬碳管複合材形成於該基材上的方式不需經高溫處理且製程簡單，再者，本發明奈米金屬碳管複合材不僅可形成於玻璃基材上，更可形成於以塑膠為材質的軟性基板上，不會導致軟性基板產生熱膨脹現象或損傷，能夠大量化製備及商業化應用，同時，因不需經高溫處理，可減少對能源的需求以及減少高溫設備的成本支出，以符合業者的使用效益及成本效益。 Compared with the conventional ITO transparent conductive film, the nano metal carbon tube composite material of the present invention is formed on the substrate without high temperature treatment and has a simple process. Furthermore, the nano metal carbon tube composite material of the present invention can be used not only It is formed on a glass substrate, and can be formed on a soft substrate made of plastic material, which does not cause thermal expansion or damage of the flexible substrate, and can be mass-produced and commercialized, and at the same time, it can be processed without high temperature. Reduce the need for energy and reduce the cost of high-temperature equipment to meet the user's efficiency and cost-effectiveness.
本發明將就以下實施例來作進一步說明，但應瞭解的是，該實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。 The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.
取1克單層奈米碳管均勻分散於電漿處理設備(為中華民國專利申請號097113028所示的電漿處理設備)內槽中，並利用攪拌匙使該單層奈米碳管混合均勻，再利用真空馬達將槽內真空度調整至1×10-2Torr後，通入氬氣並使槽內真空度保持在1.5×10-1Torr，待通入氣體穩定後，即啟動電漿 週波啟始器，控制電漿產生條件在50W和13.56MHzv下，處理時間為10分鐘。待電漿反應完畢後，加入5克的順丁烯二酸酐，且將反應溫度控制在60℃，於該槽內進行4小時的接枝反應，即可獲得具有酸酐基的奈米碳管，接枝率為18.35wt%。 1 g of a single-layer carbon nanotube is uniformly dispersed in the inner tank of the plasma processing equipment (the plasma processing equipment shown in the Republic of China Patent Application No. 097113028), and the single-layer carbon nanotube is uniformly mixed by using a stirring spoon. Then, using a vacuum motor to adjust the vacuum in the tank to 1 × 10 -2 Torr, argon gas is introduced and the vacuum in the tank is maintained at 1.5 × 10 -1 Torr. After the gas is stabilized, the plasma is started. Zhou Bo starter, control plasma production conditions at 50W and 13.56MHzv, processing time is 10 minutes. After the completion of the plasma reaction, 5 g of maleic anhydride is added, and the reaction temperature is controlled at 60 ° C, and a graft reaction is carried out in the tank for 4 hours to obtain a carbon nanotube having an acid anhydride group. The graft ratio was 18.35 wt%.
取1克單層奈米碳管均勻分散於電漿處理器內槽中，並利用攪拌匙使該單層奈米碳管混合均勻，再利用真空馬達將槽內真空度調整至1×10-2Torr後，通入氬氣並使槽內真空度保持在1.5×10-1Torr，待通入氣體穩定後，即啟動電漿週波啟始器，控制電漿產生條件在50W和13.56MHzv下，處理時間為10分鐘。待電漿反應完畢後，加入5克的甲基丙烯酸-2-羥基乙酯，且將反應溫度控制在60℃，於該槽內進行2小時的接枝反應，即可獲得具有酯基及羥基的奈米碳管，接枝率為13.2wt%。 1 g of single-layer carbon nanotubes were uniformly dispersed in the inner tank of the plasma processor, and the single-layer carbon nanotubes were uniformly mixed by using a stirring spoon, and then the vacuum degree of the tank was adjusted to 1 × 10 by a vacuum motor . After 2 Torr, argon gas was introduced and the vacuum in the tank was maintained at 1.5×10 -1 Torr. After the gas was stabilized, the plasma cycle starter was started to control the plasma generation conditions at 50 W and 13.56 MHzv. The processing time is 10 minutes. After the completion of the plasma reaction, 5 g of 2-hydroxyethyl methacrylate is added, and the reaction temperature is controlled at 60 ° C, and a graft reaction is carried out in the tank for 2 hours to obtain an ester group and a hydroxyl group. The carbon nanotubes have a graft ratio of 13.2% by weight.
取1克單層奈米碳管均勻分散於電漿處理器內槽中，並利用攪拌匙使該單層奈米碳管混合均勻，再利用真空馬達將槽內真空度調整至1×10-2Torr後，通入氬氣並使槽內真空度保持在1.5×10-1Torr，待通入氣體穩定後，即啟動電漿週波啟始器，控制電漿產生條件在50W和13.56MHzv下，處理時間為10分鐘。待電漿反應完畢後，加入10克的亞胺乙二酸與縮水甘油甲基丙烯酸酯反應後的化合物，且將反應溫度控制在60℃，於該槽內進行2小時的接枝反應， 即可獲得具有羧酸基及三級胺基及羥基的奈米碳管，接枝率為37.63wt%。 1 g of single-layer carbon nanotubes were uniformly dispersed in the inner tank of the plasma processor, and the single-layer carbon nanotubes were uniformly mixed by using a stirring spoon, and then the vacuum degree of the tank was adjusted to 1 × 10 by a vacuum motor . After 2 Torr, argon gas was introduced and the vacuum in the tank was maintained at 1.5×10 -1 Torr. After the gas was stabilized, the plasma cycle starter was started to control the plasma generation conditions at 50 W and 13.56 MHzv. The processing time is 10 minutes. After the completion of the plasma reaction, 10 g of the compound reacted with imino oxalic acid and glycidyl methacrylate was added, and the reaction temperature was controlled at 60 ° C, and a graft reaction was carried out in the tank for 2 hours, that is, A carbon nanotube having a carboxylic acid group and a tertiary amino group and a hydroxyl group can be obtained, and the graft ratio is 37.63 wt%.
將5毫克的製備例1的具有酸酐基的奈米碳管、5毫升的水及0.025克的二氯化錫(SnCl2．2H2O)反應5小時，接著過濾，並使用去離子水清洗濾餅。 5 mg of the carbon nanotubes having an acid anhydride group of Preparation Example 1, 5 ml of water, and 0.025 g of tin dichloride (SnCl 2 .2H 2 O) were reacted for 5 hours, followed by filtration, and washed with deionized water. Filter cake.
將上述5毫克濾餅及0.015克的硼氫化鈉分散於5毫升水中，接著置於一反應器中並反應2小時，待反應後可得含有具有奈米錫粒子的奈米碳管的混合液，接著，進行過濾，即可獲得具有奈米錫粒子的奈米碳管。取0.311毫克的具有奈米錫粒子的奈米碳管分散於50毫升的水中，形成一具有奈米錫粒子的奈米碳管的水溶液並將其塗佈於一基材上，待水揮發後，接著於120℃下進行加熱處理，即可製得本發明的奈米金屬碳管複合材及奈米碳管導電基板。以下記之各檢測項目進行評價，所得結果如表1所示。 The above 5 mg filter cake and 0.015 g of sodium borohydride were dispersed in 5 ml of water, and then placed in a reactor and reacted for 2 hours. After the reaction, a mixture containing carbon nanotubes having nano tin particles was obtained. Then, filtration is carried out to obtain a carbon nanotube having nano tin particles. 0.311 mg of a carbon nanotube with nano tin particles was dispersed in 50 ml of water to form an aqueous solution of a carbon nanotube having nano tin particles and coated on a substrate until the water was evaporated. Then, the nano metal carbon tube composite material and the carbon nanotube conductive substrate of the present invention can be obtained by heat treatment at 120 ° C. Each test item described below was evaluated, and the results obtained are shown in Table 1.
實施例2~5是以與實施例1相同的步驟來製備奈米金屬碳管複合材及奈米碳管導電基板，不同的地方在於：改變具有奈米錫粒子的奈米碳管使用量，依序分別為0.622毫克、0.933毫克、1.244毫克、1.555毫克。以下記之各檢測項目進行評價，所得結果如表1所示。 In the second to fifth embodiments, the nano metal carbon tube composite material and the carbon nanotube conductive substrate were prepared in the same manner as in the first embodiment, except that the amount of the carbon nanotubes having the nano tin particles was changed. The order was 0.622 mg, 0.933 mg, 1.244 mg, and 1.555 mg, respectively. Each test item described below was evaluated, and the results obtained are shown in Table 1.
將5毫克的製備例1的具有酸酐基的奈米碳管、5毫升 的水及0.025克的硝酸銀反應，接著過濾，並使用去離子水清洗濾餅。 5 mg of the carbon nanotubes having the acid anhydride group of Preparation Example 1, 5 ml The water was reacted with 0.025 grams of silver nitrate, filtered, and the filter cake was rinsed with deionized water.
將上述5毫克濾餅及0.015克的硼氫化鈉分散於5毫升水中，接著置於一反應器中並反應24小時，待反應後可得含有具有奈米銀粒子的奈米碳管的混合液，接著，進行過濾，即可獲得具有奈米銀粒子的奈米碳管。取0.298毫克的具有奈米錫粒子的奈米碳管分散於50毫升的水中，形成一具有奈米銀粒子的奈米碳管的水溶液並將其塗佈於一基材上，待水揮發後，接著於130℃下進行加熱處理，即可製得本發明的奈米金屬碳管複合材及奈米碳管導電基板。以下記之各檢測項目進行評價，所得結果如表1所示。 The above 5 mg filter cake and 0.015 g of sodium borohydride were dispersed in 5 ml of water, and then placed in a reactor and reacted for 24 hours. After the reaction, a mixture containing carbon nanotubes having nano silver particles was obtained. Then, filtration is carried out to obtain a carbon nanotube having nano silver particles. 0.298 mg of a carbon nanotube having nanotin particles was dispersed in 50 ml of water to form an aqueous solution of a carbon nanotube having nano silver particles and coated on a substrate until the water was evaporated. Then, the nano metal carbon tube composite material and the carbon nanotube conductive substrate of the present invention can be obtained by heat treatment at 130 ° C. Each test item described below was evaluated, and the results obtained are shown in Table 1.
實施例7~10是以與實施例6相同的步驟來製備奈米金屬碳管複合材及奈米碳管導電基板，不同的地方在於：改變具有奈米銀粒子的奈米碳管使用量，依序分別為0.596毫克、0.894毫克、1.192毫克、1.49毫克。以下記之各檢測項目進行評價，所得結果如表1所示。 In Examples 7 to 10, a nano metal carbon tube composite material and a carbon nanotube conductive substrate were prepared in the same manner as in Example 6, except that the amount of the carbon nanotubes having nano silver particles was changed. The order was 0.596 mg, 0.894 mg, 1.192 mg, 1.49 mg, respectively. Each test item described below was evaluated, and the results obtained are shown in Table 1.
比較例1是以與實施例1相同的步驟來製備奈米金屬碳管複合材及奈米碳管導電基板，不同的地方在於：形成一具有奈米錫粒子的奈米碳管的水溶液塗佈於一基材上，待水揮發後，不進行加熱處理。以下記之各檢測項目進行評價，所得結果如表1所示。 In Comparative Example 1, a nano metal carbon tube composite material and a carbon nanotube conductive substrate were prepared in the same manner as in Example 1, except that an aqueous solution coating of a carbon nanotube having nano tin particles was formed. On a substrate, after the water is volatilized, no heat treatment is performed. Each test item described below was evaluated, and the results obtained are shown in Table 1.
比較例2~5是以與比較例1相同的步驟來製備，不同的地方在於：具有奈米錫粒子的奈米碳管的使用量依序分別為0.622毫克、0.933毫克、1.244毫克、1.555毫克。以下記之各檢測項目進行評價，所得結果如表1所示。 Comparative Examples 2 to 5 were prepared in the same manner as in Comparative Example 1, except that the amount of the carbon nanotubes having the nano tin particles was 0.622 mg, 0.933 mg, 1.244 mg, and 1.555 mg, respectively. . Each test item described below was evaluated, and the results obtained are shown in Table 1.
比較例6是以與實施例6相同的步驟來製備奈米金屬碳管複合材，不同的地方在於：形成一具有奈米銀粒子的奈米碳管的水溶液塗佈於一基材上，待水揮發後，不進行加熱處理。以下記之各檢測項目進行評價，所得結果如表1所示。 Comparative Example 6 was a step of preparing a nano metal carbon tube composite in the same manner as in Example 6, except that an aqueous solution of a carbon nanotube having nano silver particles was formed on a substrate. After the water is volatilized, no heat treatment is performed. Each test item described below was evaluated, and the results obtained are shown in Table 1.
比較例7~10是以與比較例6相同的步驟來製備，不同的地方在於：具有奈米銀粒子的奈米碳管的使用量依序分別為0.596毫克、0.894毫克、1.192毫克、1.49毫克。以下記之各檢測項目進行評價，所得結果如表1所示。 Comparative Examples 7 to 10 were prepared in the same manner as in Comparative Example 6, except that the amount of the carbon nanotubes having nano silver particles was 0.596 mg, 0.894 mg, 1.192 mg, 1.49 mg, respectively. . Each test item described below was evaluated, and the results obtained are shown in Table 1.
將0.318毫克的製備例1的具有酸酐基的奈米碳管施予120℃溫度進行加熱處理即可。以下記之各檢測項目進行評價，所得結果如表1所示。 0.318 mg of the carbon nanotube having an acid anhydride group of Preparation Example 1 was applied to a temperature of 120 ° C for heat treatment. Each test item described below was evaluated, and the results obtained are shown in Table 1.
比較例12~13是以與比較例11相同的步驟，不同的地方在於：改變具有酸酐基的奈米碳管的使用量，依序分別為0.954及1.59毫克。以下記之各檢測項目進行評價，所得結果如表1所示。 Comparative Examples 12 to 13 were the same procedures as in Comparative Example 11, except that the amount of the carbon nanotubes having an acid anhydride group was changed to 0.954 and 1.59 mg, respectively. Each test item described below was evaluated, and the results obtained are shown in Table 1.
將5毫克的製備例1的具有酸酐基的奈米碳管、5毫升的水及0.025克的二氯化錫(SnCl2．2H2O)反應5小時，接著過濾，並使用去離子水清洗濾餅。 5 mg of the carbon nanotubes having an acid anhydride group of Preparation Example 1, 5 ml of water, and 0.025 g of tin dichloride (SnCl 2 .2H 2 O) were reacted for 5 hours, followed by filtration, and washed with deionized water. Filter cake.
將上述5毫克濾餅及0.015克的硼氫化鈉分散於5毫升水中，接著置於一反應器中並反應2小時，待反應後可得含有具有奈米錫粒子的奈米碳管的混合液，接著，進行過濾，即可獲得具有奈米錫粒子的奈米碳管。取0.311毫克的具有奈米錫粒子的奈米碳管分散於50毫升的水中，形成一具有奈米錫粒子的奈米碳管的水溶液並將其塗佈於一基材上，待水揮發後，接著於120℃下進行加熱處理，即可製得本發明的奈米金屬碳管複合材。以下記之各檢測項目進行評價，所得結果如表2所示。 The above 5 mg filter cake and 0.015 g of sodium borohydride were dispersed in 5 ml of water, and then placed in a reactor and reacted for 2 hours. After the reaction, a mixture containing carbon nanotubes having nano tin particles was obtained. Then, filtration is carried out to obtain a carbon nanotube having nano tin particles. 0.311 mg of a carbon nanotube with nano tin particles was dispersed in 50 ml of water to form an aqueous solution of a carbon nanotube having nano tin particles and coated on a substrate until the water was evaporated. Then, the nano metal carbon tube composite of the present invention can be obtained by heat treatment at 120 °C. Each test item described below was evaluated, and the results obtained are shown in Table 2.
實施例12~13及比較例14~16是以與實施例11相同的步驟來製備奈米金屬碳管複合材，不同的地方在於：改變加熱處理的溫度。以下記之各檢測項目進行評價，所得結果如表2所示。 Examples 12 to 13 and Comparative Examples 14 to 16 were prepared in the same manner as in Example 11 except that the temperature of the heat treatment was changed. Each test item described below was evaluated, and the results obtained are shown in Table 2.
將5毫克的製備例1的具有酸酐基的奈米碳管、5毫升的水、0.025克的二氯化錫(SnCl2．2H2O)、0.006克的硝酸銀反應，接著過濾，並使用去離子水清洗濾餅。 5 mg of the carbon nanotubes having the acid anhydride group of Preparation Example 1, 5 ml of water, 0.025 g of tin dichloride (SnCl 2 .2H 2 O), and 0.006 g of silver nitrate were reacted, followed by filtration, and used. Clean the filter cake with ionized water.
將上述5毫克濾餅及0.015克的硼氫化鈉分散於5毫升 水中，接著置於一反應器中並反應2小時，待反應後可得含有具有奈米錫粒子及奈米銀粒子的奈米碳管的混合液，接著，進行過濾，即可獲得具有奈米錫粒子及奈米銀粒子的奈米碳管。取0.311毫克的具有奈米錫粒子及奈米銀粒子的奈米碳管分散於50毫升的水中，形成一具有奈米錫粒子及奈米銀粒子的奈米碳管的水溶液並將其塗佈於一基材上，待水揮發後，接著於120℃下進行加熱處理，即可製得本發明的奈米金屬碳管複合材。以下記之各檢測項目進行評價，所得結果如表2所示。 Disperse the above 5 mg filter cake and 0.015 g of sodium borohydride in 5 ml The water is then placed in a reactor and reacted for 2 hours. After the reaction, a mixture containing a carbon nanotube having nanotin particles and nano silver particles can be obtained, followed by filtration to obtain a nanometer having a nanometer. Tin carbon nanotubes of tin particles and nano silver particles. 0.311 mg of a carbon nanotube having nanotin particles and nano silver particles was dispersed in 50 ml of water to form an aqueous solution of a carbon nanotube having nanotin particles and nano silver particles and coating the same. The nano metal carbon tube composite of the present invention can be obtained by subjecting the substrate to water evaporation and then heat treatment at 120 ° C. Each test item described below was evaluated, and the results obtained are shown in Table 2.
實施例15~16及比較例17~19是以與實施例14相同的步驟來製備奈米金屬碳管複合材，不同的地方在於：改變加熱處理的溫度。以下記之各檢測項目進行評價，所得結果如表2所示。 Examples 15 to 16 and Comparative Examples 17 to 19 were prepared in the same manner as in Example 14 except that the temperature of the heat treatment was changed. Each test item described below was evaluated, and the results obtained are shown in Table 2.
分別於實施例1~16及比較例1~19的奈米金屬碳管複合材上任取三點，並使用表面電阻量測器(廠牌：Loresta；型號：LORESTA-EP MCP-T360)進行測量，所得測得數值之平均值，即為片電阻(Ω/cm2)。 Three points were taken on the nano metal carbon tube composites of Examples 1 to 16 and Comparative Examples 1 to 19, respectively, and measured using a surface resistance measuring instrument (label: Loresta; model: LORESTA-EP MCP-T360) The average value of the obtained measured values is the sheet resistance (Ω/cm 2 ).
使用穿透度量測器(廠牌：Hitachi；型號：U-4100)，將實施例1~10及比較例1~13的奈米金屬碳管複合材進行測量。 The nano metal carbon tube composites of Examples 1 to 10 and Comparative Examples 1 to 13 were measured using a penetration meter (brand: Hitachi; model: U-4100).
於表1之實施例1~10及比較例11~13的數據結果可 知，相較於相同的膜厚且僅單純使用經改質的奈米碳管的片電阻，本發明奈米金屬碳管複合材具有較低的片電阻，亦即本發明奈米金屬碳管複合材具有較佳的導電性。 The data results of Examples 1 to 10 and Comparative Examples 11 to 13 in Table 1 may be It is understood that the nano metal carbon tube composite of the present invention has a lower sheet resistance, that is, the nano metal carbon tube of the present invention, compared to the same film thickness and using only the sheet resistance of the modified carbon nanotube. The composite material has better electrical conductivity.
同時，於表1之實施例1~10及比較例1~10的數據結果相比較可知，本發明奈米金屬碳管複合材因奈米金屬團間彼此相互連結，有助於降低片電阻，繼而提升導電性。 Meanwhile, in comparison with the data results of Examples 1 to 10 and Comparative Examples 1 to 10 in Table 1, it is understood that the nano metal carbon tube composite of the present invention contributes to the reduction of sheet resistance because the nano metal clusters are connected to each other. Then improve the conductivity.
圖1為本發明實施例奈米金屬碳管複合材的結構形態的示意圖。於圖1中，該奈米金屬碳管複合材透過經改質奈米碳管1上的官能基團11，使奈米金屬團2均勻分佈並連結在經改質奈米碳管1的官能基團11上而不聚集或堆積，同時，透過奈米金屬團2連結使該等經改質奈米碳管1彼此間緊密堆疊，提升電子傳遞效率，繼而使該奈米金屬碳管複合材具有較佳的導電性。 1 is a schematic view showing the structural form of a nano metal carbon tube composite according to an embodiment of the present invention. In FIG. 1, the nano metal carbon tube composite passes through the functional group 11 on the modified carbon nanotube 1 to uniformly distribute the nano metal cluster 2 and is bonded to the functionalized carbon nanotube 1 The groups 11 are not aggregated or stacked, and at the same time, the modified carbon nanotubes 1 are closely packed with each other through the nano metal cluster 2 to enhance the electron transfer efficiency, and then the nano metal carbon tube composite It has better conductivity.
圖2及圖3分別為本發明實施例1及實施例6的奈米金屬碳管複合材的表面形態。於圖2及圖3中，奈米金屬碳管複合材的大小約為30nm~40nm，且黑點的部分為奈米金屬團，由此可說明每一個奈米金屬團確實是連結於每一個經改質奈米碳管中之至少一官能基團上，且均勻分佈在經改質奈米碳管的官能基團上而不聚集或堆積。 2 and 3 are surface morphology of the nano metal carbon tube composite materials of Examples 1 and 6 of the present invention, respectively. In FIG. 2 and FIG. 3, the size of the nano metal carbon tube composite is about 30 nm to 40 nm, and the black dot portion is a nano metal cluster, thereby indicating that each nano metal cluster is indeed connected to each. The at least one functional group in the modified carbon nanotube is uniformly distributed on the functional group of the modified carbon nanotube without being aggregated or accumulated.
圖4為本發明實施例奈米金屬碳管複合材的形成過程的示意圖。每一個含有複數個官能基團11的經改質奈米碳管1與金屬離子2’連結並獲得一混合物；接著，將該混合物加入一還原劑中以使金屬離子進行還原反應，形成複數 個具有奈米金屬粒子31’的奈米碳管3’，之後施予一加熱處理，藉由奈米金屬粒子彼此相互熔融，使該等經改質奈米碳管1彼此緊密堆疊，即可獲得本發明奈米金屬碳管複合材。 4 is a schematic view showing a process of forming a nano metal carbon tube composite according to an embodiment of the present invention. Each of the modified carbon nanotubes 1 containing a plurality of functional groups 11 is bonded to the metal ions 2' to obtain a mixture; then, the mixture is added to a reducing agent to carry out a reduction reaction of the metal ions to form a complex number The carbon nanotubes 3' having the nano metal particles 31' are then subjected to a heat treatment, whereby the nano metal particles are mutually melted, and the modified carbon nanotubes 1 are closely stacked with each other to obtain The invention relates to a nano metal carbon tube composite material.
於表2之實施例11~16及比較例14~19的數據結果相比較可知，本發明奈米金屬碳管複合材於製備時使用溫度越高越有助於降低片電阻，繼而提升導電性。由此可知，溫度越高越有利於奈米金屬粒子彼此相互熔融，使該等經改質奈米碳管彼此緊密堆疊，繼而提升導電性。 Comparing the data results of Examples 11 to 16 and Comparative Examples 14 to 19 in Table 2, it can be seen that the higher the temperature of use of the nano metal carbon tube composite of the present invention, the lower the sheet resistance and the higher the conductivity. . It can be seen that the higher the temperature, the better the melting of the nano metal particles with each other, so that the modified carbon nanotubes are closely stacked with each other, and then the conductivity is improved.
綜上所述，該奈米金屬碳管複合材透過經改質奈米碳管上的官能基團，能使奈米金屬團均勻分佈並連結在經改 質奈米碳管上而不聚集或堆積，同時，透過奈米金屬團連結在經改質奈米碳管上，使該等經改質奈米碳管彼此間緊密堆疊，提升電子傳遞效率，繼而使該奈米金屬碳管複合材具有較佳的導電度，故確實能達成本發明之目的。 In summary, the nano metal carbon tube composite material passes through the functional groups on the modified carbon nanotubes, so that the nano metal clusters can be evenly distributed and linked. The carbon nanotubes are not aggregated or accumulated on the carbon nanotubes, and are connected to the modified carbon nanotubes through the nano metal clusters, so that the modified carbon nanotubes are closely stacked with each other to improve electron transport efficiency. The nano-metal carbon tube composite is then preferably made to have a good electrical conductivity, so that the object of the present invention can be achieved.
惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍，即大凡依本發明申請專利範圍及發明說明內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。 The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.
1‧‧‧經改質奈米碳管 1‧‧‧modified carbon nanotubes
11‧‧‧官能基團 11‧‧‧ functional groups
2‧‧‧奈米金屬團 2‧‧‧Nano Metals
2’‧‧‧金屬離子 2'‧‧‧metal ions
3’‧‧‧具有奈米金屬粒子的奈米碳管 3'‧‧‧Nanocarbon tubes with nano metal particles
31’‧‧‧奈米金屬粒子 31'‧‧‧Nano Metal Particles
圖1是一示意圖，說明本發明實施例奈米金屬碳管複合材的結構形態；圖2是一照片，說明運用穿透式電子顯微鏡測得本發明實施例1的奈米金屬碳管複合材表面形態；圖3是一照片，說明運用穿透式電子顯微鏡測得本發明實施例6的奈米金屬碳管複合材表面形態；及圖4是一示意圖，說明本發明實施例奈米金屬碳管複合材的形成過程。 1 is a schematic view showing the structural form of a nano metal carbon tube composite according to an embodiment of the present invention; and FIG. 2 is a photograph showing the nano metal carbon tube composite material of the first embodiment of the present invention measured by a transmission electron microscope. FIG. 3 is a photograph showing the surface morphology of the nano metal carbon tube composite of the sixth embodiment of the present invention measured by a transmission electron microscope; and FIG. 4 is a schematic view showing the nano metal carbon of the embodiment of the present invention. The formation process of the tube composite.
1‧‧‧經改質奈米碳管 1‧‧‧modified carbon nanotubes
2‧‧‧金屬團 2‧‧‧Metal
11‧‧‧官能基團 11‧‧‧ functional groups
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