JP2008100869A - Method for producing carbon nanotube - Google Patents

Method for producing carbon nanotube Download PDF

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JP2008100869A
JP2008100869A JP2006284233A JP2006284233A JP2008100869A JP 2008100869 A JP2008100869 A JP 2008100869A JP 2006284233 A JP2006284233 A JP 2006284233A JP 2006284233 A JP2006284233 A JP 2006284233A JP 2008100869 A JP2008100869 A JP 2008100869A
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carbon nanotube
carbon
discharge
catalyst
reaction tube
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Hidekazu Sugiyama
英一 杉山
Kazutaka Koshiro
和高 小城
Tadashi Imai
正 今井
Takeshi Noma
毅 野間
Sukeyuki Yasui
祐之 安井
Motofumi Tanaka
元史 田中
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Toshiba Corp
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Toshiba Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To stabilize the growth of a carbon nanotube by eliminating a carbon material excluding the carbon nanotube and/or defective crystal parts of a carbon nanotube or by uniformalizing a hydrocarbon mixture to lower molecular weights. <P>SOLUTION: In the method for producing a carbon nanotube using a catalytic growth method, reaction active species are generated by electric-discharging in a reaction tube 12 while carbon nanotube 18 is in the process of growing. The carbon material excluding the generated carbon nanotube 18 and/or defective crystal parts of the carbon nanotube 18 are eliminated by the generated reaction species. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、カーボンナノチューブの製造方法に関する。   The present invention relates to a method for producing carbon nanotubes.

近年、鋼鉄の数十倍の強さを持ち、しかも折れ曲がりに強く、耐薬品性、耐熱性、導電性に優れた素材としてカーボンナノチューブ（以下、ＣＮＴと呼ぶ）が注目されている。このＣＮＴは、カーボン（炭素）からなり、直径がナノメートル単位のチューブ状の物質である。   In recent years, carbon nanotubes (hereinafter referred to as CNT) have attracted attention as a material that is several tens of times stronger than steel, and is strong against bending, and has excellent chemical resistance, heat resistance, and conductivity. This CNT is a tube-shaped substance made of carbon and having a diameter of nanometers.

従来、ＣＮＴは、例えば図７に示すように製造されている。
図中の１は、炉２内に配置されて加熱される反応管を示す。この反応管１の内部には触媒３が配置されている。こうした反応管１を用いてＣＮＴを製造するときは、反応管１を加熱しながら原料ガス４を反応管内に流通させ、反応管内の触媒３上でＣＮＴ５を成長させる。反応後のガスは、排ガス６として反応管１から排出される。 Conventionally, CNTs are manufactured as shown in FIG. 7, for example.
1 in the figure indicates a reaction tube that is placed in the furnace 2 and heated. A catalyst 3 is disposed inside the reaction tube 1. When producing CNTs using such a reaction tube 1, the raw material gas 4 is circulated in the reaction tube while heating the reaction tube 1, and the CNT 5 is grown on the catalyst 3 in the reaction tube. The gas after the reaction is discharged from the reaction tube 1 as the exhaust gas 6.

また、従来、ＣＮＴを製造する技術としては、例えば特許文献１や特許文献２が知られている。
特許文献１には、化学蒸着法（ＣＶＤ法）を用いて、電気炉によって加熱されたチャンバ内にＣｕからなる基材上にＮｉを被着した基板を配置し、Ｃ２Ｈ４を供給するとともにフィラメントによって加熱することにより、線径が１ｎｍ〜２μｍで少なくとも一部が螺旋状の炭素物質を製造する技術が開示されている。 Conventionally, for example, Patent Document 1 and Patent Document 2 are known as techniques for manufacturing CNTs.
In Patent Document 1, a chemical vapor deposition method (CVD method) is used to place a substrate coated with Ni on a base material made of Cu in a chamber heated by an electric furnace, and supply C 2 H 4 . A technique for producing a carbon material having a wire diameter of 1 nm to 2 μm and at least a part of a spiral by heating with a filament is disclosed.

特許文献２には、金属触媒を用いて製造されたＣＮＴ粗生成物を粉砕、溶液中に攪拌し、遠心分離や浮選により非晶質炭素、グラファイトを除去し、更に酢で溶かす（或いは磁場中を通過させる）ことにより金属触媒やその金属の炭化物等の金属不純物を除去し、ＣＮＴの純度を向上させる技術が開示されている。
特開２００１−２４０４０３号公報 特開平８−１９８６１１号公報 In Patent Document 2, a CNT crude product produced using a metal catalyst is pulverized, stirred into a solution, amorphous carbon and graphite are removed by centrifugation or flotation, and further dissolved in vinegar (or a magnetic field). A technique for improving the purity of CNT by removing metal impurities such as a metal catalyst and a carbide of the metal by passing through the inside is disclosed.
JP 2001-240403 A JP-A-8-198611

しかしながら、ＣＶＤ法にプラズマや触媒を組み合せたＣＮＴの製造では、ＣＮＴ製造時にアモルファス等の他の炭素材が副生成し、この炭素材はＣＮＴと同素体の為、炭素材を分離することが困難である。また、ＣＮＴ中に結晶欠陥があると、これもＣＮＴの収率低下の要因や特性低下の原因となる。   However, in the production of CNTs by combining plasma and catalyst with the CVD method, other carbon materials such as amorphous are by-produced during the production of CNTs, and since this carbon material is an allotrope of CNTs, it is difficult to separate the carbon materials. is there. In addition, if there are crystal defects in the CNT, this also causes a decrease in the yield and characteristics of the CNT.

本発明は、こうした事情を考慮してなされたもので、触媒成長法を用いたカーボンナノチューブの製造方法において、生成した反応活性種によってＣＮＴ以外の炭素材及び／又はＣＮＴの結晶欠陥部分の除去をなしえるカーボンナノチューブの製造方法を提供することを目的とする。   The present invention has been made in consideration of such circumstances, and in the carbon nanotube production method using the catalytic growth method, the carbon material other than CNT and / or the crystal defect portion of CNT is removed by the generated reactive species. An object of the present invention is to provide a method for producing a carbon nanotube.

また、本発明は、組成変動のある炭化水素混合物を原料の少なくとも一部としたカーボンナノチューブの製造方法において、ＣＮＴを成長させる触媒の上流側、又は触媒内において放電を行うことにより、炭化水素混合物を均質・低分子化してＣＮＴ成長を安定化させることを特徴とするカーボンナノチューブの製造方法を提供することを目的とする。   The present invention also relates to a method for producing carbon nanotubes using a hydrocarbon mixture having a composition variation as at least a part of a raw material, by performing discharge on the upstream side of the catalyst for growing CNTs or in the catalyst, thereby An object of the present invention is to provide a method for producing carbon nanotubes characterized by stabilizing the growth of CNTs by homogenizing and reducing the molecular weight.

本発明のカーボンナノチューブの製造方法は、触媒成長法を用いたカーボンナノチューブの製造方法において、カーボンナノチューブの成長時に、反応管内において放電を行うことにより反応活性種を生成させ、生成した反応活性種によってカーボンナノチューブ以外の炭素材及び／又はカーボンナノチューブの結晶欠陥部分の除去を行うことを特徴とする。   The carbon nanotube production method of the present invention is a carbon nanotube production method using a catalyst growth method, wherein during the growth of the carbon nanotube, a reactive active species is generated by performing discharge in a reaction tube, and depending on the generated reactive active species, The carbon material other than the carbon nanotube and / or the crystal defect portion of the carbon nanotube is removed.

また、本発明のカーボンナノチューブの製造方法は、組成変動のある炭化水素混合物を原料の少なくとも一部としたカーボンナノチューブの製造方法において、カーボンナノチューブを成長させる触媒の上流側、又は触媒内において放電を行うことにより、炭化水素混合物を均質・低分子化してカーボンナノチューブ成長を安定化させることを特徴とする。   Further, the carbon nanotube production method of the present invention is a carbon nanotube production method using a hydrocarbon mixture having a composition variation as at least a part of a raw material, and discharge is performed on the upstream side of the catalyst for growing the carbon nanotube or in the catalyst. This is characterized by stabilizing the growth of the carbon nanotubes by homogenizing and reducing the molecular weight of the hydrocarbon mixture.

本発明によれば、生成した反応活性種によってＣＮＴ以外の炭素材の除去、あるいはＣＮＴの結晶欠陥部分の除去、の少なくともいずれか一方を行うことができる。また、本発明によれば、炭化水素混合物を均質・低分子化してカーボンナノチューブ成長を安定化させることができる。   According to the present invention, at least one of removal of a carbon material other than CNT and removal of a crystal defect portion of CNT can be performed by the generated reactive species. Further, according to the present invention, the growth of carbon nanotubes can be stabilized by homogenizing and reducing the molecular weight of the hydrocarbon mixture.

以下、本発明に係るＣＮＴの製造方法について更に詳しく説明する。
(1) 本願第１の発明は、請求項1に記載のように、触媒成長法を用いたカーボンナノチューブの製造方法において、カーボンナノチューブの成長時に、反応管内において放電を行うことにより反応活性種を生成させ、生成した反応活性種によってカーボンナノチューブ以外の炭素材及び／又はカーボンナノチューブの結晶欠陥部分の除去を行うことを特徴とするカーボンナノチューブの製造方法である。ここで、「カーボンナノチューブ以外の炭素材及び／又はカーボンナノチューブの結晶欠陥部分の除去」としては、ＣＮＴ以外の炭素材の除去、あるいはＣＮＴの結晶欠陥部分の除去、或いは両者の除去のいずれかが挙げられる。 Hereinafter, the CNT manufacturing method according to the present invention will be described in more detail.
(1) According to the first invention of this application, as described in claim 1, in the method for producing carbon nanotubes using the catalytic growth method, the reactive species are obtained by performing discharge in the reaction tube during the growth of the carbon nanotubes. A method for producing carbon nanotubes, characterized in that carbon materials other than carbon nanotubes and / or crystal defect portions of carbon nanotubes are removed by the generated reactive species. Here, “removal of carbon materials other than carbon nanotubes and / or crystal defect portions of carbon nanotubes” includes either removal of carbon materials other than CNTs, removal of crystal defect portions of CNTs, or removal of both. Can be mentioned.

(2) 本願第２の発明は、請求項2に記載のように、組成変動のある炭化水素混合物を原料の少なくとも一部としたカーボンナノチューブの製造方法において、カーボンナノチューブを成長させる触媒の上流側、又は触媒内において放電を行うことにより、炭化水素混合物を均質・低分子化してカーボンナノチューブ成長を安定化させることを特徴とするカーボンナノチューブの製造方法である。ここで、「触媒の上流側」とは、例えば後述する図２に示すように電極が炉の外に配置された状態で放電を行う場合を示す。また、「触媒内」とは、例えば後述する図3に示すように電極間に配置された触媒上で放電を行う場合を示す。   (2) The second invention of the present application is the upstream side of the catalyst for growing carbon nanotubes in the method for producing carbon nanotubes, wherein the hydrocarbon mixture having a composition variation is at least a part of the raw material. Alternatively, the carbon nanotube production method is characterized by stabilizing the growth of the carbon nanotubes by performing a discharge in a catalyst to make the hydrocarbon mixture homogeneous and low molecular. Here, the “upstream side of the catalyst” indicates a case where discharge is performed in a state where the electrodes are arranged outside the furnace as shown in FIG. 2 described later, for example. In addition, “within the catalyst” indicates, for example, a case where discharge is performed on the catalyst disposed between the electrodes as shown in FIG. 3 described later.

(3) 上記(1)又は(2)において、前記反応管内に酸素、水或いは水蒸気の少なくともいずれか１つを添加し、酸素分子及び／又は水分子に由来する反応活性種を利用することが挙げられる。ここで、「酸素、水或いは水蒸気の少なくともいずれか１つ」とは、酸素、水、水蒸気を単独に添加する場合、あるいは酸素及び水、あるいは酸素及び水蒸気、あるいは酸素と水と水蒸気を添加する場合が挙げられる。   (3) In the above (1) or (2), adding at least one of oxygen, water, or water vapor to the reaction tube and utilizing a reactive species derived from oxygen molecules and / or water molecules Can be mentioned. Here, “at least one of oxygen, water, and water vapor” means that oxygen, water, water vapor is added alone, or oxygen and water, oxygen and water vapor, or oxygen, water, and water vapor are added. There are cases.

(4) 上記(1)〜(3)において、前記反応管が放電電極を備え、この放電電極内に誘電体を配置することにより放電を安定化させることが挙げられる。ここで、放電電極は原料ガスの供給を妨げないように例えばラダー型の形状をしている。前記誘電体の形状としては、例えばハニカム状あるいはスポンジが挙げられる。   (4) In the above (1) to (3), the reaction tube includes a discharge electrode, and a discharge is stabilized by disposing a dielectric in the discharge electrode. Here, the discharge electrode has, for example, a ladder shape so as not to disturb the supply of the source gas. Examples of the shape of the dielectric include a honeycomb shape or a sponge.

(5) 上記(1)〜(4)において、炭化水素混合物を触媒内に導入する前に吸着剤に吸着させ、該吸着剤内で放電することにより、吸着能の高い炭化水素又は濃度の低い炭化水素の少なくともいずれか一方の炭化水素を低分子化して、炭化水素混合物を均質・低分子化することが好ましい。こうした構成にすることにより、吸着能の高い炭化水素又は濃度の低い炭化水素の放電場内での滞在時間が増大し、効率よく低分子化を行うことができる。   (5) In the above (1) to (4), the hydrocarbon mixture is adsorbed on the adsorbent before being introduced into the catalyst, and discharged in the adsorbent, whereby the hydrocarbon having a high adsorbing capacity or the concentration is low. It is preferable to reduce the molecular weight of at least one of the hydrocarbons to make the hydrocarbon mixture homogeneous and low molecular. With such a configuration, the residence time of the hydrocarbon having a high adsorption ability or the hydrocarbon having a low concentration in the discharge field is increased, and the molecular weight can be reduced efficiently.

次に、本発明に係るＣＮＴの製造方法の具体的な実施形態について図面を参照して説明する。
（第１の実施形態）：請求項１に対応
図１は、本発明の第１の実施形態におけるカーボンナノチューブの製造方法の概略的な説明図を示す。
図中の符番１１は、炉１２内に配置されて加熱される反応管を示す。この反応管１１の内部には触媒１３が配置されている。また、反応管１１内には、触媒１３の上流側及び下流側に位置するように一対のラダー型の放電電極１４ａ，１４ｂが配置されている。これらの放電電極１４ａ，１４ｂは、電線１５を介して電源１６に接続されている。電源１６から供給された電力により、放電電極１４ａ，１４ｂ間に放電場１７が形成される。 Next, specific embodiments of the CNT manufacturing method according to the present invention will be described with reference to the drawings.
(First Embodiment): Corresponding to Claim 1
FIG. 1 is a schematic explanatory view of a carbon nanotube production method according to the first embodiment of the present invention.
Reference numeral 11 in the figure indicates a reaction tube that is placed in the furnace 12 and heated. A catalyst 13 is disposed inside the reaction tube 11. Further, a pair of ladder-type discharge electrodes 14 a and 14 b are arranged in the reaction tube 11 so as to be positioned upstream and downstream of the catalyst 13. These discharge electrodes 14 a and 14 b are connected to a power source 16 through an electric wire 15. A discharge field 17 is formed between the discharge electrodes 14 a and 14 b by the power supplied from the power supply 16.

こうした反応管１１を用いてＣＮＴ１８を製造するときは、反応管１１を加熱するとともに、放電電極１４ａ，１４ｂ間に放電場１７を形成しながら、原料ガス１９を反応管内に流通させ、反応管内の触媒１３上でＣＮＴ１８を成長させる。反応後のガスは、排ガス２０として反応管１１から排出される。   When manufacturing the CNT 18 using such a reaction tube 11, while heating the reaction tube 11 and forming the discharge field 17 between the discharge electrodes 14 a and 14 b, the source gas 19 is circulated in the reaction tube, CNTs 18 are grown on the catalyst 13. The gas after the reaction is discharged from the reaction tube 11 as the exhaust gas 20.

第１の実施形態によれば、放電電極１４ａ，１４ｂ間に放電場１７を形成しながら、原料ガス１９を反応管内に流通させることにより、放電場１７によって精製された反応活性種がＣＮＴ以外の炭素材又はＣＮＴ１８の結晶欠陥部分を除去することになり、高品質のＣＮＴ１８を精製できる。   According to the first embodiment, while the discharge field 17 is formed between the discharge electrodes 14a and 14b, the source gas 19 is circulated in the reaction tube, so that the reactive species purified by the discharge field 17 is other than CNT. The carbon material or the crystal defect portion of the CNT 18 is removed, and the high-quality CNT 18 can be purified.

なお、図１では、一対の放電電極は触媒を挟む形で反応管内に配置されているが、触媒上に放電場を形成できれば、図１のような配置構成に限定されない。また、放電の方式としては、例えば沿面放電、パルス放電、バリア放電が挙げられる。   In FIG. 1, the pair of discharge electrodes are arranged in the reaction tube with the catalyst interposed therebetween, but the arrangement is not limited to that shown in FIG. 1 as long as a discharge field can be formed on the catalyst. Examples of the discharge method include creeping discharge, pulse discharge, and barrier discharge.

（第２の実施形態）：請求項２に対応
図２は、本発明の第２の実施形態におけるＣＮＴの製造方法の概略的な説明図を示す。但し、図１と同部材は同符番を付して説明を省略する。
図２は、一対の放電電極１４ａ，１４ｂを炉１１の外で且つ反応管１１内の上流側に配置したことを特徴とする。電源１６から供給された電力により、放電電極１４ａ，１４ｂ間に放電場１７が形成されることは、図１の場合と同様である。 (Second Embodiment): Corresponding to Claim 2
FIG. 2 is a schematic explanatory view of a CNT manufacturing method according to the second embodiment of the present invention. However, the same members as those in FIG.
FIG. 2 is characterized in that a pair of discharge electrodes 14 a and 14 b are arranged outside the furnace 11 and upstream in the reaction tube 11. The discharge field 17 is formed between the discharge electrodes 14a and 14b by the power supplied from the power source 16, as in the case of FIG.

第２の実施形態によれば、放電場１７の形成により、放電場１７によって精製された反応活性種が原料ガス中に含まれる炭化水素混合物を低分子化して均質化する。その結果、ＣＮＴ合成雰囲気を安定化させ、ＣＮＴ１８の成長を安定させることができる。
なお、図２では、一対の放電電極は炉の外部に配置されている場合について述べたが、炉内に配置してもよい。 According to the second embodiment, by forming the discharge field 17, the reactive active species purified by the discharge field 17 lowers the molecular weight of the hydrocarbon mixture contained in the source gas and homogenizes it. As a result, the CNT synthesis atmosphere can be stabilized and the growth of CNT 18 can be stabilized.
In addition, although FIG. 2 described the case where the pair of discharge electrodes are arranged outside the furnace, they may be arranged in the furnace.

（第３の実施形態）：請求項３に対応
図３は、本発明の第３の実施形態におけるＣＮＴの製造方法の概略的な説明図を示す。但し、図１と同部材は同符番を付して説明を省略する。
図３は、原料ガス１９に添加剤（酸素）２０を添加したことを特徴とする。
第３の実施形態によれば、原料ガスに添加剤２０を添加することにより、酸素分子に由来する反応活性種を生成させ、高品質なＣＮＴ１８を生成することができる。 (Third embodiment): Corresponding to claim 3
FIG. 3 is a schematic explanatory view of a CNT manufacturing method according to the third embodiment of the present invention. However, the same members as those in FIG.
FIG. 3 is characterized in that an additive (oxygen) 20 is added to the source gas 19.
According to the third embodiment, by adding the additive 20 to the raw material gas, reactive active species derived from oxygen molecules can be generated, and high-quality CNTs 18 can be generated.

なお、図３では、添加剤として酸素を用いた場合について述べたが、これに限らず、水、又は水蒸気、又は酸素と水、又は酸素と水蒸気、又は水と酸素と水蒸気のいずれかを用いてもよい。また、添加剤は炉の外部で添加した場合について述べたが、これに限らず、炉内で添加剤を添加してもよい。   In FIG. 3, the case where oxygen is used as the additive is described. However, the present invention is not limited thereto, and water, water vapor, oxygen and water, oxygen and water vapor, or water, oxygen, and water vapor are used. May be. Moreover, although the case where the additive was added outside the furnace was described, the present invention is not limited to this, and the additive may be added inside the furnace.

（第４の実施形態）：請求項４に対応
図４は、本発明の第４の実施形態におけるＣＮＴの製造方法の概略的な説明図を示す。但し、図１と同部材は同符番を付して説明を省略する。
図４は、第１の実施形態の放電電極１４ａ，１４ｂ間にポーラス状の誘電体２２を配置し、該誘電体２２に触媒１８を担持させたことを特徴とする。なお、図４では、便宜上、触媒１８が誘電体２２の一部の表面に担持されているように描かれているが、本来は誘電体２２の全ての表面及びその表面近くの内部に担持されている。
第４の実施形態によれば、放電電極１４ａ，１４ｂａ間に誘電体２２を配置してＣＮＴ１８を製造することにより、放電を安定化させることができる。また、誘電体２２に触媒１８を担持させることにより、誘電体２２に触媒としての機能を持たせることができる。 (Fourth Embodiment): Corresponding to Claim 4
FIG. 4 is a schematic explanatory view of a CNT manufacturing method according to the fourth embodiment of the present invention. However, the same members as those in FIG.
FIG. 4 is characterized in that a porous dielectric 22 is disposed between the discharge electrodes 14 a and 14 b of the first embodiment, and a catalyst 18 is supported on the dielectric 22. In FIG. 4, for convenience, the catalyst 18 is depicted as being supported on a part of the surface of the dielectric 22, but is originally supported on the entire surface of the dielectric 22 and the interior near the surface. ing.
According to the fourth embodiment, the discharge can be stabilized by arranging the dielectric 22 between the discharge electrodes 14a and 14ba to manufacture the CNT 18. In addition, by supporting the catalyst 18 on the dielectric 22, the dielectric 22 can have a function as a catalyst.

（第５の実施形態）：請求項４に対応
図５は、本発明の第５の実施形態におけるＣＮＴの製造方法の概略的な説明図を示す。但し、図１と同部材は同符番を付して説明を省略する。
図５は、第２の実施形態において、放電電極１４ａ，１４ｂ間にポーラス状の誘電体２２を配置し、該誘電体２２の表面及びその近くの内部に触媒１８を担持させたことを特徴とする。
第５の実施形態によれば、第４の実施形態と同様な効果が得られる。 (Fifth Embodiment): Corresponding to Claim 4
FIG. 5 is a schematic explanatory view of a CNT manufacturing method according to the fifth embodiment of the present invention. However, the same members as those in FIG.
FIG. 5 is characterized in that, in the second embodiment, a porous dielectric 22 is arranged between the discharge electrodes 14a and 14b, and the catalyst 18 is supported on the surface of the dielectric 22 and in the vicinity thereof. To do.
According to the fifth embodiment, the same effect as in the fourth embodiment can be obtained.

（第６の実施形態）：請求項５に対応
図６は、本発明の第６の実施形態におけるＣＮＴの製造方法の概略的な説明図を示す。但し、図１と同部材は同符番を付して説明を省略する。 (Sixth Embodiment): Corresponding to Claim 5
FIG. 6 shows a schematic explanatory view of a CNT manufacturing method in the sixth embodiment of the present invention. However, the same members as those in FIG.

図６は、第５の実施形態において、誘電体の代わりに吸着剤２３を放電電極１４ａ，１４ｂ間に配置し、反応ガス中の吸着能の高い炭化水素又は濃度の低い炭化水素を吸着剤２３に吸着させることを特徴とする。   FIG. 6 shows that, in the fifth embodiment, an adsorbent 23 is disposed between the discharge electrodes 14a and 14b in place of the dielectric, and a hydrocarbon having a high adsorption capacity or a low concentration in the reaction gas is adsorbed 23. It is made to adsorb | suck to.

第６の実施形態によれば、放電電極１４ａ，１４ｂ間の吸着剤２３に放電場１７を形成することにより、吸着能の高い炭化水素又は濃度の低い炭化水素の放電場１７内での滞在時間が増大し、効率よく低分子化が可能となる。   According to the sixth embodiment, by forming the discharge field 17 in the adsorbent 23 between the discharge electrodes 14a and 14b, the residence time in the discharge field 17 of a hydrocarbon having a high adsorption capacity or a hydrocarbon having a low concentration is obtained. Increase, and low molecular weight can be efficiently reduced.

なお、本発明は、上記実施形態そのままに限定されるものではなく、その実施の段階ではその要旨を逸脱しない範囲で構成要素を変形して具体化できる。また、上記実施形態に開示されている複数の構成要素の適宜な組み合せにより種々の発明を形成できる。例えば、実施形態に示される全構成要素から幾つかの構成要素を削除してもよい。更に、異なる実施形態に亘る構成要素を適宜組み合せてもよい。   Note that the present invention is not limited to the above-described embodiments as they are, and can be embodied by modifying the constituent elements without departing from the spirit of the invention in the stage of implementation. Further, various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in the embodiment. For example, some components may be deleted from all the components shown in the embodiment. Furthermore, you may combine suitably the component covering different embodiment.

図１は本発明の第１の実施形態に係るＣＮＴの製造方法を示す説明図である。FIG. 1 is an explanatory view showing a CNT manufacturing method according to the first embodiment of the present invention. 図２は本発明の第２の実施形態に係るＣＮＴの製造方法を示す説明図である。FIG. 2 is an explanatory view showing a CNT manufacturing method according to the second embodiment of the present invention. 図３は本発明の第３の実施形態に係るＣＮＴの製造方法を示す説明図である。FIG. 3 is an explanatory view showing a CNT manufacturing method according to the third embodiment of the present invention. 図４は本発明の第４の実施形態に係るＣＮＴの製造方法を示す説明図である。FIG. 4 is an explanatory view showing a CNT manufacturing method according to the fourth embodiment of the present invention. 図５は本発明の第５の実施形態に係るＣＮＴの製造方法を示す説明図である。FIG. 5 is an explanatory view showing a CNT manufacturing method according to the fifth embodiment of the present invention. 図６は本発明の第６の実施形態に係るＣＮＴの製造方法を示す説明図である。FIG. 6 is an explanatory view showing a CNT manufacturing method according to the sixth embodiment of the present invention. 図７は従来のＣＮＴの製造方法を示す説明図である。FIG. 7 is an explanatory view showing a conventional CNT manufacturing method.

符号の説明Explanation of symbols

１１…炉、１２…反応管、１３…カーボンナノチューブ（ＣＮＴ）、１４ａ，１４ｂ…放電電極、１６…電源、１７…放電場、１８…触媒、２１…添加剤、２２…誘電体、２３…吸着剤。   DESCRIPTION OF SYMBOLS 11 ... Furnace, 12 ... Reaction tube, 13 ... Carbon nanotube (CNT), 14a, 14b ... Discharge electrode, 16 ... Power source, 17 ... Discharge field, 18 ... Catalyst, 21 ... Additive, 22 ... Dielectric, 23 ... Adsorption Agent.

Claims (5)

触媒成長法を用いたカーボンナノチューブの製造方法において、
カーボンナノチューブの成長時に、反応管内において放電を行うことにより反応活性種を生成させ、生成した反応活性種によってカーボンナノチューブ以外の炭素材及び／又はカーボンナノチューブの結晶欠陥部分の除去を行うことを特徴とするカーボンナノチューブの製造方法。 In the carbon nanotube production method using the catalyst growth method,
It is characterized in that during the growth of carbon nanotubes, reactive active species are generated by performing discharge in a reaction tube, and carbon materials other than carbon nanotubes and / or crystal defect portions of carbon nanotubes are removed by the generated reactive active species. A method for producing carbon nanotubes. 組成変動のある炭化水素混合物を原料の少なくとも一部としたカーボンナノチューブの製造方法において、
カーボンナノチューブを成長させる触媒の上流側、又は触媒内において放電を行うことにより、炭化水素混合物を均質・低分子化してカーボンナノチューブ成長を安定化させることを特徴とするカーボンナノチューブの製造方法。 In the method of producing a carbon nanotube using a hydrocarbon mixture having a composition variation as at least a part of the raw material,
A method for producing a carbon nanotube, characterized by stabilizing the growth of a carbon nanotube by performing a discharge on the upstream side of the catalyst for growing the carbon nanotube or in the catalyst to make the hydrocarbon mixture homogeneous and low molecular. 前記反応管内に酸素、水或いは水蒸気の少なくともいずれか１つを添加し、酸素分子及び／又は水分子に由来する反応活性種を利用することを特徴とする請求項１又は請求項２記載のカーボンナノチューブの製造方法。 The carbon according to claim 1 or 2, wherein at least one of oxygen, water, and water vapor is added to the reaction tube, and a reactive species derived from oxygen molecules and / or water molecules is used. Nanotube manufacturing method. 前記反応管は放電電極を備え、この放電電極内に誘電体を配置することにより放電を安定化させることを特徴とする請求項１乃至３いずれか記載のカーボンナノチューブの製造方法。 4. The method of manufacturing a carbon nanotube according to claim 1, wherein the reaction tube includes a discharge electrode, and the discharge is stabilized by disposing a dielectric in the discharge electrode. 炭化水素混合物を触媒内に導入する前に吸着剤に吸着させ、該吸着剤内で放電することにより、吸着能の高い炭化水素又は濃度の低い炭化水素の少なくともいずれか一方の炭化水素を低分子化して、炭化水素混合物を均質・低分子化することを特徴とする請求項２乃至４いずれか記載のカーボンナノチューブの製造方法。 Before the hydrocarbon mixture is introduced into the catalyst, it is adsorbed by an adsorbent and discharged in the adsorbent, thereby reducing at least one of hydrocarbons having high adsorption capacity or low concentration hydrocarbons to low molecular weight. The method for producing carbon nanotubes according to any one of claims 2 to 4, wherein the hydrocarbon mixture is homogenized and reduced in molecular weight.
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JP2018145080A (en) * 2017-03-09 2018-09-20 大陽日酸株式会社 Manufacturing method of carbon nanotube, carbon nanotube, and substrate with oriented carbon nanotube
JP2018184319A (en) * 2017-04-26 2018-11-22 大陽日酸株式会社 Carbon-based microstructure and method for producing carbon-based microstructure

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Publication number Priority date Publication date Assignee Title
WO2018163957A1 (en) * 2017-03-09 2018-09-13 大陽日酸株式会社 Carbon nanotube, carbon-based fine structure, and base member having carbon nanotubes attached thereto, and methods respectively for producing these products
JP2018145080A (en) * 2017-03-09 2018-09-20 大陽日酸株式会社 Manufacturing method of carbon nanotube, carbon nanotube, and substrate with oriented carbon nanotube
TWI733002B (en) * 2017-03-09 2021-07-11 日商大陽日酸股份有限公司 Carbon nanotube, carbon-based fine structure, and substrate with carbon nanotube and methods of manufacturing the same
JP2018184319A (en) * 2017-04-26 2018-11-22 大陽日酸株式会社 Carbon-based microstructure and method for producing carbon-based microstructure
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