JP2009167031A - Method for producing metal-encapsulated carbon nanotube and metal-encapsulated carbon nanotube produced thereby - Google Patents
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Abstract
【課題】
金属内包ＣＮＴの製造方法において、簡便かつ安価な方法で、充填率の高い金属内包ＣＮＴの製造方法を提供すること。又、その製造方法で得られた金属内包ＣＮＴを提供すること。
【解決手段】
金属を含有させた炭素電極を用いて、水素を含む気体（０．０９〜０．２ＭＰａの気圧）中でアークプラズマを発生させ、電極の炭素材料と金属を同時に蒸発させる製造方法において、概鉛直方向に放電することを特徴とする、金属内包ＣＮＴの製造方法。及び、該製造方法によって得られた金属充填率９０％以上の金属内包ＣＮＴによって、上記課題を解決する。
【選択図】 図２
【Task】
To provide a method for producing metal-encapsulated CNTs having a high filling rate by a simple and inexpensive method in the method for producing metal-encapsulated CNTs. Moreover, the metal inclusion CNT obtained by the manufacturing method is provided.
[Solution]
In a manufacturing method in which arc plasma is generated in a gas containing hydrogen (atmospheric pressure of 0.09 to 0.2 MPa) using a metal-containing carbon electrode, and the carbon material and metal of the electrode are simultaneously evaporated. A method for producing metal-encapsulated CNTs, characterized by discharging in a direction. And the said subject is solved by metal inclusion CNT with 90% or more of metal filling rates obtained by this manufacturing method.
[Selection] Figure 2
Description
本発明は、金属内包カーボンナノチューブの製造方法及びそれにより製造された金属内包カーボンナノチューブに関する。 The present invention relates to a method for producing metal-encapsulated carbon nanotubes and metal-encapsulated carbon nanotubes produced thereby.
電池電極材料や水素吸蔵材料、そして電子材料などの次世代ナノデバイス材料の１つとして、金属ナノワイヤの研究が近年盛んに行われている。しかし、金属ナノワイヤの高結晶性一次元成長や、酸化に対する安定性の向上などが困難であり、高品質の金属ナノワイヤを安定して大量に製造するためには、解決すべき課題が多く残されている。 In recent years, research on metal nanowires has been actively conducted as one of next-generation nanodevice materials such as battery electrode materials, hydrogen storage materials, and electronic materials. However, high-dimensional one-dimensional growth of metal nanowires and improvement of oxidation stability are difficult, and many problems remain to be solved in order to stably produce large quantities of high-quality metal nanowires. ing.
これらの課題を解決する１つの方法として、カーボンナノチューブ（以下、ＣＮＴと略記する）の一次元内部空洞に金属を内包させる方法がある。ＣＮＴの内部空間に金属、あるいは金属ナノワイヤを内包させる従来技術は「充填法」と「同時蒸発法」の２種類に分類することができる。 As one method for solving these problems, there is a method of enclosing a metal in a one-dimensional internal cavity of a carbon nanotube (hereinafter abbreviated as CNT). Conventional techniques for encapsulating metal or metal nanowires in the internal space of CNT can be classified into two types: “filling method” and “simultaneous evaporation method”.
酸化処理等によりＣＮＴ先端を開口した後に、その開口部より金属を導入する多段階の処理を必要とする方法が「充填法」である。一方、プラズマなどの高温（１０００〜３０００℃）の反応場中で金属と炭素材料を同時に蒸発させることにより、ＣＮＴ成長と同時に金属が内部に取り込まれる反応を利用した方法が「同時蒸発法」である。 The “filling method” is a method that requires a multi-step process of introducing metal from the opening after opening the CNT tip by oxidation treatment or the like. On the other hand, a method using a reaction in which a metal and a carbon material are evaporated at the same time in a reaction field of high temperature (1000 to 3000 ° C.) such as plasma, and the metal is taken into the inside simultaneously with the CNT growth is a “simultaneous evaporation method” is there.
「充填法」は簡便な方法ではあるが、収率はＣＮＴ先端部の開口の割合に大きく依存する。すべてのＣＮＴ先端部を効率よく開口することは非常に困難であり、「充填法」では高い充填率で金属を導入することは難しい。充填率の点では「同時蒸発法」の方が優れており、これまでにいくつかの方法が公知となっている。中でもアークプラズマを利用したアーク放電法による製造例が多く、例えば、Daiらは、５００Ｔｏｒｒの水素ガス中でのアーク放電によって銅内包ＣＮＴを生成している（非特許文献１）。また、Wangらは、炭素源としてコールを用いたアーク放電によって銅内包ＣＮＴを生成している（非特許文献２）。 Although the “filling method” is a simple method, the yield greatly depends on the opening ratio of the CNT tip. It is very difficult to efficiently open all CNT tips, and it is difficult to introduce metal at a high filling rate by the “filling method”. The “simultaneous evaporation method” is superior in terms of filling rate, and several methods have been known so far. Among them, there are many production examples by an arc discharge method using arc plasma. For example, Dai et al. Generate copper-encapsulated CNTs by arc discharge in 500 Torr hydrogen gas (Non-patent Document 1). Wang et al. Produced copper-encapsulated CNTs by arc discharge using coal as a carbon source (Non-patent Document 2).
アーク放電法を援用しない「同時蒸発法」では、金属板表面に炭化水素の分子ビームを照射することによって、金属内包ＣＮＴ（金属充填率９５％）を９５％以上含有するＣＮＴ凝集体を生成する方法（特許文献１）が公知となっている。 In the “simultaneous evaporation method” not using the arc discharge method, a CNT aggregate containing 95% or more of metal-encapsulated CNT (metal filling rate 95%) is generated by irradiating the surface of a metal plate with a hydrocarbon molecular beam. A method (Patent Document 1) is known.
これまでのアーク放電法をベースにした製造方法では収率ならびに金属の充填率が低く、完全な金属ナノワイヤ構造にはなっていないという問題点があった。非特許文献１では銅が断続的に内包されており、収率はよくない。又、非特許文献率２では銅の充填率が４０〜５０％であると報告している。特許文献１では、高収率で金属内包ＣＮＴを生成できるが、分子ビーム等の装置が必要である点や、金属基板上での生成であるため全収量が基板の面積に限定されてしまう点などで生成効率、コストの面で問題があった。
Conventional manufacturing methods based on the arc discharge method have a problem in that the yield and metal filling rate are low, and a complete metal nanowire structure is not obtained. In
又、「同時蒸発法」においてアーク放電法を援用した場合、陽極は放電の経過とともに先端部分から蒸発するため、電極の長さが短くなる欠点があった。安定して放電を続けるためには、陽極及び陰極の先端を一定の間隔に保つ必要があるため、陽極蒸発の進行とともに、陽極または陰極をスライドさせ、両極の先端の間隔を一定に保たなければならなかった。 In addition, when the arc discharge method is used in the “simultaneous evaporation method”, the anode evaporates from the tip portion as the discharge progresses, so that there is a drawback that the length of the electrode is shortened. In order to continue the discharge stably, it is necessary to keep the tip of the anode and the cathode at a constant interval. Therefore, as the anode evaporates, the anode or the cathode must be slid to keep the distance between the tips of both electrodes constant. I had to.
その問題を解決するため従来技術では、図１に示すような電動シリンダにより電極をスライドさせる機構を用いて、両極の間隔を調整する作業が行われている。該機構は、その構造から、炭素棒が横向きとなるよう一般的に使用されている。しかし、電極に含有させる金属の融点が低い場合、電極が横向きに設置されている構造では放電中に溶融した金属が流出するため、炭素と金属の反応効率が低下し、金属内包ＣＮＴ収率の低下につながるという問題があった。 In order to solve this problem, in the prior art, an operation of adjusting the distance between the two electrodes is performed using a mechanism for sliding the electrodes by an electric cylinder as shown in FIG. This mechanism is generally used so that the carbon rod is oriented sideways because of its structure. However, when the melting point of the metal contained in the electrode is low, the molten metal flows out during discharge in the structure in which the electrode is installed sideways, so that the reaction efficiency between carbon and metal decreases, and the metal-encapsulated CNT yield increases. There was a problem that led to a decline.
さらに、非特許文献１及び非特許文献２では、「同時蒸発法」を希ガス中で実施している。この場合、放電の経過とともに、陽極から蒸発した炭素及び金属が陰極表面に堆積する欠点があった。そのため、上述の陽極及び陰極の先端を一定の間隔に保つ作業を行う際、間隔決定の妨げとなるという問題があった。
Further, in
本発明は、金属を非常に高い充填率で内包するＣＮＴを高効率で大量に、かつ簡便で安価に製造できる方法を提供する。 The present invention provides a method capable of producing a large amount of CNT encapsulating a metal at a very high filling rate in a simple and inexpensive manner.
本発明に係わる金属内包カーボンナノチューブの製造方法は、水素を含む気体中で、金属を含有させた炭素電極をアーク放電により蒸発させ、金属内包カーボンナノチューブの製造する方法において、該気体の圧力が０．０９〜０．２ＭＰａであることを特徴とする。 The method for producing metal-encapsulated carbon nanotubes according to the present invention is a method for producing metal-encapsulated carbon nanotubes in which a metal-containing carbon electrode is evaporated by arc discharge in a gas containing hydrogen. 0.09 to 0.2 MPa.
又、本発明に係わる金属内包カーボンナノチューブの製造方法は、水素を含む気体中で、金属を含有させた炭素電極をアーク放電により蒸発させ、金属内包カーボンナノチューブの製造する方法において、概鉛直方向に放電することを特徴とする。次に、該気体の圧力が０．０９〜０．２ＭＰａであることを特徴とする。 The method for producing metal-encapsulated carbon nanotubes according to the present invention is a method for producing metal-encapsulated carbon nanotubes in a gas containing hydrogen by evaporating a metal-containing carbon electrode by arc discharge. It is characterized by discharging. Next, the gas pressure is 0.09 to 0.2 MPa.
さらに、本発明は、上記製造方法を用いて製造された金属内包ＣＮＴを提供するものである。 Furthermore, this invention provides the metal inclusion CNT manufactured using the said manufacturing method.
本発明によれば、分子ビーム等の装置や金属基板等を用いることなく、簡便かつ安価な方法で、金属を非常に高い充填率（９０％以上）で内包するＣＮＴ（金属充填率９０％以上）を高効率かつ大量に製造できる。 According to the present invention, a CNT (metal filling rate of 90% or more) encapsulating a metal with a very high filling rate (90% or more) by a simple and inexpensive method without using an apparatus such as a molecular beam or a metal substrate. ) Can be manufactured in high efficiency and in large quantities.
製造方法には直流アーク放電法を用いる。この場合、わずかな間隔（１〜２ｍｍ）をあけて配置した陽極と陰極の間にアークプラズマが形成される。その際、陽極先端部が最も高温（３０００℃以上）になり、陽極に用いた材料そのものを蒸発させることができる。又、図１に示した機構の炭素電極棒が概鉛直下向きになるよう設置し、図２に示すような陽極と陰極を概鉛直方向に配置する。これにより陽極に銅のような低融点の金属（銅の融点は１０８３℃）を多量に含む場合でも、放電中に溶融した金属が流出することを防ぐことができる。 A direct current arc discharge method is used as a manufacturing method. In this case, arc plasma is formed between the anode and the cathode arranged with a slight interval (1-2 mm). At that time, the tip of the anode becomes the highest temperature (3000 ° C. or higher), and the material itself used for the anode can be evaporated. Further, the carbon electrode rod of the mechanism shown in FIG. 1 is installed so as to be substantially vertically downward, and the anode and the cathode as shown in FIG. 2 are arranged in a substantially vertical direction. Accordingly, even when the anode contains a large amount of a low melting point metal such as copper (the melting point of copper is 1083 ° C.), the molten metal can be prevented from flowing out during discharge.
陽極には炭素棒を用い、その概中心部に穴をあけ、内部に粉末状の金属を充填する。陰極材料は、炭素、タングステン、モリブデン等、電気伝導性を有し、高温に耐えうる材料であれば特に限定されない。電極に用いる棒の直径・大きさ及び金属を充填する穴の直径・深さは、チャンバーの大きさや炭素と金属の反応に支障をきたさなければ特に限定されない。 A carbon rod is used for the anode, a hole is made in the approximate center, and a powdered metal is filled inside. The cathode material is not particularly limited as long as it is a material that has electrical conductivity and can withstand high temperatures, such as carbon, tungsten, and molybdenum. The diameter and size of the rod used for the electrode and the diameter and depth of the hole for filling the metal are not particularly limited as long as they do not hinder the size of the chamber and the reaction between carbon and metal.
アークチャンバー内部には水素を含む気体を充填する。水素を含む気体とは、メタン、アセチレン、水素のいずれかからなる気体をさす。該気体の濃度は、２０％、好ましくは８０％、より好ましくは１００％である。該気体の圧力は、特に限定されないが、好ましくは０．２ＭＰａ以下、より好ましくは０．０９〜０．２ＭＰａである。上記水素を含む気体中で反応を行うことにより、１）酸化されやすい銅を還元することによって、常に金属銅として保つ効果、２）炭素棒から供給される炭素を水素化しＣｎＨｍ種を形成することによって反応性を増す効果がある。さらに、放電経過の際に陰極表面にＣＮＴが堆積せず、陽極と陰極の間隔を調整する作業において、両極の間隔を放電開始から終了まで一定に保つことができる。 The arc chamber is filled with a gas containing hydrogen. The gas containing hydrogen refers to a gas composed of any one of methane, acetylene, and hydrogen. The concentration of the gas is 20%, preferably 80%, more preferably 100%. Although the pressure of this gas is not specifically limited, Preferably it is 0.2 MPa or less, More preferably, it is 0.09-0.2 MPa. By carrying out the reaction in the gas containing hydrogen, 1) the effect of always reducing copper that is easily oxidized to keep it as metallic copper, 2) hydrogenating the carbon supplied from the carbon rod, and C n H m species The formation has the effect of increasing the reactivity. Further, CNT does not accumulate on the cathode surface during the discharge process, and in the operation of adjusting the distance between the anode and the cathode, the distance between the two electrodes can be kept constant from the start to the end of the discharge.
アーク溶接用電源を用いて９０Ａの電流を流し、１分間放電を行う。電流の値及び放電時間は、陽極である炭素棒と含有させた金属の反応が起こりうる範囲であれば上記の値に限定するものではない。放電開始とともに陽極の炭素及び金属が溶融し、炭素棒の長さが短くなるため、電動シリンダにより陰極をスライドさせ、陽極と陰極の間隔を１〜２ｍｍに保つ。なお、陽極と陰極の間隔は、安定したアーク放電を生じさせることができれば上記の値に限定するものではない。放電終了後、チャンバーの内壁に堆積した煤の中から金属内包ＣＮＴを含むＣＮＴ凝集体を得る。 Using a power source for arc welding, a current of 90 A is applied to discharge for 1 minute. The value of the current and the discharge time are not limited to the above values as long as the reaction between the carbon rod as the anode and the contained metal can occur. Since the carbon and metal of the anode melt as the discharge starts and the length of the carbon rod becomes shorter, the cathode is slid by an electric cylinder, and the distance between the anode and the cathode is kept at 1 to 2 mm. The interval between the anode and the cathode is not limited to the above value as long as stable arc discharge can be generated. After the end of the discharge, a CNT aggregate containing metal-encapsulated CNTs is obtained from the soot deposited on the inner wall of the chamber.
以下に本発明の好適な一実施の形態を実施例によって具体的に説明するが、本発明の技術的範囲は下記の実施形態によって限定されるものでなく、本発明の範囲で様々に改変して実施することができる。 One preferred embodiment of the present invention will be specifically described below by way of examples. However, the technical scope of the present invention is not limited by the following embodiments, and various modifications may be made within the scope of the present invention. Can be implemented.
陽極に直径５ｍｍの炭素棒を用いた。その中心部に直径３ｍｍ、深さ３ｃｍの穴をあけ、内部に粉末状の金属を充填した。陰極には直径２０ｍｍの炭素棒を用いた。該陽極を下側、該陰極を上側にし、両電極が鉛直線上に位置するように配置した（図２）。これにより陽極に低融点の金属を多量に含む場合でも、放電中に溶融した金属が流出することを防ぐことができる。陽極に充填する金属は、銅、銀、ニッケル、シリコンそれぞれの場合において実験を行った。 A carbon rod having a diameter of 5 mm was used for the anode. A hole with a diameter of 3 mm and a depth of 3 cm was made in the center, and the inside was filled with powdered metal. A carbon rod having a diameter of 20 mm was used as the cathode. The anode was placed on the bottom, the cathode on the top, and both electrodes were placed on the vertical line (FIG. 2). Thereby, even when the anode contains a large amount of low melting point metal, it is possible to prevent the molten metal from flowing out during discharge. Experiments were conducted in the case of copper, silver, nickel, and silicon as the metal filling the anode.
チャンバー内部には、水素ガスを５００ｍｌ／ｍｉｎで流入させ、チャンバー内部の圧力を０．１ＭＰａ（７６０Ｔｏｒｒ）とした。アーク溶接用電源を用いて９０Ａの電流を流し、１分間放電を行った。放電終了後チャンバーの内壁に堆積した煤の中に金属内包ＣＮＴが含まれていることが確認できた。 Hydrogen gas was allowed to flow into the chamber at 500 ml / min, and the pressure inside the chamber was set to 0.1 MPa (760 Torr). Using a power source for arc welding, a current of 90 A was applied to discharge for 1 minute. It was confirmed that the metal-encapsulated CNTs were contained in the soot deposited on the inner wall of the chamber after the discharge was completed.
通常、アーク放電で得られるＣＮＴは多層ＣＮＴであり、陰極の堆積物中に生成することが知られている。しかし、本方法では、放電が経過しても陰極表面にＣＮＴの堆積が認められず、チャンバーの内壁に堆積した煤中に金属内包ＣＮＴが含まれていた。これは金属内包ＣＮＴが気相中の反応で成長していることを示唆している。 Usually, CNTs obtained by arc discharge are multi-layer CNTs, and are known to be generated in deposits on the cathode. However, in this method, even when discharge progressed, CNT deposition was not observed on the cathode surface, and the metal-encapsulated CNT was contained in the soot deposited on the inner wall of the chamber. This suggests that the metal-encapsulated CNT is grown by a reaction in the gas phase.
又、陰極表面にＣＮＴが堆積しないことから、両極の間隔を放電開始から終了まで一定に保持・調整することができた。よって、放電を効率良く行うことができ、収率、充填率ともに高い金属内包ＣＮＴを生成することができた。 In addition, since CNT does not accumulate on the cathode surface, the distance between the two electrodes can be kept and adjusted constant from the start to the end of discharge. Therefore, discharge could be performed efficiently and metal-encapsulated CNTs with high yield and filling rate could be generated.
充填金属に銅を用いたときの、走査型電子顕微鏡（以下「ＳＥＭ」と略記する）観察結果を図３、透過型電子顕微鏡（以下「ＴＥＭ」と略記する）観察の結果を図４、図５に示す。銅内包ＣＮＴがよく成長していることが分かる。本実験により得られたＳＥＭ画像を用いて、画像の二値化処理を行い、単位面積当たりにおける金属内包ＣＮＴの含有率ならびに金属充填率を計算したところ、生成された全ＣＮＴに対する銅内包ＣＮＴの含有率は９０％以上であり、得られた銅内包ＣＮＴの銅充填率は９０％以上である。 FIG. 3 shows the observation result of a scanning electron microscope (hereinafter abbreviated as “SEM”) when copper is used as the filling metal, and FIG. 4 shows the result of observation of a transmission electron microscope (hereinafter abbreviated as “TEM”). As shown in FIG. It can be seen that the copper-encapsulated CNT grows well. Using the SEM image obtained by this experiment, binarization processing of the image was performed, and the content of metal-encapsulated CNT per unit area and the metal filling rate were calculated. A content rate is 90% or more, and the copper filling rate of the obtained copper inclusion CNT is 90% or more.
充填金属に銀を用いたときのＳＥＭ観察の結果を図７、ニッケルを用いたときのＳＥＭ観察の結果を図８、シリコンを用いたときのＴＥＭ観察の結果を図９に示す。銅以外の金属の場合においても、金属内包ＣＮＴが生成されていることが分かる。 FIG. 7 shows the result of SEM observation when silver is used as the filling metal, FIG. 8 shows the result of SEM observation when nickel is used, and FIG. 9 shows the result of TEM observation when silicon is used. It can be seen that even in the case of a metal other than copper, metal-encapsulated CNTs are generated.
本実験により得られた金属内包ＣＮＴの直径は約１０〜４５ｎｍである。特徴的なのは、生成されたすべての金属内包ＣＮＴのナノチューブ層が１０層未満ということである。 The diameter of the metal-encapsulated CNT obtained by this experiment is about 10 to 45 nm. What is characteristic is that the nanotube layers of all the metal-encapsulated CNTs produced are less than ten.
金属に銅を用いた場合、内部の銅ナノワイヤ部に関しては、面心立方格子構造の（１１１）面（格子間隔０．２１ｎｍ）が広範囲にわたって連続して観察できた。つまり、銅内包ＣＮＴは高結晶性の銅ナノワイヤが薄いナノチューブ層によって被覆された構造である（図６）。 When copper was used as the metal, the (111) plane (lattice spacing 0.21 nm) of the face-centered cubic lattice structure could be continuously observed over a wide range with respect to the internal copper nanowire portion. In other words, the copper-encapsulated CNT has a structure in which highly crystalline copper nanowires are covered with a thin nanotube layer (FIG. 6).
本製造方法により得られた金属内包ＣＮＴはナノマニュピュレーションの素材としても用いることができる。又、金属ナノワイヤへのインターカレーションを利用した安定かつ高効率のリチウムイオン電池、高性能キャパシタや電界放出源などへの適用展開が見込まれる。 The metal-encapsulated CNT obtained by this production method can also be used as a material for nano manipulation. In addition, application to stable and high-efficiency lithium-ion batteries, high-performance capacitors, field emission sources and the like using intercalation into metal nanowires is expected.
Claims (4)
The metal inclusion carbon nanotube manufactured using the method in any one of Claims 1-3.
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