JP5099300B2 - Nanocarbon material composite and method for producing the same - Google Patents

Nanocarbon material composite and method for producing the same Download PDF

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JP5099300B2
JP5099300B2 JP2006070029A JP2006070029A JP5099300B2 JP 5099300 B2 JP5099300 B2 JP 5099300B2 JP 2006070029 A JP2006070029 A JP 2006070029A JP 2006070029 A JP2006070029 A JP 2006070029A JP 5099300 B2 JP5099300 B2 JP 5099300B2
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zinc oxide
nanocarbon
particles
oxide particles
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寿浩 安藤
清晴 中川
美香 蒲生
秀典 蒲生
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National Institute for Materials Science
Toppan Inc
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本発明は、強度補強材料、電子放出素子材料、電池の電極材料、電磁波吸収材料、触媒材料、或いは、光学材料としての応用が期待されるナノ炭素材料に関し、特に、導電性の粒子を核に持つナノ炭素材料複合体及びその製造方法に関する。   The present invention relates to a nanocarbon material that is expected to be applied as a strength reinforcing material, an electron-emitting device material, a battery electrode material, an electromagnetic wave absorbing material, a catalyst material, or an optical material. The present invention relates to a nanocarbon material composite having the same and a method for producing the same.

ナノ炭素材料は、炭素のｓｐ2 混成軌道で構成された、ナノメートル（ｎｍ）サイズの微細形状を有することから、従来の材料を凌駕する、或いは、従来の材料にはない特性を有し、次世代の、強度補強材料、電子放出素子材料、電池の電極材料、電磁波吸収材料、触媒材料或いは光学材料としての応用が期待されている。 The nanocarbon material has a nanometer (nm) size fine shape composed of sp 2 hybrid orbitals of carbon, so that it surpasses the conventional material, or has characteristics not found in the conventional material, Application as a next-generation strength reinforcing material, electron-emitting device material, battery electrode material, electromagnetic wave absorbing material, catalyst material, or optical material is expected.

例えば、ナノ炭素材料はｓｐ2 混成軌道に基づく導電性を有しており、また、ナノメートルサイズの微細形状に基づくグラファイトエッジを高密度に有することから、電気二重層キャパシタ・電池の電極として応用すれば、従来の活性炭を電極とした電気二重層キャパシタ・電池よりも蓄電容量が大きくなることが報告されている（特許文献１参照）。 For example, nanocarbon materials have conductivity based on sp 2 hybrid orbitals, and have a high density of graphite edges based on nanometer-sized fine shapes, so they can be used as electrodes for electric double layer capacitors and batteries. In this case, it has been reported that the storage capacity is larger than that of the conventional electric double layer capacitor / battery using activated carbon as an electrode (see Patent Document 1).

ところで、カーボンナノチューブ等のナノ炭素材料の合成方法としては、アーク放電法（非特許文献１参照）、化学気相成長法（非特許文献２参照）、或いは、固液界面接触分解法（特許文献２参照）等が知られているが、合成したナノ炭素材料を使用形態に加工する、例えば電池の電極の形状に加工する際には、黒鉛粒子や不定形炭素等のナノ炭素材料以外の炭素不純物を含んだ反応生成物中からナノ炭素材料を精製したり、或いは基板上に成長したカーボンナノチューブを掻き落として、必要な量のカーボンナノチューブを収集することが必要であり、低コストで大量にナノ炭素材料を使用した部材を製造することができなかった。   By the way, as a method for synthesizing nanocarbon materials such as carbon nanotubes, an arc discharge method (see Non-Patent Document 1), a chemical vapor deposition method (see Non-Patent Document 2), or a solid-liquid interface catalytic decomposition method (Patent Document). 2)) is known, but when the synthesized nanocarbon material is processed into a use form, for example, when processing into the shape of a battery electrode, carbon other than the nanocarbon material such as graphite particles and amorphous carbon is used. It is necessary to purify the nanocarbon material from the reaction product containing impurities, or scrape the carbon nanotubes grown on the substrate to collect the required amount of carbon nanotubes. A member using a nanocarbon material could not be manufactured.

上記の課題を解決するナノ炭素材料として、粒子を核に持つナノ炭素材料及びその製造方法が開示されている（特許文献３参照）。この方法は、図５に示すように、表面が酸化されたダイヤモンド粒子上に触媒微粒子が担持されたダイヤモンド触媒粒子１２を包含する、垂直に配設された反応槽１３と、反応槽１３の下部及び上部にそれぞれ設けられた炭化水素からなるガス１４を導入する導入口１５と、ガス１４を排出する排出口１６と、反応槽１３を取り囲んで配設される加熱装置１７と、ダイヤモンド触媒粒子１２は通過させず、ガス１４は通過させるフィルター１８とからなる装置を用い、ダイヤモンド触媒粒子１２を、フィルター１８上に配置し、炭化水素からなるガス１４を導入口１５から所定の流量で導入すると共に排出口１６から排出し、ダイヤモンド触媒粒子１２を反応槽１３中で浮遊し且つ撹拌される状態とし、４００℃から６００℃の範囲で加熱して、ダイヤモンド触媒粒子１２に担持された触媒微粒子上にナノ炭素材料を成長する。この方法は、浮遊気相成長法と呼ばれ、この方法によれば、表面が酸化されたダイヤモンド粒子と、この表面に担持した遷移金属触媒と、遷移金属触媒から放射状に成長したナノ炭素繊維とから構成された、黒鉛粒子や不定形炭素等のナノ炭素材料以外の炭素不純物を含まない、マリモカーボンと呼ぶナノ炭素材料複合体が得られる。
このナノ炭素材料複合体をそのままナノ炭素材料として用いれば、反応生成物中からカーボンナノチューブを精製したり、或いは基板上に成長したカーボンナノチューブを掻き落として、必要な量のカーボンナノチューブを収集する必要ないので、低コストで大量にナノ炭素材料を使用した部材を製造することができる。
特開２００５−１３６０２０号公報 特開２００３−１２３１２号公報 特開２００５−３３５９６８号公報 独立行政法人 産業技術総合研究所 ナノカーボン研究センター 編 「ナノカーボン材料」 丸善株式会社 平成１６年５月２５日発行，ｐｐ１８７−１９１ 独立行政法人 産業技術総合研究所 ナノカーボン研究センター 編 「ナノカーボン材料」 丸善株式会社 平成１６年５月２５日発行，ｐｐ１９１−１９２ As a nanocarbon material that solves the above problems, a nanocarbon material having particles as a nucleus and a method for producing the nanocarbon material have been disclosed (see Patent Document 3). As shown in FIG. 5, the method includes a vertically disposed reaction tank 13 including diamond catalyst particles 12 having catalyst fine particles supported on diamond particles whose surfaces are oxidized, and a lower part of the reaction tank 13. And an inlet 15 for introducing a gas 14 made of hydrocarbon, an exhaust port 16 for discharging the gas 14, a heating device 17 disposed surrounding the reaction tank 13, and diamond catalyst particles 12. Is not allowed to pass through, and a device comprising a filter 18 through which gas 14 is passed, diamond catalyst particles 12 are arranged on the filter 18, and hydrocarbon gas 14 is introduced from the inlet 15 at a predetermined flow rate. The diamond catalyst particles 12 are discharged from the discharge port 16, floated in the reaction tank 13 and stirred, and heated in the range of 400 ° C. to 600 ° C. To grow a nano-carbon material on the catalyst fine particles supported on the diamond catalyst particles 12. This method is called a floating vapor phase growth method. According to this method, diamond particles having an oxidized surface, a transition metal catalyst supported on the surface, nanocarbon fibers grown radially from the transition metal catalyst, A nanocarbon material composite called marimocarbon that is free from carbon impurities other than nanocarbon materials such as graphite particles and amorphous carbon, is obtained.
If this nanocarbon material composite is used as it is as a nanocarbon material, it is necessary to purify the carbon nanotubes from the reaction product or scrape the carbon nanotubes grown on the substrate and collect the required amount of carbon nanotubes. Therefore, it is possible to manufacture a member using a nanocarbon material in a large amount at a low cost.
JP 2005-136020 A JP 2003-12312 A JP 2005-335968 A National Institute of Advanced Industrial Science and Technology, Nanocarbon Research Center, “Nanocarbon Materials” Maruzen Co., Ltd. May 25, 2004, pp 187-191 National Institute of Advanced Industrial Science and Technology, Nanocarbon Research Center, “Nanocarbon Materials” Maruzen Co., Ltd. May 25, 2004, pp191-192

ところで、特許文献３のナノ炭素材料複合体に使用する核となる粒子はダイヤモンド粒子であり、ダイヤモンドは電気の絶縁体であるので、例えば、このナノ炭素材料複合体を電気二重層キャパシタ・電池、燃料電池、或いは、一般的な二次電池の電極材料として使用した場合には、ダイヤモンド粒子部分の電気抵抗が電極全体の抵抗値を大きくしてしまい、結果的に内部抵抗の大きな電池となってしまうと言う課題がある。
本発明者らは導電性を有する粒子を核とすればこの課題は解決できることに想到した。しかしながら、ナノ炭素材料の触媒合成反応は、触媒と触媒を担持する物質の組み合わせによって左右されるので、単に導電性物質からなる粒子を選択しただけではナノ炭素材料の触媒合成反応を生じさせることができない。因みに、従来のナノ炭素材料の触媒合成反応が生じ得る触媒と触媒を担持する物質の組み合わせは、触媒が遷移金属である場合に触媒を担持する粒子としてダイヤモンドの他に、シリカ（ＳｉＯ2 ）、アルミナ（Ａｌ2 Ｏ）、ジルコニア（ＺｒＯ2 ）、或いはゼオライトなどの金属酸化物粒子が知られているがいずれも絶縁物であり、導電性の物質からなる触媒担体粒子は知られていなかった。
本発明者らは、核となる粒子に導電性を有する酸化亜鉛（ＺｎＯ）粒子を用いることで、ナノ炭素材料が成長すること見いだし、本発明に到ったものである。 By the way, since the particle | grains used as the nucleus used for the nano carbon material composite_body | complex of patent document 3 are diamond particles, and diamond is an electrical insulator, for example, this nano carbon material composite is used for an electric double layer capacitor and a battery, When used as an electrode material for a fuel cell or a general secondary battery, the electrical resistance of the diamond particle portion increases the resistance value of the entire electrode, resulting in a battery with a large internal resistance. There is a problem to say.
The present inventors have conceived that this problem can be solved by using conductive particles as a core. However, since the catalyst synthesis reaction of the nanocarbon material depends on the combination of the catalyst and the substance supporting the catalyst, simply selecting particles made of a conductive substance may cause the catalyst synthesis reaction of the nanocarbon material. Can not. Incidentally, a combination of a catalyst capable of causing a catalytic synthesis reaction of a conventional nanocarbon material and a substance supporting the catalyst includes silica (SiO 2 ) in addition to diamond as particles supporting the catalyst when the catalyst is a transition metal, Metal oxide particles such as alumina (Al 2 O), zirconia (ZrO 2 ), or zeolite are known, but all are insulators, and catalyst carrier particles made of a conductive material have not been known.
The present inventors have found that a nanocarbon material grows by using conductive zinc oxide (ZnO) particles as core particles, and have reached the present invention.

上記説明から理解されるように、本発明は、導電性を有する粒子を核とし、この粒子上にナノカーボン繊維が成長したナノ炭素材料を提供することを一目的とする。本発明の他の目的はその製造方法を提供することにある。   As will be understood from the above description, an object of the present invention is to provide a nanocarbon material in which conductive particles are used as nuclei and nanocarbon fibers are grown on the particles. Another object of the present invention is to provide a manufacturing method thereof.

上記目的を達成するために本発明のナノ炭素材料複合体は、酸素空孔を有した導電性酸化亜鉛粒子と、この導電性粒子の表面に担持したＣｏ又はＮｉからなる触媒微粒子と、この触媒微粒子を担持した導電性酸化亜鉛粒子上に成長したナノ炭素繊維とからなることを特徴とする。
触媒上に成長したナノ炭素繊維は、カーボンナノチューブ、カーボンナノフィラメント及びカーボンナノファイバーで成るグループから選択される何れか一つ又は複数であってよい。
In order to achieve the above object, the nanocarbon material composite of the present invention comprises conductive zinc oxide particles having oxygen vacancies, catalyst fine particles comprising Co or Ni supported on the surface of the conductive particles, and the catalyst. It is characterized by comprising nanocarbon fibers grown on conductive zinc oxide particles carrying fine particles.
The nanocarbon fibers grown on the catalyst may be any one or more selected from the group consisting of carbon nanotubes, carbon nanofilaments, and carbon nanofibers.

本発明のナノ炭素材料複合体の製造方法は、酸化亜鉛粒子を空気中又は真空中で焼結して酸素空孔を有する導電性酸化亜鉛粒子とし、導電性酸化亜鉛粒子の表面にＣｏ又はＮｉからなる触媒微粒子を担持し、触媒微粒子が担持された導電性酸化亜鉛粒子を、炭化水素からなる気相中でナノ炭素繊維が合成される触媒反応温度に加熱し、導電性酸化亜鉛粒子上にナノ炭素材料を成長することを特徴とする。
上記構成において、Ｃｏ塩又はＮｉ塩の水溶液に導電性酸化亜鉛粒子を含浸して放置した後、過剰な水を蒸発させて乾燥し、空気中で焼成してＣｏ塩又はＮｉ塩の分解と酸化をおこさせることでＣｏ酸化物又はＮｉ酸化物を得、該Ｃｏ酸化物又はＮｉ酸化物を還元してＣｏ又はＮｉからなる触媒微粒子とし、該Ｃｏ又はＮｉからなる触媒微粒子を、前記導電性酸化亜鉛粒子上に担持してもよい。
気相中でのナノ炭素繊維の合成は、酸化亜鉛粒子を炭化水素からなる気相中で浮遊させて成長する方法であれば好ましく、この場合には、酸化亜鉛粒子から、均等に、放射状に、ナノ炭素繊維が成長したナノ炭素材料が得られる。酸化亜鉛粒子の粒径は１００μｍ以下であれば好ましい。炭化水素はエチレンであれば好ましい。
また、ナノ炭素繊維の合成をする触媒反応温度は、好ましくは４００℃から７５０℃の温度範囲の何れかの温度である。
In the method for producing a nanocarbon material composite of the present invention, zinc oxide particles are sintered in air or in vacuum to form conductive zinc oxide particles having oxygen vacancies, and Co or Ni is formed on the surface of the conductive zinc oxide particles. The conductive zinc oxide particles carrying the catalyst fine particles are heated to the catalytic reaction temperature at which the nanocarbon fibers are synthesized in the gas phase comprising hydrocarbons, and the conductive zinc oxide particles are supported on the conductive zinc oxide particles. It is characterized by growing nanocarbon materials.
In the above configuration, after impregnating conductive zinc oxide particles in an aqueous solution of Co salt or Ni salt and leaving it to stand, the excess water is evaporated and dried, followed by firing in air to decompose and oxidize the Co salt or Ni salt. give the Co oxide or Ni oxide by cause a, by reducing the Co oxide or Ni oxide as a catalyst fine particles of Co or Ni, the catalyst particles made of the Co or Ni, the conductive You may carry | support on a zinc oxide particle.
The synthesis of nanocarbon fibers in the gas phase is preferably a method in which zinc oxide particles are grown in a gas phase composed of hydrocarbons. In this case, the zinc oxide particles are evenly and radially formed from the zinc oxide particles. A nanocarbon material in which nanocarbon fibers are grown is obtained. The particle diameter of the zinc oxide particles is preferably 100 μm or less. The hydrocarbon is preferably ethylene.
The catalytic reaction temperature for synthesizing the nanocarbon fiber is preferably any temperature in the temperature range of 400 ° C to 750 ° C.

本発明のナノ炭素材料複合体は、導電性を有する粒子上に導電性を有する繊維状のナノカーボン材料が成長しているので、本発明のナノ炭素材料複合体を、電気二重層キャパシタ・電池、燃料電池、或いは、一般的な二次電池の電極材料として使用すれば、蓄電容量が大きいと共に内部抵抗が小さい電池を実現できる。また、電磁波吸収材料として用いれば、抵抗成分が小さいので、優れた電磁波吸収特性を実現できる。
本発明のナノ炭素材料複合体の製造方法によれば、導電性を有する粒子上に導電性を有する繊維状のナノカーボン材料が成長したナノ炭素材料複合体を製造できる。 In the nanocarbon material composite of the present invention, since a fibrous nanocarbon material having conductivity is grown on conductive particles, the nanocarbon material composite of the present invention is used as an electric double layer capacitor / battery. When used as an electrode material for a fuel cell or a general secondary battery, a battery having a large storage capacity and a low internal resistance can be realized. Further, when used as an electromagnetic wave absorbing material, since the resistance component is small, excellent electromagnetic wave absorbing characteristics can be realized.
According to the method for producing a nanocarbon material composite of the present invention, a nanocarbon material composite in which a fibrous nanocarbon material having conductivity is grown on conductive particles can be produced.

以下、本発明の最良の実施の形態を図面に基づいて詳細に説明する。
図１は本発明のナノ炭素材料複合体の構成を示す模式断面図である。図において、本発明のナノ炭素材料複合体１は、核となる導電性粒子２と、導電性粒子２上に担持した遷移金属触媒微粒子３と、触媒微粒子３を担持した導電性粒子２上に成長したナノ炭素繊維４とからなる。図１では、触媒微粒子３が導電性粒子２上に存在する場合を示しているが、これに限らず、触媒微粒子３はナノ炭素繊維４の中や表面に存在する場合もある。 DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the best mode for carrying out the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing the configuration of the nanocarbon material composite of the present invention. In the figure, the nanocarbon material composite 1 of the present invention comprises conductive particles 2 serving as nuclei, transition metal catalyst fine particles 3 supported on the conductive particles 2, and conductive particles 2 supporting the catalyst fine particles 3. It consists of the grown nanocarbon fiber 4. Although FIG. 1 shows a case where the catalyst fine particles 3 are present on the conductive particles 2, the present invention is not limited to this, and the catalyst fine particles 3 may be present in or on the nanocarbon fibers 4.

次に、導電性粒子１が導電性を有する酸化亜鉛粒子である場合を例に取り、本発明のナノ炭素材料の製造方法を説明する。
導電性粒子１は、一般に市販されている酸化亜鉛粒子１を空気中又は真空中で焼結することによって得られる。穴径の異なるフィルターを用いて粒径毎に分級し、用途によって粒径を選択すれば好ましい。 Next, taking the case where the conductive particles 1 are conductive zinc oxide particles as an example, the method for producing a nanocarbon material of the present invention will be described.
The electroconductive particle 1 is obtained by sintering the zinc oxide particle 1 generally marketed in the air or in a vacuum. It is preferable to classify for each particle diameter using filters having different hole diameters and select the particle diameter depending on the application.

遷移金属触媒微粒子３は、遷移金属塩溶液を用いた含浸法を用いることによって、導電性粒子２である酸化亜鉛粒子２上に担持させることができる。例えば、硝酸ニッケル等の飽和水溶液に酸化亜鉛粒子２を含浸し、一昼夜放置後、過剰な水を蒸発させて乾燥させ、空気中で焼成して遷移金属塩の分解と酸化をおこさせ、次に、遷移金属酸化物を水素中で還元すれば、粒径が１０〜１００ｎｍ程度の触媒金属微粒子３を酸化亜鉛粒子２上に担持することができる。   The transition metal catalyst fine particles 3 can be supported on the zinc oxide particles 2 as the conductive particles 2 by using an impregnation method using a transition metal salt solution. For example, a saturated aqueous solution of nickel nitrate or the like is impregnated with zinc oxide particles 2 and allowed to stand for a whole day and night, after which excess water is evaporated and dried, and calcined in air to decompose and oxidize transition metal salts. If the transition metal oxide is reduced in hydrogen, the catalyst metal fine particles 3 having a particle size of about 10 to 100 nm can be supported on the zinc oxide particles 2.

次に、図２に示すように、電気炉５中に遷移金属触媒微粒子３が担持された酸化亜鉛粒子２を配置し、炭化水素６からなるガスを流し、電気炉５をナノ炭素繊維が合成される触媒反応温度に加熱し、酸化亜鉛粒子２の表面の遷移金属触媒微粒子３上にナノ炭素材料４を成長させる。炭化水素６は、炭素数が１〜３０の炭化水素であり、メタン、エタン、プロパン等の飽和炭化水素の他、エチレンやアセチレン等の不飽和炭化水素でも良い。合成温度は、４００〜７００℃の範囲内のいずれかであることが好ましい。
また、図５に示した装置を用いて、遷移金属触媒微粒子３が担持された酸化亜鉛粒子２を炭化水素ガス中で浮遊させて合成すれば、酸化亜鉛粒子から、等方向的に均等に、且つ、放射状にナノ炭素繊維が成長したナノ炭素材料が得られる。
次に、実施例を説明する。 Next, as shown in FIG. 2, zinc oxide particles 2 carrying transition metal catalyst fine particles 3 are arranged in an electric furnace 5, a gas composed of hydrocarbons 6 is flown, and nanocarbon fibers are synthesized in the electric furnace 5. The nanocarbon material 4 is grown on the transition metal catalyst fine particles 3 on the surface of the zinc oxide particles 2 by heating to the catalytic reaction temperature. The hydrocarbon 6 is a hydrocarbon having 1 to 30 carbon atoms, and may be an unsaturated hydrocarbon such as ethylene or acetylene in addition to a saturated hydrocarbon such as methane, ethane, or propane. The synthesis temperature is preferably in the range of 400 to 700 ° C.
Further, by using the apparatus shown in FIG. 5 to synthesize the zinc oxide particles 2 on which the transition metal catalyst fine particles 3 are supported by being suspended in a hydrocarbon gas, the zinc oxide particles are evenly and uniformly distributed. In addition, a nanocarbon material in which nanocarbon fibers are radially grown is obtained.
Next, examples will be described.

市販（和光純薬工業製）の平均粒径５μｍの酸化亜鉛粒子を原料として用い、約３００℃、約１０分間の焼結により導電性粒子原料とした。遷移金属触媒微粒子は、Ｃｏの硝酸塩（Ｃｏ（ＮＯ3 ）2 ・６Ｈ2 Ｏ）水溶液を用いた含浸法により酸化亜鉛粒子上にＣｏ触媒微粒子を担持した。ここで、触媒の担持量は５ｗ％（重量％）とした。
次に、電気炉中に遷移金属触媒微粒子を担持した酸化亜鉛粒子を挿入し、アルゴンで希釈したエチレンガスを流し、約６５０℃、３０分加熱した。遷移金属触媒微粒子を担持した酸化亜鉛粒子の量は１００ｍｇ、エチレンとアルゴンの流量比は１：１、総流量は３０ｓｃｃｍとした。 Commercially available (made by Wako Pure Chemical Industries, Ltd.) zinc oxide particles having an average particle size of 5 μm were used as raw materials, and conductive particles were obtained by sintering at about 300 ° C. for about 10 minutes. The transition metal catalyst fine particles were supported on the zinc oxide particles by an impregnation method using an aqueous solution of Co nitrate (Co (NO 3 ) 2 .6H 2 O). Here, the supported amount of the catalyst was 5 w% (% by weight).
Next, zinc oxide particles carrying transition metal catalyst fine particles were inserted into an electric furnace, and ethylene gas diluted with argon was flowed and heated at about 650 ° C. for 30 minutes. The amount of the zinc oxide particles supporting the transition metal catalyst fine particles was 100 mg, the flow rate ratio of ethylene and argon was 1: 1, and the total flow rate was 30 sccm.

図３は、本実施例において作製した、本発明のナノ炭素材料複合体の走査型電子顕微鏡（ＳＥＭ）像を示す図である。やや角を持った酸化亜鉛粒子の表面に、ほぼ均一に繊維状のナノ炭素材料が形成されていることがわかる。また、透過型電子顕微鏡（ＴＥＭ）により、繊維状のナノ炭素材料部分を観察したところ、カーボンナノチューブ、カーボンナノフィラメントおよびカーボンナノファイバーから成ることがわかった。   FIG. 3 is a diagram showing a scanning electron microscope (SEM) image of the nanocarbon material composite of the present invention produced in this example. It can be seen that a fibrous nanocarbon material is formed almost uniformly on the surface of the zinc oxide particles having a slight angle. Further, when the fibrous nanocarbon material portion was observed with a transmission electron microscope (TEM), it was found to be composed of carbon nanotubes, carbon nanofilaments, and carbon nanofibers.

市販（和光純薬工業製）の平均粒径５μｍの酸化亜鉛粒子を原料として用い、約３００℃、約１０分の焼結により導電性粒子原料とした。遷移金属触媒微粒子は、ニッケル（Ｎｉ）の硝酸塩（Ｎｉ（ＮＯ3 ）2 ・６Ｈ2 Ｏ）水溶液を用いた含浸法により酸化亜鉛粒子上にＮｉ触媒微粒子を担持した。ここで、触媒の担持量は５ｗ％とした。
次に、電気炉中に遷移金属触媒微粒子を担持した酸化亜鉛粒子を挿入し、アルゴンで希釈したエチレンガスを流し、約７００℃、３０分加熱した。遷移金属触媒微粒子を担持した酸化亜鉛粒子の量は１００ｍｇ、エチレンとアルゴンの流量比は１：１、総流量は３０ｓｃｃｍとした。 Commercially available (made by Wako Pure Chemical Industries, Ltd.) zinc oxide particles having an average particle diameter of 5 μm were used as raw materials, and were made into conductive particle raw materials by sintering at about 300 ° C. for about 10 minutes. The transition metal catalyst fine particles were supported on the zinc oxide particles by an impregnation method using a nickel (Ni) nitrate (Ni (NO 3 ) 2 .6H 2 O) aqueous solution. Here, the supported amount of the catalyst was 5 w%.
Next, zinc oxide particles carrying transition metal catalyst fine particles were inserted into an electric furnace, and ethylene gas diluted with argon was allowed to flow and heated at about 700 ° C. for 30 minutes. The amount of the zinc oxide particles supporting the transition metal catalyst fine particles was 100 mg, the flow rate ratio of ethylene and argon was 1: 1, and the total flow rate was 30 sccm.

図４に本実施例において作製した、本発明のナノ炭素材料の走査型電子顕微鏡（ＳＥＭ）像を示す。やや角を持った酸化亜鉛粒子の表面に、ほぼ均一に繊維状のナノ炭素材料が形成されていることがわかる。また、透過型電子顕微鏡（ＴＥＭ）により、繊維状のナノ炭素材料部分を観察したところ、カーボンナノチューブ、カーボンナノフィラメントおよびカーボンナノファイバーから成ることがわかった。   FIG. 4 shows a scanning electron microscope (SEM) image of the nanocarbon material of the present invention produced in this example. It can be seen that a fibrous nanocarbon material is formed almost uniformly on the surface of the zinc oxide particles having a slight angle. Further, when the fibrous nanocarbon material portion was observed with a transmission electron microscope (TEM), it was found to be composed of carbon nanotubes, carbon nanofilaments, and carbon nanofibers.

上記説明から理解されるように、本発明のナノ炭素材料は、導電性粒子を核として繊維状のナノ炭素材料が成長しているので、例えば、電池の電極に用いれば、蓄電容量が大きく、且つ内部抵抗が小さい電池を実現できる。また、電磁波吸収体に用いれば、極めて効率よく電磁波を吸収できる。   As understood from the above description, the nano-carbon material of the present invention has a fibrous nano-carbon material growing with conductive particles as nuclei. For example, when used for a battery electrode, the storage capacity is large. In addition, a battery with low internal resistance can be realized. Moreover, if it uses for an electromagnetic wave absorber, electromagnetic waves can be absorbed very efficiently.

本発明のナノ炭素材料複合体の構成を示す断面模式図である。It is a cross-sectional schematic diagram which shows the structure of the nano carbon material composite_body | complex of this invention. 本発明のナノ炭素材料複合体の製造方法を示す図である。It is a figure which shows the manufacturing method of the nano carbon material composite_body | complex of this invention. 本発明の実施例により作製されたナノ炭素材料複合体のＳＥＭ像である。It is a SEM image of the nanocarbon material composite produced by the Example of this invention. 本発明の他の実施例により作製されたナノ炭素材料複合体のＳＥＭ像である。It is a SEM image of the nanocarbon material composite produced by other examples of the present invention. 従来のダイヤモンド微粒子を核としたナノ炭素材料複合体の製造に用いる装置を示す概略図である。It is the schematic which shows the apparatus used for manufacture of the nanocarbon material composite which used the conventional diamond fine particle as a nucleus.

符号の説明Explanation of symbols

１ ナノ炭素材料複合体
２ 酸化亜鉛粒子
３ 遷移金属触媒微粒子
４ 繊維状のナノ炭素材料
５ 電気炉
６ 炭化水素
１２ ダイヤモンド触媒粒子
１３ 反応槽
１４ 炭化水素
１５ 導入口
１６ 排出口
１７ 電気炉
１８ フィルター DESCRIPTION OF SYMBOLS 1 Nanocarbon material composite 2 Zinc oxide particle 3 Transition metal catalyst fine particle 4 Fibrous nanocarbon material 5 Electric furnace 6 Hydrocarbon 12 Diamond catalyst particle 13 Reaction tank 14 Hydrocarbon 15 Inlet 16 Outlet 17 Electric furnace 18 Filter

Claims (8)

酸素空孔を有した導電性酸化亜鉛粒子と、この導電性粒子の表面に担持したＣｏ又はＮｉからなる触媒微粒子と、この触媒微粒子を担持した上記導電性酸化亜鉛粒子上に成長したナノ炭素繊維とからなることを特徴とする、ナノ炭素材料複合体。   Conductive zinc oxide particles having oxygen vacancies, catalyst fine particles made of Co or Ni supported on the surfaces of the conductive particles, and nanocarbon fibers grown on the conductive zinc oxide particles supporting the catalyst fine particles A nanocarbon material composite characterized by comprising: 前記ナノ炭素繊維は、カーボンナノチューブ、カーボンナノフィラメント及びカーボンナノファイバーで成るグループから選択される何れか一つ又は複数であることを特徴とする、請求項１に記載のナノ炭素材料複合体。   2. The nanocarbon material composite according to claim 1, wherein the nanocarbon fiber is one or more selected from the group consisting of carbon nanotubes, carbon nanofilaments, and carbon nanofibers. 酸化亜鉛粒子を空気中又は真空中で焼結して酸素空孔を有する導電性酸化亜鉛粒子とし、
上記導電性酸化亜鉛粒子の表面にＣｏ又はＮｉからなる触媒微粒子を担持し、
上記触媒微粒子が担持された導電性酸化亜鉛粒子を、炭化水素からなる気相中でナノ炭素繊維が合成される触媒反応温度に加熱し、
上記導電性酸化亜鉛粒子上にナノ炭素材料を成長することを特徴とする、ナノ炭素材料複合体の製造方法。 Zinc oxide particles are sintered in air or in vacuum to form conductive zinc oxide particles having oxygen vacancies,
A catalyst fine particle made of Co or Ni is supported on the surface of the conductive zinc oxide particles,
Heating the conductive zinc oxide particles carrying the catalyst fine particles to a catalytic reaction temperature at which nanocarbon fibers are synthesized in a gas phase composed of hydrocarbons,
A method for producing a nanocarbon material composite, comprising growing a nanocarbon material on the conductive zinc oxide particles. Ｃｏ塩又はＮｉ塩の水溶液に前記導電性酸化亜鉛粒子を含浸して放置した後、過剰な水を蒸発させて乾燥し、空気中で焼成して上記Ｃｏ塩又はＮｉ塩の分解と酸化をおこさせることでＣｏ酸化物又はＮｉ酸化物を得、
該Ｃｏ酸化物又はＮｉ酸化物を還元して前記Ｃｏ又はＮｉからなる触媒微粒子とし、
該Ｃｏ又はＮｉからなる触媒微粒子を、前記導電性酸化亜鉛粒子上に担持することを特徴とする、請求項３に記載のナノ炭素材料複合体の製造方法。 After impregnating the conductive zinc oxide particles in an aqueous solution of Co salt or Ni salt and leaving it to stand, the excess water is evaporated and dried, and calcined in air to decompose and oxidize the Co salt or Ni salt. To obtain Co oxide or Ni oxide ,
By reducing the Co oxide or Ni oxide as a catalyst fine particles composed of the Co or Ni,
4. The method for producing a nanocarbon material composite according to claim 3, wherein the catalyst fine particles comprising Co or Ni are supported on the conductive zinc oxide particles. 前記気相中でのナノ炭素繊維の合成が、前記酸化亜鉛粒子を炭化水素からなる気相中で浮遊させて成長する方法であることを特徴とする、請求項３に記載のナノ炭素材料複合体の製造方法。   The nanocarbon material composite according to claim 3, wherein the synthesis of the nanocarbon fiber in the gas phase is a method in which the zinc oxide particles are grown in a gas phase composed of hydrocarbons. Body manufacturing method. 前記酸化亜鉛粒子の粒径は１００μｍ以下であることを特徴とする、請求項３に記載のナノ炭素材料複合体の製造方法。   The method for producing a nanocarbon material composite according to claim 3, wherein the zinc oxide particles have a particle size of 100 μm or less. 前記炭化水素はエチレンであることを特徴とする、請求項３又は５に記載のナノ炭素材料複合体の製造方法。   The said hydrocarbon is ethylene, The manufacturing method of the nano carbon material composite_body | complex of Claim 3 or 5 characterized by the above-mentioned. 前記ナノ炭素繊維の合成をする触媒反応温度は４００℃から７５０℃の温度範囲の何れかの温度であることを特徴とする、請求項３又は５に記載のナノ炭素材料複合体の製造方法。   The method for producing a nanocarbon material composite according to claim 3 or 5, wherein a catalytic reaction temperature for synthesizing the nanocarbon fiber is any temperature within a temperature range of 400 ° C to 750 ° C.
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