JP2006240938A - Fluorine-modified double-walled carbon nanotube - Google Patents
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本発明は、フッ素修飾２層カーボンナノチューブに関する。 The present invention relates to a fluorine-modified double-walled carbon nanotube.
カーボンナノチューブ（ＣＮＴ）をフッ素で修飾したフッ素化カーボンナノチューブは知られている（特開２００３−３０６３２０等）。
フッ素化カーボンナノチューブは、潤滑性が良好で、摺動材の原料等として好適に利用でき、あるいはリチウム一次電池の正極材に用いて優れた性質を発揮する。
ところで、一般的に、ＣＮＴ等の炭素繊維をフッ素化するには、上記特許文献１に記載されているように、５００℃程度の高温条件下で反応を起こさせる必要があるとされている。
しかしながら、例えば単層ＣＮＴ（ＳＷＣＮＴ）の場合、５００℃程度の高温化でフッ素化を行うと、白っぽい粉状となってしまい、強度、導電性、熱伝導性などのＣＮＴ本来もつ機能が失われてしまうという課題がある。
本発明の目的は、フッ素化による機能と、単層（ＳＷ）ＣＮＴの優れた機能とを併せもつフッ素修飾２層カーボンナノチューブを提供するにある。
Fluorinated carbon nanotubes have good lubricity and can be suitably used as a raw material for a sliding material, or exhibit excellent properties when used as a positive electrode material for a lithium primary battery.
By the way, in general, in order to fluorinate carbon fibers such as CNTs, as described in Patent Document 1, it is necessary to cause a reaction under a high temperature condition of about 500 ° C.
However, for example, in the case of single-walled CNT (SWCNT), if fluorination is performed at a high temperature of about 500 ° C., it becomes a whitish powder and the original functions of CNT such as strength, conductivity, and thermal conductivity are lost. There is a problem that it ends up.
An object of the present invention is to provide a fluorine-modified double-walled carbon nanotube having both a function by fluorination and an excellent function of single-walled (SW) CNT.
本発明に係るフッ素修飾２層カーボンナノチューブは、２層カーボンナノチューブの外側チューブがフッ素によって修飾されていることを特徴とする。
発明者等は、フッ素化を２００℃程度の低温でも行えることを見出した。このような低温でフッ素化を行うことにより、中部形態を維持するとともに、外側チューブのみフッ素修飾され、内側チューブはほとんど影響を受けず、単層ＣＮＴの優れた機能を維持していることがわかった。
すなわち、内側チューブがフッ素によって修飾されていないことを特徴とする。
また、外側チューブのフッ素化比：Ｆ／Ｃが０．１〜０．５であることを特徴とする。
また、内側チューブが単層カーボンナノチューブの機能を維持していることを特徴とする。
The fluorine-modified double-walled carbon nanotube according to the present invention is characterized in that the outer tube of the double-walled carbon nanotube is modified with fluorine.
The inventors have found that fluorination can be performed at a low temperature of about 200 ° C. By performing fluorination at such a low temperature, it is understood that while maintaining the middle shape, only the outer tube is modified with fluorine, the inner tube is hardly affected, and the excellent function of the single-walled CNT is maintained. It was.
That is, the inner tube is not modified with fluorine.
Further, the fluorination ratio of the outer tube: F / C is 0.1 to 0.5.
The inner tube maintains the function of the single-walled carbon nanotube.
本発明によれば、フッ素化による機能と、単層（ＳＷ）ＣＮＴの優れた機能とを併せもつフッ素修飾２層カーボンナノチューブを提供できる。したがって、表層がフッ素化されていることにより樹脂等の材料とのなじみがよく、優れた複合材料とすることができる。また、内側チューブが単層ＣＮＴの機能を維持していることにより、導電性、熱伝導性、強度にも優れ、電気二重層キャパシタの電極材料、リチウム一次電池の正極材料、ナノワイヤ等、種々の電子、電気デバイスに適用することができる。 ADVANTAGE OF THE INVENTION According to this invention, the fluorine modification double-walled carbon nanotube which has the function by fluorination and the outstanding function of single-walled (SW) CNT can be provided. Therefore, since the surface layer is fluorinated, it is compatible with a material such as a resin, and an excellent composite material can be obtained. In addition, since the inner tube maintains the function of the single-walled CNT, it is excellent in conductivity, thermal conductivity, and strength, and various materials such as an electrode material for an electric double layer capacitor, a positive electrode material for a lithium primary battery, and a nanowire. It can be applied to electronic and electrical devices.
以下本発明における最良の実施の形態を詳細に説明する。
本発明は、２層カーボンナノチューブ(double-walled carbon nanotube : ＤＷＣＮＴ)のフッ素修飾に関するものであり、フッ素原子はＤＷＣＮＴの２層構造を破壊することなく、選択的にその外側チューブを修飾する。そこでのフッ素修飾ＤＷＣＮＴの化学量論的組成はCF0.30である。
The best mode of the present invention will be described in detail below.
The present invention relates to fluorine modification of double-walled carbon nanotube (DWCNT), and fluorine atoms selectively modify the outer tube without destroying the two-layer structure of DWCNT. The stoichiometric composition of fluorine-modified DWCNT there is CF 0.30 .
２層カーボンナノチューブ：Double-walled carbon nanotubes(ＤＷＣＮＴ)は２本の同心円筒で構成しており、非常に多くの科学者から注目されている。なぜならＳＷＣＮＴ(single-walled carbon nanotubes)と比較した場合、熱的に化学的に、そして機械的にも優れているからである。さらにはＳＷＣＮＴのように、ＤＷＣＮＴも細い直径(２ｎｍ以下)を有することから量子細線としての振る舞いが起こると期待されている。 Double-walled carbon nanotubes (DWCNT) are composed of two concentric cylinders, and are attracting attention from a great number of scientists. This is because when compared with SWCNT (single-walled carbon nanotubes), it is superior in terms of heat, chemical and mechanical properties. Furthermore, like SWCNT, DWCNT also has a thin diameter (2 nm or less), so that it is expected to behave as a quantum wire.
しかしカーボンナノチューブの応用を制限している技術的要因は、気相成長法によって製造した場合、典型的なＳＷＣＮＴの場合と同様に、多数本が束となったバンドル状をなしていることであり、その機能を発揮させるためには、この束状となっているＤＷＣＮＴを１本づつにほぐす必要がある。 However, the technical factor that limits the application of carbon nanotubes is that when they are produced by vapor phase growth, they are in the form of bundles in which many are bundled, as is the case with typical SWCNTs. In order to exert the function, it is necessary to loosen the bundled DWCNTs one by one.
それらのことから、最近ではカーボンナノチューブを化学修飾して、束状となっているカーボンナノチューブを１本づつにほぐす研究が活発に行われている。数々の手法の中でカーボンナノチューブの化学修飾法の強力なツールとしてフッ素化がある。ＳＷＣＮＴのフッ素化はその分散性、電子状態、チューブ長の制御などを可能としている。 For these reasons, recently, active research has been conducted on chemically modifying carbon nanotubes to loosen the bundled carbon nanotubes one by one. Among many methods, fluorination is a powerful tool for chemical modification of carbon nanotubes. Fluorination of SWCNT enables control of its dispersibility, electronic state, tube length, and the like.
本実施の形態では、ＤＷＣＮＴをフッ素原子により２００℃程度の低温でフッ素化した。もちろん、フッ素化は２００℃に限定されるものではない。このフッ素化したＤＷＣＮＴをＸ線光電子分光分析(XPS)、高分解能透過型電子顕微鏡(HR-TEM)、ラマン分光分析により構造解析を行ったところ、フッ素原子が選択的にＤＷＣＮＴの外側チューブをフッ素修飾し、ＤＷＣＮＴの内側チューブは影響を受けずに残っていることが判明した。 In this embodiment, DWCNT was fluorinated with fluorine atoms at a low temperature of about 200 ° C. Of course, fluorination is not limited to 200 ° C. When this fluorinated DWCNT was subjected to structural analysis by X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscope (HR-TEM), and Raman spectroscopy, fluorine atoms selectively fluorinated the outer tube of DWCNT. After modification, it was found that the inner tube of DWCNT remained unaffected.
外側チューブがフッ素によって修飾されることから、樹脂等との複合材にした場合、樹脂とのなじみ、密着性に優れるというフッ素化による機能が発揮される。また、内側チューブがフッ素化の影響をほとんど受けず、したがってＳＷＣＮＴがそのまま残存しているような状況となり、ＳＷＣＮＴの優れた性質、すなわち、導電性、熱伝導性、高強度の特性が維持される。すなわち、フッ素化による機能と、単層（ＳＷ）ＣＮＴの優れた機能とを併せもつフッ素修飾２層カーボンナノチューブが得られる。 Since the outer tube is modified with fluorine, when it is made into a composite material with a resin or the like, a function by fluorination that is compatible with the resin and excellent in adhesion is exhibited. In addition, the inner tube is hardly affected by fluorination, so that the SWCNT remains as it is, and the excellent properties of the SWCNT, that is, conductivity, thermal conductivity, and high strength characteristics are maintained. . That is, a fluorine-modified double-walled carbon nanotube having both the function of fluorination and the excellent function of single-walled (SW) CNT can be obtained.
ＤＷＣＮＴの製法は種々報告されている。一般的には、ＤＷＣＮＴは、ＣＣＶＤ(Catalytic Chemical Vapor Deposition)法により生成することができる。
本実施の形態では、ＤＷＣＮＴの作製は、横型反応炉を使用し、炉心中央部にFe/MgO、炉心入り口側にはMo/Al2O3を配置した。Ar雰囲気中で８７５℃まで昇温し、後に炭素源(CH4+Ar : 1:1)を２００cc/minで10分間流した。そこで生成されたサンプルを２段階の精製処理を施した。すなわち、酸（HCl）処理をして、サポート触媒(MgO)を除去し、次いで５００℃の空気酸化により化学的に活性であるＳＷＣＮＴ（僅かに生成している）やアモルファスカーボンを除去し、ＤＷＣＮＴを作製した。
Various methods for producing DWCNT have been reported. Generally, DWCNT can be produced by a CCVD (Catalytic Chemical Vapor Deposition) method.
In the present embodiment, the production of DWCNT was performed using a horizontal reactor, and Fe / MgO was arranged at the center of the core, and Mo / Al 2 O 3 was arranged at the core entrance side. The temperature was raised to 875 ° C. in an Ar atmosphere, and then a carbon source (CH 4 + Ar: 1: 1) was allowed to flow at 200 cc / min for 10 minutes. The sample thus produced was subjected to a two-stage purification process. That is, it is treated with acid (HCl) to remove the support catalyst (MgO), and then SWCNT (which is slightly produced) and amorphous carbon are removed by air oxidation at 500 ° C., and DWCNT Was made.
注意深いHR-TEM観察によりＤＷＣＮＴの純度（割合）が９５％でバンドル状態であることを確認した。高純度ＤＷＣＮＴのフッ素化条件は以下の通りである。前処理として、ＤＷＣＮＴに含まれる残存酸素ガスや水蒸気を除去するために２００℃で数時間真空処理を行った。その処理されたＤＷＣＮＴを１気圧（atm）のフッ素ガスが挿入された反応チャンバーで２００℃、５時間フッ素修飾(Ｆ−ＤＷＣＮＴ)を施すことを基本操作とする。 It was confirmed by careful HR-TEM observation that the purity (ratio) of DWCNT was 95% and in a bundle state. The fluorination conditions for high-purity DWCNT are as follows. As pretreatment, vacuum treatment was performed at 200 ° C. for several hours in order to remove residual oxygen gas and water vapor contained in DWCNT. The basic operation is to subject the treated DWCNT to fluorine modification (F-DWCNT) at 200 ° C. for 5 hours in a reaction chamber in which fluorine gas at 1 atm (atm) is inserted.
熱電対を備えた内容積約360 mLのNi金属反応容器に、ＤＷＣＮＴを19.6mgのせたNi金属製ボートを設置した。反応容器内を密閉し0.01-0.030torrに減圧し、その後外部ヒーターを取り付け２００℃まで加熱し一晩真空乾燥を行った。ヒーターを調整し反応温度を２００℃とし、フッ素ガスをゆっくり導入した。1気圧に達するまで15分を要した。このとき反応による反応容器内の温度上昇は１６℃であった。この状態で５時間反応を行った。反応終了後容器内を室温付近まで冷却した後、アルゴンガスで内部を十分に置換し、反応容器を開放しボート上の黒色粉末：フッ素修飾２層カーボンナノチューブ（Ｆ−ＤＷＣＮＴ）約２０ mgを回収した。 A Ni metal boat with 19.6 mg of DWCNT was installed in a Ni metal reaction vessel having an internal volume of about 360 mL equipped with a thermocouple. The inside of the reaction vessel was sealed and the pressure was reduced to 0.01-0.030 torr, and then an external heater was attached and heated to 200 ° C. and vacuum dried overnight. The heater was adjusted to a reaction temperature of 200 ° C., and fluorine gas was slowly introduced. It took 15 minutes to reach 1 atmosphere. At this time, the temperature rise in the reaction vessel due to the reaction was 16 ° C. In this state, the reaction was carried out for 5 hours. After completion of the reaction, the inside of the container was cooled to near room temperature, and then the inside was sufficiently replaced with argon gas. The reaction container was opened and black powder on the boat: about 20 mg of fluorine-modified double-walled carbon nanotubes (F-DWCNT) was recovered. did.
得られたＦ−ＤＷＣＮＴのXPS測定(Ulvac-phi社製 model 5600, non-monochoromatized Mg Kα：1253.6eV)、Arイオンレーザー線を用いたラマン分光分析(Kaiser Hololab 5000system)、加速電圧200kVによるHR-TEM観察(JEOL JEM-2010FEF)によりフッ素修飾したＤＷＣＮＴの構造解析を行った。 XPS measurement of the obtained F-DWCNT (Ulvac-phi model 5600, non-monochoromatized Mg Kα: 1253.6 eV), Raman spectroscopic analysis using Ar ion laser beam (Kaiser Hololab 5000system), HR- with acceleration voltage 200 kV Structural analysis of fluorine-modified DWCNT was performed by TEM observation (JEOL JEM-2010FEF).
図１に未処理及びＦ−ＤＷＣＮＴのC1sスペクトルを示した。284.9eVの強いC1sピークは炭素sp2結合に起因し、弱いピークである288.9eVは炭素がフッ素原子と共有結合したことを示す炭素sp3結合に起因する。図２では、フッ素化により共有C-F結合(687.75eV)によるピークが出ることを示している。Ｆ−ＤＷＣＮＴ(CF0.30)の化学論的組成はC1sピークの積算強度をF1sピークの積算強度の割り算により決定した。
図１のF200の二つのC1sの積算強度(C1s288.9/C1sall=0.32)の比とF1sピーク(F/Cの比：0.30)の一致はフッ素がＤＷＣＮＴの外側チューブをフッ素修飾し、内側チューブは影響を受けていないこと間接的に示す。一般的にフッ素修飾ナノチューブは低導電性を示すことが知られており、その結合エネルギーの決定はXPS測定中に帯電効果による補正をしなければならない。しかし今回のＦ−ＤＷＣＮＴはそのような帯電効果がなかった。このことは大きな導電性低下がなかったことを指し、ＤＷＣＮＴの内側チューブが影響をうけなかったと予想できる。
FIG. 1 shows the C1s spectra of untreated and F-DWCNT. The strong C1s peak at 284.9 eV is attributed to the carbon sp2 bond, and the weak peak 288.9 eV is attributed to the carbon sp3 bond indicating that the carbon is covalently bonded to the fluorine atom. FIG. 2 shows that a peak due to a covalent CF bond (687.75 eV) appears due to fluorination. The chemical composition of F-DWCNT (CF0.30) was determined by dividing the integrated intensity of the C1s peak by the integrated intensity of the F1s peak.
The coincidence of the ratio of the integrated strength of two C1s (C1s288.9 / C1sall = 0.32) and F1s peak (F / C ratio: 0.30) of F200 in Fig. 1 indicates that the outer tube of fluorine is modified with fluorine and the inner tube Indicates indirectly that it is not affected. In general, fluorine-modified nanotubes are known to exhibit low conductivity, and the determination of their binding energy must be corrected by the charging effect during XPS measurement. However, the current F-DWCNT did not have such a charging effect. This indicates that there was no significant decrease in conductivity, and it can be expected that the inner tube of DWCNT was not affected.
低倍TEM観察による図３によると、上記ＤＷＣＮＴは主にバンドル状態で存在し、そのバンドルサイズは10-50nmであり、典型的なその断面は6角形にパッキングされた構造をしている(図４参照)。フッ素修飾による独特な構造変化は見られなかった（図５）。注目すべき点はHR-TEMによる高倍観察で２層円筒構造がはっきり見える点である（図６）。さらには6角形にパックされたチューブが乱されており、これはＤＷＣＮＴの外層にフッ素原子が化学的に導入されたからである。 According to FIG. 3 by low-magnification TEM observation, the DWCNT mainly exists in a bundle state, the bundle size is 10-50 nm, and the typical cross section has a structure packed in a hexagon (see FIG. 3). 4). No unique structural change due to fluorine modification was observed (FIG. 5). What should be noted is that the two-layered cylindrical structure can be clearly seen by high magnification observation with HR-TEM (Fig. 6). Furthermore, the hexagonal packed tube is disturbed because fluorine atoms are chemically introduced into the outer layer of DWCNT.
ラマン分光分析はカーボンナノチューブの解析に広く使用されている。なぜならラマン散乱はチューブの構造やその直径に敏感だからである。低周波数領域における未処理のDWNTとF-DWNTのラマンスペクトルを図７に示した。その低周波数領域はRBMと呼ばれ、チューブの直径に反比例することが知られている。約250cm-1以上に現れるラマン線(ＤＷＣＮＴの内側チューブと一致する)と250cm-1以下のラマン線(ＤＷＣＮＴの外側チューブ)が未処理のＤＷＣＮＴでは得られる。チューブ径(図７)に数値を挿入した)はRBM周波数をもとに計算した。そこで用いた計算式はωrbm=234/dt+10, dt=tube diameter(nm),ωrbm=RBM frequency(cm-1)である。 Raman spectroscopy is widely used for the analysis of carbon nanotubes. This is because Raman scattering is sensitive to the structure of the tube and its diameter. FIG. 7 shows Raman spectra of untreated DWNT and F-DWNT in the low frequency region. The low frequency region is called RBM and is known to be inversely proportional to the tube diameter. An untreated DWCNT has a Raman line appearing at about 250 cm -1 or more (corresponding to the inner tube of DWCNT) and a Raman line of 250 cm -1 or less (outer tube of DWCNT). The tube diameter (Figure 9) was calculated based on the RBM frequency. The calculation formula used there is ωrbm = 234 / dt + 10, dt = tube diameter (nm), and ωrbm = RBM frequency (cm −1 ).
未処理のＤＷＣＮＴは２つの径の組み合わせがあることが分かる；(内側のチューブ：外側のチューブ)＝(0.7nm:1.3nm)、(0.9nm:1.58nm)である。Ｆ−ＤＷＣＮＴでは内側チューブである270cm-1と324cm-1は変化しないが、外側チューブによるRBMが明らかに減少している点と、HR-TEM観察によるＦ−ＤＷＣＮＴが２層構造をしていることがはっきりと分かっていることを考慮すると、内層は構造的に変化していないことが納得できる。外側チューブは内側チューブへのフッ素ガスによる化学的攻撃からの保護層の役割を果たし、内側チューブは影響を受けずに残ることを示している。 It can be seen that the untreated DWCNT has a combination of two diameters; (inner tube: outer tube) = (0.7 nm: 1.3 nm), (0.9 nm: 1.58 nm). F-DWCNT 270 cm -1 and 324cm -1 in a inner tube does not change, and that the RBM by outer tube is clearly reduced, F-DWCNT by HR-TEM observation is a two-layer structure Considering that this is clearly known, it can be convinced that the inner layer has not changed structurally. The outer tube serves as a protective layer from chemical attack by fluorine gas on the inner tube, indicating that the inner tube remains unaffected.
図８は未処理のＤＷＣＮＴとフッ素修飾したものの高周波数領域におけるラマンスペクトルである。フッ素修飾を通し、1590cm-1のGバンド(E2g2モード)の少しの減少と、1346cm-1のDバンド(欠陥モード)の高強度化といった変化が見られた。そこでのR値(Dバンドの強度をGバンドの強度で割ったもの)の大幅な増強はＤＷＣＮＴへのフッ素の化学修飾がフッ素修飾ＳＷＣＮＴのようなsp3混成軌道によるＤＷＣＮＴ外側チューブの構造歪を引き起こしたといえる。Ｆ−ＤＷＣＮＴのR値(R=0.45)がフッ素化ＳＷＣＮＴ(R=0.85,DWCNTと同じ条件でフッ素化したもの)より低R値であることは、ＤＷＣＮＴの内側チューブがフッ素修飾されていないことを改めて指し示している。 FIG. 8 shows a Raman spectrum in a high frequency region of untreated DWCNT and fluorine-modified one. Through fluorine modification, changes such as a slight decrease in the 1590 cm -1 G band (E2g2 mode) and an increase in the 1346 cm -1 D band (defect mode) were observed. The significant increase in the R value (D band intensity divided by G band intensity) caused the chemical modification of fluorine to DWCNT to cause structural distortion of the DWCNT outer tube due to sp3 hybrid orbit like fluorine-modified SWCNT. It can be said that. The R value (R = 0.45) of F-DWCNT is lower than that of fluorinated SWCNT (R = 0.85, fluorinated under the same conditions as DWCNT). This means that the inner tube of DWCNT is not fluorinated. Is pointing again.
要約すると、フッ素ガスを２００℃で５時間、ＤＷＣＮＴと直接反応させることによりＤＷＣＮＴの外層だけをフッ素修飾することに成功した。XPS解析をもとにＦ−ＤＷＣＮＴの化学量論的組成はCF0.30であるが、HR-TEM観察によるとフッ素修飾した後も２層構造を保っている。一部のRBMの減少とDバンドの高強度化はＤＷＣＮＴの外側チューブから起因しており、それはsp3混成軌道の導入により、チューブ断面が幾何学的変化を受けたからである。これらのことから、フッ素修飾はＳＷＣＮＴからＤＷＣＮＴを区別する重要なツールとなることがわかる。更にＤＷＣＮＴはＳＷＣＮＴよりも構造が安定であることから、２００℃のフッ素修飾温度の条件においてもその形状を維持していることが分かった。フッ素修飾を通して２層同心円構造を壊すことなくＤＷＣＮＴの外側チューブだけの電子特性を調整したり、分散性の制御をすることにより、機能的センサーやナノコンポジット、電子デバイスなどへの応用が期待できる。 In summary, we succeeded in fluorine-modifying only the outer layer of DWCNT by reacting fluorine gas directly with DWCNT at 200 ° C. for 5 hours. Based on XPS analysis, the stoichiometric composition of F-DWCNT is CF0.30. According to HR-TEM observation, the two-layer structure is maintained even after fluorine modification. Some reductions in RBM and higher D-band strength are attributed to the outer tube of DWCNT because the tube cross-section has undergone a geometric change due to the introduction of sp3 hybrid orbits. From these, it can be seen that fluorine modification is an important tool for distinguishing DWCNT from SWCNT. Furthermore, since the structure of DWCNT is more stable than that of SWCNT, it was found that the shape was maintained even under the condition of a fluorine modification temperature of 200 ° C. Application to functional sensors, nanocomposites, electronic devices, etc. can be expected by adjusting the electronic properties of only the outer tube of DWCNT without breaking the two-layer concentric structure through fluorine modification, or by controlling the dispersibility.
Claims (4)
The fluorine-modified double-walled carbon nanotube according to any one of claims 1 to 3, wherein the inner tube maintains the function of the single-walled carbon nanotube.
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