WO2010104200A1 - Onion-like carbon and method for producing same - Google Patents
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- WO2010104200A1 WO2010104200A1 PCT/JP2010/054469 JP2010054469W WO2010104200A1 WO 2010104200 A1 WO2010104200 A1 WO 2010104200A1 JP 2010054469 W JP2010054469 W JP 2010054469W WO 2010104200 A1 WO2010104200 A1 WO 2010104200A1
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Definitions
- the present invention relates to onion-like carbon and a method for producing the same.
- Onion-like carbon is also called carbon onion, carbon onion, nano-sized spherical graphite, onion graphite, onion fullerene, and the like. It is a synonym of fullerene and carbon nanotube, and is a material attracting attention as a new carbon material. Its shape is a concentric spherical carbon structure, and spherical carbon structures are nested and overlapped like an onion.
- ⁇ Onion-like carbon is lightweight and stable, and has excellent resistance to radiation and resistance at high temperatures.
- high elasticity is expected from its shape, and application as a solid lubricant that can be used in a vacuum or non-lubricated environment is considered.
- Applications for hydrogen storage carbon materials for pharmaceuticals, cosmetics, and fuel cells are also considered.
- Patent Document 2 A method in which diamond fine powder is heated at 1600 to 1800 ° C. in an inert gas atmosphere (see Patent Document 2), and (3) Diamond fine powder in an inert gas at 1700 ° C. using an infrared lamp. The heating method has been disclosed above (see Patent Document 3).
- a method for producing onion-like carbon containing hollow or metal by irradiating a carbon material having a double bond or triple bond with one or more of X-rays, microwaves and ultrasonic waves (patent) Reference 7).
- a method for producing onion-like carbon by irradiating a material having a double bond or a triple bond with light, an electron beam or an ion beam is also shown (see Patent Document 8).
- Patent Document 9 A method for producing an onion-like carbon film by an unbalanced magnetron sputtering method is disclosed (see Patent Document 9).
- the method (1) requires an expensive apparatus corresponding to high-pressure synthesis of diamond, and the production cost is considered to be comparable to that of synthetic diamond, and is not versatile.
- the methods (2 and 3) since the raw material powder is expensive, there is a problem that onion graphite is more expensive than the raw material powder.
- all of these methods have a limited amount of energy input to the target raw material, and there is a limit to mass production.
- the method (9) because of the thin film method, there is a limit to the production of onion-like carbon powder, the production rate is low, and the quantity is limited.
- the method (11) has a problem that the selectivity of the reaction is low, a large amount of amorphous carbon is produced, and separation is difficult.
- an object of the present invention is to provide a method capable of producing onion-like carbon stably on an industrial scale.
- the inventors of the present invention have made extensive studies to achieve the above object, and found that onion-like carbon can be obtained by generating pulse plasma between carbon metal electrodes in a solvent in the presence of a catalyst. It came to.
- a method for producing onion-like carbon which comprises performing pulsed plasma discharge between carbon electrodes in a liquid.
- Onion-like carbon having a graphite interlayer distance of 0.40 nm or more.
- onion-like carbon can be produced with a relatively low voltage, low current, low energy such as pulse discharge. Moreover, the onion-like carbon of the present invention has a wide graphite interlayer distance and is useful for electrode applications of Li ion secondary batteries.
- Example 1 It is a TEM photograph of the black powder obtained in Example 1 (magnification: 100,000 times). It is a TEM photograph of the black powder obtained in Example 1 (magnification: 500,000 times). It is a TEM photograph of the black powder obtained in Example 2 (magnification: 100,000 times). It is a TEM photograph of the black powder obtained in Example 2 (magnification: 500,000 times). It is a TEM photograph of black powder obtained by a comparative example (magnification: 200,000 times).
- the onion-like carbon of the present invention has a concentric spherical carbon structure, but is characterized by a graphite interlayer distance of 0.40 nm or more, more specifically 0.50 nm or more.
- Onion-like carbon having such a wide graphite interlayer distance has not been obtained by the prior art method and is novel.
- Various ions can be accommodated between the graphite layers, and is particularly useful for electrode applications of Li ion secondary batteries.
- the onion-like carbon production method of the present invention is characterized in that pulse plasma discharge is performed between carbon electrodes in a liquid, and any carbon material such as graphite, amorphous carbon, and glassy carbon is used as the carbon electrode. can do.
- the electrode may have any shape such as a rod, wire, or plate. Regarding the size of both poles, it may have a shape such that one of the sizes is different. Moreover, both poles may use the same carbon material or a different material, and may use what was shape
- onion-like carbon is generated in the liquid.
- the liquid (solvent) that can be used is not particularly limited as long as it does not affect the reaction.
- the liquid may be a mixture of two or more compounds.
- Saturated hydrocarbons such as hexane, octane, decane, cyclohexane, cyclooctane, aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, water, methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, 1,4 -Alcohols such as butanediol, esters such as methyl acetate, ethyl acetate, butyl acetate, methyl benzoate and dimethyl phthalate, ethers such as tetrahydrofuran, tetrahydropyran, dipropyl ether, dibutyl ether, diethylene glycol and
- the amount of liquid used is not particularly limited as long as both electrodes are in the liquid. More preferably, it is sufficient that the liquid scatters due to the generation of plasma or the diffusibility of the liquid is not lost depending on the product concentration.
- the temperature at which the pulse plasma discharge is performed is not particularly limited and depends on the type of liquid used. Usually, it is carried out in the range of room temperature to 300 ° C. An excessively high temperature is not preferable because the vapor pressure of the solvent to be used increases and there is a possibility of being ignited by plasma. An excessively low temperature is not preferable because the viscosity of the solvent increases and the diffusibility of the product is impaired.
- onion-like carbon is generated by performing pulsed plasma discharge between carbon electrodes in a liquid.
- the voltage for generating the plasma is not particularly limited, and is preferably in the range of 60V to 400V, and in the range of 80V to 300V in consideration of the necessity of a range of 20V to 500V, safety and special equipment. More preferred.
- the current for generating plasma is not particularly limited, and it is preferable that the current be in the range of 0.1 to 20 A and in the range of 0.2 to 10 A in consideration of energy efficiency.
- the interval for applying the pulsed plasma is not particularly limited, but is preferably 5 to 100 milliseconds, and more preferably 6 to 50 milliseconds. If the plasma application interval is too short, the generation of carbon radicals is further induced before the disappearance of the carbon radicals generated by the plasma discharge, which leads to the growth of onion-like carbon and the formation of amorphous carbon, which is not preferable. In addition, an excessively long discharge interval is not preferable because much energy used for inducing plasma is required, and the production efficiency of onion-like carbon is reduced.
- the duration per pulsed plasma also varies depending on the applied voltage and current, but is usually 1 to 50 microseconds, preferably in the range of 2 to 30 microseconds in consideration of discharge efficiency. If the plasma generation time is too long, a large amount of carbon radicals generated by plasma discharge are induced, leading to the growth of onion-like carbon and the generation of amorphous carbon, which reduces the selectivity. Moreover, if the discharge time is too short, sufficient energy is not supplied, and a lot of energy used to induce plasma is required, which is not preferable because the production efficiency of onion-like carbon is reduced.
- vibration it is also possible to apply vibration to the electrode.
- vibration By giving vibration, there is no stagnation of the carbon compound deposited between the electrodes, and it is possible not only to suppress the attachment of the reactive biological material on the stagnation, but also to discharge efficiently, which is preferable.
- a method for applying vibration is not particularly limited, and a method for applying vibration periodically or a method for applying vibration intermittently may be used.
- the atmosphere for carrying out the present invention is not particularly limited, and it can be carried out under reduced pressure, under pressure, or under normal pressure, but usually, in consideration of safety and operability, nitrogen, argon, etc. It can be carried out under an inert gas.
- the produced onion-like carbon is deposited in the liquid, it is possible to obtain the onion-like carbon by a general method, for example, filtering and removing the used liquid by an operation such as decompression.
- Example 1 Take 200g of toluene in a 300ml beaker, insert 2 columnar graphite electrodes (purity 99% or more) with a diameter of 6mm and a length of 100mm into the toluene, fix the distance between the electrodes to 1mm, and reaction products on the electrode surface Vibrating was applied to prevent the deposition of and to increase the reaction efficiency.
- Each electrode was connected to an AC power source and subjected to pulse discharge at 200V and 2A. The interval between pulse plasmas was 20 milliseconds, and the duration per pulse plasma was 10 microseconds. Simultaneously with the start of discharge, it was observed that the black powder was dispersed in the liquid and the reaction occurred. The reaction was continued for 30 minutes, the sediment was separated, the black solution was centrifuged, and an appropriate amount of toluene was added for washing and separation. The consumption of the electrode was 380 mg.
- the obtained black powder was dried by heating under vacuum.
- the obtained black powder is 254.6 mg, and a TEM photograph (magnification: 100,000 times) of the obtained black powder is shown in FIG. 1 (scale of FIG. 1 is 20 nm), and a TEM photograph (magnification: 500,000 times).
- FIG. 2 the scale of FIG. 2 is 10 nm, and the interlayer distance is shown by two arrows in FIG. 2). From the photograph, it can be seen that the obtained black powder is onion-like carbon having an interlayer distance of 0.62 nm. The yield was 67%.
- Example 2 In Example 1, it carried out like Example 1 except having used water as a solvent. A TEM photograph (magnification: 100,000 times) of the obtained black powder is shown in FIG. 3 (scale of FIG. 3 is 10 nm), and a TEM photograph (magnification: 500,000 times) is shown in FIG. 4 (scale of FIG. 4 is 5 nm). The consumption of the electrode was 412 mg, the obtained black powder was 271.9 mg, the yield was 66%, and it can be seen from the photograph that it is onion-like carbon having an interlayer distance of 0.55 nm.
- Comparative Example The same procedure as in Example 1 was performed except that the electrode was connected to a DC power source and was continuously discharged at 200 V 2A.
- the obtained black powder is 312 mg, and a TEM photograph (magnification: 200,000 times) of the obtained black powder is shown in FIG. 5 (the scale of FIG. 5 is 5 nm). Concentric spherical onion-like carbon was not observed.
- onion-like carbon can be produced with a relatively low voltage, a low current, low energy such as pulse discharge, and has great industrial utility.
Abstract
Disclosed is a method by which an onion-like carbon can be stably produced on a commercial scale.
Specifically disclosed is a method for producing an onion-like carbon, wherein pulse plasma is discharged between carbon electrodes in a liquid.
Description
本発明は、オニオンライクカーボンおよびその製造方法に関する。
The present invention relates to onion-like carbon and a method for producing the same.
オニオンライクカーボンはカーボンオニオン、炭素オニオン、ナノサイズ真球状黒鉛、オニオングラファイト、オニオンフラーレンなどとも呼ばれ、フラーレンやカーボンナノチューブの同属体であり、新しい炭素材料として注目されている材料である。その形状は、同心球状の炭素構造で、タマネギのように球状炭素構造が入れ子を成して重なっている。
Onion-like carbon is also called carbon onion, carbon onion, nano-sized spherical graphite, onion graphite, onion fullerene, and the like. It is a synonym of fullerene and carbon nanotube, and is a material attracting attention as a new carbon material. Its shape is a concentric spherical carbon structure, and spherical carbon structures are nested and overlapped like an onion.
オニオンライクカーボンは、軽量かつ安定であり、放射線に対する耐性、高温での耐性が優れている。また、その形状から、高弾性が期待され、真空下あるいは無潤滑環境下で使用できる固体潤滑剤としての応用が考えられている。また、医薬品、化粧品、燃料電池用水素吸蔵炭素材料としての用途も考えられている。
¡Onion-like carbon is lightweight and stable, and has excellent resistance to radiation and resistance at high temperatures. In addition, high elasticity is expected from its shape, and application as a solid lubricant that can be used in a vacuum or non-lubricated environment is considered. Applications for hydrogen storage carbon materials for pharmaceuticals, cosmetics, and fuel cells are also considered.
しかし、オニオンライクカーボンはその生産性に大きな課題があり、従来より様々な製造方法が提案されているが、未だ、実用に供するにはいずれの方法も問題があった。
However, onion-like carbon has a major problem in productivity, and various production methods have been proposed so far, but there are still problems in any method for practical use.
すなわち、(1)オニオンライクカーボンの合成法としては、グラッシーカーボンからなる成形体を熱間静水圧加圧法で、1000~3000気圧下、2000~3000℃の熱処理を行って製造する方法が示されている(特許文献1参照)。
That is, (1) as a method for synthesizing onion-like carbon, a method is shown in which a molded body made of glassy carbon is subjected to heat treatment at 1000 to 3000 atmospheres and 2000 to 3000 ° C. by hot isostatic pressing. (See Patent Document 1).
また、(2)ダイヤモンド微粉末を不活性ガス雰囲気中にて1600~1800℃で加熱する方法(特許文献2参照)、(3)ダイヤモンド微粉末を不活性ガス中で赤外線ランプを用いて1700℃以上に加熱する方法が開示されている(特許文献3参照)。
(2) A method in which diamond fine powder is heated at 1600 to 1800 ° C. in an inert gas atmosphere (see Patent Document 2), and (3) Diamond fine powder in an inert gas at 1700 ° C. using an infrared lamp. The heating method has been disclosed above (see Patent Document 3).
また、(4)ポリインに光、電子線またはイオンビームを照射、あるいは加熱処理を施すことによりオニオンライクカーボンを製造する方法が示されている(特許文献4参照)。さらに、(5)ポリテトラフルオロエチレン、ポリ塩化ビニリデンまたはポリフッ化ビニリデンに光、電子線またはイオンビームを照射する方法(特許文献5参照)、(6)煤状炭素に電子線、ガンマ線、X線、イオン線などの高エネルギービームを照射してオニオンライクカーボンへ転換する方法が示されている(特許文献6参照)。
Also, (4) a method for producing onion-like carbon by irradiating polyin with light, an electron beam or an ion beam, or by subjecting it to heat treatment (see Patent Document 4). Furthermore, (5) a method of irradiating polytetrafluoroethylene, polyvinylidene chloride or polyvinylidene fluoride with light, an electron beam or an ion beam (see Patent Document 5), (6) electron beam, gamma ray, X-ray on rod-like carbon A method of converting to onion-like carbon by irradiating a high energy beam such as an ion beam is disclosed (see Patent Document 6).
(7)二重結合または三重結合を持つ炭素材料にX線、マイクロ波および超音波の1種以上を照射し、中空または金属を内包するオニオンライクカーボンを製造する方法が示されている(特許文献7参照)。(8)二重結合または三重結合を持つ材料に光、電子線またはイオンビームを照射し、オニオンライクカーボンを製造する方法も示されている(特許文献8参照)。
(7) A method for producing onion-like carbon containing hollow or metal by irradiating a carbon material having a double bond or triple bond with one or more of X-rays, microwaves and ultrasonic waves (patent) Reference 7). (8) A method for producing onion-like carbon by irradiating a material having a double bond or a triple bond with light, an electron beam or an ion beam is also shown (see Patent Document 8).
(9)アンバランスドマグネトロンスパッタリング法でオニオンライクカーボン膜を製造する方法が示されている(特許文献9参照)。
(9) A method for producing an onion-like carbon film by an unbalanced magnetron sputtering method is disclosed (see Patent Document 9).
(10)SiC粉末とCu粉末の加圧成形体に35万気圧以上、2700℃以上の超高圧・超高温の圧縮衝撃を加えて生成する方法が示されている(特許文献10参照)。
(10) A method of generating a compression molded body of SiC powder and Cu powder by applying a compression impact of 350,000 atmospheres or higher and 2700 ° C. or higher (see Patent Document 10).
更に、放電現象を使用した方法としては、(11)水中で、炭素電極間にアーク放電を発生させ、オニオンライクカーボンを製造する方法が示されている(非特許文献1参照)。
Furthermore, as a method using a discharge phenomenon, (11) a method of producing onion-like carbon by generating an arc discharge between carbon electrodes in water (see Non-Patent Document 1) is shown.
(1)の方法には、ダイヤモンドの高圧合成に相当する高価な装置を必要とし、製造原価も合成ダイヤモンドに匹敵するものと考えられ、汎用的ではない。
(2、3)の方法では、これらの方法は、原料粉末が高価であることから、オニオングラファイトは原料粉末よりさらに高価になるという問題がある。
(4,5,6,7,8)の方法では、これらの方法はいずれも対象とする原料への投入エネルギーが限られており、量産には限界がある。
(9)の方法では、薄膜法ゆえ、オニオンライクカーボン粉末の製造には限界があり、生成速度も低く、量的にも限界がある。
(10)の方法では、高温・高圧という極限環境を作る必要があり装置上の対応が困難であることに加え、合成後の分離精製にも課題を残している。
(11)の方法では、反応の選択率が低く、アモルファス炭素が多量に生成し、分離が困難という問題点がある。 The method (1) requires an expensive apparatus corresponding to high-pressure synthesis of diamond, and the production cost is considered to be comparable to that of synthetic diamond, and is not versatile.
In the methods (2 and 3), since the raw material powder is expensive, there is a problem that onion graphite is more expensive than the raw material powder.
In the methods (4, 5, 6, 7, 8), all of these methods have a limited amount of energy input to the target raw material, and there is a limit to mass production.
In the method (9), because of the thin film method, there is a limit to the production of onion-like carbon powder, the production rate is low, and the quantity is limited.
In the method (10), it is necessary to create an extreme environment of high temperature and high pressure, and it is difficult to cope with the apparatus, and there is also a problem in separation and purification after synthesis.
The method (11) has a problem that the selectivity of the reaction is low, a large amount of amorphous carbon is produced, and separation is difficult.
(2、3)の方法では、これらの方法は、原料粉末が高価であることから、オニオングラファイトは原料粉末よりさらに高価になるという問題がある。
(4,5,6,7,8)の方法では、これらの方法はいずれも対象とする原料への投入エネルギーが限られており、量産には限界がある。
(9)の方法では、薄膜法ゆえ、オニオンライクカーボン粉末の製造には限界があり、生成速度も低く、量的にも限界がある。
(10)の方法では、高温・高圧という極限環境を作る必要があり装置上の対応が困難であることに加え、合成後の分離精製にも課題を残している。
(11)の方法では、反応の選択率が低く、アモルファス炭素が多量に生成し、分離が困難という問題点がある。 The method (1) requires an expensive apparatus corresponding to high-pressure synthesis of diamond, and the production cost is considered to be comparable to that of synthetic diamond, and is not versatile.
In the methods (2 and 3), since the raw material powder is expensive, there is a problem that onion graphite is more expensive than the raw material powder.
In the methods (4, 5, 6, 7, 8), all of these methods have a limited amount of energy input to the target raw material, and there is a limit to mass production.
In the method (9), because of the thin film method, there is a limit to the production of onion-like carbon powder, the production rate is low, and the quantity is limited.
In the method (10), it is necessary to create an extreme environment of high temperature and high pressure, and it is difficult to cope with the apparatus, and there is also a problem in separation and purification after synthesis.
The method (11) has a problem that the selectivity of the reaction is low, a large amount of amorphous carbon is produced, and separation is difficult.
したがって、本発明の目的は、工業的規模で安定的に、オニオンライクカーボンを製造できる方法を提供することにある。
Therefore, an object of the present invention is to provide a method capable of producing onion-like carbon stably on an industrial scale.
本発明者らは、上記目的を達成すべく鋭意検討を重ね、溶媒中、触媒存在下で炭素金属電極間にパルスプラズマを発生することにより、オニオンライクカーボンを得ることができることを見出し、本発明に至った。
The inventors of the present invention have made extensive studies to achieve the above object, and found that onion-like carbon can be obtained by generating pulse plasma between carbon metal electrodes in a solvent in the presence of a catalyst. It came to.
すなわち、本発明によれば、以下のものが提供される。
[1]オニオンライクカーボンの製造方法であって、液体中で炭素電極間にパルスプラズマ放電させることを特徴とするオニオンライクカーボンの製造方法。
[2]グラファイト層間距離が0.40nm以上のオニオンライクカーボン。 That is, according to the present invention, the following is provided.
[1] A method for producing onion-like carbon, which comprises performing pulsed plasma discharge between carbon electrodes in a liquid.
[2] Onion-like carbon having a graphite interlayer distance of 0.40 nm or more.
[1]オニオンライクカーボンの製造方法であって、液体中で炭素電極間にパルスプラズマ放電させることを特徴とするオニオンライクカーボンの製造方法。
[2]グラファイト層間距離が0.40nm以上のオニオンライクカーボン。 That is, according to the present invention, the following is provided.
[1] A method for producing onion-like carbon, which comprises performing pulsed plasma discharge between carbon electrodes in a liquid.
[2] Onion-like carbon having a graphite interlayer distance of 0.40 nm or more.
本発明の製造方法により、オニオンライクカーボンを比較的低電圧、低電流であり、パルス放電を行うなどの低エネルギーで製造することができる。また、本発明のオニオンライクカーボンは、グラファイト層間距離が広く、Liイオン2次電池の電極用途などにも有用である。
By the production method of the present invention, onion-like carbon can be produced with a relatively low voltage, low current, low energy such as pulse discharge. Moreover, the onion-like carbon of the present invention has a wide graphite interlayer distance and is useful for electrode applications of Li ion secondary batteries.
本発明のオニオンライクカーボンは、その形状が同心球状の炭素構造をしているが、グラファイト層間距離が0.40nm以上、より特定的には0.50nm以上であることが特徴的である。このような広いグラファイト層間距離をもったオニオンライクカーボンは先行技術の方法では得られておらず、新規である。グラファイト層間に各種イオンを収容することができ、特に、Liイオン2次電池の電極用途などに有用である。
The onion-like carbon of the present invention has a concentric spherical carbon structure, but is characterized by a graphite interlayer distance of 0.40 nm or more, more specifically 0.50 nm or more. Onion-like carbon having such a wide graphite interlayer distance has not been obtained by the prior art method and is novel. Various ions can be accommodated between the graphite layers, and is particularly useful for electrode applications of Li ion secondary batteries.
本発明のオニオンライクカーボンの製造方法は、液体中に炭素電極間にパルスプラズマ放電させることを特徴とするものであり、炭素電極としては、グラファイト、アモルファスカーボン、グラッシーカーボンなどいずれの炭素材料を使用することができる。
The onion-like carbon production method of the present invention is characterized in that pulse plasma discharge is performed between carbon electrodes in a liquid, and any carbon material such as graphite, amorphous carbon, and glassy carbon is used as the carbon electrode. can do.
電極の形態としては、棒状、針金状、板状などいずれの形態であってもかまわない。両極の大きさに関しても、どちらかの大きさが異なるなどの形状を有していてもかまわない。また、両極は、同一の炭素材料または異なった材料を使用しても良く、単一または複数の炭素材料で成型されたものを使用しても構わない。
The electrode may have any shape such as a rod, wire, or plate. Regarding the size of both poles, it may have a shape such that one of the sizes is different. Moreover, both poles may use the same carbon material or a different material, and may use what was shape | molded by the single or several carbon material.
本発明では、液体中でオニオンライクカーボンを生成させる。使用できる液体(溶媒)としては、特に限定されるものではなく、反応に影響を与えないものであれば、特に制限されない。液体は2種以上の化合物の混合物でもよい。ヘキサン、オクタン、デカン、シクロヘキサン、シクロオクタンなどの飽和炭化水素、ベンゼン、トルエン、キシレン、ナフタレンのような芳香族炭化水素、水、メタノール、エタノール、プロパノール、ブタノール、エチレングリコール、プロピレングリコール、1,4−ブタンジオールなどのアルコール類、酢酸メチル、酢酸エチル、酢酸ブチル、安息香酸メチル、フタル酸ジメチルなどのエステル類、テトラヒドロフラン、テトラヒドロピラン、ジプロピルエーテル、ジブチルエーテル、ジエチレングリコール、テトラエチレングリコールなどのエーテル類を使用することもできる。生成する炭素生成物の分散、引火、酸化性を考慮して、水、飽和炭化水素、芳香族炭化水素およびアルコール類の使用が好ましく、メタノール、エタノールの使用が好ましい。
In the present invention, onion-like carbon is generated in the liquid. The liquid (solvent) that can be used is not particularly limited as long as it does not affect the reaction. The liquid may be a mixture of two or more compounds. Saturated hydrocarbons such as hexane, octane, decane, cyclohexane, cyclooctane, aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, water, methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, 1,4 -Alcohols such as butanediol, esters such as methyl acetate, ethyl acetate, butyl acetate, methyl benzoate and dimethyl phthalate, ethers such as tetrahydrofuran, tetrahydropyran, dipropyl ether, dibutyl ether, diethylene glycol and tetraethylene glycol Can also be used. In consideration of dispersion, flammability, and oxidizability of the produced carbon product, use of water, saturated hydrocarbons, aromatic hydrocarbons and alcohols is preferred, and use of methanol and ethanol is preferred.
液体の使用量としては、特に制限されるものではなく、両電極が液体中にあればよい。より好ましくは、プラズマの発生により液体が飛散したり、生成物濃度によって、液の拡散性がなくならない程度にあればよい。
The amount of liquid used is not particularly limited as long as both electrodes are in the liquid. More preferably, it is sufficient that the liquid scatters due to the generation of plasma or the diffusibility of the liquid is not lost depending on the product concentration.
パルスプラズマ放電させる温度としては、特に制限されるものではなく、使用する液体の種類にも依存する。通常、室温~300℃の範囲で実施される。高すぎる温度では、使用する溶媒の蒸気圧が上がり、プラズマにより引火する可能性があるため好ましくなく、低すぎる温度では、溶媒の粘度が上がり、生成物の拡散性が損なわれるため好ましくない。
The temperature at which the pulse plasma discharge is performed is not particularly limited and depends on the type of liquid used. Usually, it is carried out in the range of room temperature to 300 ° C. An excessively high temperature is not preferable because the vapor pressure of the solvent to be used increases and there is a possibility of being ignited by plasma. An excessively low temperature is not preferable because the viscosity of the solvent increases and the diffusibility of the product is impaired.
本発明では、液体中で炭素電極間にパルスプラズマ放電させることにより、オニオンライクカーボンが生成される。プラズマを発生させる電圧としては、特に制限されるものではなく、20V~500Vの範囲、安全性、特殊な装置の必要性を考慮して、60V~400Vの範囲が好ましく、80V~300Vの範囲がより好ましい。
In the present invention, onion-like carbon is generated by performing pulsed plasma discharge between carbon electrodes in a liquid. The voltage for generating the plasma is not particularly limited, and is preferably in the range of 60V to 400V, and in the range of 80V to 300V in consideration of the necessity of a range of 20V to 500V, safety and special equipment. More preferred.
プラズマを発生させる電流としては、特に制限されるものではなく、0.1~20Aの範囲、エネルギー効率を考慮して、0.2~10Aの範囲で実施することが好ましい。
The current for generating plasma is not particularly limited, and it is preferable that the current be in the range of 0.1 to 20 A and in the range of 0.2 to 10 A in consideration of energy efficiency.
パルスプラズマを与える間隔に関しては、特に制限されるものではないが、5~100ミリ秒が好ましく、6~50ミリ秒のサイクルがより好ましい。プラズマを与える間隔が短すぎると、プラズマ放電により発生した炭素ラジカルの消失前に、更に炭素ラジカルの発生を誘発するため、オニオンライクカーボンへの成長のほか、アモルファス炭素の生成に繋がるため好ましくない。また、長すぎる放電間隔では、プラズマを誘起するために使用されるエネルギーが多く必要となり、オニオンライクカーボンの生成効率が低下するため好ましくない。
The interval for applying the pulsed plasma is not particularly limited, but is preferably 5 to 100 milliseconds, and more preferably 6 to 50 milliseconds. If the plasma application interval is too short, the generation of carbon radicals is further induced before the disappearance of the carbon radicals generated by the plasma discharge, which leads to the growth of onion-like carbon and the formation of amorphous carbon, which is not preferable. In addition, an excessively long discharge interval is not preferable because much energy used for inducing plasma is required, and the production efficiency of onion-like carbon is reduced.
パルスプラズマ1回あたりの持続時間もまた、与える電圧および電流によって異なるが、通常1~50マイクロ秒、放電の効率を考慮して、好ましくは2~30マイクロ秒の範囲で実施される。プラズマ発生時間が長すぎると、プラズマ放電により発生した炭素ラジカルが多量に誘発されるため、オニオンライクカーボンへの成長のほか、アモルファス炭素の生成に繋がり、選択性が低下するため好ましくない。また、短すぎる放電時間では、十分なエネルギーが供給されず、プラズマを誘起するために使用されるエネルギーが多く必要となり、オニオンライクカーボンの生成効率が低下するため好ましくない。
The duration per pulsed plasma also varies depending on the applied voltage and current, but is usually 1 to 50 microseconds, preferably in the range of 2 to 30 microseconds in consideration of discharge efficiency. If the plasma generation time is too long, a large amount of carbon radicals generated by plasma discharge are induced, leading to the growth of onion-like carbon and the generation of amorphous carbon, which reduces the selectivity. Moreover, if the discharge time is too short, sufficient energy is not supplied, and a lot of energy used to induce plasma is required, which is not preferable because the production efficiency of onion-like carbon is reduced.
本発明では、電極に振動を与えることも可能である。振動を与えることで、電極間に析出する炭素化合物の滞留もなく、滞留物上への反応性生物付着を抑制できるだけでなく、放電が効率的に行われるため好ましい。振動を与える方法としては、特に限定されるものではなく、定期的に振動を与えても、間欠的に振動を与える方法でもかまわない。
In the present invention, it is also possible to apply vibration to the electrode. By giving vibration, there is no stagnation of the carbon compound deposited between the electrodes, and it is possible not only to suppress the attachment of the reactive biological material on the stagnation, but also to discharge efficiently, which is preferable. A method for applying vibration is not particularly limited, and a method for applying vibration periodically or a method for applying vibration intermittently may be used.
本発明を実施する雰囲気としては特に限定するものではなく、減圧下、加圧下、常圧下いずれの状態でも実施することができるが、通常、安全、操作性を考慮して、窒素、アルゴンなどの不活性ガス下で実施することができる。
The atmosphere for carrying out the present invention is not particularly limited, and it can be carried out under reduced pressure, under pressure, or under normal pressure, but usually, in consideration of safety and operability, nitrogen, argon, etc. It can be carried out under an inert gas.
生成するオニオンライクカーボンは、液体中に堆積するので、一般的な方法、例えば、ろ過し、使用した液体を減圧等の操作で除去することにより、オニオンライクカーボンを得ることができる。
Since the produced onion-like carbon is deposited in the liquid, it is possible to obtain the onion-like carbon by a general method, for example, filtering and removing the used liquid by an operation such as decompression.
実施例1
300mlビーカーにトルエン200gを取り、直径6mm、長さ100mmの円柱状のグラファイト電極(純度99%以上)2本を該トルエン中に挿入し、電極間を1mmに固定し、電極表面に反応生成物が堆積することを防止して反応効率を高めるために振動を与えた。各電極を交流電源に接続し、200V、2Aでパルス放電した。パルスプラズマの間隔は20ミリ秒、パルスプラズマ1回あたりの持続時間は10マイクロ秒で行った。放電開始と同時に、黒色の粉体が液中に分散して、反応が起こったことが観測された。30分間反応を継続し、既沈降物を分離、黒色溶液を遠心分離、トルエンを適量加えて、洗浄と分離を行った。電極の消費量は、380mgであった。 Example 1
Take 200g of toluene in a 300ml beaker, insert 2 columnar graphite electrodes (purity 99% or more) with a diameter of 6mm and a length of 100mm into the toluene, fix the distance between the electrodes to 1mm, and reaction products on the electrode surface Vibrating was applied to prevent the deposition of and to increase the reaction efficiency. Each electrode was connected to an AC power source and subjected to pulse discharge at 200V and 2A. The interval between pulse plasmas was 20 milliseconds, and the duration per pulse plasma was 10 microseconds. Simultaneously with the start of discharge, it was observed that the black powder was dispersed in the liquid and the reaction occurred. The reaction was continued for 30 minutes, the sediment was separated, the black solution was centrifuged, and an appropriate amount of toluene was added for washing and separation. The consumption of the electrode was 380 mg.
300mlビーカーにトルエン200gを取り、直径6mm、長さ100mmの円柱状のグラファイト電極(純度99%以上)2本を該トルエン中に挿入し、電極間を1mmに固定し、電極表面に反応生成物が堆積することを防止して反応効率を高めるために振動を与えた。各電極を交流電源に接続し、200V、2Aでパルス放電した。パルスプラズマの間隔は20ミリ秒、パルスプラズマ1回あたりの持続時間は10マイクロ秒で行った。放電開始と同時に、黒色の粉体が液中に分散して、反応が起こったことが観測された。30分間反応を継続し、既沈降物を分離、黒色溶液を遠心分離、トルエンを適量加えて、洗浄と分離を行った。電極の消費量は、380mgであった。 Example 1
Take 200g of toluene in a 300ml beaker, insert 2 columnar graphite electrodes (purity 99% or more) with a diameter of 6mm and a length of 100mm into the toluene, fix the distance between the electrodes to 1mm, and reaction products on the electrode surface Vibrating was applied to prevent the deposition of and to increase the reaction efficiency. Each electrode was connected to an AC power source and subjected to pulse discharge at 200V and 2A. The interval between pulse plasmas was 20 milliseconds, and the duration per pulse plasma was 10 microseconds. Simultaneously with the start of discharge, it was observed that the black powder was dispersed in the liquid and the reaction occurred. The reaction was continued for 30 minutes, the sediment was separated, the black solution was centrifuged, and an appropriate amount of toluene was added for washing and separation. The consumption of the electrode was 380 mg.
得られた黒色粉末を真空下加熱乾燥した。得られた黒色粉末は、254.6mgであり、得られた黒色粉末のTEM写真(倍率:10万倍)を図1に(図1のスケールは20nm)、TEM写真(倍率:50万倍)を図2に示す(図2のスケールは10nmであり、図2において層間距離を2つの矢印で示す)。写真から、得られた黒色粉末が、層間距離0.62nmのオニオンライクカーボンであることがわかる。収率は67%であった。
The obtained black powder was dried by heating under vacuum. The obtained black powder is 254.6 mg, and a TEM photograph (magnification: 100,000 times) of the obtained black powder is shown in FIG. 1 (scale of FIG. 1 is 20 nm), and a TEM photograph (magnification: 500,000 times). Is shown in FIG. 2 (the scale of FIG. 2 is 10 nm, and the interlayer distance is shown by two arrows in FIG. 2). From the photograph, it can be seen that the obtained black powder is onion-like carbon having an interlayer distance of 0.62 nm. The yield was 67%.
実施例2
実施例1において、溶媒として水を用いた以外は、実施例1と同様に行った。得られた黒色粉末のTEM写真(倍率:10万倍)を図3(図3のスケールは10nm)、TEM写真(倍率:50万倍)を図4に示す(図4のスケールは5nm)。電極の消費量は412mgであり、得られた黒色粉末は271.9mg、収率は66%であり、写真から、層間距離0.55nmのオニオンライクカーボンであることがわかる。 Example 2
In Example 1, it carried out like Example 1 except having used water as a solvent. A TEM photograph (magnification: 100,000 times) of the obtained black powder is shown in FIG. 3 (scale of FIG. 3 is 10 nm), and a TEM photograph (magnification: 500,000 times) is shown in FIG. 4 (scale of FIG. 4 is 5 nm). The consumption of the electrode was 412 mg, the obtained black powder was 271.9 mg, the yield was 66%, and it can be seen from the photograph that it is onion-like carbon having an interlayer distance of 0.55 nm.
実施例1において、溶媒として水を用いた以外は、実施例1と同様に行った。得られた黒色粉末のTEM写真(倍率:10万倍)を図3(図3のスケールは10nm)、TEM写真(倍率:50万倍)を図4に示す(図4のスケールは5nm)。電極の消費量は412mgであり、得られた黒色粉末は271.9mg、収率は66%であり、写真から、層間距離0.55nmのオニオンライクカーボンであることがわかる。 Example 2
In Example 1, it carried out like Example 1 except having used water as a solvent. A TEM photograph (magnification: 100,000 times) of the obtained black powder is shown in FIG. 3 (scale of FIG. 3 is 10 nm), and a TEM photograph (magnification: 500,000 times) is shown in FIG. 4 (scale of FIG. 4 is 5 nm). The consumption of the electrode was 412 mg, the obtained black powder was 271.9 mg, the yield was 66%, and it can be seen from the photograph that it is onion-like carbon having an interlayer distance of 0.55 nm.
比較例
実施例1において、電極を直流電源に接続し、200V 2Aで連続放電した以外は、実施例1と同様におこなった。得られた黒色粉末は312mgであり、得られた黒色粉末のTEM写真(倍率:20万倍)を図5に示す(図5のスケールは5nm)。同心球状のオニオンライクカーボンは観測されなかった。 Comparative Example The same procedure as in Example 1 was performed except that the electrode was connected to a DC power source and was continuously discharged at 200 V 2A. The obtained black powder is 312 mg, and a TEM photograph (magnification: 200,000 times) of the obtained black powder is shown in FIG. 5 (the scale of FIG. 5 is 5 nm). Concentric spherical onion-like carbon was not observed.
実施例1において、電極を直流電源に接続し、200V 2Aで連続放電した以外は、実施例1と同様におこなった。得られた黒色粉末は312mgであり、得られた黒色粉末のTEM写真(倍率:20万倍)を図5に示す(図5のスケールは5nm)。同心球状のオニオンライクカーボンは観測されなかった。 Comparative Example The same procedure as in Example 1 was performed except that the electrode was connected to a DC power source and was continuously discharged at 200 V 2A. The obtained black powder is 312 mg, and a TEM photograph (magnification: 200,000 times) of the obtained black powder is shown in FIG. 5 (the scale of FIG. 5 is 5 nm). Concentric spherical onion-like carbon was not observed.
本発明の製造方法によれば、オニオンライクカーボンを比較的低電圧、低電流であり、パルス放電を行うなどの低エネルギーで製造することができ、産業上の有用性が大きい。
According to the production method of the present invention, onion-like carbon can be produced with a relatively low voltage, a low current, low energy such as pulse discharge, and has great industrial utility.
Claims (2)
- オニオンライクカーボンの製造方法であって、液体中で炭素電極間にパルスプラズマ放電させることを特徴とするオニオンライクカーボンの製造方法。 An onion-like carbon production method, characterized in that pulsed plasma discharge is performed between carbon electrodes in a liquid.
- グラファイト層間距離が0.40nm以上のオニオンライクカーボン。 An onion-like carbon with a graphite interlayer distance of 0.40 nm or more.
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JP2014152095A (en) * | 2013-02-13 | 2014-08-25 | Nagoya Univ | Method for producing graphene |
CN104209062A (en) * | 2013-05-20 | 2014-12-17 | 燕山大学 | Ultrahigh hard nano twin diamond block material and preparation method thereof |
JP2015227253A (en) * | 2014-05-30 | 2015-12-17 | 国立大学法人 熊本大学 | Graphene dispersion and production method of graphene |
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JP2017222538A (en) * | 2016-06-15 | 2017-12-21 | 国立大学法人 熊本大学 | Method for producing graphene and chemically modified graphene |
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