JPWO2008152680A1 - Method for producing carbon nanosheet - Google Patents
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Abstract
カーボンナノシートを工業的に大量生産することができるカーボンナノシート製造方法を提供することを目的とし、カーボンナノシートの原料を強酸化剤に浸し電気化学酸化反応を生起させる化学酸化処理工程と、洗浄時に超音波を投射する水洗・超音波処理工程と、固液分離する固液分離処理工程と、カーボン固体を乾燥し加熱する乾燥・加熱処理工程と、加熱したカーボン固体を水又はアルカリで洗浄し該洗浄時に超音波を投射する水洗・超音波処理工程と、洗浄し超音波処理を加えたカーボン固体を固液分離する固・液分離処理工程と、固液分離したカーボン固体に水を加え発泡剤を添加してカーボンナノシートを選別する浮遊選別処理工程と、選別したカーボンナノシートを水洗いした後液体とカーボンナノシートを固液分離する水洗・固・液分離処理工程と、乾燥処理工程とを備えている。Aiming at providing a carbon nanosheet manufacturing method that can mass-produce carbon nanosheets industrially, a chemical oxidation treatment process in which a raw material of carbon nanosheets is immersed in a strong oxidizing agent to cause an electrochemical oxidation reaction, Water washing / ultrasonic treatment process for projecting sound waves, solid-liquid separation treatment process for solid-liquid separation, drying / heat treatment process for drying and heating carbon solids, and washing the heated carbon solids with water or alkali Water washing / sonication process that sometimes projects ultrasonic waves, solid / liquid separation treatment process for solid-liquid separation of the washed and ultrasonically treated carbon solid, and water added to the solid-liquid separated carbon solid to add foaming agent Floating sorting process that sorts carbon nanosheets by addition, and water that separates liquid and carbon nanosheets after washing the sorted carbon nanosheets with water · Comprises solid and, liquid separation process, and a drying step.
Description
本発明は、フレイク状の黒鉛（グラファイト）粉末等を原料としたカーボンナノシートの製造方法に関する。 The present invention relates to a method for producing a carbon nanosheet using flaky graphite (graphite) powder or the like as a raw material.
ナノスケール即ち原子、分子のレベルで精密に調整した材料や素子を作り出そうという試みが近年盛んになってきた。ナノ材料で現在最も注目され、研究が進展しているのがカーボン系である。炭素といえば、結晶構造により黒鉛にもダイヤモンドにもなる材料であることがよく知られているが、さらに近年、中空の針状分子であるカーボンナノチューブ、サッカーボール状分子であるフラーレンといったナノ構造体が発見された。また高純度の同軸カーボンナノチューブシートが従来知られている（例えば特許文献１参照）。
炭素は数ある元素の中でも非常に多様性のある変幻自在な材料であることが明らかになりつつある。カーボンナノシートはそのひとつである。カーボンナノシートの特徴はその形状である。結晶構造の基本最小単位を取り出したものであることから、厚さは１〜数十ｎｍ前後と原子数個分しかないのに対して、横サイズは通常ミクロン以上であり、極めて高い２次元異方性を持っている。ナノスケールと極めて高い２次元異方性によってカーボンナノシートは高い反応性、大比表面積、量子閉じこめ効果と高導電性などの特性を持つ。しかるに現在、このカーボンナノシートの製造方法の報告例はまだない。
本発明はカーボンナノシートの製造方法を提供することを目的とし、簡便に工業的な生産が可能な方法を提供することを目的とする。 It is becoming clear that carbon is an extremely versatile material among many elements. Carbon nanosheets are one of them. The feature of the carbon nanosheet is its shape. Since the basic minimum unit of the crystal structure is taken out, the thickness is only about 1 to several tens of nanometers and several atoms, whereas the lateral size is usually more than a micron and extremely high two-dimensional difference. Has a direction. Carbon nanosheets have high reactivity, large specific surface area, quantum confinement effect and high conductivity due to nanoscale and extremely high two-dimensional anisotropy. However, there are no reports on the method for producing this carbon nanosheet.
An object of this invention is to provide the manufacturing method of a carbon nanosheet, and it aims at providing the method which can be industrially produced simply.
上記目的を達成するため本発明は、フレイク状のカーボン固体よりなる粉状のカーボンナノシート原料を強酸化剤に浸し電気化学酸化反応を生起させる化学酸化処理工程と、前記化学酸化処理工程で酸化させたカーボンナノシート原料を水又はアルカリで洗浄し該洗浄時に超音波を投射する水洗・超音波処理工程と、前記水洗いしたカーボンナノシートの原料を遠心分離機・ろ過機により液体とカーボン固体とに固液分離する固・液分離処理工程と、前記固液分離した後のカーボン固体を乾燥し加熱する乾燥・加熱処理工程と、前記乾燥し加熱したカーボン固体を水又はアルカリで洗浄し該洗浄時に超音波を投射する水洗・超音波処理工程と、前記洗浄し超音波処理を加えたカーボン固体を遠心分離機・ろ過機により液体とカーボン固体とに固液分離する固・液分離処理工程と、前記固液分離したカーボン固体に水を加え発泡剤を添加してカーボンナノシートを選別する浮遊選別処理工程と、選別したカーボンナノシートを水洗いした後液体とカーボンナノシートを固液分離する水洗・固・液分離処理工程と、前記固液分離したカーボンナノシートを乾燥する乾燥処理工程とを備えたものである。
また本発明は、前記カーボンナノシート原料は、カーボンブラック、アセチレンブラック、グラファイト又はグラファイト酸化物の中のいずれかであることを特徴とする。
また本発明は、前記化学酸化処理工程において、酸化剤を添加したものである。
また本発明は、前記酸化剤として、濃硫酸と濃シュウ酸の混合酸、過酸化水素、オゾン、過酸化ナトリウム、過酸化カリウム、過マンガン酸ナトリウム、過硫酸のような無機過酸化物、過シュウ酸、過酢酸、過酸化ベンゾイル、ペルフルオロ過酢酸などの有機過酸化物の中のいずれかを用いたことを特徴とする。
また本発明は、前記酸化剤として、濃硫酸と濃シュウ酸の混合酸を用いたことを特徴とする。
また本発明は、前記酸化剤として、過酸化水素を用いたことを特徴とする。
また本発明は、前記浮遊選別処理工程において、捕収剤を添加したことを特徴とする。
また本発明は、前記浮遊選別処理工程において、空気を導入することによってカーボンナノシートを無数の泡に吸着させカーボンナノシートが泡とともに浮上するようにしたものである。In order to achieve the above object, the present invention comprises a chemical oxidation treatment step in which a powdery carbon nanosheet raw material made of a flake-like carbon solid is immersed in a strong oxidizing agent to cause an electrochemical oxidation reaction, and is oxidized in the chemical oxidation treatment step. The carbon nanosheet raw material is washed with water or alkali, and a water washing / ultrasonic treatment process for projecting ultrasonic waves at the time of the washing, and the water-washed carbon nanosheet raw material is solid-liquid into a liquid and a carbon solid by a centrifuge / filter. A solid / liquid separation treatment step for separating, a drying / heating treatment step for drying and heating the carbon solid after the solid-liquid separation, and washing the dried and heated carbon solid with water or an alkali and performing ultrasonic treatment during the washing. The water washing and ultrasonic treatment process for projecting and the carbon solid after the washing and ultrasonic treatment are converted into a liquid and a carbon solid by a centrifuge / filter. A solid / liquid separation process for liquid separation, a floating sorting process for sorting the carbon nanosheets by adding water to the solid-liquid separated carbon solid and adding a foaming agent, and washing the sorted carbon nanosheets with water and carbon It comprises a water washing / solid / liquid separation treatment step for solid-liquid separation of the nanosheet, and a drying treatment step for drying the solid-liquid separated carbon nanosheet.
In the invention, it is preferable that the carbon nanosheet raw material is any one of carbon black, acetylene black, graphite, and graphite oxide.
In the present invention, an oxidizing agent is added in the chemical oxidation treatment step.
In the present invention, the oxidizing agent may be a mixed acid of concentrated sulfuric acid and concentrated oxalic acid, hydrogen peroxide, ozone, sodium peroxide, potassium peroxide, sodium permanganate, an inorganic peroxide such as persulfuric acid, peroxide. Any one of organic peroxides such as oxalic acid, peracetic acid, benzoyl peroxide, and perfluoroperacetic acid is used.
Further, the present invention is characterized in that a mixed acid of concentrated sulfuric acid and concentrated oxalic acid is used as the oxidizing agent.
The present invention is characterized in that hydrogen peroxide is used as the oxidizing agent.
Further, the present invention is characterized in that a collecting agent is added in the floating sorting process.
Further, the present invention is such that in the floating sorting process step, air is introduced to adsorb carbon nanosheets to a myriad of bubbles so that the carbon nanosheets float with the bubbles.
サイズ２００〜２０００ナノメートル、厚み１０〜５０ナノメートルのカーボンナノシートを工業的に大量生産することができる。 Carbon nanosheets having a size of 200 to 2000 nanometers and a thickness of 10 to 50 nanometers can be industrially mass-produced.
以下に本発明の実施の形態を添付した図面を参照して詳細に説明する。
ナノシートはインターカレーションにより、無機層状化合物のホスト層を１枚ずつ剥離することによって得られる物質で、厚さ１〜数十ナノメートル（１ナノメートル＝１０−９メートル）、横方向のサイズが数百ナノメートルと高い形状異方性を持つことから、バルク物質には見られない様々な特徴がある。Embodiments of the present invention will be described below in detail with reference to the accompanying drawings.
A nanosheet is a substance obtained by exfoliating a host layer of an inorganic layered compound one by one by intercalation, and has a thickness of 1 to several tens of nanometers (1 nanometer = 10 −9 meters) and a lateral size. Since it has a high shape anisotropy of several hundred nanometers, it has various characteristics not found in bulk materials.
本発明のカーボンナノシートとしては、たとえばカーボンブラック、アセチレンブラック、グラファイト又はグラファイト酸化物などのナノシートであり、これらは層状の炭素、たとえばカーボンブラック、アセチレンブラック、グラファイト又はその酸化物たとえばグラファイト酸化物などを膨潤及び剥離させて得ることができる。これらの層状体はいずれも層間に無機、有機化合物をインターカレートすれば膨潤性を示すが剥離性の観点からはグラファイト酸化物が好ましい。 Examples of the carbon nanosheet of the present invention include nanosheets such as carbon black, acetylene black, graphite or graphite oxide, and these include layered carbon such as carbon black, acetylene black, graphite or oxide thereof such as graphite oxide. It can be obtained by swelling and peeling. Any of these layered bodies exhibits swelling properties when an inorganic or organic compound is intercalated between the layers, but graphite oxide is preferred from the viewpoint of peelability.
この層状のグラファイト酸化物を十分に剥離させるには、酸化物層間のプロトンをアルカリで処理し、イオン交換させればよい。このようなアルカリとして、アルカリ金属の水酸化物やアンモニア、有機アンモニウムの水酸化物などを用いることができるが、層間のプロトンをイオン交換できるアルカリであれば特に制限はない。またポリオキシエチレン、ドデシル硫酸塩などの界面活性剤を用いて行うこともできる。
次に本発明に係るカーボンナノシートの製造方法の実施の形態について説明する。In order to sufficiently exfoliate the layered graphite oxide, protons between the oxide layers may be treated with an alkali and ion exchanged. As such an alkali, an alkali metal hydroxide, ammonia, an organic ammonium hydroxide, or the like can be used, but there is no particular limitation as long as it is an alkali capable of ion exchange of protons between layers. Moreover, it can also carry out using surfactant, such as polyoxyethylene and dodecyl sulfate.
Next, an embodiment of a method for producing a carbon nanosheet according to the present invention will be described.
図１はカーボンナノシートの製造工程を示す流れ図である。本発明に係るカーボンナノシートの原料は、人造又は天然のフレイク状の黒鉛（グラファイト）粉末が用いられる。原料としては、たとえばカーボンブラック、アセチレンブラック、グラファイト酸化物を用いることができる。本実施形態では、グラファイトを用いた場合について説明する。 FIG. 1 is a flowchart showing a manufacturing process of a carbon nanosheet. As a raw material of the carbon nanosheet according to the present invention, artificial or natural flaky graphite (graphite) powder is used. As a raw material, for example, carbon black, acetylene black, or graphite oxide can be used. In this embodiment, a case where graphite is used will be described.
［化学酸化処理］
前記原料を強酸化剤の中に浸し、電気化学酸化反応を生起させる。この化学酸化処理において、電気化学酸化反応をより迅速に進めるためには、酸化の促進剤として、酸化剤の添加が好ましい。このような酸化剤としては、たとえば濃硫酸と濃シュウ酸の混合酸、過酸化水素、オゾン、過酸化ナトリウム、過酸化カリウム、過マンガン酸ナトリウム、過硫酸のような無機過酸化物、過シュウ酸、過酢酸、過酸化ベンゾイル、ペルフルオロ過酢酸などの有機過酸化物が用いられるが、入手が容易で取り扱い易い点で濃硫酸と濃シュウ酸の混合酸又は、過酸化水素が好ましい。グラファイトと混合酸化物添加の比率はグラファイト質量に対し１〜１０倍の範囲が好ましい。できれば４〜６倍が良い。[Chemical oxidation treatment]
The raw material is immersed in a strong oxidizing agent to cause an electrochemical oxidation reaction. In this chemical oxidation treatment, in order to advance the electrochemical oxidation reaction more rapidly, it is preferable to add an oxidant as an oxidation accelerator. Examples of such oxidizing agents include mixed acids of concentrated sulfuric acid and concentrated oxalic acid, hydrogen peroxide, ozone, sodium peroxide, potassium peroxide, sodium permanganate, inorganic peroxides such as persulfuric acid, and persulfuric acid. Organic peroxides such as acid, peracetic acid, benzoyl peroxide, and perfluoroperacetic acid are used, but a mixed acid of concentrated sulfuric acid and concentrated oxalic acid or hydrogen peroxide is preferable because it is easily available and easy to handle. The ratio of graphite and mixed oxide addition is preferably in the range of 1 to 10 times the graphite mass. 4-6 times better if possible.
図２はインターカレーション量と混合酸（濃硫酸／濃シュウ酸）の混合比率の関係を示している。インターカレーションとは、無機層状結晶の層と層の間に、異種の分子やイオンを取り込ませる反応を意味し、インターカレーションによってできる物質は、無機シートの間に分子が組織的に配置されたハイブリッドである。
グラファイトの酸化時間は、１０〜１５０分の範囲が好ましい。できれば３０〜６０分が良い。図３はインターカレーション量とグラファイトの酸化時間の関係を示している。FIG. 2 shows the relationship between the amount of intercalation and the mixing ratio of mixed acid (concentrated sulfuric acid / concentrated oxalic acid). Intercalation means a reaction that incorporates different types of molecules and ions between layers of inorganic layered crystals. In intercalation, substances are systematically arranged between inorganic sheets. Hybrid.
The oxidation time of graphite is preferably in the range of 10 to 150 minutes. 30-60 minutes is good if possible. FIG. 3 shows the relationship between the amount of intercalation and the oxidation time of graphite.
［水洗、超音波処理］
酸化したグラファイトは更に水又はアルカリの溶液で洗浄する。洗浄するとき、強力な超音波処理を加える。この超音波エネルギーの強度は５００Ｗ／ｃｍ２以上が好ましい。処理時間は１時間から１２時間までが良いが、２〜３時間が好ましい。
［固・液分離処理］
次に、酸化したグラファイトの固体と水分とを遠心分離機とろ過機とを用いて、固液分離する。この工程は一回又は複数回必要な場合がある。[Washing, ultrasonic treatment]
The oxidized graphite is further washed with water or an alkaline solution. When washing, apply powerful sonication. The intensity of the ultrasonic energy is preferably 500 W / cm 2 or more. The treatment time is preferably 1 to 12 hours, but preferably 2 to 3 hours.
[Solid / liquid separation]
Next, the solid and moisture of the oxidized graphite are subjected to solid-liquid separation using a centrifuge and a filter. This step may be required once or multiple times.
［乾燥・加熱処理］
遠心分離機により得た固体は更に乾燥機で乾燥させる。この乾燥は５０〜１２０度Ｃの温度で行うが、８０度Ｃより低い温度が好ましい。更に乾燥させた固体を電気炉の中で加熱する。この加熱は５００〜１２００度Ｃの温度で行うが、８００度Ｃが好ましい。加熱時間は短い方が好ましく、たとえば１分間加熱する。以上のインターカレーション処理によりナノハイブリッドと呼ばれる層状のグラファイト酸化物が生成される。[Drying and heat treatment]
The solid obtained by the centrifuge is further dried by a dryer. This drying is performed at a temperature of 50 to 120 ° C., but a temperature lower than 80 ° C. is preferable. Further, the dried solid is heated in an electric furnace. This heating is performed at a temperature of 500 to 1200 ° C., preferably 800 ° C. A shorter heating time is preferable, for example, heating is performed for 1 minute. Through the above intercalation treatment, a layered graphite oxide called nanohybrid is generated.
［水洗・超音波処理］
上記の層状のグラファイト酸化物を膨潤させ、剥離させてカーボンナノシートを得るには、層状のグラファイト酸化物を水中に分散させ洗浄する。洗浄するとき、強力な超音波投射処理が好ましい。超音波のエネルギーは、５００Ｗ／ｃｍ２が好ましい。またこの超音波処理時間は１時間から１２時間までが良いが、２〜３時間が好ましい。[Washing / Sonication]
In order to swell and exfoliate the above layered graphite oxide to obtain a carbon nanosheet, the layered graphite oxide is dispersed in water and washed. When cleaning, a powerful ultrasonic projection process is preferred. The ultrasonic energy is preferably 500 W / cm 2 . The sonication time is preferably 1 to 12 hours, but preferably 2 to 3 hours.
［固・液分離処理］
超音波処理をした後、水洗いした層状のグラファイト酸化物を遠心分離機・ろ過機の中でアルカリ又は界面活性剤を添加して振り混ぜる。アルカリ又は界面活性剤の添加量はグラファイト酸化物の性質で異なってくるが、その混合物のＰＨは、１〜７の範囲で、好ましくは３〜４の範囲が良い。遠心分離機・ろ過機の中で層状のグラファイト酸化物は固液分離される。[Solid / liquid separation]
After ultrasonic treatment, the layered graphite oxide washed with water is added with an alkali or a surfactant in a centrifuge / filter and shaken. The amount of alkali or surfactant added varies depending on the nature of the graphite oxide, but the pH of the mixture is in the range of 1 to 7, preferably in the range of 3 to 4. The layered graphite oxide is solid-liquid separated in the centrifuge / filter.
［浮遊選別処理］
更に固液分離された固体は、浮遊選別機により、カーボンナノシートが選別される。当該浮遊選別処理工程における残渣（残り滓）は化学酸化処理工程に戻され、化学酸化処理工程と浮遊選別処理工程が繰り返し実行される。当該工程ではカーボンナノシートを選別するため、固体に水を加える。この水の添加量はカーボン固体物の濃度が５〜２０％となるようにし、できれば１０％の濃度が好ましい。[Floating sorting process]
Furthermore, carbon nanosheets are separated from the solid separated into solid and liquid by a floating sorter. The residue (residual residue) in the floating sorting process is returned to the chemical oxidation process, and the chemical oxidation process and the floating sorting process are repeated. In this process, water is added to the solid in order to select the carbon nanosheet. The amount of water added is such that the concentration of the carbon solid is 5 to 20%, preferably 10%.
さらに本工程において選別に使用される捕収剤としては、ケロシン（灯油）、ディーゼル油、重油などの炭化水素基を有する油系捕収剤（捕収油）やタール油が好ましい。捕収剤の添加量は水溶液質量に対して５０〜２００ｇ／ｔ（グラム／トン）とするが、１００ｇ／ｔが好ましい。更に本工程で添加される発泡剤はＭＩＢＣ（メチルイソブチルカルビノール）に代表される芳香族アルコール系の非イオン浮遊選別剤や不飽和炭化水素系列のパイン油などが好ましく、添加量はカーボン固体物に対して５０〜３００ｇ／ｔとするが、１００ｇ／ｔが好ましい。 Furthermore, as the collection agent used for selection in this step, oil-based collection agents (collection oil) having a hydrocarbon group such as kerosene (kerosene), diesel oil, heavy oil, and tar oil are preferable. Although the addition amount of a collection agent shall be 50-200 g / t (gram / ton) with respect to aqueous solution mass, 100 g / t is preferable. Further, the blowing agent added in this step is preferably an aromatic alcohol-based nonionic floating sorter represented by MIBC (methyl isobutyl carbinol) or an unsaturated hydrocarbon series pine oil, and the amount added is a carbon solid. However, it is preferably 100 g / t.
また、このとき油系捕収剤を使用せず発泡剤のみの添加でもカーボンナノシートを選別することが可能である。更にカーボンナノシートを浮遊選別機で撹拌しながら、スラリーの中に空気を導入することによって、カーボンナノシートが無数の泡に吸着され、泡とともに浮上し、これによってカーボンナノシートの選出が可能となる。導入する空気量は１ｍ３スラリーに対して０．０５〜０．２ｍ３とするが、０．１ｍ３が好ましい。Further, at this time, the carbon nanosheet can be selected by adding only the foaming agent without using the oil-based collector. Furthermore, by introducing air into the slurry while stirring the carbon nanosheets with a floating sorter, the carbon nanosheets are adsorbed by countless bubbles and floated together with the bubbles, which makes it possible to select the carbon nanosheets. The amount of air introduced is a 0.05～0.2M 3 against 1 m 3 slurry, preferably 0.1 m 3.
［水洗・固・液分離処理］
選別したカーボンナノシートは、水洗いされ、且つ遠心分離機・ろ過機で固液分離が行われる。
［乾燥処理］
固液分離されたカーボンナノシートは２３０度Ｃで乾燥される。
以上の工程によって、サイズ２００〜２０００ナノメートル、厚み１０〜５０ナノメートルのカーボンナノシートを大量に製造することができる。[Washing / Solid / Liquid separation]
The selected carbon nanosheet is washed with water and subjected to solid-liquid separation with a centrifuge / filter.
[Drying process]
The solid-liquid separated carbon nanosheet is dried at 230 ° C.
Through the above steps, carbon nanosheets having a size of 200 to 2000 nanometers and a thickness of 10 to 50 nanometers can be produced in large quantities.
本発明は、サイズ２００〜２０００ナノメートル、厚み１０〜５０ナノメートルのカーボンナノシートを大量に製造することができるので、その製品カーボンナノシートはアルカリ電池、リチウム電池、電気二重層キャパシタ、導電塗料などの分野に広く応用できる。 Since the present invention can produce a large amount of carbon nanosheets having a size of 200 to 2000 nanometers and a thickness of 10 to 50 nanometers, the product carbon nanosheets can be used for alkaline batteries, lithium batteries, electric double layer capacitors, conductive paints, etc. Widely applicable in the field.
上記目的を達成するため本発明は、フレイク状のカーボン固体よりなる粉状のカーボンナノシート原料を強酸化剤に浸し電気化学酸化反応を生起させる化学酸化処理工程と、前記化学酸化処理工程で酸化させたカーボンナノシート原料を水又はアルカリで洗浄し該洗浄時に超音波を投射する水洗・超音波処理工程と、前記水洗いしたカーボンナノシートの原料を遠心分離機・ろ過機により液体とカーボン固体とに固液分離する固・液分離処理工程と、前記固液分離した後のカーボン固体を乾燥し加熱する乾燥・加熱処理工程と、前記乾燥し加熱したカーボン固体を水又はアルカリで洗浄し該洗浄時に超音波を投射する水洗・超音波処理工程と、前記洗浄し超音波処理を加えたカーボン固体を遠心分離機・ろ過機により液体とカーボン固体とに固液分離する固・液分離処理工程と、前記固液分離したカーボン固体に水を加え発泡剤を添加してカーボンナノシートを選別する浮遊選別処理工程と、選別したカーボンナノシートを水洗いした後液体とカーボンナノシートを固液分離する水洗・固・液分離処理工程と、前記固液分離したカーボンナノシートを乾燥する乾燥処理工程とを備えたものである。
また本発明は、前記カーボンナノシート原料は、カーボンブラック、アセチレンブラック、グラファイト又はグラファイト酸化物の中のいずれかであることを特徴とする。
また本発明は、前記化学酸化処理工程において、酸化剤を添加したものである。
また本発明は、前記酸化剤として、濃硫酸と濃ショウ酸の混合酸、過酸化水素、オゾン、過酸化ナトリウム、過酸化カリウム、過マンガン酸ナトリウム、過硫酸のような無機過酸化物、過シュウ酸、過酢酸、過酸化ベンゾイル、ペルフルオロ過酢酸などの有機過酸化物の中のいずれかを用いたことを特徴とする。
また本発明は、前記酸化剤として、濃硫酸と濃ショウ酸の混合酸を用いたことを特徴とする。
また本発明は、前記酸化剤として、過酸化水素を用いたことを特徴とする。
また本発明は、前記浮遊選別処理工程において、捕収剤を添加したことを特徴とする。
また本発明は、前記浮遊選別処理工程において、空気を導入することによってカーボンナノシートを無数の泡に吸着させカーボンナノシートが泡とともに浮上するようにしたものである。
In order to achieve the above object, the present invention includes a chemical oxidation treatment step in which a powdery carbon nanosheet raw material made of a flake-like carbon solid is immersed in a strong oxidizing agent to cause an electrochemical oxidation reaction, and is oxidized in the chemical oxidation treatment step. The carbon nanosheet raw material is washed with water or alkali, and a water washing / ultrasonic treatment process for projecting ultrasonic waves at the time of the washing, and the water-washed carbon nanosheet raw material is solid-liquid into a liquid and a carbon solid by a centrifuge / filter. A solid / liquid separation treatment step for separating, a drying / heating treatment step for drying and heating the carbon solid after the solid-liquid separation, and washing the dried and heated carbon solid with water or an alkali and performing ultrasonic treatment during the washing. The water washing and ultrasonic treatment process for projecting and the carbon solid after the washing and ultrasonic treatment are converted into a liquid and a carbon solid by a centrifuge / filter. A solid / liquid separation process for liquid separation, a floating sorting process for sorting the carbon nanosheets by adding water to the solid-liquid separated carbon solid and adding a foaming agent, and washing the sorted carbon nanosheets with water and carbon A water washing / solid / liquid separation treatment step for solid-liquid separation of the nanosheet and a drying treatment step for drying the carbon-nanosheet separated by solid-liquid separation are provided.
In the invention, it is preferable that the carbon nanosheet raw material is any one of carbon black, acetylene black, graphite, and graphite oxide.
In the present invention, an oxidizing agent is added in the chemical oxidation treatment step.
The present invention, as the oxidizing agent, a mixed acid of concentrated sulfuric acid and stiffness ® c acid, hydrogen peroxide, ozone, sodium peroxide, potassium peroxide, sodium permanganate, inorganic peroxides such as persulfate Any one of organic peroxides such as peroxalic acid, peracetic acid, benzoyl peroxide, and perfluoroperacetic acid is used.
The present invention, as the oxidizing agent, characterized by using a mixed acid of concentrated sulfuric acid and stiffness ® c acid.
The present invention is characterized in that hydrogen peroxide is used as the oxidizing agent.
Further, the present invention is characterized in that a collecting agent is added in the floating sorting process.
Further, the present invention is such that in the floating sorting process step, by introducing air, the carbon nanosheets are adsorbed by countless bubbles so that the carbon nanosheets float together with the bubbles.
［化学酸化処理］
前記原料を強酸化剤の中に浸し、電気化学酸化反応を生起させる。この化学酸化処理において、電気化学酸化反応をより迅速に進めるためには、酸化の促進剤として、酸化剤の添加が好ましい。このような酸化剤としては、たとえば濃硫酸と濃ショウ酸の混合酸、過酸化水素、オゾン、過酸化ナトリウム、過酸化カリウム、過マンガン酸ナトリウム、過硫酸のような無機過酸化物、過シュウ酸、過酢酸、過酸化ベンゾイル、ペルフルオロ過酢酸などの有機過酸化物が用いられるが、入手が容易で取り扱い易い点で濃硫酸と濃ショウ酸の混合酸又は、過酸化水素が好ましい。グラファイトと混合酸化物添加の比率はグラファイト質量に対し１〜１０倍の範囲が好ましい。できれば４〜６倍が良い。
[Chemical oxidation treatment]
The raw material is immersed in a strong oxidizing agent to cause an electrochemical oxidation reaction. In this chemical oxidation treatment, in order to advance the electrochemical oxidation reaction more rapidly, it is preferable to add an oxidant as an oxidation accelerator. Such oxidizing agents, e.g. mixed acid, hydrogen peroxide, ozone, sodium peroxide in concentrated sulfuric acid and stiffness ® c acid, potassium peroxide, sodium permanganate, inorganic peroxides such as peracetic acid, excessive oxalate, peracetic acid, benzoyl peroxide, and organic peroxides such as perfluoro peracetic acid is used, a mixed acid of concentrated sulfuric acid and stiffness ® c acid in terms of ease of handling and ready availability, or hydrogen peroxide preferable. The ratio of graphite and mixed oxide addition is preferably in the range of 1 to 10 times the graphite mass. 4-6 times better if possible.
図２はインターカレーション量と混合酸（濃硫酸Ｈ ２ ＳＯ ４ ／濃ショウ酸ＨＮＯ ３ ）の混合比率の関係を示している。インターカレーションとは、無機層状結晶の層と層の間に、異種の分子やイオンを取り込ませる反応を意味し、インターカレーションによってできる物質は、無機シートの間に分子が組織的に配置されたハイブリッドである。
グラファイトの酸化時間は、１０〜１５０分の範囲が好ましい。できれば３０〜６０分が良い。図３はインターカレーション量とグラファイトの酸化時間の関係を示している。
Figure 2 shows the relationship between the mixing ratio of intercalation amount of mixed acid (concentrated sulfuric acid H 2 SO 4 / waist ® U acid HNO 3). Intercalation means a reaction that incorporates different types of molecules and ions between layers of inorganic layered crystals. In intercalation, substances are systematically arranged between inorganic sheets. Hybrid.
The oxidation time of graphite is preferably in the range of 10 to 150 minutes. 30-60 minutes is good if possible. FIG. 3 shows the relationship between the amount of intercalation and the oxidation time of graphite.
Claims (8)
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| JP2011195432A (en) * | 2010-02-26 | 2011-10-06 | Sekisui Chem Co Ltd | Method for producing flaky graphite and flaky graphite |
| CN103253662B (en) * | 2013-06-01 | 2015-04-15 | 上海轻丰新材料科技有限公司 | Large-scale controllable low-cost graphene preparation method |
| CN103288078B (en) * | 2013-07-05 | 2016-01-20 | 何钊 | The preparation method of graphene oxide |
| JP6538415B2 (en) * | 2015-04-28 | 2019-07-03 | 株式会社ダイセル | Method of oxidizing carbon material, graphene oxide and composition |
| CN104891474B (en) * | 2015-05-26 | 2017-04-12 | 南昌大学 | Method for preparing ultrathin carbon nanosheets |
| CN106044756B (en) * | 2016-05-31 | 2019-05-24 | 湖北航天化学技术研究所 | A kind of method of graphene oxide functional modification |
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