CN103570006A

CN103570006A - Preparation method of graphene

Info

Publication number: CN103570006A
Application number: CN201210268343.7A
Authority: CN
Inventors: 周明杰; 袁新生; 王要兵
Original assignee: Oceans King Lighting Science and Technology Co Ltd; Shenzhen Oceans King Lighting Engineering Co Ltd
Current assignee: Oceans King Lighting Science and Technology Co Ltd; Shenzhen Oceans King Lighting Science and Technology Co Ltd; Shenzhen Oceans King Lighting Engineering Co Ltd
Priority date: 2012-07-31
Filing date: 2012-07-31
Publication date: 2014-02-12

Abstract

The invention provides a preparation method of grapheme, and the preparation method comprises the following steps: cleaning a metal substrate and drying, putting into a reaction chamber of chemical vapor deposition equipment, vacuumizing, heating the metal substrate to 300 to 500 DEG C, starting surface wave plasma equipment to the power of 2 ~ 5kW, introducing a protective gas with the flow rate of 50-500sccm, then introducing a carbon containing gas with the flow rate of 10-500sccm, reacting for 30 ~ 300min to obtain the graphene on the surface of the metal substrate, wherein, in the reaction chamber, the volume ratio of carbon containing gas to protective gas being 1:1 to 1:10. The preparation method provided by the invention is low in reaction temperature, short in reaction time, and high in preparation efficiency and output.

Description

A kind of preparation method of Graphene

Technical field

The invention belongs to the synthetic preparation field of new carbon, particularly relate to a kind of preparation method of Graphene.

Background technology

Graphene is a kind of Two-dimensional Carbon atomic crystal of the discoveries such as the strong K sea nurse of the peace moral of Univ Manchester UK in 2004 (Andre K.Geim), and obtains the physics Nobel prize in 2010, again causes carbon material research boom.It,, owing to having unique structure and photoelectric property, becomes the study hotspot in the fields such as carbon material, nanotechnology, Condensed Matter Physics and functional materials, has attracted many scientific workers.Graphene has good conduction, heat conductivility and low thermal expansivity, can be used for preparing electrode materials, matrix material etc.

Preparing at present Graphene method has a lot, as chemistry redox method, chemical Vapor deposition process, mechanically peel method etc., at present these methods respectively have shortcoming at aspects such as the quality of Graphene, output, temperature of reaction, and for example the standby Graphene lattice defect of chemistry redox legal system is many, of poor quality; Conventional chemical vapour deposition process temperature of reaction is high; Mechanically peel method yields poorly.In addition, the application of plasma body in preparing graphene through chemical vapor deposition has been reported, see the method for a patent application CN102260858A(growing graphene in various substrates), but in the method, use radio-frequency plasma, energy distribution, in whole reaction chamber, makes the temperature of reaction process high (500～1200 ℃).

Summary of the invention

For addressing the above problem, the present invention aims to provide a kind of preparation method of Graphene, is that a kind of surface wave plasma that utilizes carries out chemical vapour deposition, reaction energy is concentrated on to substrate surface, and then low temperature is prepared the method for Graphene.

The preparation method of a kind of Graphene provided by the invention, comprises the following steps:

Clean metal substrate is also dry, put into the reaction chamber of chemical vapor depsotition equipment, vacuumize, metal base is heated to 300～500 ℃, and opening surface wave plasma equipment to power is 2～5kW, then passes into the shielding gas that flow is 50 ~ 500sccm, pass into subsequently the carbonaceous gas that flow is 10 ~ 500sccm, the maintenance reaction times is 30 ~ 300min, and stopped reaction, makes Graphene in metal substrate surface; Wherein, in reaction chamber, the volume ratio of carbonaceous gas and shielding gas is 1:1～1:10.

At power, be under 2～5kW, the energy suitable size producing in metal substrate surface, thus generating structure is complete, the Graphene that defect is few.Preferably, the power of described surface wave plasma equipment is 2.5～4kW.

The density of reactant in the corresponding reaction process of gas pressure intensity in reaction chamber, with together with the power of gas flow and surface wave plasma equipment, affects structure and the performance of final reacting product.After reaction finishes, be cooled to reaction chamber in the process of room temperature and be also full of protection gas.Preferably, in described reaction process, controlling operating pressure in reaction chamber is 100 ~ 1000Pa, and operating pressure is gas pressure intensity in reaction chamber.More preferably, controlling operating pressure in reaction chamber is 150 ~ 800Pa.

Preferably, described metal base specifically can be: a kind of or its arbitrary combination in iron foil, Copper Foil, nickel foil, cobalt paper tinsel or aluminium foil.Described clean metal substrate is to carry out ultrasonic cleaning with organic solvent and deionized water.Described organic solvent is one or both in ethanol or acetone, and the similar organic solvent of other character is also available, and the object of cleaning is to remove the greasy dirt of metal substrate surface.

Preferably, described in, be evacuated to 0.1 ~ 10Pa.Be evacuated to 0.1 ~ 10Pa to get rid of the air in reaction chamber as far as possible.

Preferably, described carbonaceous gas specifically can be: a kind of or its arbitrary combination in methane, ethane, acetylene or ethanol.

Preferably, described shielding gas specifically can be: a kind of or its arbitrary combination in nitrogen or rare gas element.

In metal substrate surface, make after Graphene, remove metal base, with washed with de-ionized water to filtrate, be neutral, in 80～100 ℃ of dry 1～2h, obtain Graphene subsequently.The operation of removing metal base can be specifically that the metal base of surface growth Graphene is put into concentration is that the acid solution of 0.01～1mol/L or the ferric chloride Solution of 0.1～1mol/L soak, and removes metal base.Described acid solution specifically can be one or more in hydrochloric acid, nitric acid or sulfuric acid.

The preparation method of a kind of Graphene provided by the invention, has following excellent effect:

1. the present invention utilizes surface wave plasma to carry out preparing graphene through chemical vapor deposition, and temperature of reaction is low, and the reaction times is short, and preparation efficiency and output are higher, and product performance are controlled.

2. due to surface wave plasma concentration of energy, make metal substrate surface energy distribution even, gained Graphene surfacing, continuous, structural integrity, quality is high, and lattice defect is few.

Accompanying drawing explanation

Fig. 1 is the SEM figure of the Graphene of embodiment mono-preparation.

Embodiment

The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.

Embodiment mono-

A preparation method for Graphene, comprises the following steps:

Iron foil is passed through respectively to ethanol, acetone and deionized water ultrasonic cleaning are dried after removing surface and oil contaminant, be placed in chemical vapor depsotition equipment, sealing, while being evacuated to 10Pa, start heating, to iron foil temperature be 500 ℃, opening surface wave plasma equipment to power is 5kW, passing into flow is the carbonaceous gas methane of 10sccm, pass into nitrogen simultaneously, the volume ratio that makes methane and nitrogen is 1:10, on iron foil, react subsequently, and by air-bleed system, to control operating pressure in reaction chamber be 100Pa, keep reaction times 30min, growing graphene, reaction finishes, closing surface ripple plasma apparatus, stop passing into methane, be cooled to room temperature under nitrogen protection after, stop passing into nitrogen, close air-bleed system, on iron foil surface, make Graphene.

It is that the hydrochloric acid of 0.01mol/L soaks that the iron foil of surface growth Graphene is put into concentration, removes iron foil, then filters, and with washed with de-ionized water to filtrate, is after neutrality in vacuum drying oven in 100 ℃ of dry 1h, obtains Graphene.

Fig. 1 is the SEM figure of the Graphene of embodiment mono-preparation, and as can be seen from Figure 1, the thickness of Graphene is 1～2nm, and width is 5～10 μ m, surfacing, continuous, structural integrity.

Embodiment bis-, three, four, five, six all adopts the operation steps identical with embodiment mono-, operating parameters in each step and the concrete material using, and the conductivity data of the Graphene of being prepared by four point probe resistance meter test implementation example one ~ six is in Table 1.Wherein, the routine operation that the cleaning of metal base is the art, the cleaning operation in embodiment mono-~ six is all identical, and in preparation process, the kind of shielding gas is all consistent.

The specific conductivity test result of the concrete operations parameter of table 1 embodiment mono-~ six and the Graphene of preparation

Note:

1, in table 1, methane/10 represent that carbon containing source of the gas kind is methane, and 10 represent that the ventilation flow rate of methane is 10sccm.

2, in table 1, it is hydrochloric acid with solution that hydrochloric acid/0.01 represents to soak, and 0.01 represents that the volumetric molar concentration of hydrochloric acid is 0.01mol/l.

As seen from the data in Table 1, the Graphene specific conductivity that prepared by preparation method of the present invention is 1.3 ~ 15.6 * 10 ⁴s/cm.

To sum up, the preparation method of a kind of Graphene provided by the invention, has following excellent effect:

The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.

Claims

1. a preparation method for Graphene, is characterized in that, comprises the following steps:

2. the preparation method of a kind of Graphene as claimed in claim 1, is characterized in that, described metal base is a kind of or its arbitrary combination in iron foil, Copper Foil, nickel foil, cobalt paper tinsel or aluminium foil.

3. the preparation method of a kind of Graphene as claimed in claim 1, is characterized in that, the power of described surface wave plasma equipment is 2.5～4kW.

4. the preparation method of a kind of Graphene as claimed in claim 1, is characterized in that, in described reaction process, controlling operating pressure in reaction chamber is 100 ~ 1000Pa.

5. the preparation method of a kind of Graphene as claimed in claim 4, is characterized in that, in described reaction process, controlling operating pressure in reaction chamber is 150 ~ 800Pa.

6. the preparation method of a kind of Graphene as claimed in claim 1, is characterized in that, described shielding gas is a kind of or its arbitrary combination in nitrogen or rare gas element.

7. the preparation method of a kind of Graphene as claimed in claim 1, is characterized in that, described carbonaceous gas is a kind of or its arbitrary combination in methane, ethane, acetylene or ethanol.