WO2014114081A1 - Method for preparing graphene film - Google Patents

Method for preparing graphene film Download PDF

Info

Publication number
WO2014114081A1
WO2014114081A1 PCT/CN2013/082523 CN2013082523W WO2014114081A1 WO 2014114081 A1 WO2014114081 A1 WO 2014114081A1 CN 2013082523 W CN2013082523 W CN 2013082523W WO 2014114081 A1 WO2014114081 A1 WO 2014114081A1
Authority
WO
WIPO (PCT)
Prior art keywords
solvent
substrate temperature
substrate
temperature
sample
Prior art date
Application number
PCT/CN2013/082523
Other languages
French (fr)
Chinese (zh)
Inventor
孙立涛
毕恒昌
万树
吴幸
尹奎波
谢骁
徐峰
贺龙兵
Original Assignee
东南大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 东南大学 filed Critical 东南大学
Publication of WO2014114081A1 publication Critical patent/WO2014114081A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C01B32/192—Preparation by exfoliation starting from graphitic oxides

Definitions

  • the present invention relates to a method of regulating the wettability of a graphene film.
  • the present invention provides a method for controlling the wettability of graphene from a hydrophilic-hydrophobic-strong hydrophobic-superhydrophobic transition of a graphene film.
  • the method for regulating the wettability of graphene of the present invention comprises the following steps:
  • the graphite oxide is added to the solvent, ultrasonically dispersed to form a 0.1 mg/ml to 5 mg/l graphene oxide dispersion, and then the substrate is placed on a heating table, the substrate temperature is adjusted, and the graphene oxide dispersion is sprayed with a spray gun.
  • a graphene oxide film is obtained, and then the obtained graphene oxide film is subjected to xenon steam reduction, that is, the graphene oxide film is placed in a closed container filled with crucible, and then heated to 75 to 110 ° C and maintained. From 5h to 48h, the product obtained by steam reduction is finally subjected to carbon particle modification.
  • the solvent is water, ethanol, acetone, methanol, diethyl ether, chloroform, carbon tetrachloride, benzene, propylene glycol methyl ether, butanol, methyl ethyl ketone, xylene, toluene, tetrahydrofuran, methyl acetate, ethyl acetate, Any one of isopropyl alcohol, n-heptane, and n-hexane.
  • the temperature of the substrate is determined according to the type of the solvent, and the correspondence between the solvent type and the substrate temperature is: the solvent is water, the substrate temperature is set at 25-95 ° C; the solvent is Ethanol, substrate temperature is set at 25-70 ° C; solvent is acetone, substrate temperature is set at 25-50 ° C; solvent is methanol, substrate temperature is set at 25-60 ° C; solvent is diethyl ether, substrate temperature is set at 25 -30 ° C; solvent is chloroform, substrate temperature is set at 25-56 ° C; solvent is carbon tetrachloride, substrate temperature is set at 25-70 ° C; solvent is benzene, substrate temperature is set at 25-75 ° C; solvent Is propylene glycol methyl ether, the substrate temperature is set at 25-65 ° C; the solvent is butanol, the substrate temperature is set at 25-110 ° C; the solvent is butanone, the substrate temperature is
  • the carbon particle modification in the present invention is a product obtained by reducing hydrazine vapor, and is completely placed in a flame for 2 seconds to 5 seconds.
  • the carbon particles in the method of the invention are modified, and the flame source is the combustion of any of the following substances to produce a flame: candles, alcohol, gasoline, diesel oil and various alkane compounds.
  • the material of the substrate is glass, silicon wafer, metal sheet, or polydimethylsiloxane.
  • the invention adopts the spraying method combined with the change of the substrate temperature to obtain the surface with different roughness, thereby realizing the transition from hydrophilic-hydrophobic-strong hydrophobic, and in addition, in order to achieve superhydrophobicity, the surface must be modified with carbon particles, and This process is accomplished by burning a graphene film on a flame.
  • the invention has the following advantages:
  • the present invention in combination with the actual situation, uses a new method to obtain graphene films having different wettabilities.
  • the method is low in cost, simple, and easy to mass produce.
  • the invention utilizes temperature regulation in combination with surface modification to achieve controllable modulation of the surface wettability of the graphene film.
  • the method is simple and easy to implement, and the cost is low, and mass production can also be achieved.
  • Fig. 1 is a scanning electron micrograph of the surface of a film when ethanol is used as a solvent at a substrate temperature of 25 °C.
  • Figure 2 is a wetting angle test of the sample of Figure 1, with a wetting angle of 82°.
  • Figure 3 is a surface scanning electron micrograph of ethanol at a solvent temperature of 50 °C.
  • Figure 4 is a wetting angle test of the sample of Figure 3 with a wetting angle of 105°.
  • Figure 5 is a surface scanning electron micrograph of ethanol at a solvent temperature of 70 °C.
  • Figure 6 is a wetting angle test of the sample of Figure 5 with a wetting angle of 137°.
  • Figure 7 is a scanning electron micrograph of the sample of Figure 5 after carbon particle modification.
  • Figure 8 is a wetting angle test of the sample of Figure 7, with a wetting angle of 155°.
  • the glass substrate was ultrasonically washed with acetone, ethanol and deionized water for 30 minutes, then dried and placed on a heating table, and the temperature was set to 25 °C.
  • the dispersion is sprayed onto the substrate by means of a spray gun to obtain a graphene oxide film.
  • the obtained graphene oxide film is placed in a vessel containing hydrazine hydrate, sealed, heated to 95 ° C for 24 h, and reduced by hydrazine vapor to finally obtain a graphene film.
  • Figure 1 is a picture of the surface topography of the film.
  • the obtained graphene film was subjected to a wetting angle test. As shown in Fig. 2, it can be seen that the wetting angle is about 82°, which indicates that the film is hydrophilic (less than 90°). It is hydrophilic).
  • the control method is basically the same as that in Embodiment 1, except that the substrate temperature is 50 ° C, and the surface picture of the obtained sample is shown in FIG. 3 , which is more rough than FIG. 1 ;
  • FIG. 4 is a wet angle test chart. The wetting angle was 105° and exhibited hydrophobic properties.
  • the control method is basically the same as that in Embodiment 1, except that the substrate temperature is 70 ° C, and the scanning electron microscope of the obtained sample is as shown in FIG. 5, and the surface becomes rougher than in FIG. 1 and FIG. 3; FIG. 6 is the flow.
  • Wet angle test chart the wetting angle is about 137 °, showing strong hydrophobic properties.
  • the obtained strong hydrophobic sample is subjected to carbon particle modification, that is, the sample is burned in a candle flame.
  • FIG. 7 is a scanning electron microscope image, and it is obvious that carbon particles are attached to the graphene sheet;
  • FIG. 8 is a wetting angle test, and wetting The angle is 155° and exhibits superhydrophobic properties.
  • the control method is basically the same as that in Example 1, except that the solvent is water and the concentration is 0.1 mg/ml, the substrate is silicon wafer, and the temperature is set to 25 ° C.
  • the scanning electron micrograph and the wetting angle test of the obtained sample are very similar.
  • the control method was basically the same as that of Example 4, except that the temperature was set to 65 ° C, and the SEM image and the wetting angle test of the obtained sample were very similar to those of FIG. 3 and FIG. 4 .
  • the control method is basically the same as that in Example 4, except that the temperature is set to 95 ° C.
  • the scanning electron micrograph and the wetting angle test of the obtained sample are very similar to those of FIG. 5 and FIG. 6 , and the obtained sample is modified with carbon particles, and the flame source is The candle burns and the results are similar to Figure 7, Figure 8.
  • the control method is basically the same as that in Example 1, except that the solvent is acetone, the concentration of the graphite oxide dispersion is 5 mg/ml, the substrate is a copper sheet, and in the process of preparing the graphene oxide film, the substrate temperature is set to 25 ° C.
  • the SEM image and the wetting angle test of the final sample are very similar to the results obtained in Figure 1 and Figure 2 of Example 1.
  • control method was basically the same as that of Example 7, except that the substrate temperature was set to 35 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those of FIG. 3 and FIG. 4 in Example 1.
  • the control method was basically the same as that of Example 7, except that the substrate temperature was set to 50 ° C, and the scanning electron microscope image and the wetting angle test of the final sample were very similar to those of FIG. 5 and FIG. 6 in Example 1.
  • the sample was then subjected to carbon particle modification, and the flame source was ethanol combustion.
  • the scanning electron micrograph and the wetting angle test of the obtained sample were very similar to those of FIG. 7 and FIG.
  • the control method is basically the same as that in Example 1, except that the solvent is methanol, the temperature during the steam reduction process is 75 ° C and maintained for 48 h. In the process of preparing the graphene oxide film, the substrate temperature is set to 25 ° C, and finally The SEM image and the wetting angle test of the obtained sample are very similar to those obtained in Fig. 1 and Fig. 2.
  • the control method was basically the same as that of Example 10, except that the temperature of the substrate was set to 40 ° C, and the SEM image and the wetting angle test of the finally obtained sample were very similar to those obtained in FIG. 3 and FIG. 4 .
  • the control method was basically the same as that of Example 10 except that the temperature of the substrate was set to 60 ° C, and the SEM image and the wetting angle test of the finally obtained sample were very similar to those obtained in Fig. 5 and Fig. 6. The sample was then placed on the flame of the candle, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
  • the control method is basically the same as that in Example 1, except that the solvent is chloroform, the temperature for reduction is 110 ° C and maintained for 5 h, and the temperature of the substrate is set to 25 ° C.
  • the scanning electron micrograph and the wetting angle test of the final sample are very similar. The results obtained in Figure 1, Figure 2.
  • the control method was basically the same as that of Example 13, except that the temperature of the substrate was set to 35 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
  • the control method was basically the same as that of Example 13, except that the temperature of the substrate was set to 56 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in Fig. 5 and Fig. 6. The sample was then placed on a gasoline-burning flame, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
  • the control method is basically the same as that in Example 1, except that the solvent is carbon tetrachloride and the temperature of the substrate is set to 25 ° C.
  • the scanning electron microscope image and the wetting angle test of the final sample are very similar to those of FIG. 1 and FIG. 2 . result.
  • the control method was basically the same as that of Example 16, except that the temperature of the substrate was set to 50 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
  • the control method was basically the same as that of Example 16, except that the temperature of the substrate was set to 70 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in Fig. 5 and Fig. 6. The sample was then placed in a diesel-burning flame and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
  • the control method was basically the same as that in Example 1, except that the solvent was benzene and the temperature of the substrate was set to 25 ° C.
  • the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 1 and FIG. 2 .
  • the control method was basically the same as that of Example 19, except that the temperature of the substrate was set to 55 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
  • the control method was basically the same as that of Example 19, except that the temperature of the substrate was set to 75 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in Fig. 5 and Fig. 6. The sample was then placed in a flame of methane combustion. The SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
  • the control method is basically the same as that in Example 1, except that the solvent is butanol, the substrate is polydimethylsiloxane and the temperature is set to 25 ° C.
  • the scanning electron micrograph and the wetting angle test of the final sample are very similar to the graph. 1, the results obtained in Figure 2.
  • control method is basically the same as that of Embodiment 22, except that the substrate temperature is set to At 85 ° C, the SEM image and the Wetting Angle test of the final sample are very similar to the results obtained in Figure 3 and Figure 4.
  • the control method is basically the same as that of Embodiment 22, except that the substrate temperature is set to
  • the scanning electron micrograph and wetting angle test of the final sample at 110 ° C is very similar to the results obtained in Figure 5 and Figure 6.
  • the sample was then placed in a flame of ethane combustion.
  • the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
  • the control method was basically the same as that in Example 1, except that the solvent was methyl ethyl ketone and the temperature of the substrate was set to 25 ° C.
  • the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 1 and FIG. 2 .
  • the control method was basically the same as that of Example 25, except that the temperature of the substrate was set to 55 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
  • the control method was basically the same as that of Example 25, except that the temperature of the substrate was set to 75 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in Fig. 5 and Fig. 6.
  • the sample was then placed in a flame of octane combustion, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
  • the control method was basically the same as that in Example 1, except that the solvent was toluene and the temperature of the substrate was set to 25 ° C.
  • the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 1 and FIG. 2 .
  • the control method was basically the same as that of Example 28, except that the temperature of the substrate was set to 75 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
  • the control method was basically the same as that of Example 28, except that the temperature of the substrate was set to 105 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 5 and FIG. 6 .
  • the sample was then placed in a hexane-burning flame, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
  • the control method was basically the same as that in Example 1, except that the solvent was tetrahydrofuran and the temperature of the substrate was set to 25 ° C.
  • the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 1 and FIG. 2 .
  • the control method was basically the same as that of Example 31, except that the temperature of the substrate was set to 45 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
  • the control method was basically the same as that of Example 31, except that the temperature of the substrate was set to 60 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in Fig. 5 and Fig. 6.
  • the sample was then placed in a flame of ethanol combustion, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
  • the control method was basically the same as that in Example 1, except that the solvent was ethyl acetate and the temperature of the substrate was set to 25 ° C.
  • the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 1 and FIG. 2 .
  • the control method was basically the same as that of Example 34, except that the temperature of the substrate was set to 50 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in Fig. 3 and Fig. 4.
  • the control method was basically the same as that of Example 34, except that the temperature of the substrate was set to 70 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in Fig. 5 and Fig. 6. The sample was then placed in a dodecane-burning flame, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
  • the control method is basically the same as that in Example 1, except that the solvent is isopropyl alcohol and the temperature of the substrate is set to 25 ° C.
  • the scanning electron micrograph and the wetting angle test of the final sample are very similar to those of FIG. 1 and FIG. 2 . .
  • the control method was basically the same as that of Example 37, except that the temperature of the substrate was set to 55 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
  • the control method was basically the same as that of Example 37 except that the temperature of the substrate was set to 75 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in Fig. 5 and Fig. 6.
  • the sample was then placed in a flame of ethanol combustion, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
  • the control method was basically the same as that in Example 1, except that the solvent was n-hexane and the temperature of the substrate was set to 25 ° C.
  • the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 1 and FIG. 2 .
  • the control method was basically the same as that of Example 40, except that the temperature of the substrate was set to 45 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
  • the control method was basically the same as that of Example 40, except that the substrate temperature was set to 65 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in FIG. 5 and FIG.
  • the sample was then placed in a flame of candle burning, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
  • the control method was basically the same as that in Example 1, except that the solvent was diethyl ether and the temperature of the substrate was set to 25 ° C.
  • the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 1 and FIG. 2 .
  • the control method was basically the same as that of Example 43, except that the temperature of the substrate was set to 27 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
  • the control method was basically the same as that of Example 43, except that the temperature of the substrate was set to 30 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in Fig. 5 and Fig. 6. The sample was then placed in a flame of candle burning, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
  • the control method is basically the same as that in Example 1, except that the solvent is propylene glycol methyl ether, the temperature of the substrate is set to 40 ° C, and the scanning electron micrograph and the wetting angle test of the final sample are very similar to those of FIG. result.
  • the control method was basically the same as that of Example 46, except that the temperature of the substrate was set to 55 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those of the sample obtained in Fig. 3 and Fig. 4.
  • the control method was basically the same as that of Example 46, except that the temperature of the substrate was set to 65 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those of the sample obtained in Fig. 5 and Fig. 6. The sample was then placed in a flame of candle burning, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
  • the control method is basically the same as that in Example 1, except that the solvent is xylene and the temperature of the substrate is set to 85 ° C.
  • the scanning electron micrograph and the wetting angle test of the final sample are very similar to the results of the sample obtained in Figure 1. .
  • the control method was basically the same as that of Example 49, except that the temperature of the substrate was set to 105 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those of the sample obtained in FIG. 3 and FIG.
  • the control method was basically the same as that of Example 49, except that the temperature of the substrate was set to 130 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those of the sample obtained in Fig. 5 and Fig. 6.
  • the sample was then placed in a flame of candle burning, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
  • the control method is basically the same as that in Example 1, except that the solvent is methyl acetate, the temperature of the substrate is set to 42 ° C, and the scanning electron microscope image and the wetting angle test of the final sample are very similar to those of FIG. result.
  • the control method was basically the same as that of Example 52, except that the temperature of the substrate was set to 48 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those of the sample obtained in FIG. 3 and FIG. 4 .
  • the control method was basically the same as that of Example 52 except that the temperature of the substrate was set to 53 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those of the sample obtained in Fig. 5 and Fig. 6.
  • the sample was then placed in a flame of candle burning, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
  • the control method is basically the same as that in Example 1, except that the solvent is n-heptane and the temperature of the substrate is set to 50 ° C.
  • the scanning electron micrograph and the wetting angle test of the final sample are very similar to those of FIG. result.
  • control method was basically the same as that of Example 55, except that the temperature of the substrate was set to 70 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those of the sample obtained in FIG. 3 and FIG.
  • the control method was basically the same as that of Example 55, except that the temperature of the substrate was set to 90 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those of the sample obtained in Fig. 5 and Fig. 6.
  • the sample was then placed in a flame of candle burning, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.

Abstract

Provided is a method for preparing graphene film, comprising: adding graphite oxide into a solvent to form a graphene oxide dispersion; putting a substrate on a heating platform; adjusting the temperature of the substrate; using a spray gun to spray the graphene oxide dispersion onto the heated substrate to obtain a graphene oxide film; then carrying out hydrazine vapor reduction on the obtained graphene oxide film; and finally conducting carbon granule modification on the hydrazine vapor reduced product.

Description

一种制备石墨烯薄膜的方法  Method for preparing graphene film 技术领域Technical field
本发明涉及一种调控石墨烯薄膜润湿性的方法。 The present invention relates to a method of regulating the wettability of a graphene film.
背景技术Background technique
随着石墨烯的发现，其优异的电学性质、力学性质、热学性质和磁学性质引起了人们的广泛关注。同时制备石墨烯的方法也层出不穷，主要有微机械剥离法（Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV et al. Science 2004，306, 666）、化学法（Stankovich S, Dikin DA, et al. Carbon 2007，45, 1558）和外延生长（Kim KS, Zhao Y, et al. Nature 2009，457, 706）。另外对于材料与环境的兼容方面，材料的表面起到了非常重要的作用。在很多情况下，尽管材料的特性对于一些特殊的应用显得非常优异，但是很多情况下要对其表面进行相应的处理以满足特定的需要（Wang SR, Zhang Y, Abibi N, Cabrales L, Langmuir 2009, 25, 11078）。而这些在复合材料、涂料和生物介质上显得更加尤为重要。目前尽管有大量的工作集中在石墨烯的制备上，但很少有对石墨烯的表面特性进行研究的，为了扩大石墨烯的应用领域，必须能够得到不同表面特性的石墨烯。 With the discovery of graphene, its excellent electrical, mechanical, thermal and magnetic properties have attracted widespread attention. At the same time, the methods for preparing graphene are also endless, mainly including micro-mechanical stripping method (Novoselov). KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV et al. Science 2004, 306, 666), chemical method (Stankovich S, Dikin DA, et al. Carbon 2007, 45, 1558) and epitaxial growth (Kim KS, Zhao Y, et al. Nature 2009,457, 706). In addition, the surface of the material plays a very important role in the compatibility of materials with the environment. In many cases, although the properties of the material are excellent for some special applications, in many cases the surface is treated accordingly to meet specific needs (Wang SR, Zhang Y, Abibi N, Cabrales L, Langmuir 2009, 25, 11078). These are even more important in composites, coatings and biological media. At present, although a large amount of work is concentrated on the preparation of graphene, few studies have been made on the surface characteristics of graphene. In order to expand the application field of graphene, it is necessary to obtain graphene with different surface characteristics.
技术问题technical problem
本发明提供一种可以实现石墨烯薄膜从亲水-疏水-强疏水-超疏水转变的调控石墨烯润湿性的方法。 The present invention provides a method for controlling the wettability of graphene from a hydrophilic-hydrophobic-strong hydrophobic-superhydrophobic transition of a graphene film.
技术解决方案Technical solution
本发明的调控石墨烯润湿性的方法，包括以下步骤：The method for regulating the wettability of graphene of the present invention comprises the following steps:
首先将氧化石墨加入溶剂中，超声分散形成0.1mg/ml到5mg/l的氧化石墨烯分散液，然后将衬底放在加热台上，调节衬底温度，用喷枪将氧化石墨烯分散液喷到加热的衬底上，得到氧化石墨烯薄膜，接着对所得氧化石墨烯薄膜进行肼蒸汽还原，即将氧化石墨烯薄膜置于盛有肼的密闭容器中，然后加热到75到110℃，并维持5h到48h，最后对肼蒸汽还原所得产物进行碳颗粒修饰。First, the graphite oxide is added to the solvent, ultrasonically dispersed to form a 0.1 mg/ml to 5 mg/l graphene oxide dispersion, and then the substrate is placed on a heating table, the substrate temperature is adjusted, and the graphene oxide dispersion is sprayed with a spray gun. On the heated substrate, a graphene oxide film is obtained, and then the obtained graphene oxide film is subjected to xenon steam reduction, that is, the graphene oxide film is placed in a closed container filled with crucible, and then heated to 75 to 110 ° C and maintained. From 5h to 48h, the product obtained by steam reduction is finally subjected to carbon particle modification.
本发明中，溶剂是水、乙醇、丙酮、甲醇、***、氯仿、四氯化碳、苯、丙二醇甲醚、丁醇、丁酮、二甲苯、甲苯、四氢呋喃、乙酸甲酯、乙酸乙酯、异丙醇、正庚烷、正己烷中的任意一种。In the present invention, the solvent is water, ethanol, acetone, methanol, diethyl ether, chloroform, carbon tetrachloride, benzene, propylene glycol methyl ether, butanol, methyl ethyl ketone, xylene, toluene, tetrahydrofuran, methyl acetate, ethyl acetate, Any one of isopropyl alcohol, n-heptane, and n-hexane.
本发明中，氧化石墨烯薄膜的制备过程中，衬底的温度根据溶剂种类来确定，溶剂种类与衬底温度的对应关系为：溶剂为水，衬底温度设置在25-95℃；溶剂为乙醇，衬底温度设置在25-70℃；溶剂为丙酮，衬底温度设置在25-50℃；溶剂为甲醇，衬底温度设置在25-60℃；溶剂为***，衬底温度设置在25-30℃；溶剂为氯仿，衬底温度设置在25-56℃；溶剂为四氯化碳，衬底温度设置在25-70℃；溶剂为苯，衬底温度设置在25-75℃；溶剂为丙二醇甲醚，衬底温度设置在25-65℃；溶剂为丁醇，衬底温度设置在25-110℃；溶剂为丁酮，衬底温度设置在25-75℃；溶剂为二甲苯，衬底温度设置在25-130℃；溶剂为甲苯，衬底温度设置在25-105℃；溶剂为四氢呋喃，衬底温度设置在25-60℃；溶剂为乙酸甲酯，衬底温度设置在25-53℃；溶剂为乙酸乙酯，衬底温度设置在25-70℃；溶剂为异丙醇，衬底温度设置在25-75℃；溶剂为正庚烷，衬底温度设置在25-90℃；溶剂为正己烷，衬底温度设置在25-65℃。In the present invention, during the preparation of the graphene oxide film, the temperature of the substrate is determined according to the type of the solvent, and the correspondence between the solvent type and the substrate temperature is: the solvent is water, the substrate temperature is set at 25-95 ° C; the solvent is Ethanol, substrate temperature is set at 25-70 ° C; solvent is acetone, substrate temperature is set at 25-50 ° C; solvent is methanol, substrate temperature is set at 25-60 ° C; solvent is diethyl ether, substrate temperature is set at 25 -30 ° C; solvent is chloroform, substrate temperature is set at 25-56 ° C; solvent is carbon tetrachloride, substrate temperature is set at 25-70 ° C; solvent is benzene, substrate temperature is set at 25-75 ° C; solvent Is propylene glycol methyl ether, the substrate temperature is set at 25-65 ° C; the solvent is butanol, the substrate temperature is set at 25-110 ° C; the solvent is butanone, the substrate temperature is set at 25-75 ° C; the solvent is xylene, The substrate temperature is set at 25-130 ° C; the solvent is toluene, the substrate temperature is set at 25-105 ° C; the solvent is tetrahydrofuran, the substrate temperature is set at 25-60 ° C; the solvent is methyl acetate, and the substrate temperature is set at 25 -53 ° C; the solvent is ethyl acetate, the substrate temperature is set at 25-70 ° C; the solvent is isopropyl , The substrate temperature is set at 25-75 deg.] C; n-heptane solvent, the substrate temperature is set at 25-90 deg.] C; the solvent is n-hexane, the substrate temperature was set at 25-65 ℃.
本发明中的碳颗粒修饰，是将肼蒸汽还原所得产物，完全置于火焰中灼烧2秒到5秒。The carbon particle modification in the present invention is a product obtained by reducing hydrazine vapor, and is completely placed in a flame for 2 seconds to 5 seconds.
本发明方法中的碳颗粒修饰，火焰来源为以下任一物质的燃烧燃烧产生火焰的物质为：蜡烛、酒精、汽油、柴油及各种烷烃类化合物。The carbon particles in the method of the invention are modified, and the flame source is the combustion of any of the following substances to produce a flame: candles, alcohol, gasoline, diesel oil and various alkane compounds.
本发明中，衬底的材质为玻璃、硅片、金属片、聚二甲基硅氧烷。 In the present invention, the material of the substrate is glass, silicon wafer, metal sheet, or polydimethylsiloxane.
本发明利用喷涂法结合衬底温度的改变，可以得到不同粗糙程度的表面，进而实现由亲水-疏水-强疏水的转变，另外，为了实现超疏水，必须对其表面进行碳颗粒修饰，而该过程是通过将石墨烯薄膜置于火焰上燃烧实现的。The invention adopts the spraying method combined with the change of the substrate temperature to obtain the surface with different roughness, thereby realizing the transition from hydrophilic-hydrophobic-strong hydrophobic, and in addition, in order to achieve superhydrophobicity, the surface must be modified with carbon particles, and This process is accomplished by burning a graphene film on a flame.
有益效果Beneficial effect
本发明与现有技术相比，具有以下优点：Compared with the prior art, the invention has the following advantages:
现有的资料中，只是研究石墨烯片本身具有疏水特性，并没有人研究通过改变石墨烯膜的表面结构进而设计出不同润湿性的薄膜。本发明第一次利用喷涂结合加热的方法，实现了石墨烯薄膜表面结构的可控制备，进而得到了不同润湿性的石墨烯薄膜。石墨烯由于具有非常好的耐磨性，因此，其在涂层方面具有极大的应用前景，但作为涂层，润湿性将是一个非常重要的指标，不同的领域要求涂层具有不同的润湿性，因此，本发明结合实际情况，利用新方法得到了具有不同润湿性的石墨烯薄膜。该方法成本低、简单、易于大规模生产。本发明利用温度调节结合表面修饰，从而实现了石墨烯薄膜表面润湿性的可控调制。该方法简单易行，成本低，还可以实现大规模生产。In the existing data, only the graphene sheet itself has been studied to have hydrophobic properties, and no one has studied to design a film having different wettability by changing the surface structure of the graphene film. For the first time, the method of spraying and heating is used to realize the controllable preparation of the surface structure of the graphene film, and the graphene film with different wettability is obtained. Because graphene has very good wear resistance, it has great application prospects in coatings, but as a coating, wettability will be a very important indicator. Different fields require different coatings. Wettability, therefore, the present invention, in combination with the actual situation, uses a new method to obtain graphene films having different wettabilities. The method is low in cost, simple, and easy to mass produce. The invention utilizes temperature regulation in combination with surface modification to achieve controllable modulation of the surface wettability of the graphene film. The method is simple and easy to implement, and the cost is low, and mass production can also be achieved.
附图说明DRAWINGS
图1是乙醇为溶剂，衬底温度为25℃时的薄膜表面的扫描电镜图片。Fig. 1 is a scanning electron micrograph of the surface of a film when ethanol is used as a solvent at a substrate temperature of 25 °C.
图2是图1样品的润湿角测试图，润湿角为82°。Figure 2 is a wetting angle test of the sample of Figure 1, with a wetting angle of 82°.
图3是乙醇为溶剂，衬底温度为50℃的表面扫描电镜图片。Figure 3 is a surface scanning electron micrograph of ethanol at a solvent temperature of 50 °C.
图4是图3中样品的润湿角测试图，润湿角为105°。Figure 4 is a wetting angle test of the sample of Figure 3 with a wetting angle of 105°.
图5是乙醇为溶剂，衬底温度为70℃的表面扫描电镜图片。Figure 5 is a surface scanning electron micrograph of ethanol at a solvent temperature of 70 °C.
图6是图5中样品的润湿角测试图，润湿角为137°。Figure 6 is a wetting angle test of the sample of Figure 5 with a wetting angle of 137°.
图7是对图5中样品进行碳颗粒修饰后的扫描电镜图片。Figure 7 is a scanning electron micrograph of the sample of Figure 5 after carbon particle modification.
图8是图7中样品的润湿角测试图，润湿角为155°。Figure 8 is a wetting angle test of the sample of Figure 7, with a wetting angle of 155°.
本发明的实施方式Embodiments of the invention
下面通过实施例对本发明做进一步具体说明。The invention will be further specifically described below by way of examples.
实施例1：Example 1:
第一步，取2mg/ml的氧化石墨烯乙醇分散液200ml，并倒入喷枪中。In the first step, 200 ml of a 2 mg/ml graphene oxide ethanol dispersion was taken and poured into a spray gun.
第二步，将玻璃衬底先后用丙酮，乙醇，去离子水各超声清洗30分钟，然后烘干并置于加热台上，温度设置为25℃。In the second step, the glass substrate was ultrasonically washed with acetone, ethanol and deionized water for 30 minutes, then dried and placed on a heating table, and the temperature was set to 25 °C.
第三步，利用喷枪将分散液喷到衬底上，得到氧化石墨烯薄膜。In the third step, the dispersion is sprayed onto the substrate by means of a spray gun to obtain a graphene oxide film.
第四步，将所得的氧化石墨烯薄膜，放入盛有水合肼的容器中，并密封好，加热到95℃并维持24h，利用肼蒸汽对其进行还原，最终得到石墨烯薄膜。图1为该薄膜的表面形貌图片。In the fourth step, the obtained graphene oxide film is placed in a vessel containing hydrazine hydrate, sealed, heated to 95 ° C for 24 h, and reduced by hydrazine vapor to finally obtain a graphene film. Figure 1 is a picture of the surface topography of the film.
第五步，接着对所制得的石墨烯薄膜进行了润湿角测试，如图2所示，可以看出，润湿角大概为82°，这表明该薄膜是亲水的（小于90°就是亲水的）。In the fifth step, the obtained graphene film was subjected to a wetting angle test. As shown in Fig. 2, it can be seen that the wetting angle is about 82°, which indicates that the film is hydrophilic (less than 90°). It is hydrophilic).
实施例2：Example 2:
调控方法基本同实施例1，不同之处为：衬底温度为50℃，所得样品的表面图片为图3所示，相比于图1，显得更加粗糙；图4为其润湿角测试图，润湿角为105°，表现出疏水特性。The control method is basically the same as that in Embodiment 1, except that the substrate temperature is 50 ° C, and the surface picture of the obtained sample is shown in FIG. 3 , which is more rough than FIG. 1 ; FIG. 4 is a wet angle test chart. The wetting angle was 105° and exhibited hydrophobic properties.
实施例3：Example 3:
调控方法基本同实施例1，不同之处为：衬底温度为70℃，所得样品的扫描电镜如图5所示，表面变得更加粗糙相比于图1、图3；图6是其润湿角测试图，润湿角大概为137°，呈现出强疏水特性。接着对得到的强疏水样品进行碳颗粒修饰，即将样品至于蜡烛火焰中燃烧，图7是其扫描电镜图片，很明显，石墨烯片上附着着碳颗粒；图8是其润湿角测试，润湿角为155°，表现出超疏水特性。The control method is basically the same as that in Embodiment 1, except that the substrate temperature is 70 ° C, and the scanning electron microscope of the obtained sample is as shown in FIG. 5, and the surface becomes rougher than in FIG. 1 and FIG. 3; FIG. 6 is the flow. Wet angle test chart, the wetting angle is about 137 °, showing strong hydrophobic properties. Next, the obtained strong hydrophobic sample is subjected to carbon particle modification, that is, the sample is burned in a candle flame. FIG. 7 is a scanning electron microscope image, and it is obvious that carbon particles are attached to the graphene sheet; FIG. 8 is a wetting angle test, and wetting The angle is 155° and exhibits superhydrophobic properties.
实施例4：Example 4:
调控方法基本同实施例1，不同之处为：溶剂为水，且浓度为0.1mg/ml，衬底为硅片，温度设置为25℃，所得样品的扫描电镜图片及润湿角测试非常类似于图1，图2。The control method is basically the same as that in Example 1, except that the solvent is water and the concentration is 0.1 mg/ml, the substrate is silicon wafer, and the temperature is set to 25 ° C. The scanning electron micrograph and the wetting angle test of the obtained sample are very similar. Figure 1, Figure 2.
实施例5：Example 5:
调控方法基本同实施例4，不同之处为：温度设置为65℃，所得样品的扫描电镜图片及润湿角测试非常类似于图3，图4。The control method was basically the same as that of Example 4, except that the temperature was set to 65 ° C, and the SEM image and the wetting angle test of the obtained sample were very similar to those of FIG. 3 and FIG. 4 .
实施例6：Example 6
调控方法基本同实施例4，不同之处为：温度设置为95℃，所得样品的扫描电镜图片及润湿角测试非常类似于图5，图6，对所得样品进行碳颗粒修饰，火焰来源是蜡烛燃烧，所得结果类似于图7，图8。The control method is basically the same as that in Example 4, except that the temperature is set to 95 ° C. The scanning electron micrograph and the wetting angle test of the obtained sample are very similar to those of FIG. 5 and FIG. 6 , and the obtained sample is modified with carbon particles, and the flame source is The candle burns and the results are similar to Figure 7, Figure 8.
实施例7：Example 7
调控方法基本同实施例1，不同之处为：溶剂为丙酮，氧化石墨分散液浓度为5mg/ml，衬底为铜片，且在制备氧化石墨烯薄膜过程中，衬底温度设置为25℃，最终样品的扫描电镜图片及润湿角测试非常类似于实施例1中的图1，图2所得结果。The control method is basically the same as that in Example 1, except that the solvent is acetone, the concentration of the graphite oxide dispersion is 5 mg/ml, the substrate is a copper sheet, and in the process of preparing the graphene oxide film, the substrate temperature is set to 25 ° C. The SEM image and the wetting angle test of the final sample are very similar to the results obtained in Figure 1 and Figure 2 of Example 1.
实施例8：Example 8
调控方法基本同实施例7，不同之处为：衬底温度设置为35℃，最终样品的扫描电镜图片及润湿角测试非常类似于实施例1中的图3，图4所得结果。The control method was basically the same as that of Example 7, except that the substrate temperature was set to 35 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those of FIG. 3 and FIG. 4 in Example 1.
实施例9：Example 9
调控方法基本同实施例7，不同之处为：衬底温度设置为50℃，最终样品的扫描电镜图片及润湿角测试非常类似于实施例1中的图5，图6所得结果。接着对样品进行碳颗粒修饰，火焰来源是乙醇燃烧，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8。The control method was basically the same as that of Example 7, except that the substrate temperature was set to 50 ° C, and the scanning electron microscope image and the wetting angle test of the final sample were very similar to those of FIG. 5 and FIG. 6 in Example 1. The sample was then subjected to carbon particle modification, and the flame source was ethanol combustion. The scanning electron micrograph and the wetting angle test of the obtained sample were very similar to those of FIG. 7 and FIG.
实施例10：Example 10:
调控方法基本同实施例1，不同之处为：溶剂为甲醇，肼蒸汽还原过程中的温度为75℃并维持48h，在制备氧化石墨烯薄膜过程中，衬底的温度设置为25℃，最终所得样品的扫描电镜图片及润湿角测试非常类似于图1，图2所得的结果。The control method is basically the same as that in Example 1, except that the solvent is methanol, the temperature during the steam reduction process is 75 ° C and maintained for 48 h. In the process of preparing the graphene oxide film, the substrate temperature is set to 25 ° C, and finally The SEM image and the wetting angle test of the obtained sample are very similar to those obtained in Fig. 1 and Fig. 2.
实施例11：Example 11
调控方法基本同实施例10，不同之处为：衬底的温度设置为40℃，最终所得样品的扫描电镜图片及润湿角测试非常类似于图3，图4所得的结果。The control method was basically the same as that of Example 10, except that the temperature of the substrate was set to 40 ° C, and the SEM image and the wetting angle test of the finally obtained sample were very similar to those obtained in FIG. 3 and FIG. 4 .
实施例12：Example 12
调控方法基本同实施例10，不同之处为：衬底的温度设置为60℃，最终所得样品的扫描电镜图片及润湿角测试非常类似于图5，图6所得的结果。接着将样品至于蜡烛的火焰上，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8所得的结果。The control method was basically the same as that of Example 10 except that the temperature of the substrate was set to 60 ° C, and the SEM image and the wetting angle test of the finally obtained sample were very similar to those obtained in Fig. 5 and Fig. 6. The sample was then placed on the flame of the candle, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
实施例13：Example 13
调控方法基本同实施例1，不同之处为：溶剂为氯仿，还原用的温度为110℃并维持5h，衬底的温度设置为25℃，最终样品的扫描电镜图片及润湿角测试非常类似于图1，图2所得的结果。The control method is basically the same as that in Example 1, except that the solvent is chloroform, the temperature for reduction is 110 ° C and maintained for 5 h, and the temperature of the substrate is set to 25 ° C. The scanning electron micrograph and the wetting angle test of the final sample are very similar. The results obtained in Figure 1, Figure 2.
实施例14：Example 14
调控方法基本同实施例13，不同之处为：衬底的温度设置为35℃，最终样品的扫描电镜图片及润湿角测试非常类似于图3，图4所得的结果。The control method was basically the same as that of Example 13, except that the temperature of the substrate was set to 35 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
实施例15：Example 15
调控方法基本同实施例13，不同之处为：衬底的温度设置为56℃，最终样品的扫描电镜图片及润湿角测试非常类似于图5，图6所得的结果。接着将样品置于汽油燃烧的火焰上，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8所得的结果。The control method was basically the same as that of Example 13, except that the temperature of the substrate was set to 56 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in Fig. 5 and Fig. 6. The sample was then placed on a gasoline-burning flame, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
实施例16：Example 16:
调控方法基本同实施例1，不同之处为：溶剂为四氯化碳，衬底的温度设置为25℃，最终样品的扫描电镜图片及润湿角测试非常类似于图1，图2所得的结果。The control method is basically the same as that in Example 1, except that the solvent is carbon tetrachloride and the temperature of the substrate is set to 25 ° C. The scanning electron microscope image and the wetting angle test of the final sample are very similar to those of FIG. 1 and FIG. 2 . result.
实施例17：Example 17
调控方法基本同实施例16，不同之处为：衬底的温度设置为50℃，最终样品的扫描电镜图片及润湿角测试非常类似于图3，图4所得的结果。The control method was basically the same as that of Example 16, except that the temperature of the substrate was set to 50 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
实施例18：Example 18
调控方法基本同实施例16，不同之处为：衬底的温度设置为70℃，最终样品的扫描电镜图片及润湿角测试非常类似于图5，图6所得的结果。接着将样品置于柴油燃烧的火焰中，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8所得的结果。The control method was basically the same as that of Example 16, except that the temperature of the substrate was set to 70 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in Fig. 5 and Fig. 6. The sample was then placed in a diesel-burning flame and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
实施例19：Example 19
调控方法基本同实施例1，不同之处为：溶剂为苯，衬底的温度设置为25℃，最终样品的扫描电镜图片及润湿角测试非常类似于图1，图2所得的结果。The control method was basically the same as that in Example 1, except that the solvent was benzene and the temperature of the substrate was set to 25 ° C. The scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 1 and FIG. 2 .
实施例20：Example 20
调控方法基本同实施例19，不同之处为：衬底的温度设置为55℃，最终样品的扫描电镜图片及润湿角测试非常类似于图3，图4所得的结果。The control method was basically the same as that of Example 19, except that the temperature of the substrate was set to 55 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
实施例21：Example 21:
调控方法基本同实施例19，不同之处为：衬底的温度设置为75℃，最终样品的扫描电镜图片及润湿角测试非常类似于图5，图6所得的结果。接着将样品置于甲烷燃烧的火焰中，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8所得的结果。The control method was basically the same as that of Example 19, except that the temperature of the substrate was set to 75 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in Fig. 5 and Fig. 6. The sample was then placed in a flame of methane combustion. The SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
实施例22：Example 22
调控方法基本同实施例1，不同之处为：溶剂为丁醇，衬底为聚二甲基硅氧烷且温度设置为25℃，最终样品的扫描电镜图片及润湿角测试非常类似于图1，图2所得的结果。The control method is basically the same as that in Example 1, except that the solvent is butanol, the substrate is polydimethylsiloxane and the temperature is set to 25 ° C. The scanning electron micrograph and the wetting angle test of the final sample are very similar to the graph. 1, the results obtained in Figure 2.
实施例23：Example 23
调控方法基本同实施例22，不同之处为：衬底温度设为 85℃，最终样品的扫描电镜图片及润湿角测试非常类似于图3，图4所得的结果。The control method is basically the same as that of Embodiment 22, except that the substrate temperature is set to At 85 ° C, the SEM image and the Wetting Angle test of the final sample are very similar to the results obtained in Figure 3 and Figure 4.
实施例24：Example 24:
调控方法基本同实施例22，不同之处为：衬底温度设为 110℃，最终样品的扫描电镜图片及润湿角测试非常类似于图5，图6所得的结果。接着将样品置于乙烷燃烧的火焰中，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8所得的结果。The control method is basically the same as that of Embodiment 22, except that the substrate temperature is set to The scanning electron micrograph and wetting angle test of the final sample at 110 ° C is very similar to the results obtained in Figure 5 and Figure 6. The sample was then placed in a flame of ethane combustion. The SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
实施例25：Example 25
调控方法基本同实施例1，不同之处为：溶剂为丁酮，衬底的温度设置为25℃，最终样品的扫描电镜图片及润湿角测试非常类似于图1，图2所得的结果。The control method was basically the same as that in Example 1, except that the solvent was methyl ethyl ketone and the temperature of the substrate was set to 25 ° C. The scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 1 and FIG. 2 .
实施例26：Example 26:
调控方法基本同实施例25，不同之处为：衬底的温度设置为55℃，最终样品的扫描电镜图片及润湿角测试非常类似于图3，图4所得的结果。The control method was basically the same as that of Example 25, except that the temperature of the substrate was set to 55 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
实施例27：Example 27:
调控方法基本同实施例25，不同之处为：衬底的温度设置为75℃，最终样品的扫描电镜图片及润湿角测试非常类似于图5，图6所得的结果。接着将样品置于辛烷燃烧的火焰中，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8所得的结果。The control method was basically the same as that of Example 25, except that the temperature of the substrate was set to 75 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in Fig. 5 and Fig. 6. The sample was then placed in a flame of octane combustion, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
实施例28：Example 28
调控方法基本同实施例1，不同之处为：溶剂为甲苯，衬底的温度设置为25℃，最终样品的扫描电镜图片及润湿角测试非常类似于图1，图2所得的结果。The control method was basically the same as that in Example 1, except that the solvent was toluene and the temperature of the substrate was set to 25 ° C. The scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 1 and FIG. 2 .
实施例29：Example 29
调控方法基本同实施例28，不同之处为：衬底的温度设置为75℃，最终样品的扫描电镜图片及润湿角测试非常类似于图3，图4所得的结果。The control method was basically the same as that of Example 28, except that the temperature of the substrate was set to 75 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
实施例30：Example 30:
调控方法基本同实施例28，不同之处为：衬底的温度设置为105℃，最终样品的扫描电镜图片及润湿角测试非常类似于图5，图6所得的结果。接着将样品置于己烷燃烧的火焰中，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8所得的结果。The control method was basically the same as that of Example 28, except that the temperature of the substrate was set to 105 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 5 and FIG. 6 . The sample was then placed in a hexane-burning flame, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
实施例31：Example 31:
调控方法基本同实施例1，不同之处为：溶剂为四氢呋喃，衬底的温度设置为25℃，最终样品的扫描电镜图片及润湿角测试非常类似于图1，图2所得的结果。The control method was basically the same as that in Example 1, except that the solvent was tetrahydrofuran and the temperature of the substrate was set to 25 ° C. The scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 1 and FIG. 2 .
实施例32：Example 32:
调控方法基本同实施例31，不同之处为：衬底的温度设置为45℃，最终样品的扫描电镜图片及润湿角测试非常类似于图3，图4所得的结果。The control method was basically the same as that of Example 31, except that the temperature of the substrate was set to 45 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
实施例33：Example 33:
调控方法基本同实施例31，不同之处为：衬底的温度设置为60℃，最终样品的扫描电镜图片及润湿角测试非常类似于图5，图6所得的结果。接着将样品置于乙醇燃烧的火焰中，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8所得的结果。The control method was basically the same as that of Example 31, except that the temperature of the substrate was set to 60 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in Fig. 5 and Fig. 6. The sample was then placed in a flame of ethanol combustion, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
实施例34：Example 34:
调控方法基本同实施例1，不同之处为：溶剂为乙酸乙酯，衬底的温度设置为25℃，最终样品的扫描电镜图片及润湿角测试非常类似图1，图2所得的结果。The control method was basically the same as that in Example 1, except that the solvent was ethyl acetate and the temperature of the substrate was set to 25 ° C. The scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 1 and FIG. 2 .
实施例35：Example 35:
调控方法基本同实施例34，不同之处为：衬底的温度设置为50℃，最终样品的扫描电镜图片及润湿角测试非常类似图3，图4所得的结果。The control method was basically the same as that of Example 34, except that the temperature of the substrate was set to 50 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in Fig. 3 and Fig. 4.
实施例36：Example 36:
调控方法基本同实施例34，不同之处为：衬底的温度设置为70℃，最终样品的扫描电镜图片及润湿角测试非常类似图5，图6所得的结果。接着将样品置于十二烷燃烧的火焰中，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8所得的结果。The control method was basically the same as that of Example 34, except that the temperature of the substrate was set to 70 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in Fig. 5 and Fig. 6. The sample was then placed in a dodecane-burning flame, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
实施例37：Example 37:
调控方法基本同实施例1，不同之处为：溶剂为异丙醇，衬底的温度设置为25℃，最终样品的扫描电镜图片及润湿角测试非常类似于图1，图2所得的结果。The control method is basically the same as that in Example 1, except that the solvent is isopropyl alcohol and the temperature of the substrate is set to 25 ° C. The scanning electron micrograph and the wetting angle test of the final sample are very similar to those of FIG. 1 and FIG. 2 . .
实施例38：Example 38:
调控方法基本同实施例37，不同之处为：衬底的温度设置为55℃，最终样品的扫描电镜图片及润湿角测试非常类似于图3，图4所得的结果。The control method was basically the same as that of Example 37, except that the temperature of the substrate was set to 55 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
实施例39：Example 39:
调控方法基本同实施例37，不同之处为：衬底的温度设置为75℃，最终样品的扫描电镜图片及润湿角测试非常类似于图5，图6所得的结果。接着将样品置于乙醇燃烧的火焰中，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8所得的结果。The control method was basically the same as that of Example 37 except that the temperature of the substrate was set to 75 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in Fig. 5 and Fig. 6. The sample was then placed in a flame of ethanol combustion, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
实施例40：Example 40:
调控方法基本同实施例1，不同之处为：溶剂为正己烷，衬底的温度设置为25℃，最终样品的扫描电镜图片及润湿角测试非常类似于图1，图2所得的结果。The control method was basically the same as that in Example 1, except that the solvent was n-hexane and the temperature of the substrate was set to 25 ° C. The scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 1 and FIG. 2 .
实施例41：Example 41:
调控方法基本同实施例40，不同之处为：衬底的温度设置为45℃，最终样品的扫描电镜图片及润湿角测试非常类似于图3，图4所得的结果。The control method was basically the same as that of Example 40, except that the temperature of the substrate was set to 45 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
实施例42Example 42
调控方法基本同实施例40，不同之处为：衬底的温度设置为65℃，最终样品的扫描电镜图片及润湿角测试非常类似于图5，图6所得的结果。接着将样品置于蜡烛燃烧的火焰中，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8所得的结果。The control method was basically the same as that of Example 40, except that the substrate temperature was set to 65 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in FIG. 5 and FIG. The sample was then placed in a flame of candle burning, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
实施例43Example 43
调控方法基本同实施例1，不同之处为：溶剂为***，衬底的温度设置为25℃，最终样品的扫描电镜图片及润湿角测试非常类似于图1，图2所得的结果。The control method was basically the same as that in Example 1, except that the solvent was diethyl ether and the temperature of the substrate was set to 25 ° C. The scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 1 and FIG. 2 .
实施例44Example 44
调控方法基本同实施例43，不同之处为：衬底的温度设置为27℃，最终样品的扫描电镜图片及润湿角测试非常类似于图3，图4所得的结果。The control method was basically the same as that of Example 43, except that the temperature of the substrate was set to 27 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those obtained in FIG. 3 and FIG. 4 .
实施例45Example 45
调控方法基本同实施例43，不同之处为：衬底的温度设置为30℃，最终样品的扫描电镜图片及润湿角测试非常类似于图5，图6所得的结果。接着将样品置于蜡烛燃烧的火焰中，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8所得的结果。The control method was basically the same as that of Example 43, except that the temperature of the substrate was set to 30 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those obtained in Fig. 5 and Fig. 6. The sample was then placed in a flame of candle burning, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
实施例46：Example 46:
调控方法基本同实施例1，不同之处为：溶剂为丙二醇甲醚，衬底的温度设置为40℃，最终样品的扫描电镜图片及润湿角测试非常类似于图1，图2所得样品的结果。The control method is basically the same as that in Example 1, except that the solvent is propylene glycol methyl ether, the temperature of the substrate is set to 40 ° C, and the scanning electron micrograph and the wetting angle test of the final sample are very similar to those of FIG. result.
实施例47：Example 47:
调控方法基本同实施例46，不同之处为：衬底的温度设置为55℃，最终样品的扫描电镜图片及润湿角测试非常类似于图3，图4所得样品的结果。The control method was basically the same as that of Example 46, except that the temperature of the substrate was set to 55 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those of the sample obtained in Fig. 3 and Fig. 4.
实施例48：Example 48:
调控方法基本同实施例46，不同之处为：衬底的温度设置为65℃，最终样品的扫描电镜图片及润湿角测试非常类似于图5，图6所得样品的结果。接着将样品置于蜡烛燃烧的火焰中，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8所得的结果。The control method was basically the same as that of Example 46, except that the temperature of the substrate was set to 65 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those of the sample obtained in Fig. 5 and Fig. 6. The sample was then placed in a flame of candle burning, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
实施例49：Example 49
调控方法基本同实施例1，不同之处为：溶剂为二甲苯，衬底的温度设置为85℃，最终样品的扫描电镜图片及润湿角测试非常类似于图1，图2所得样品的结果。The control method is basically the same as that in Example 1, except that the solvent is xylene and the temperature of the substrate is set to 85 ° C. The scanning electron micrograph and the wetting angle test of the final sample are very similar to the results of the sample obtained in Figure 1. .
实施例50Example 50
调控方法基本同实施例49，不同之处为：衬底的温度设置为105℃，最终样品的扫描电镜图片及润湿角测试非常类似于图3，图4所得样品的结果。The control method was basically the same as that of Example 49, except that the temperature of the substrate was set to 105 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those of the sample obtained in FIG. 3 and FIG.
实施例51Example 51
调控方法基本同实施例49，不同之处为：衬底的温度设置为130℃，最终样品的扫描电镜图片及润湿角测试非常类似于图5，图6所得样品的结果。接着将样品置于蜡烛燃烧的火焰中，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8所得的结果。The control method was basically the same as that of Example 49, except that the temperature of the substrate was set to 130 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those of the sample obtained in Fig. 5 and Fig. 6. The sample was then placed in a flame of candle burning, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
实施例52Example 52
调控方法基本同实施例1，不同之处为：溶剂为乙酸甲酯，衬底的温度设置为42℃，最终样品的扫描电镜图片及润湿角测试非常类似于图1，图2所得样品的结果。The control method is basically the same as that in Example 1, except that the solvent is methyl acetate, the temperature of the substrate is set to 42 ° C, and the scanning electron microscope image and the wetting angle test of the final sample are very similar to those of FIG. result.
实施例53Example 53
调控方法基本同实施例52，不同之处为：衬底的温度设置为48℃，最终样品的扫描电镜图片及润湿角测试非常类似于图3，图4所得样品的结果。The control method was basically the same as that of Example 52, except that the temperature of the substrate was set to 48 ° C, and the scanning electron micrograph and the wetting angle test of the final sample were very similar to those of the sample obtained in FIG. 3 and FIG. 4 .
实施例54Example 54
调控方法基本同实施例52，不同之处为：衬底的温度设置为53℃，最终样品的扫描电镜图片及润湿角测试非常类似于图5，图6所得样品的结果。接着将样品置于蜡烛燃烧的火焰中，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8所得的结果。The control method was basically the same as that of Example 52 except that the temperature of the substrate was set to 53 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those of the sample obtained in Fig. 5 and Fig. 6. The sample was then placed in a flame of candle burning, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.
实施例55：Example 55:
调控方法基本同实施例1，不同之处为：溶剂为正庚烷，衬底的温度设置为50℃，最终样品的扫描电镜图片及润湿角测试非常类似于图1，图2所得样品的结果。The control method is basically the same as that in Example 1, except that the solvent is n-heptane and the temperature of the substrate is set to 50 ° C. The scanning electron micrograph and the wetting angle test of the final sample are very similar to those of FIG. result.
实施例56：Example 56
调控方法基本同实施例55，不同之处为：衬底的温度设置为70℃，最终样品的扫描电镜图片及润湿角测试非常类似于图3，图4所得样品的结果。The control method was basically the same as that of Example 55, except that the temperature of the substrate was set to 70 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those of the sample obtained in FIG. 3 and FIG.
实施例57：Example 57
调控方法基本同实施例55，不同之处为：衬底的温度设置为90℃，最终样品的扫描电镜图片及润湿角测试非常类似于图5，图6所得样品的结果。接着将样品置于蜡烛燃烧的火焰中，所得样品的扫描电镜图片及润湿角测试非常类似于图7，图8所得的结果。The control method was basically the same as that of Example 55, except that the temperature of the substrate was set to 90 ° C, and the SEM image and the wetting angle test of the final sample were very similar to those of the sample obtained in Fig. 5 and Fig. 6. The sample was then placed in a flame of candle burning, and the SEM image and the wetting angle test of the resulting sample were very similar to those obtained in Figure 7, Figure 8.

Claims (6)

  1. 一种制备石墨烯薄膜的方法，其特征在于，该方法包括以下步骤： A method of preparing a graphene film, characterized in that the method comprises the following steps:
    首先将氧化石墨加入溶剂中，超声分散形成0.1mg/ml到5mg/l的氧化石墨烯分散液，然后将衬底放在加热台上，调节衬底温度，用喷枪将所述氧化石墨烯分散液喷到加热的衬底上，得到氧化石墨烯薄膜，接着对所得氧化石墨烯薄膜进行肼蒸汽还原，即将氧化石墨烯薄膜置于盛有肼的密闭容器中，然后加热到75到110℃，并维持5h到48h，最后对所述肼蒸汽还原所得产物进行碳颗粒修饰。 First, the graphite oxide is added to the solvent, ultrasonically dispersed to form a 0.1 mg/ml to 5 mg/l graphene oxide dispersion, and then the substrate is placed on a heating table, the substrate temperature is adjusted, and the graphene oxide is dispersed by a spray gun. The liquid is sprayed onto the heated substrate to obtain a graphene oxide film, and then the obtained graphene oxide film is subjected to xenon steam reduction, that is, the graphene oxide film is placed in a sealed container filled with crucible, and then heated to 75 to 110 ° C, And maintaining for 5h to 48h, and finally the carbon granule modification is performed on the product obtained by the steam reduction of the hydrazine.
  2. 根据权利要求1所述的制备石墨烯薄膜的方法，其特征在于，所述的溶剂是水、乙醇、丙酮、甲醇、***、氯仿、四氯化碳、苯、丙二醇甲醚、丁醇、丁酮、二甲苯、甲苯、四氢呋喃、乙酸甲酯、乙酸乙酯、异丙醇、正庚烷、正己烷中的任意一种。The method for preparing a graphene film according to claim 1, wherein the solvent is water, ethanol, acetone, methanol, diethyl ether, chloroform, carbon tetrachloride, benzene, propylene glycol methyl ether, butanol, butyl Any one of ketone, xylene, toluene, tetrahydrofuran, methyl acetate, ethyl acetate, isopropanol, n-heptane, and n-hexane.
  3. 根据权利2所述的制备石墨烯薄膜的方法，其特征在于，所述氧化石墨烯薄膜的制备过程中，衬底的温度根据溶剂种类来确定，溶剂种类与衬底温度的对应关系为：溶剂为水，衬底温度设置在25-95℃；溶剂为乙醇，衬底温度设置在25-70℃；溶剂为丙酮，衬底温度设置在25-50℃；溶剂为甲醇，衬底温度设置在25-60℃；溶剂为***，衬底温度设置在25-30℃；溶剂为氯仿，衬底温度设置在25-56℃；溶剂为四氯化碳，衬底温度设置在25-70℃；溶剂为苯，衬底温度设置在25-75℃；溶剂为丙二醇甲醚，衬底温度设置在25-65℃；溶剂为丁醇，衬底温度设置在25-110℃；溶剂为丁酮，衬底温度设置在25-75℃；溶剂为二甲苯，衬底温度设置在25-130℃；溶剂为甲苯，衬底温度设置在25-105℃；溶剂为四氢呋喃，衬底温度设置在25-60℃；溶剂为乙酸甲酯，衬底温度设置在25-53℃；溶剂为乙酸乙酯，衬底温度设置在25-70℃；溶剂为异丙醇，衬底温度设置在25-75℃；溶剂为正庚烷，衬底温度设置在25-90℃；溶剂为正己烷，衬底温度设置在25-65℃。The method for preparing a graphene film according to claim 2, wherein in the preparation of the graphene oxide film, the temperature of the substrate is determined according to the kind of the solvent, and the correspondence between the solvent type and the substrate temperature is: a solvent For water, the substrate temperature is set at 25-95 ° C; the solvent is ethanol, the substrate temperature is set at 25-70 ° C; the solvent is acetone, the substrate temperature is set at 25-50 ° C; the solvent is methanol, and the substrate temperature is set at 25-60 ° C; the solvent is diethyl ether, the substrate temperature is set at 25-30 ° C; the solvent is chloroform, the substrate temperature is set at 25-56 ° C; the solvent is carbon tetrachloride, the substrate temperature is set at 25-70 ° C; The solvent is benzene, the substrate temperature is set at 25-75 ° C; the solvent is propylene glycol methyl ether, the substrate temperature is set at 25-65 ° C; the solvent is butanol, the substrate temperature is set at 25-110 ° C; the solvent is butanone, The substrate temperature is set at 25-75 ° C; the solvent is xylene, the substrate temperature is set at 25-130 ° C; the solvent is toluene, the substrate temperature is set at 25-105 ° C; the solvent is tetrahydrofuran, and the substrate temperature is set at 25- 60 ° C; the solvent is methyl acetate, the substrate temperature is set at 25-53 ° C; the solvent is Ethyl acetate, substrate temperature is set at 25-70 ° C; solvent is isopropanol, substrate temperature is set at 25-75 ° C; solvent is n-heptane, substrate temperature is set at 25-90 ° C; solvent is n-hexane The substrate temperature was set at 25-65 °C.
  4. 根据权利要求1、2或3所述的制备石墨烯薄膜的方法，其特征在于，所述的碳颗粒修饰，是将肼蒸汽还原所得产物，完全置于火焰中灼烧2秒到5秒。The method for producing a graphene film according to claim 1, 2 or 3, wherein the carbon particle modification is a product obtained by reducing hydrazine vapor, and is completely placed in a flame for 2 seconds to 5 seconds.
  5. 根据权利要求4所述的制备石墨烯薄膜的方法，其特征在于，所述的碳颗粒修饰中，火焰来源为以下任一物质的燃烧燃烧产生火焰的物质为：蜡烛、酒精、汽油、柴油及各种烷烃类化合物。The method for preparing a graphene film according to claim 4, wherein in the modification of the carbon particles, the flame is derived from the combustion of any of the following substances: a candle, an alcohol, a gasoline, a diesel oil, and the like. Various alkane compounds.
  6. 根据权利要求1、2或3所述的制备石墨烯薄膜的方法，其特征在于，所述的衬底的材质为玻璃、硅片、金属片、聚二甲基硅氧烷。The method for preparing a graphene film according to claim 1, 2 or 3, wherein the substrate is made of glass, silicon wafer, metal sheet or polydimethylsiloxane.
PCT/CN2013/082523 2013-01-24 2013-08-29 Method for preparing graphene film WO2014114081A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310026890.9A CN103101908B (en) 2013-01-24 2013-01-24 Method for preparing graphene film
CN201310026890.9 2013-01-24

Publications (1)

Publication Number Publication Date
WO2014114081A1 true WO2014114081A1 (en) 2014-07-31

Family

ID=48310156

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2013/082523 WO2014114081A1 (en) 2013-01-24 2013-08-29 Method for preparing graphene film

Country Status (2)

Country Link
CN (1) CN103101908B (en)
WO (1) WO2014114081A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105084858A (en) * 2015-08-07 2015-11-25 常州富烯科技股份有限公司 Method for preparing graphene film

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103101908B (en) * 2013-01-24 2015-06-03 东南大学 Method for preparing graphene film
CN104698042B (en) 2013-12-05 2017-07-18 中国科学院苏州纳米技术与纳米仿生研究所 Biological enzyme sensor that super-hydrophobic solid-liquid-gas three phase coexists and preparation method thereof
CN103710685B (en) * 2013-12-24 2016-02-17 同济大学 A kind of spraying method directly preparing transparent graphene conductive film on a flexible substrate
CN103924188B (en) * 2014-05-07 2016-06-08 山东师范大学 The method of atmospheric environment lower pair flame method growth in situ Graphene on a dielectric base
CN104085143B (en) * 2014-05-29 2016-05-04 深圳市铭晶科技有限公司 Preparation method and the product of Graphene composite guide hotting mask
KR102314988B1 (en) * 2014-12-26 2021-10-21 솔브레인 주식회사 Graphene Membrane Film and Method for Solvent Purification and Solvent Purification System using the Same
CN104591164B (en) * 2014-12-30 2016-09-07 常州碳星科技有限公司 A kind of preparation method of Graphene microbody
CN104609409B (en) * 2015-01-22 2016-11-16 东南大学 A kind of preparation method of Graphene millimeter sheet
CN104909580A (en) * 2015-05-20 2015-09-16 苏州大学 Transparent hydrophobic grating glass and preparation method thereof
CN105271209A (en) * 2015-11-05 2016-01-27 北京旭碳新材料科技有限公司 Graphene film and method and device for continuously producing graphene film
CN108571913A (en) * 2017-03-07 2018-09-25 中国科学院工程热物理研究所 A kind of super-hydrophobic condensing surface and preparation method thereof
CN107640764A (en) * 2017-10-13 2018-01-30 南京旭羽睿材料科技有限公司 A kind of industrial high efficiency prepares big size graphene production technology
CN108840320B (en) * 2018-06-29 2020-05-22 北京石油化工学院 Method for preparing carbon film by using water drop stripping mode
CN108946709A (en) * 2018-07-10 2018-12-07 东南大学 A kind of preparation method of the three-dimensional high-densit more fold graphene oxides of high-hydroscopicity
CN108975316B (en) * 2018-09-26 2020-02-04 西北有色金属研究院 Preparation method of graphene film
CN113444470A (en) * 2021-07-16 2021-09-28 安徽省奥佳建材有限公司 Self-adhesive waterproof coiled material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102020270A (en) * 2009-09-09 2011-04-20 中国科学院金属研究所 Macro-preparation for big size graphene
CN102070142A (en) * 2010-12-14 2011-05-25 四川大学 Method for preparing graphene by chemical oxidation reduction
US20120269717A1 (en) * 2011-04-21 2012-10-25 The Aerospace Corporation Method for growth of high quality graphene films
CN102787445A (en) * 2012-07-18 2012-11-21 上海大学 Method of preparing porous graphene film by using electrostatic spray process
CN103101908A (en) * 2013-01-24 2013-05-15 东南大学 Method for preparing graphene film

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101474898A (en) * 2009-01-16 2009-07-08 南开大学 Conductive carbon film based on graphene as well as preparation method and application
KR101071224B1 (en) * 2009-05-11 2011-10-10 울산대학교 산학협력단 Methods for fabricating the thin film graphene
KR101260433B1 (en) * 2010-04-30 2013-05-06 연세대학교 산학협력단 Graphene thin film by electrostatic spraying deposition and manufacturing method thereof
CN102021573B (en) * 2010-12-27 2013-01-02 湖南大学 Self-assembly preparation method of noble metal-graphene double-layer composite conductive film
CN102750998B (en) * 2012-07-09 2014-11-19 深圳市贝特瑞纳米科技有限公司 Transparent graphene conductive thin film and preparation method thereof
CN102815695A (en) * 2012-08-02 2012-12-12 许子寒 Preparation method of low-cost large-area graphene transparent conductive film

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102020270A (en) * 2009-09-09 2011-04-20 中国科学院金属研究所 Macro-preparation for big size graphene
CN102070142A (en) * 2010-12-14 2011-05-25 四川大学 Method for preparing graphene by chemical oxidation reduction
US20120269717A1 (en) * 2011-04-21 2012-10-25 The Aerospace Corporation Method for growth of high quality graphene films
CN102787445A (en) * 2012-07-18 2012-11-21 上海大学 Method of preparing porous graphene film by using electrostatic spray process
CN103101908A (en) * 2013-01-24 2013-05-15 东南大学 Method for preparing graphene film

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105084858A (en) * 2015-08-07 2015-11-25 常州富烯科技股份有限公司 Method for preparing graphene film
CN105084858B (en) * 2015-08-07 2018-05-18 常州富烯科技股份有限公司 A kind of preparation method of graphene film

Also Published As

Publication number Publication date
CN103101908B (en) 2015-06-03
CN103101908A (en) 2013-05-15

Similar Documents

Publication Publication Date Title
WO2014114081A1 (en) Method for preparing graphene film
WO2012064102A2 (en) Graphene-coated steel sheet, and method for manufacturing same
WO2014104693A1 (en) Graphene, composition for preparing graphene, and method for preparing graphene using same
US20110171427A1 (en) Method of manufacturing deformation-capable graphene sheet, deformation-capable graphene sheet, and device using the same
WO2016167583A1 (en) Method for doping graphene, method for manufacturing graphene composite electrode, and graphene structure comprising same
WO2021125798A1 (en) Mxene fibers and preparation method thereof
WO2017065530A1 (en) Low-temperature graphene transfer method
WO2016163670A1 (en) Aerogel-containing composition and heat insulation blanket prepared by using same
Rouhi et al. Three separated growth sequences of vertically-aligned carbon nanotubes on porous silicon: field emission applications
WO2020022725A1 (en) Method for preparing carbon nanotubes
WO2018164472A1 (en) Conductive ceramic composition having excellent electrical conductivity
TW202016349A (en) An antistatic liquid proof nano coating and preparation method thereof
WO2014137180A1 (en) Carbon based electronic device using partial reduction of graphene oxide and method for manufacturing same
WO2016032227A1 (en) Method for preparing in situ nanomaterial having functional material coating, and nanomaterial prepared by means of same
WO2012063991A1 (en) Method for manufacturing aluminum electrode using wetting process and aluminum electrode manufactured thereby
WO2016003196A1 (en) Super water repellent cerium oxide nano/microstructure directly grown on various substrates, and preparation method therefor
WO2015102157A1 (en) Composition for preparing graphene and method for preparing graphene using same
WO2015133776A1 (en) Scroll composite containing amphoteric material therein and method for preparing same
WO2013062221A1 (en) Titanium-nickel alloy thin film, and preparation method of titanium-nickel alloy thin film using multiple sputtering method
JP2000306986A (en) Electrostatic chuck
KR20190101235A (en) Polymer for transferring graphene and transfer method of graphene using the same
JP2001506572A (en) Method of forming diamond film by vapor phase synthesis
CN114171370A (en) Method for preparing graphene in relatively closed area by solid phase method
WO2020116770A1 (en) Group 4 transition metal compound, method for preparing same and method for forming thin film using same
WO2019017693A1 (en) Graphene and method for preparing same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13872435

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13872435

Country of ref document: EP

Kind code of ref document: A1