CN103332686B - Preparation method of three-dimensional graphene-based foam material - Google Patents
Preparation method of three-dimensional graphene-based foam material Download PDFInfo
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Abstract
The invention relates to a preparation method of a three-dimensional graphene-based foam material, which comprises the steps of stripping graphite to obtain graphite oxide with an improved Hummers method, taking graphite oxide with dispersed furfuryl alcohol as a carbon source and a high polymer foam material as a template, obtaining a high polymer foam material obtaining graphite oxide with a simple impregnation method, and obtaining the three-dimensional graphene-based foam material by heat treatment of high polymer foam under an anaerobic condition. The three-dimensional graphene-based foam material prepared by the method is provided with a graphene-based foam macro body in a three-dimensional continuous structure; the method is easy and simple to operate, and high in productivity; a foam structure is easy to adjust and control; the prepared three-dimensional graphene-based foam material has the advantages of high electroconductivity, large specific surface area, lipophilicity, hydrophobicity and the like; and a foundation is laid for the application of the three-dimensional graphene-based foam material in the fields of heat-conducting composites, catalytical materials, energy storage materials, phase separation materials, adsorbing materials and the like.
Description
Technical field
The present invention relates to a kind of preparation method of grapheme material, particularly a kind of preparation method of three-dimensional graphite thiazolinyl foam, belongs to field of functional materials.
Background technology
Graphene is by the bi-dimensional cellular shape crystalline structure of the tightly packed one-tenth of monolayer carbon atom, is the basic structural unit building other dimension carbon material (as zero dimension soccerballene, one dimension carbon nanotube, three-dimensional graphite).The crystalline structure of Graphene uniqueness makes it have excellent electricity, calorifics and mechanical property.Single-layer graphene can be used for field-effect transistor, high-frequency element, super microprocessor and single-molecule detection device etc.And be the three-dimensional structure that elementary cell is formed by Graphene, as bulk material or film, be likely applied to the fields such as controllability air-permeable envelope, anisotropy ion-conducting material, ultracapacitor, lithium ion battery, energy catalysis, sewage disposal.
A Major Difficulties prepared by three-dimensional grapheme material is that graphene sheet layer is assembled mutually, causes its density to be difficult to reach minimum, then makes its performance and application scope be greatly limited.Graphene oxide hydrothermal reduction method and templated chemistry vapour deposition process (CVD) realize the effective ways that grapheme material prepared on a large scale at present.Although hydrothermal method can realize scale operation three-dimensional grapheme, the cleanliness factor of three-dimensional grapheme of synthesis is not high and with the caking of graphene film, structure is easily caved in simultaneously, reduces its application performance; And CVD method growth conditions is harsh, be difficult to the production in enormous quantities realizing three-dimensional grapheme.
The present invention proposes a kind of preparation method of three-dimensional graphite thiazolinyl foam, can overcome existing Problems existing, at present, there is not been reported for domestic and international public publication and patent.
Summary of the invention
The object of the invention is, a kind of preparation method of three-dimensional graphite thiazolinyl foam is provided, the method utilizes the Hummers method improved to peel off graphite and obtains graphite oxide, with furfuryl alcohol dispersion graphene oxide be Graphene carbon source, with polymeric foamed material for template, obtain the polymeric foamed material containing graphene oxide by simple pickling process, then thermal treatment polymeric foam obtains three-dimensional graphite thiazolinyl foam materials under anaerobic.The three-dimensional graphite thiazolinyl foam obtained by the method for the invention has the graphene-based foam macroscopic body of three-dimensional continuous structure, the method is easy and simple to handle, productive rate is high and foamy structure easy-regulating, gained three-dimensional graphite thiazolinyl foam materials has that electric conductivity is high, specific surface area is large and the advantage such as oleophilic drainage, for its application in heat-conductive composite material, catalysis, energy storage material, the field such as material and sorbing material that is separated is laid a good foundation.
The preparation method of a kind of three-dimensional graphite thiazolinyl foam materials of the present invention, follows these steps to carry out:
A, with natural flake graphite or Graphite Powder 99 for raw material, utilize the Hummers method improved to carry out oxidation and obtain graphene oxide;
B, be distributed in furfuryl alcohol solution by the graphite oxide ene product of gained, it is 1-8 mg/mL graphene oxide-furfuryl alcohol mixed solution that ultrasonic disperse forms homogeneous concentration, then adds oxalic acid and stir;
C, be that urethane, polyethylene, polyvinyl chloride foam or polystyrene foam flood in step b gained furfuryl alcohol solution by polymeric foam, after foam is evenly extruded, polymerizing curable 1-4 hour in temperature 60-160 DEG C of baking oven, obtains the mixture foam solidified;
D, will obtain solidify mixture foam in oxygen-free environment, with temperature 1-5 DEG C/min, slow intensification 800-1000 DEG C, is incubated and heat-treats for 1-6 hour, can obtain three-dimensional graphite thiazolinyl foam materials after naturally cooling to room temperature.
The mol ratio of step b mesoxalic acid and furfuryl alcohol solution is 4.3 × 10
-3~ 0.13:1.
In steps d, oxygen-free environment is vacuum or argon gas or nitrogen rare gas element.
The preparation method of a kind of three-dimensional graphite thiazolinyl foam materials of the present invention, the method combines has the graphene oxide of three-dimensional full-mesh network and simple chelating polymer template method to realize the preparation in macroscopic quantity of grapheme foam.The present invention have easy and simple to handle, cost is low and be easy to the feature of controlled material structure, is expected the extensive preparation realizing graphene-based foam materials.
Accompanying drawing explanation
Fig. 1 is the polymeric foam figure containing graphene oxide-furfuryl alcohol cured article that the embodiment of the present invention 1 obtains; Wherein a is the polymeric foam containing graphene oxide-furfuryl alcohol cured article; B is the three-dimensional graphite thiazolinyl foam that embodiment 1 obtains;
Fig. 2 is that the obtained three-dimensional graphite thiazolinyl foam of the embodiment of the present invention 2 is to the adsorption process figure of the machine oil of water float.
Embodiment
The present embodiment premised on technical solution of the present invention under implement, but be not limited to following embodiment;
Embodiment 1
Prepare graphene oxide:
First, in round-bottomed flask, (92 g) to add the 50 mL vitriol oils, temperature 80-90 DEG C is heated in oil bath, then add 10 g Potassium Persulphates and 10 g Vanadium Pentoxide in FLAKESs, then 10 g natural graphite powder are added lentamente, keep 4 hours, after cool to room temperature, mixture deionized water is diluted, then vacuum filtration, with 3 L deionized water wash, by solid drying more than one day under vacuum, finally obtain preoxidation Graphite Powder 99, secondly, in 2L beaker, add 230 mL (4.3 mol) vitriol oil, be cooled to 0 DEG C, then 5 g (0.42 mol) the first step preoxidation powdered graphite is added, then 30 g (0.19 mol) potassium permanganate is added in beaker in batches, simultaneous temperature remains on less than 10 DEG C, then in temperature 38 DEG C of water-baths, Best Times is kept 2 hours, again with 0.6 L deionized water dilution, stir 2 hours, add 1.4 L deionized waters again, then 50 mL 30% hydrogen peroxide are added, obtain brown graphite suspending liquid, after question response terminates, by suspension filtered, obtain tawny filter cake, with 1 L 10% hydrochloric acid soln washing, with deionized water, filter cake is washed again, until elutant arrives neutral, then filter cake is dispersed in 600ml water, after centrifugal treating, by the gel graphite oxide that obtains vacuum drying oven temperature 40 DEG C, 24 hours dry graphene oxides obtaining chocolate,
The graphite oxide ene product of gained is distributed in 20 mL furfuryl alcohol solution and forms graphene oxide-furfuryl alcohol solution that concentration is 2 mg/mL, ultrasonic disperse forms homogeneous graphene oxide-furfuryl alcohol mixed solution, add oxalic acid again to stir, the mol ratio of its mesoxalic acid and furfuryl alcohol solution is 0.05:1;
Polymeric foam urethane is flooded 0.5 hour in gained furfuryl alcohol solution, then after foam evenly being extruded, polymerizing curable 1 hour in temperature 60 C baking oven, obtain the mixture foam of graphene-containing-furfuryl alcohol cured article, the foamy appearance after solidification is as shown in Figure 1a;
Mixture foam after solidification is placed in quartz boat, 800 DEG C are slowly warming up to temperature 1 DEG C/min in tube furnace under a nitrogen atmosphere, be incubated and heat-treat for 1 hour, obtain three-dimensional graphite thiazolinyl foam materials after naturally cooling to room temperature, foamy appearance as shown in Figure 1 b.
Embodiment 2
Prepare graphene oxide to be undertaken by embodiment 1;
The graphite oxide ene product of gained is distributed in 20mL furfuryl alcohol solution and forms graphene oxide-furfuryl alcohol solution that concentration is 4 mg/mL, ultrasonic disperse forms homogeneous graphene oxide-furfuryl alcohol mixed solution, add oxalic acid again to stir, the mol ratio of its mesoxalic acid and furfuryl alcohol solution is 0.09:1;
Flooded 0.5 hour in gained furfuryl alcohol solution by polymeric foam polyethylene, after then evenly being extruded by foam, polymerizing curable 2 hours in temperature 100 DEG C of baking ovens, obtains the polymeric foam after solidifying;
Mixture foam after solidification is placed in quartz boat, is slowly warming up to 900 DEG C with temperature 2 DEG C/min in the tube furnace under argon gas condition, is incubated 2 hours, three-dimensional graphite thiazolinyl foam materials after naturally cooling to room temperature, can be obtained;
In the culture dish that water is housed, (0.2 g), and it swims on the water surface for the machine oil of dropping oil red mark, then by the machine oil of the graphene-based foam contacting oil red mark of drying, after about 30 seconds, machine oil adsorbs by graphene-based foam completely, does not see that the machine oil that the water surface has oil red to mark occurs.
Embodiment 3
Prepare graphene oxide to be undertaken by embodiment 1;
The graphite oxide ene product of gained is distributed in 20mL furfuryl alcohol solution and forms graphene oxide-furfuryl alcohol solution that concentration is 6 mg/mL, ultrasonic disperse forms homogeneous graphene oxide-furfuryl alcohol mixed solution, add oxalic acid again to stir, the mol ratio of its mesoxalic acid and furfuryl alcohol solution is 0.13:1;
Flooded 0.5 hour in gained furfuryl alcohol solution by polymeric foam polyvinyl chloride foam, after evenly being extruded by foam, polymerizing curable 3 hours in temperature 120 DEG C of baking ovens, obtains the mixture foam solidified;
By obtaining the mixture foam of solidification in nitrogen environment, being slowly warming up to 950 DEG C with temperature 4 DEG C/min, being incubated and heat-treating for 4 hours, three-dimensional graphite thiazolinyl foam materials after naturally cooling to room temperature, can be obtained.
Embodiment 4
Prepare graphene oxide to be undertaken by embodiment 1;
The graphite oxide ene product of gained is distributed in 20 mL furfuryl alcohol solution and forms graphene oxide-furfuryl alcohol solution that concentration is 8 mg/mL, ultrasonic disperse forms homogeneous graphene oxide-furfuryl alcohol mixed solution, add oxalic acid again to stir, the mol ratio of its mesoxalic acid and furfuryl alcohol solution is 4.3 × 10
-3: 1;
Flooded 0.5 hour in gained furfuryl alcohol solution by polymeric foam polystyrene foam, after evenly being extruded by foam, polymerizing curable 4 hours in temperature 160 DEG C of baking ovens, obtains the mixture foam solidified;
By obtaining the mixture foam of solidification in nitrogen environment, slowly rising to 1000 DEG C with temperature 5 DEG C/min, being incubated and heat-treating for 6 hours, three-dimensional graphite thiazolinyl foam materials after naturally cooling to room temperature, can be obtained.
Claims (1)
1. a preparation method for three-dimensional graphite thiazolinyl foam materials, is characterized in that following these steps to carry out:
A, with natural flake graphite or Graphite Powder 99 for raw material, utilize the Hummers method improved to carry out oxidation and obtain graphene oxide;
B, be distributed in furfuryl alcohol solution by the graphite oxide ene product of gained, it is 1-8 mg/mL graphene oxide-furfuryl alcohol mixed solution that ultrasonic disperse forms homogeneous concentration, then adds oxalic acid and stir, and the mol ratio of its mesoxalic acid and furfuryl alcohol solution is 4.3 × 10
-3~ 0.13:1;
C, be that urethane, polyethylene, polyvinyl chloride foam or polystyrene foam flood in step b gained graphene oxide furfuryl alcohol solution by polymeric foam, after foam is evenly extruded, polymerizing curable 1-4 hour in temperature 60-160 DEG C of baking oven, obtains the mixture foam solidified;
D, by the mixture foam obtaining solidifying in oxygen-free environment is vacuum or argon gas or nitrogen rare gas element, with temperature 1-5 DEG C/min, slow intensification 800-1000 DEG C, is incubated and heat-treats for 1-6 hour, can obtain three-dimensional graphite thiazolinyl foam materials after naturally cooling to room temperature.
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| GB0805640D0 (en) * | 2008-03-28 | 2008-04-30 | Hexcel Composites Ltd | Improved composite materials |
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| CN102344700A (en) * | 2011-07-07 | 2012-02-08 | 南京大学 | Preparation method of polystyrene/graphene composite particle |
| CN102557022B (en) * | 2012-03-02 | 2013-12-18 | 杭州电子科技大学 | Preparation method of graphene conductive foam |
| CN102718983A (en) * | 2012-06-28 | 2012-10-10 | 四川大学 | Preparation method of polymer-based conductive microporous foam composite material |
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