CN108569687B - Preparation method of graphene three-dimensional porous material - Google Patents
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Abstract
The invention provides a preparation method of a graphene three-dimensional porous material, which comprises the following steps: (i) providing a graphene suspension, and carrying out solvent removal treatment on the graphene suspension; (ii) (ii) after the step (i), heating and annealing to obtain the graphene three-dimensional porous material; wherein the solvent in the graphene suspension is a solvent with the surface tension of 18-25 mN/m. The method is simple and rapid to operate and low in cost, and the prepared graphene three-dimensional porous material is excellent in performance and stable in structure.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of a graphene three-dimensional porous material.
Background
The graphene is represented by sp2The two-dimensional honeycomb periodic lattice structure formed by hybridized planar carbon atoms is also a basic structural unit for constructing zero-dimensional fullerene, one-dimensional carbon nano tube and three-dimensional graphite. Graphene, as a two-dimensional carbon material, has many special properties such as excellent mechanical properties, high thermal conductivity, high-speed electron mobility at room temperature, ultra-high specific surface area, ultra-high light transmittance, and the like.
The three-dimensional graphene is a three-dimensional network structure formed by two-dimensional graphene sheets through space interaction, has unique advantages in the aspects of space heat conduction, electric conduction and macro high-quality preparation besides the inherent performance of the two-dimensional graphene, and can be applied to electronic packaging heat dissipation and joule heat sources. In addition, the problem of dispersion of graphene in a matrix can be effectively solved by compounding the three-dimensional graphene with the material, so that the graphene composite material with excellent comprehensive performance is prepared.
The general methods for synthesizing three-dimensional graphene are Chemical Vapor Deposition (CVD) and "soft template" methods (hydrothermal methods). However, the CVD method has harsh growth conditions and high preparation cost, and is difficult to realize the mass production of the three-dimensional graphene; the graphene three-dimensional porous material prepared by the hydrothermal method is low in strength, and the density and the porosity are difficult to control, so that the application field of the three-dimensional graphene is limited.
In conclusion, a method for preparing a graphene three-dimensional porous material with simple operation and low cost is not available in the field.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the existing technology for preparing the graphene three-dimensional porous material, and provides a method for preparing the graphene three-dimensional porous material, which is simple to operate and low in cost.
In a first aspect of the present invention, there is provided a method for preparing a graphene three-dimensional porous material, the method comprising the steps of:
(i) providing a graphene suspension;
(ii) carrying out desolventizing treatment on the suspension to obtain the graphene three-dimensional porous material;
wherein the graphene suspension comprises a low surface tension solvent and graphene suspended therein; the low surface tension solvent is a solvent with surface tension of 18-30mN/m (25 ℃).
In another preferred embodiment, the graphene suspension is prepared by suspending graphene nanoplatelets in a low surface tension solvent, and preferably, after the graphene nanoplatelets are added into the low surface tension solvent, the graphene suspension is obtained by performing ultrasonic treatment.
In another preferred embodiment, the low surface tension solvent is a solvent having a surface tension of 18 to 25mN/m (25 ℃).
In another preferred example, the ultrasonic power of the ultrasonic treatment is 50-800W.
In another preferred example, the ultrasonic power of the ultrasonic treatment is 120-600W.
In another preferred example, the ultrasonic time of the ultrasonic treatment is 1-30 min.
In another preferred example, the ultrasonic time of the ultrasonic treatment is 3-10 min.
In another preferred example, the method further comprises the steps of: (iii) after said step (ii) further comprising the steps of: (iii) and heating and/or annealing the graphene three-dimensional porous material to obtain the high-performance graphene three-dimensional porous material.
In another preferred embodiment, the heating temperature in step (iii) is 1000-.
In another preferred embodiment, in the step (iii), the heating is heating under vacuum.
In another preferred embodiment, in the step (iii), the heating temperature is 1200-1600 ℃.
In another preferred embodiment, in the step (iii), the heating time is 0.5 to 4 hours.
In another preferred example, the number of layers of the graphene nanoplatelets is 1-100.
In another preferred example, the number of layers of the graphene nanoplatelets is 5-50.
In another preferred example, the planar size of the graphene nano-sheet is 5-30 um.
In another preferred example, the solvent in the graphene suspension is selected from the group consisting of: methanol, ethanol, isopropanol, n-butanol, cyclohexane, n-hexane, n-octane, acetone, methyl isobutyl ketone, or a combination thereof.
In another preferred example, the solvent in the graphene suspension is selected from the group consisting of: ethanol, n-hexane, acetone, or combinations thereof.
In another preferred embodiment, the concentration of the graphene suspension is 1-50 mg/ml.
In another preferred example, the concentration of the graphene suspension in the step (i) is 5-30 mg/ml.
In another preferred embodiment, the solvent removal treatment in step (ii) comprises the steps of: and heating and drying the graphene suspension to obtain the graphene three-dimensional porous material.
In another preferred embodiment, the temperature for heating and drying is 40-90 ℃.
In another preferred embodiment, in the step (ii), the heating temperature is 60 to 80 ℃.
In another preferred embodiment, in the step (ii), the heating time is 1-20 h.
In another preferred example, in the step (ii), the heating time is 8-16 h.
In a second aspect of the present invention, there is provided a graphene three-dimensional porous material prepared by the method according to the first aspect of the present invention.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be repeated herein, depending on the space.
Drawings
Fig. 1 is a macroscopic photograph of the graphene three-dimensional porous material obtained in example 1.
Fig. 2 is a scanning electron micrograph of the graphene three-dimensional porous material obtained in example 1.
Fig. 3 is a comparison chart of raman of the graphene three-dimensional porous material obtained in example 1 before and after the thermal annealing treatment.
Detailed Description
The present inventors have extensively and intensively studied and unexpectedly found that a graphene three-dimensional porous material with a stable structure and excellent performance can be obtained by using a low surface tension solvent as a graphene dispersion solution and preparing the graphene three-dimensional porous material with high temperature treatment after controllable solvent removal. The use of the low surface tension solvent avoids the problem that the graphene structure collapses due to surface tension in the solvent removing process, and the density and porosity of the prepared graphene three-dimensional porous material are controlled by adjusting the temperature and time of the solvent removing process. The defects of the graphene can be effectively removed through high-temperature annealing, the interaction between graphene interfaces is enhanced, and the strength and the electric and heat conducting properties of the prepared graphene three-dimensional porous material are improved. On the basis of this, the present invention has been completed.
Preparation method of graphene three-dimensional porous material
The invention provides a preparation method of a graphene three-dimensional porous material, which comprises the following steps: uniformly dispersing graphene nano sheets in a solvent to obtain a graphene suspension, and carrying out desolventizing treatment on the suspension to obtain the graphene three-dimensional porous material; wherein the solvent in the graphene suspension is a solvent with the surface tension of 18-25mN/m (25 ℃).
In the preparation method of the present invention, the graphene nanoplatelets used are not particularly limited. Preferably, the number of layers of the graphene nanoplatelets is 5-50. Preferably, the planar size of the graphene nanoplatelets is 5-30 um.
Preferably, the solvent in the graphene suspension is selected from the group consisting of: methanol, ethanol, isopropanol, n-butanol, cyclohexane, n-hexane, n-octane, acetone, methyl isobutyl ketone, or a combination thereof. More preferably, the solvent in the graphene suspension is selected from the group consisting of: ethanol, n-hexane, acetone, or combinations thereof.
In a preferred embodiment, the graphene suspension requires ultrasonic treatment, and the power and time of ultrasonic treatment are not particularly limited. Preferably, the ultrasonic power of the ultrasonic treatment is 50-800W, more preferably 120-600W. Preferably, the sonication time of the sonication is 1-30min, more preferably 3-10 min. In a preferred embodiment, the concentration of the graphene suspension is 1-50 mg/ml. More preferably at a concentration of 5-30 mg/ml.
The solvent removal treatment method is to remove the solvent by heating and drying, and the heating temperature is not particularly limited. Preferably, the heating temperature is 40-100 ℃. More preferably, the heating temperature is 60 to 80 ℃. The heating time is also not particularly limited. Preferably, the heating time is 1-20 h. More preferably, the heating time is 8-16 h.
In a preferred embodiment, the method further comprises the steps of: and after the solvent removal treatment, heating and annealing treatment are carried out to obtain the graphene three-dimensional porous material. Preferably, the heating temperature is 1000-. More preferably, the heating temperature is 1200-. In a preferred embodiment, the heating in step (ii) is heating under vacuum. The heating time is not particularly limited, and preferably, the heating time in the step (ii) is 0.5 to 4 hours.
The advantages of the invention include:
according to the invention, a low surface tension solvent is used as a graphene dispersion liquid, and the graphene three-dimensional porous material prepared by high-temperature treatment after solvent removal is used as an auxiliary material, so that excellent electrical and thermal properties of graphene are maintained. The operation method is simple and rapid, the cost is low, the aperture of the prepared graphene three-dimensional porous material is in a micron scale, the porosity is about 90%, the structure is very stable, the graphene three-dimensional porous material has good electric and heat conduction performance, and the graphene three-dimensional porous material can be widely applied to the fields of heat conduction composite materials, electromagnetic shielding materials and the like.
The invention is further illustrated below with reference to specific embodiments and the accompanying drawings. It is to be understood that the following description is only of the most preferred embodiments of the present invention and should not be taken as limiting the scope of the invention. In the following examples, the experimental methods without specific conditions, usually according to the conventional conditions or according to the conditions suggested by the manufacturers, can be modified by those skilled in the art without essential changes, and such modifications should be considered as included in the protection scope of the present invention.
In the following embodiments of the present invention, the number of graphene layers is 5 to 30, and the average diameter is 3 to 25 μm.
Example 1
(1) And (3) dispersing 1g of graphene nanosheet in 100mL of ethanol solution, and performing ultrasonic treatment for 3min under the power of 120W to obtain a stable graphene suspension with the concentration of 10 mg/mL.
(2) And (2) drying the graphene suspension in the step (1) at 60 ℃ for 10h to remove ethanol, and carrying out vacuum heat treatment at 1250 ℃ for 2 h to obtain the graphene three-dimensional porous material.
Fig. 1 is a macroscopic picture of the graphene three-dimensional porous material prepared in this example, and fig. 2 is a scanning electron micrograph, from which it can be seen that the prepared graphene is a three-dimensional porous structure. FIG. 3 is a Raman contrast diagram of the three-dimensional porous graphene material before and after the thermal annealing treatment in this example, which can be seen to be located at 1337cm -1The D peak is obviously reduced, and the intrinsic defects of the graphene are effectively eliminated by high-temperature annealing. The graphite in the step (2) is addedThe graphene three-dimensional porous material is filled with an epoxy resin material to obtain a graphene/epoxy resin composite material with 6.8 wt% of graphene filler, the horizontal thermal conductivity is 15W/mK, and the electrical conductivity is 35S/cm.
Example 2
The preparation procedure and procedure in this example were substantially the same as in example 1 above, except that: the mass of the graphene nanosheet raw material used in the step (1) is 3 g. And (3) filling the graphene three-dimensional porous material in the step (2) with an epoxy resin material to obtain a graphene/epoxy resin composite material with 5.2 wt% of graphene filler, wherein the thermal conductivity in the horizontal direction is 12W/mK, and the electrical conductivity is 30S/cm.
Example 3
The preparation procedure and procedure in this example were substantially the same as in example 1 above, except that: the solvent used in the step (1) is n-hexane. And (3) filling the graphene three-dimensional porous material in the step (2) with an epoxy resin material to obtain a graphene/epoxy resin composite material with 4.6 wt% of graphene filler, wherein the thermal conductivity in the horizontal direction is 8.6W/mK, and the electric conductivity is 27S/cm.
Example 4
The preparation procedure and procedure in this example are substantially the same as in example 1 above, except that: the solvent used in the step (1) is acetone. And (3) filling the graphene three-dimensional porous material in the step (2) with an epoxy resin material to obtain a graphene/epoxy resin composite material with 5.3 wt% of graphene filler, wherein the thermal conductivity in the horizontal direction is 7.3W/mK, and the electric conductivity is 24S/cm.
Example 5
The preparation procedure and procedure in this example were substantially the same as in example 1 above, except that: in the step (2), the desolventizing temperature is 80 ℃, and the time is 8 h. And (3) filling the graphene three-dimensional porous material in the step (2) with an epoxy resin material to obtain a graphene/epoxy resin composite material with 6.2 wt% of graphene filler, wherein the thermal conductivity in the horizontal direction is 14W/mK, and the electrical conductivity is 32S/cm.
Example 6
The preparation procedure and procedure in this example were substantially the same as in example 1 above, except that: the high-temperature annealing temperature in the step (2) is 1400 ℃, and the time is 4 h. And (3) filling the graphene three-dimensional porous material in the step (2) with an epoxy resin material to obtain a graphene/epoxy resin composite material with 6.8 wt% of graphene filler, wherein the thermal conductivity in the horizontal direction is 30W/mK, and the electrical conductivity is 58S/cm.
Example 7
(1) 3g of graphene nanosheet is dispersed in 100mL of cyclohexane solution, and ultrasonic treatment is carried out for 10min under the power of 600W to obtain stable graphene suspension with the concentration of 30 mg/mL.
(2) And (2) drying the graphene suspension in the step (1) at the temperature of 60 ℃ for 16h to remove cyclohexane, and carrying out vacuum heat treatment at the temperature of 1600 ℃ for 4h to obtain the graphene three-dimensional porous material.
And (3) filling the graphene three-dimensional porous material in the step (2) with an epoxy resin material to obtain a graphene/epoxy resin composite material with 5.1 wt% of graphene filler, wherein the horizontal thermal conductivity is 34W/mK, and the electrical conductivity is 68S/cm.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (2)
1. A preparation method of a graphene/epoxy resin composite material is characterized by comprising the following steps:
(1) dispersing 3g of graphene nanosheets in 100mL of cyclohexane solution, and performing ultrasonic treatment for 10min under the power of 600W to obtain a stable graphene suspension with the concentration of 30 mg/mL;
(2) drying the graphene suspension liquid in the step (1) at the temperature of 60 ℃ for 16h to remove cyclohexane, and carrying out vacuum heat treatment at the temperature of 1600 ℃ for 4 h to obtain a graphene three-dimensional porous material;
(3) and (3) filling the graphene three-dimensional porous material in the step (2) with an epoxy resin material to obtain the graphene/epoxy resin composite material with 5.1 wt% of graphene filler.
2. The method for preparing the graphene/epoxy resin composite material according to claim 1, wherein the composite material has the following characteristics:
1) the horizontal thermal conductivity is 34W/mK;
2) conductivity was 68S/cm.
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